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Electrochemical Properties of Coumarin 500 Encapsulated in a Liquid Crystal Guided Electrospun Fiber Core and Their Supercapacitor Application

Cite this: ACS Appl. Energy Mater. 2022, 5, 10, 12078–12089
Publication Date (Web):September 20, 2022
https://doi.org/10.1021/acsaem.2c01287

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Abstract

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Here, we first report a study on coumarin 500 and liquid crystal including polyacrylonitrile nanofibers in terms of synthesis, characterizations, and supercapacitor performances. SEM, POM, FTIR, and DSC measurements showed that liquid crystal was inserted into the fine polyacrylonitrile nanofibers successfully. Because a strong molecular interaction took place between coumarin 500 and liquid crystal and coumarin 500 was sensitive to the polarity of the medium, the liquid crystal behaved as a guide material for coumarin 500, and it was expected that coumarin 500 was oriented by the director of the liquid crystal along the core of the fiber. The average polyacrylonitrile nanofiber size was between 0.19 to 0.25 μm, and liquid-crystal-doped and liquid-crystal+coumarin-500-doped fibers exhibited a similar distribution, which is approximately in the 0.30 to 0.60 μm interval. This proved that the fibers maintained their structure after modifications. Electrochemical evaluation of the different composite nanofibers showed that there was not a significant current increase upon liquid crystal addition into polyacrylonitrile nanofibers at voltammograms. Cs values were enhanced after the coumarin 500 addition into liquid-crystal-doped nanofiber and obtained as 410.60 F/g with a specific energy value of 57.03 Wh/kg. Additionally, the long-term charge–discharge test of the liquid-crystal+coumarin-500-doped polyacrylonitrile graphite electrode showed a very steady distribution between 100th and the 2500th cycles with a 14.12% Cs deviation. This is attributed to the stable and robust network of the PAN nanofiber and the synergetic effect between liquid crystal and coumarin 500 in the nanofiber net.

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1. Introduction

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Coumarin (2H-1-benzopyran-2-one) is known as a lactone and provides extremely interesting electrochemical and spectro-electrochemical features due to its benzopyrone structure. (1) The adjacent hydrogen atoms and both of the oxygen atoms, which host very active lone electron pairs, easily undergo reduction or oxidation under an electrochemical process or can serve as a useful modifier for conductive polymers. (2,3) Coumarin or its derivatives can be synthesized by Perkin, Pechman, or Kostanecki reactions, and it is naturally produced by a lactonization reaction in various plants. (4) Its odor and taste serve as an allelopathy agent for animals, and a wide range of foods have coumarin. (5) It has been used in medical applications with the name of warfarin as an anticoagulation agent, (6) in the rodenticide industry as 4-hydroxycoumarin to avoid predators such as rats, (7) and used as flavor or to aromatize food or perfumes due to its odor being very like vanilla, (5) but high concentrations of coumarin cause many defects in living organisms. (8,9) The main applications of coumarin are intensively based on the dye laser industry (10) and especially solar energy panels and OLEDs because of the high chromogenic structure it has. (11,12)
To the best of our knowledge, there has not been reported any study about the supercapacitor application of coumarin. Several utilizations were examined, but solely coumarin or its derivatives have never been studied in terms of energy storage applications. Here we tried to create a synergetic effect with another functional molecule between polyacrylonitrile nanofibers and liquid crystals (LCs). LCs are very specific materials which exhibit an intermediate state between isotropic liquids and solid crystals. Both the rheological properties of isotropic liquids and the crystalline order properties of solid crystals are simultaneously represented by LCs in a certain temperature range, namely in a mesophase. Considered the simplest among the mesophases, the nematic (N) mesophase has a weak orientational order where the molecules are arranged on an average along an n-direction vector. These materials are very responsive to external fields such as temperature, electrical, etc., because of having anisotropy. Dielectric properties of LCs are related to their molecular properties such as the orientational order, number density, and any interactions between molecules. The dielectric behavior of liquid crystals conveys the aggregate response of mesogens─meaning the type of liquid crystal exhibiting a particular mesophase─as well as their molecular properties, and there is a relation between the macroscopic polarization and the molecular response via the internal electric field. (13−15) LCs could be mixed with polymers that play the role of host material for example in electrospun fibers. Lagerwall’s research group is one of the leading groups to investigate the coaxial electrospun LC/polymer structures and their potential applications. Lagerwall et al. have generated the coaxial electrospun fibers using a thermotropic nematic LC as a core material and poly(vinylpyrrolidone)/TiO2 mixture as a sheath material. (16) Also, scientists have investigated some potential applications of LC/polymer electrospun fibers such as gas sensors. (17−19) Single-needle electrospinning is a different version of electrospinning apart from the coaxial electrospinning method to generate phase-separated LC/polymer electrospun fibers. Not only the authors (20−23) but also other scientists have reported such fibers containing LCs were formed by a single-needle electrospinning of a precursor of liquid crystal and polymer, and these could be used in various applications. (24−26)
Here, the chemical, optical, and energy storage capabilities of a combination of a nematic LC with the coumarin species in polyacrylonitrile nanofibers are reported for the first time. The study was based on the superior electroactive structure of the coumarin, and the electrocapacitive charge–discharge capability of the electrode was enhanced. The electrode structure is composed of a moderately conductive LC and polyacrylonitrile structures, but the electrochemical catalytic effect of the coumarin is indicated well by using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results. It has been reported another photocatalytic structure added polyacrylonitrile nanofiber as a supercapacitor application, successfully. (27,28) Here again another spectro-electrochemically active large bandgap providing material, coumarin, was utilized as a composite material and examined. The LC and the coumarin were entrapped in the polyacrylonitrile nanofibers by simultaneous electrochemical electrospinning. There is a strong molecular interaction between LCs and azo-dyes, and azo-dyes have intense sensitivity to the polarity of the medium. Thus, LCs behave as a guide material for azo-dyes, and azo-dyes can be oriented by the director of LCs. (29−33) It was shown by the authors (20,21) and even other scientific groups (24−26) that LCs could be encapsulated as a core–sheath structure utilizing the high electric field of single-needle electrospinning. In the case the coumarin is electrospun alone, there might be a possibility that the coumarin may not be fully encapsulated in the core and it may be distributed along the radius of fiber. Therefore, during the electrochemical measurement, some of the coumarin may be dissolved in measurement medium. Then, the possible time-dependent diminishment in the coumarin concentration of fiber may affect the results of long-term electrochemical measurements. The aim was that the coumarin was encapsulated within the core of the spun fibers, so an LC was used as a guide in the present work. Therewithal, the LC was used to supply an electron tunneling effect between nanofibers and coumarin molecules on the pencil graphite electrode (PGE) surface. The electrochemical characterizations are used as initial tests prior to the supercapacitor measurements. Here, the main point is that coumarin was first utilized in a supercapacitor study, and the results exhibited significant Cs values.
In this paper, the preparation of the fiber precursor and fabrication of the modified PGE electrode are presented. The fabricated nanofiber net has been characterized by DSC, POM, SEM, and FTIR. The electrochemical and the supercapacitor measurements revealed the potential of the coumarin and liquid crystal + polyacrylonitrile modified electrode.

2. Experimental Section

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2.1. Chemicals and Apparatus

4′-Heptyl-4-biphenyl carbonitrile (7cb), which is a member of 4-cyano-4′-alkylbiphenyls (nCB) liquid crystals has a rod-like shape with a length of almost 20 Å. (34)Figure 1a demonstrates the molecular formula of 7cb. It was purchased from TCI Inc. and was used as an LC dopant for electrospun fibers. nCBs are one of the well-known liquid crystalline fragments, where the n symbolizes the numbers of carbon atoms in the alkyl chain. 7cb exhibits a nematic (N) mesophase between 20.10 to 39.60 °C in the bulk state. It becomes an isotropic phase and solid crystalline phase above 39.60 °C and below 20.10 °C, respectively. Phase transition temperatures might change depending on research conditions. Due to the presence of a strong dipole moment, good chemical stability, and a convenient temperature range of the liquid crystalline phase, 7cb is a favorable material for LC/polymer composites. (35,36)

Figure 1

Figure 1. Chemical structure of (a) 7cb and (b) c500. (c) Schematic diagram of the electrospinning diagram. (d) A picture of the nanofiber-coated electrode.

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Potassium dihydrogen phosphate (KH2PO4), potassium chloride (KCl), nitric acid HNO3 (99.9%), potassium hydroxide (KOH), sodium nitrate NaNO3(aq), sodium hydroxide NaOH (98.00%), polyacrylonitrile (PAN) (Mw ≈ 150 000), and N,N-dimethylformamide (DMF) (99.80%) were bought from Sigma-Aldrich. Scanning electron microscopy (SEM) with energy dispersive spectroscopy analyzes (EDS) monitored with JEOL, JSM-7600F. Fourier transform infrared spectroscopy (FTIR) measurements were performed with a PerkinElmer-ATR supported FTIR analyzer. Thermogravimetric measurements were recorded with a PerkinElmer-Pyris 6 TGA analyzer for a 4.8 mg sample under 20 mL/min of 2.5 bar of nitrogen gas flow. An Autolab PGSTAT 204 potentiostat/galvanostat (Metrohm) was utilized for electrochemical measurements. NOVA 2.1.4 software was used for the electrochemical measurements.

2.2. Preparation of the Coumarin and LC Composite PAN Nanofibers

The electrospinning method is performed by using several setups including either a collector or needle. One method uses a flat stationary collector depositing the fiber in any orientation. The other specific designs for the collector are to produce fibers aligned in a preferred orientation. (37−39) Here, a rod-shaped electrode collector was used and rotated about an axis parallel to the E-field.
Before the electrospinning process, precursors were prepared with various contents. For electrospinning all fiber types, first, precursor-1 was prepared, for which 7.6 wt % polyacrylonitrile was dissolved in DMF, in accordance with the authors’ previous work, where a fine LC/PAN fiber was obtained. (20) In order to electrospin pure PAN fibers, precursor-1 was used. Then, 7cb was added to the precursor-1 in a 1:1 mass ratio with polyacrylonitrile, and so, precursor-2, which was used for generating the PAN/7CB fibers, was obtained. The last solution, which was named as precursor-3, was prepared by adding c500, individually weighed to 0.27, 0.37, 0.56, 0.65, and 0.75% by mass of 7cb and polyacrylonitrile, to precursor-2. All precursors were gently stirred for 24 h over a magnetic stirrer.
Fibers were electrospun by using the Inovenso S1 electrospinning device, which is schematically given in Figure 1. The device is equipped with a programmable syringe pump of 0.001 mL/h accuracy, a 30.0 kV high voltage source, and a syringe needle of 0.8 mm outer and 0.5 mm inner diameter. In the experimental setup, the syringe needle and the collector were adjusted as the positive pole and negative pole, respectively. The electrode is connected through a conductive shaft to the negative pole. The advantage of the rotating rod method is to maintain that the nanofiber covers the entire electrode surface (Figure 1d). The distance between the needle and the PGE, z, was set and kept constant at 23.0 cm during the electrospinning processes. All fiber types were electrospun under a constant 12.0 kV voltage corresponding to a 522.0 V/cm electric field and were carried out at room temperature with a relative humidity of about 15–20%. Throughout the electrospinning process of the nanofibers, to acquire a fine-electrospinning jet, the feeding rate of precursor was adjusted from 0.13 to 0.25 mL/h depending on the type of the precursor.

2.3. Electrochemical Measurements

Electrochemical measurements of PGE and nanofiber-coated composite electrodes were examined using CV and EIS methods. A 3.00 mL aliquot of 3.00 M KOH (pH 7.20) solution was placed as the electrolyte in the electrochemical cell using the triple-electrode system. In the system where the examined electrode is used as the working electrode, the reference and counter electrodes were Ag/AgCl (containing 3.0 M KCl, CHI115) and a Pt wire electrode (CH Instruments Inc. CHI 111), respectively. CV measurements were performed in the range of −1.00 to 0.0 V, using various scan rates changing from 5 to 100 mV/s scan rate. The frequency range used in EIS measurements is 10–1 to 10–4 Hz. In EIS measurements, 6.00 M KOH solution was used as the electrolyte medium.
Specific capacitance (Cs) (F/g) and specific energy (E) (Wh/kg) values were calculated for composite electrodes using the following equations. (40) Here, m is the mass of electroactive substance on the electrode surface (mg), ΔV is the applied charge–discharge potential (V), S is the scan rate (mV/s), and I refers to the current value (A) obtained from the electrode. The Cs value obtained by using these data was used in the calculation of E.
(1)
(2)
Prior to the characterization and supercapacitor measurements, the amount optimization was conducted for c500 modified electrodes by CV method. As obviously seen in Figure 2, the highest electrochemical signal was obtained for 0.65% c500-containing composite structure. Therefore, it was determined as the optimum c500 amount for further measurements.

Figure 2

Figure 2. Electrochemical evaluation of the c500 amount in the composite electrode structure. Cyclic voltammograms of (a) 0.27, (b) 0.37, (c) 0.56, (d) 0.65, and (e) 0.75%-added electrodes.

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Electrospun fiber precursors were prepared in three different compositions of 7cb, PAN, and c500, and called as samples 1 to 7, tabulated in Table 1. According to the result of amount optimization, so as to become comprehensible, sample-1, sample-2, and sample-6, whose characterization and supercapacitor measurements were carried out, were encoded as PAN, PAN/7CB, and PAN/7CB/C500, respectively.
Table 1. Composition of Each Sample
specimen PAN:DMF (wt %) 7cb:PAN (wt ratio) c500:7cb+PAN (wt ratio) codes of fibers
sample-1 7.6% - - PAN
sample-2 7.6% 1:1 - PAN/7CB
sample-3 7.6% 1:1 0.27:99.73 -
sample-4 7.6% 1:1 0.37:99.63 -
sample-5 7.6% 1:1 0.56:99.44 -
sample-6 7.6% 1:1 0.65:99.35 PAN/7CB/C500
sample-7 7.6% 1:1 0.75:99.25 -

3. Results and Discussion

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3.1. SEM Analysis

High-resolution SEM images of all samples electrospun under 12.0 kV electrospinning voltage are given in Figure 33. All the fibers had no beads, which means inhomogeneity along the fiber. As seen in Figure 3a, the thinnest fibers existed in PAN fibers, which were composed of pure polyacrylonitrile. In the literature, it is given that some electrospinning parameters, which are the viscosity of precursor, the net charge density carried by the electrospinning jet, feeding rate, and the surface tension of precursor, affect the bead formation in electrospun fibers. (41−48) The fibers without beads might be obtained with a rise in surface tension, although beads might exist in fibers with rising in precursor viscosity and charge density. (47)7cb LC was surrounded by a polymer sheath as seen in Figure 3b,c. The thickness distribution of fibers for all samples was examined from 10 000× magnification SEM images by means of the ImageJ analyzing program. Figure 3d–f represents the distribution of the fiber thickness of PAN, PAN/7CB, PAN/7CB/C500, respectively. In the figure, blue columns give the distribution of fiber thickness, and red lines show the Gaussian distribution. A total of 100 different fibers were evaluated at a minimum for each distribution plot. As indicated above, the thinnest fibers were observed for PAN as 0.19 to 0.30 μm despite the substantial distribution between 0.19 to 0.25 μm. The fibers of PAN/7CB and PAN/7CB/C500 have exhibited a similar distribution, which is approximately 0.30 to 0.60 μm (Figure 3e,f); it means that there is not an important effect of the addition of c500 in the change of thickness of fibers, even if c500 is added to precursor at a very low weight. Regarding the enlargement of fiber diameter, it increases with the increase in viscosity of precursor at a fixed needle-to-collector distance, feeding rate, and electrospinning voltage. In a similar vein, average fiber diameter increases with an increase in feeding rate at a fixed needle-to-collector distance, viscosity, and electrospinning voltage. (48) Before PAN/7CB was electrospun, the viscosity of the precursor-2 became a little less than precursor-1 because of adding the LC. As a consequence, it was expected that the thickness of PAN/7CB and PAN/7CB/C500 would be wider than PAN. However, in order to supply a fine fiber jet, the feeding rates for each precursor were 0.13, 0.21, and 0.21 mL/h for precursor-1 to -3, respectively. Considering the change in feeding rate, it was expected that the fiber thickness of PAN was less than PAN/7CB and PAN/7CB/C500 and also the fiber thickness of PAN/7CB and PAN/7CB/C500 was approximately closer to each other, as it has been observed. Here, one might say that the change in feeding rate was more dominant than the change in viscosity of precursor for the variation of the fiber thickness. Besides, the effort of LCs to self-assemble along the fiber axis as a core due to the high electric field might be the reason why PAN/7CB and PAN/7CB/C500, which had LCs in their compositions, existed as thicker fibers.

Figure 3

Figure 3. SEM images of fibers which belong to (a) PAN, (b) PAN/7CB, and (c) PAN/7CB/C500; the thickness distribution of the fibers of (d) PAN, (e) PAN/7CB, and (f) PAN/7CB/C500.

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Fibers were electrospun at a 12.0 kV electrospinning voltage and a 23.0 cm needle-to-collector distance. The scale bar represents 1 μm. The thickness of fibers was analyzed from SEM images. PAN, PAN/7CB, and PAN/7CB/C500 correspond to Figure 3(d–f), respectively. Blue columns give the distribution of fiber thickness, and red lines point out Gaussian distribution. The scale bar in SEM images represents 1 μm.

3.2. POM Analysis

Fiber morphology was investigated using POM aside from SEM, and relative images are given in Figure 4. In accordance with SEM results, it has obviously occurred that the thickness of PAN fiber was narrower than the others (Figure 4a). Similarly, fiber structures appeared quite homogeneous, i.e., beadless or barely beads, accordingly in SEM images. Images were shot under crossed polarizers with and without an optical retarder so as to show the presence of LCs in the fiber structure utilizing the difference between the birefringence of polyacrylonitrile and 7cb, which is almost 0.01 (49) and 0.25 (50) at 23.0 °C, respectively. As seen in Figure 4a,b, PAN fibers were clearly seen by means of an optical retarder, but the fibers were not appearing under crossed polarizers as polyacrylonitrile had low birefringence. On the contrary, PAN/7CB and PAN/7CB/C500 fibers appeared under crossed polarizers both with and without an optical retarder as shining stripes (Figure 4d–f). The shining magnitude of LCs depends on the plenary angle of fiber with respect to one of the polarizers in straight aligned LCs. (51) The authors have reported in their previous work that a low-molecular-weight LC was planarly self-ordered within the core of the polymer sheath owing to the large ordering force during the electrospinning. (20) The fiber stripes, which include 7cb, appear brighter as the stripes approach an angle of 45° as to the polarizer, whereas the stripes appear darker as they approach 0°.

Figure 4

Figure 4. POM images of fibers cumulated on microscope slides are presented in (a,c,e) between crossed polarizers with a 137 nm optical retarder and in (b,d,f) without any retarder. (a,b), (c,d), and (e,f) are associated with PAN, PAN/7CB, and PAN/7CB/C500, respectively. Fibers were electrospun at a 12.0 kV application voltage and a 23.0 cm needle-to-collector distance. The scale bar represents 100 μm.

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3.3. DSC Analysis

To prove the existence of the 7cb LC within the fiber, DSC measurement was performed as well. DSC is a beneficial technique that enables information about the phase transition region of LCs. (20,26,52) DSC thermographs of bulk PAN, bulk 7cb, and PAN/7CB fiber for both heating and cooling were merged in Figure 5. Measurements were carried out from 32.0 to 50.0 °C for all specimens with a 5.0 °C/min scanning rate. As seen in Figure 5, bulk polyacrylonitrile did not exhibit any peak during both heating and cooling; namely, there was not any phase transition in this temperature interval. However, for 7cb, a small endothermic peak and a small exothermic peak were taken place at 39.5 and 38.5 °C; the peaks stood for nematic–isotropic (N–I) and isotropic–nematic (I–N) phase transitions, respectively. These peaks pointed out a weak first order phase transition between N and I phases. (53) Comparably, a few weak peaks rose at 41.1 °C for heating and 40.0 °C for cooling in the DSC thermograph of PAN/7CB(Figure 5). These peaks were associated with phase transition between the N and I phase and were due to the presence of 7cb in the composite. In Figure 5, N–I and I–N phase transition peaks did not point at the same temperature for both bulk 7cb and PAN/7CB that included 7cb. For LCs, temperature shifts at phase transitions during heating and cooling like this, which are due to superheating and supercooling of LC, represent thermal hysteresis that means a first-order phase transition and is a characteristic behavior for such LCs. (54−58) Thereafter, the existence of 7cb within the fiber could be verified with the results of DSC. It is crucial to state that showing the DSC analyses of c500-doped fiber (PAN/7CB/C500) was found unnecessary here since the c500 does not possess any phase transition at the scanning temperature interval in which the DSC analysis was done.

Figure 5

Figure 5. DSC thermographs of bulk 7cb, bulk polyacrylonitrile, and the PAN/7CB fiber.

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3.4. FTIR Analysis

The IR analysis has been carried out in the range of 4000–600 cm–1 presented in Figure 6. The IR spectra of bulk polyacrylonitrile, 7cb, and c500 have been analyzed in comparison with that of their fibers, PAN/7CB and PAN/7CB/C500. Basically, it has been found the fibers of PAN/7CB and PAN/7CB/C500 reflect the absorption of its compositions. Being a rigid chain, the PAN fiber showed slight absorption in its IR spectra in a comparison with that of its PAN/7CB and PAN/7CB/C500 fibers. 7cb and c500 exhibit characteristic and strong absorptions in both IR spectra of 7cb and c500, and these peaks are maintained in the PAN/7CB and PAN/7CB/C500 fibers. Some of the absorptions are tabulated in Table 2.
Table 2. Some Distinguishing Vibration Frequencies of the Samples
  mode PAN 7CB PAN/7CB PAN/7CB/C500
wavenumber (cm–1) υ(C≡N) 2243 2227 2227 2227
υ(C=C) --- 1605 1606 1605
υ(C–F) --- --- --- 1113

Figure 6

Figure 6. FTIR spectra of PAN, 7cb, c500, and their nanofiber composites.

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3.5. Electrochemical Measurement Results

A series of electrochemical characterizations were carried out to evaluate the electroactivity of both 7cband c500in PAN nanofiber on the PGE electrode surface for further supercapacitor measurements. Voltammetric measurements and impedance spectra of PGE/PAN, PGE/PAN/C500, PGE/PAN/7CB, and PGE/PAN/7CB/C500 electrodes were examined in terms of peak current changes and Nyquist plots (Figure 7a–c). In general, the coating of the active PGE surface creates an electron hindrance effect, and the current value of the PGE electrode decreases. (22) However, the point is that using electron tunneling and the host effect of these fine PAN nanofibers is an exciting area and needs to be explored. (59) There has been reported plenty of supercapacitors with excellent outputs, (60−63) and the contribution of these nanofibers can contribute to the responses significantly. Here, the electrochemical contributions of the individual modifiers (7cb and c500) to the PAN-coated PGE was evaluated. It has seen that both 7cb and c500 increased the electrochemical response of the PGE/PAN electrode as given in Figure 7a,b. A detailed comparison of the voltammograms obtained from PGE/PAN and PGE/PAN/7CB electrodes is shown in Figure 7b. In this figure, one can conclude that there has been no significant current increase after the 7cb addition into the PAN nanofiber structure. This behavior is attributed to the long neutral chain of the 7cb ionic liquid structure, and it is used for the remote and the entrapment of c500 molecules, which are really abundant in electron donor groups. Apparently, c500 addition into the electrode structure made a significant increase at the peaks even higher than that of the PGE/PAN/C500 electrode. The peak current increased 10-fold (Figure 7a) after the c500 addition, due to the chromogenic groups that c500 has exhibited excellent electroactive performance. And the current increment between PGE/PAN/C500 and PGE/PAN/7CB/C500 electrodes is related to the host and rotating effect of the IL structure on the c500 molecules, which give a healthy gate through the electrode surface. Such electron wiring and tunneling effects have been used for decades by many electrochemists for triggering diffusion of the electrons. (64,65) When the Nyquist plots are examined, they are observed as linear spectra, and the best fitting circuit was found as [RCW] indicating Warburg’s impedance process. Here, the circuit elements are referring to Rct, the charge transfer resistance, C, the capacitance, W, the Warburg’s impedance; corresponding parameter values are indicated on the Figure 7d. Also, chi-square value is observed as 0.054, which indicates high correlation with the fitting curve. The electron transfer capability of the electrode surface increases proportionally with the slopes of these linear parts of Nyquist plots. Therefore, PGE/PAN, PGE/PAN/C500, PGE/PAN/7CB, and PGE/PAN/7CB/C500 electrodes showed compatible spectra with the current value increments obtained from CV results. Here, c500 showed the maximum slope value, and then, the 7cb-added electrode has a lower slope, and the PGE/PAN electrode showed the minimum slope (Figure 7c).

Figure 7

Figure 7. Electrochemical characterizations of developed electrodes. (a) Cyclic voltammogram of (a) all nanofiber modified PGE electrodes, (b) detailed CV presentation of the PGE/PAN and PGE/PAN/7CB electrodes, (c) Nyquist plot of the nanofiber modified PGE electrodes, and (d) Nyquist plot of the 7cb-c500 nanofiber modified PGE electrode and its equivalent circuit.

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3.6. Electrochemical Supercapacitance Measurements

After the CV and EIS characterizations of the developed nanofibers, it has been evaluated that c500 made the highest electrochemical contribution to the composite nanofiber structure. Then, the supercapacitive performances of the different nanofibers were evaluated in the 3.00 M KOH (pH 7.20) solution for different scan rates given in Table 3 with the corresponding Cs values. The results showed that the capacitance of the PGE/PAN electrode was decreased after 7cb addition into the structure. Cs values of the PGE/PAN were obtained higher than the PGE/PAN/7CB for all scan rates even at the best scan rate performances (15.77 F/g for PGE/PAN and 11.85 F/g for PGE/PAN/7CB). This is attributed to the electrochemical inhibition effect of the 7cb structure, which does not provide free and active polar and electroactive pairs or functional groups’ instead, it has nonpolar rings and a long alkane chain. So, the charge–discharge capability of the nanofiber is hindered; hence, the structure has two ends. The one end is nonpolar, and it is easy to penetrate the pores of the nonpolar PAN nanofiber, but the CN end is very likely to act as a Lewis acid toward c500 molecules. Thereafter, the Cs values obtained from the PGE/PAN/7CB/C500 electrode showed a significant increase due to most probably this Lewis acid–base interaction between the very reactive O and CN groups of c500 and 7cb. Also, the specific energy value was obtained as 57.03 Wh/kg. Here, the main point is the presence of PAN nanofiber as a supporting backbone. In Figure 8, the current density–potential results are overlapped, and the best Cs values obtained from different scan rate measurements are indicated on each electrode configuration. Here, the synergetic effect of the polyacrylonitrile, 7cb, and c500 structures can be indicated more clearly. As the peak resolutions and the current density values were examined with the corresponding Cs values given in Table 3, it can be clearly concluded that the electron controlling mechanism is enhanced by the combination of 7cb with c500 in those PAN nanofiber cores (Table 3).
Table 3. Cs Values of the PAN, PAN/7CB, and PAN/7CB/C500 Modified PGE Electrodes for Different Scan Rates
  specific capacitances of electrodes (F/g)
scan rate (mV/s) PGE/PAN PGE/PAN/7CB PGE/PAN/7CB/C500
5 10.88 9.69 24.56
10 10.03 10.03 39.70
20 15.77 9.35 52.63
50 3.80 11.85 86.54
100 1.18 10.79 410.60

Figure 8

Figure 8. Cyclic voltammograms of (a) PGE/PAN, (b) PGE/PAN/7CB, and (c) PGE/PAN/7CB/C500 electrodes at scan rate from 5 to 100 mV/s.

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In Figure 9a, the charge–discharge cycling behavior of PGE/PAN/7CB/C500 electrode, and the long-term specific capacitance stability of the electrode are given in Figure 9b. Since the best Cs value was observed at the 100 mV/s scan rate for PGE/PAN/7CB/C500, the long-term measurements were recorded at 100 mV/s for 2500 cycles. Obtained Cs values were as 410.60 F/g for the first cycle and 597.13 F/g for the 2500th cycle. Due to the electron transfer and diffusion of the electrons controlled by multiple mechanisms─especially in the presented electrode composition─the Cs values were stabilized after the 100th cycle, and the obtained recoveries were given in Figure 9b for every 100th measurement. This is attributed to the relatively low stabilization behavior of the carbonaceous materials in high charge–discharge occurrence. (66) The results showed a very steady distribution among 100% values, and the difference between the 100th and the 2500th Cs values was observed as 86.00%.

Figure 9

Figure 9. Cyclic stability of the PGE/PAN/7CB/C500 electrode. (a) Plots of 1st and 2500th cycles, and (b) Cs values of each 100th measurement and their correlation.

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In Table 4, Cs values of materials investigated in recent studies are given. Comparing our study and the results in the literature, the Cs value of PGE/PAN/7CB/C500 is almost 2 times larger than those of the electrodes previously reported.
Table 4. Comparison of Cs Values Obtained from the Present Study and the Literature
supercapacitor composition specific capacitance value (F/g) measurement medium
PEDOT polymerized into cellulose paper matrix (67) 179 PVA
zirconia-based carbon nanofiber (68) 140 6 M KOH
nanocellulose cathode, HPC/NiCo2O4 (69) 235, 211, 196, 170, and 150 -
N-doped graphene obtained by microwave irradiation (70) 200 1 M H2SO4
N-doped graphene obtained by microwave irradiation (70) 130 6 M KOH
d-MOF-808@PANI at d-MOF/PANI (71) 188.00 1.0 M KOH
nitrogen-doped carbon foam was prepared on the basis of polyacrylamide gel (72) 224.4 3.0 M KOH
MnO2 nanoparticles with acetylene black and polyvinylidene fluoride electrode (73) 202 1 M Na2SO4
peanut-like Mn2O3/C, carbon black, and polytetrafluoroethylene (PTFE) (74) 158.8 1.0 M Na2SO4
Mn2O3@MnO2 composite nanofibers (75) 225.0 1 M Na2SO4
deep-eutectic solvent with porous nitrogen-doped carbon (76) 235.8 6 M KOH
PAN/7CB/C500 (present study) 410.60 6 M KOH
In our previously reported supercapacitor studies, original modifications of carbon-based electrodes have been investigated. It has to be underlined that there is an excellent improvement at the specific capacitance values. Our first supercapacitor study was about the modification of carbon paste electrodes with human-hair-sourced activated carbons with a very low Cs value of 26.88 F/g. (77) This value was improved with the addition of graphene-like hair fibers to the electrode structure, and the Cs value was obtained as 139.00 F/g. (78) In the most recent PAN nanofiber and TiO2 nanoparticle including paper, a 156.00 F/g value was reached. (27) This is very important in that TiO2 nanoparticles and PAN nanofibers created a synergetic effect, and here, the same effect is seen between 7cb and c500 in the nanofiber net. As it is always sought for recycled materials to contribute to the energy field, here, two radical structures such as 7cb and c500 were used in a supercapacitor application for the first time. This makes the presented examination very valuable.

4. Conclusions

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Here polyacrylonitrile, 7cb, and c500 were first combined in a nanofiber net and examined in terms of physical, chemical, and electrochemical properties and finally applied as an energy storage device. Therefore, SEM, POM, FTIR, and DSC measurements were carried out. Because of the strong molecular interaction between 7cb and c500 and the high sensitivitiy of c500 to the polarity of the medium, 7cb was used as a guide material in order to align the c500 molecules throughout the fiber core.

  • SEM results showed that fine and beadless nanofibers were achieved, and besides, the thinnest fibers were observed for PAN, as 0.19 to 0.30 μm, even though they were substantially distributed between 0.19 to 0.25 μm. Whereas, PAN/7CB and PAN/7CB/C500 exhibited a similar distribution, which is approximately 0.30 to 0.60 μm. Therefore, it means that there was not an important effect of 7cb and c500 in the change of thickness of PAN nanofibers.

  • POM and DSC measurements were carried out to explain 7cb presence in the PAN nanofibers. POM analysis shows that 7cb exists in the core of fibers considering the irradiance of images of PAN and 7cb, which possess different birefringence. Moreover, the thermic peaks for the fiber with 7cb (PAN/7CB), which are comparable with thermic peaks of bulk 7cb, are associated with phase transition between N and I phases, namely, DSC results proved the existence of 7cb in the PAN/7CB fiber.

  • FTIR measurements supported the existence of 7cb and c500 in the fiber net. The enhancement of the peak intensities of corresponding −CN, −CC, and −CF bonds proved that the modified PAN nanofibers were successfully produced.

  • Electrochemical evaluation of the different composite nanofibers showed that there was not a significant current increase upon 7cb addition into PAN nanofibers. Cs values were also lowered after 7cb addition. The main peak increment and the Cs value enhancement were seen after c500 addition into PAN/7CB nanofiber as 410.60 F/g, and the specific energy value was obtained as 57.03 Wh/kg. Additionally, a long-term charge–discharge test of the PAN/7CB/C500 modified PGE showed a very steady distribution among 100% value, and the difference between the 1st and the 2500th Cs values was observed as 145.43%. This is attributed to the stable and robust network of PAN nanofiber and the synergetic effect between 7cb and c500 in the nanofiber network.

Author Information

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  • Corresponding Author
  • Authors
    • Atilla Eren Mamuk - Department of Physics, Faculty of Science, Mugla Sitki Kocman University, 48050 Mugla, Turkiye;  Orcidhttps://orcid.org/0000-0002-1524-3342
    • Sema Aslan - Department of Chemistry, Faculty of Science, Mugla Sitki Kocman University, 48050 Mugla, Turkiye
    • Derya Bal Altuntaş - Department of Bioengineering, Faculty of Engineering and Architecture, Recep Tayyip Erdogan University, 53100 Rize, Turkiye
  • Author Contributions

    A.E.M.: generating the electrospun-fiber-coated electrodes; analyzing and interpreting the POM, SEM, and DSC data; writing the paper. Ç.K.: generating the electrospun-fiber-coated electrodes; analyzing and interpreting the FTIR data; enhancing the rod-shaped electrode–collector setup; organizing the process. S.A.: performing the electrochemical measurements and analyzing the relevant data; writing the paper; interpreting the electrochemical properties of the electrodes. D.B.A.: performing the electrochemical measurements and analyzing the relevant data; interpreting the electrochemical properties of the electrodes.

  • Funding

    This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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The authors acknowledge the technical support of The Center of Research Laboratories and Molecular Nano Materials Laboratory, which are incorporated with Mugla Sitki Kocman University.

Abbreviations

ARTICLE SECTIONS
Jump To
LC

liquid crystal
7cb

4′-heptyl-4-biphenyl carbonitrile (bulk)
nCB

4-cyano-4′-alkylbiphenyls
PAN

polyacrylonitrile (bulk)
c500

coumarin 500 (bulk)
POM

polarized optical microscopy
SEM

scanning electron microscopy
FTIR

Fourier transform infrared spectroscopy
DSC

differential scanning calorimetry
PAN

polyacrylonitrile fiber
PAN/7CB

7cb-doped polyacrylonitrile fiber
PAN/7CB/C500

7cb and c500-doped polyacrylonitrile fiber
PGE

pencil graphite electrode
PGE/PAN

polyacrylonitrile fiber coated over pencil graphite
PGE/PAN/7CB

7cb-doped polyacrylonitrile fiber coated over pencil graphite
PGE/PAN/7CB/C500

7cb and c500-doped polyacrylonitrile fiber coated over pencil graphite
CV

cyclic voltammetry EIS electrochemical impedance spectroscopy

References

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    Introduction
    Chipot, Christophe; Shell, M. Scott; Pohorille, Andrew
    Springer Series in Chemical Physics (2007), 86 (Free Energy Calculations), 1-31CODEN: SSCPDA; ISSN:0172-6218. (Springer GmbH)
    A review on free energy calcns. To understand fully the vast majority of chem. processes, it is often necessary to examine their underlying free energy behavior. This is the case, for instance, in protein-ligand binding and drug partitioning across the cell membrane. These processes, which are of paramount importance in the field of computer-aided, rational drug design, cannot be predicted reliably without knowledge of the assocd. free energy changes. The reliable detn. of free energy changes using numerical simulations based on the fundamental principles of statistical mechanics is now within reach. Developments on the methodol. front in conjunction with the continuous increase in computational power have contributed to bringing free energy calcns. to the level of robust and well-characterized modeling tools, while widening their field of applications.
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  15. 15
    Al-Ahmed, A.; Sarı, A.; Mazumder, M. A. J.; Hekimoǧlu, G.; Al-Sulaiman, F. A.; Inamuddin Thermal Energy Storage and Thermal Conductivity Properties of Octadecanol-MWCNT Composite PCMs as Promising Organic Heat Storage Materials. Sci. Reports 2020, 10, 9168,  DOI: 10.1038/s41598-020-64149-3
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    15
    Thermal energy storage and thermal conductivity properties of Octadecanol-MWCNT composite PCMs as promising organic heat storage materials
    Al-Ahmed, Amir; Sari, Ahmet; Mazumder, Mohammad Abu Jafar; Hekimoglu, Gokhan; Al-Sulaiman, Fahad A.; Inamuddin
    Scientific Reports (2020), 10 (1), 9168CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)
    Fatty alcs. have been identified as promising org. phase change materials (PCMs) for thermal energy storage, because of their suitable temp. range, nontoxicity and can be obtained from both natural and synthetic sources. Like all other org. PCMs, octadecanol (OD) as PCM suffers from low thermal cond. (TC). In this work, to enhance its TC, it was grafted on the functionalized MWCNT and were used as a conductive filler to enhance overall thermal properties of OD in a composite PCM (CPCMs) structure. The OD/OD-g-MWCNT sample showed better dispersion within the composites and the presence of addnl. OD boosted the overall heat storage enthalpy compared to that of plane composite sample with OD/MWCNT. In a non-quant. approach, it was obsd. that, any increase in grafting ratio of OD increases the heat storage enthalpy of the composites. The heat storage enthalpy of (267.7 J/g) OD/OD-g-MWCNT(4:1)-5wt% composite PCM had reached very close to the heat storage enthalpy value of pure OD (269.3 J/g), and much higher than that of OD/MWCNT-5wt% (234.5 J/g). Champion sample i.e.OD/OD-g-MWCNT (4:1)-5wt%, showed good heat storage enthalpy, cycling performance, thermal stability and TC enhancement by 262.5%.
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  16. 16
    Lagerwall, J. P. F.; McCann, J. T.; Formo, E.; Scalia, G.; Xia, Y. Coaxial Electrospinning of Microfibres with Liquid Crystal in the Core.. Chem. Commun. 2008, 42, 5420,  DOI: 10.1039/b810450f
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  17. 17
    Reyes, C. G.; Sharma, A.; Lagerwall, J. P. F. Non-Electronic Gas Sensors from Electrospun Mats of Liquid Crystal Core Fibres for Detecting Volatile Organic Compounds at Room Temperature.. Liq. Cryst. 2016, 43 (13–15), 1986– 2001,  DOI: 10.1080/02678292.2016.1212287
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    17
    Non-electronic gas sensors from electrospun mats of liquid crystal core fibres for detecting volatile organic compounds at room temperature
    Reyes, Catherine G.; Sharma, Anshul; Lagerwall, Jan P. F.
    Liquid Crystals (2016), 43 (13-15), 1986-2001CODEN: LICRE6; ISSN:0267-8292. (Taylor & Francis Ltd.)
    Non-woven mats comprised of liq. crystal-functionalized fibers are coaxially electrospun to create soft gas sensors that function non-electronically, thus requiring no power supply, detecting org. vapors at room temp. The fibers consist of a poly(vinylpyrrolidone) (PVP) sheath surrounding a core of nematic 4-cyano-4'pentylbiphenyl (5CB) liq. crystal. Several types of mats, contg. uniformly cylindrical or irregular beaded fibers, in uniform or random orientations, are exposed to toluene vapor as a representative volatile org. compd. Between crossed polarizers all mats respond with a fast (response time on the order of a second or faster) redn. in brightness during gas exposure, and they return to the original state upon removal of the gas almost as quickly. With beaded fibers, the response of the mats is visible even without polarizers. We discuss how variations in fiber spinning conditions such as humidity level and the ratio of core-sheath fluid flow rates can be used to tune fiber morphol. and thereby the response. Considering future development perspectives, we argue that fibers turned responsive through the incorporation of a liq. crystal core show promise as a new generation of sensors with textile form factor, ideal for wearable technol. applications.
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  18. 18
    Schelski, K.; Reyes, C. G.; Pschyklenk, L.; Kaul, P.-M.; Lagerwall, J. Quantitative Volatile Organic Compound (VOC) Sensing with Liquid Crystal Core Fibers.. Cell Reports Phy. Sci. 2021, 2, 100661,  DOI: 10.1016/j.xcrp.2021.100661
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    18
    Quantitative volatile organic compound sensing with liquid crystal core fibers
    Schelski, Katrin; Reyes, Catherine G.; Pschyklenk, Lukas; Kaul, Peter-Michael; Lagerwall, Jan P. F.
    Cell Reports Physical Science (2021), 2 (12), 100661CODEN: CRPSF5; ISSN:2666-3864. (Elsevier Inc.)
    Polymer fibers with liq. crystals (LCs) in the core have potential as autonomous sensors of airborne volatile org. compds. (VOCs), with a high surface-to-vol. ratio enabling fast and sensitive response and an attractive non-woven textile form factor. We demonstrate their ability to continuously and quant. measure the concn. of toluene, cyclohexane, and isopropanol as representative VOCs, via the impact of each VOC on the LC birefringence. The response is fully reversible and repeatable over several cycles, the response time can be as low as seconds, and high sensitivity is achieved when the operating temp. is near the LC-isotropic transition temp. We propose that a broad operating temp. range can be realized by combining fibers with different LC mixts., yielding autonomous VOC sensors suitable for integration in apparel or in furniture that can compete with existing consumer-grade electronic VOC sensors in terms of sensitivity and response speed.
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  19. 19
    Reyes, C.; Lagerwall, J. P.; Muševič, I.; Chien, L.-C.; Broer, D. J.; Chigrinov, V. G. Advancing Flexible Volatile Compound Sensors Using Liquid Crystals Encapsulated in Polymer Fibers. SPIE 10555, Emerging Liquid Crystal Technologies XIII 2018, 105550O,  DOI: 10.1117/12.2292533
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  20. 20
    Mamuk, A. E.; Koçak, Ç.; Demirci Dönmez, Ç. E. Production and Characterization of Liquid Crystal/Polyacrylonitrile Nano-Fibers by Electrospinning Method.. Colloid Polym. Sci. 2021, 299 (7), 1209– 1221,  DOI: 10.1007/s00396-021-04842-5
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    20
    Production and characterization of liquid crystal/polyacrylonitrile nano-fibers by electrospinning method
    Mamuk, Atilla Eren; Kocak, Cagdas; Demirci Donmez, Cigdem Elif
    Colloid and Polymer Science (2021), 299 (7), 1209-1221CODEN: CPMSB6; ISSN:0303-402X. (Springer)
    We present that high birefringent nematic liq. crystal, 4-n-pentyl-4'-cyanobiphenyl, was incorporated into the polyacrylonitrile precursor which has a strong polar cyano group so as to produce electrospun nano-fibers, as the first time. Optical textures of nano-fibers were taken by polarized optical microscopy with different angles to det. the orientation degree of liq. crystal mols. in the center of the fiber. The mols. of liq. crystal self-ordered within the core of the fiber. Variation in morphol. of liq. crystal/polymer nano-fibers were examd. by utilizing both SEM and polarized optical microscopy depending on liq. crystal concn. in precursor and application voltage during electrospinning. Morphol. of nano-fibers was significantly affected by electrospinning parameters and liq. crystal/polymer ratio. To understand phase sepn. and thermal stability of nano-fibers, calorimetric and thermogravimetric analyzes were performed.
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  21. 21
    Koçak, Ç.; Mamuk, A. E.; Demirci Dönmez, E. Ç.; Poyraz, M. Electrospun Fibers of Liquid Crystal Mixtures.. J. Mater. Sci. Mater. Electron. 2022, 33, 15209– 15221,  DOI: 10.1007/s10854-022-08439-8
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    21
    Electrospun fibers of liquid crystal mixtures
    Kocak, Cagdas; Mamuk, Atilla Eren; Demirci Donmez, Cigdem Elif; Poyraz, Mehmet
    Journal of Materials Science: Materials in Electronics (2022), 33 (18), 15209-15221CODEN: JSMEEV; ISSN:0957-4522. (Springer)
    Electrospinning is a powerful and promising technique in prodn. of nano-materials namely nano-fibers. Nano-sized materials show properties apart from their macroscopic/bulk sizes, and enable us to fabricate materials that could be designed as functional composites of different kinds of materials. We electrospun to form core-sheath nanofibers composed of polyacrylonitrile (PAN) sheath with a core of widely used nematic liq. crystals (6CB and 8CB) by blending them in various ratios. The nano-fibers were fabricated in different conditions regarding the feeding rate and electrospinning voltage. The phys. properties were investigated. Optical properties revealed the birefringence of the nano-fibers which is an important property for the light modulating devices. The thicknesses of the nano-fibers were detd. from SEM images and the distribution of the thickness was shown in a histogram. The thermal studies put forward the N-I transition temps. of the liq. crystal/PAN nano-fibers, that the temps. were in compliance with that of liq. crystals. It can control light modulation by tuning such liq. crystal/fiber material known to be usable in optoelectronics.
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  22. 22
    Aslan, S.; Bal Altuntaş, D.; Koçak, Ç.; Kara Subaşat, H. Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes.. Electroanalysis 2021, 33 (1), 120– 128,  DOI: 10.1002/elan.202060239
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    22
    Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes
    Aslan, Sema; Bal Altuntas, Derya; Kocak, Cagdas; Kara Subasat, Huelya
    Electroanalysis (2021), 33 (1), 120-128CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The TiO2 nanoparticles are electrospun with polyacrylonitrile (PAN) polymer soln. onto the discharged battery coal (DBC) electrode and the results are evaluated as a supercapacitor. The morphol. and chem. compn. of the synthesized TiO2 nanoparticles and PAN+TiO2 nanocomposite fibers were characterized by SEM, thermogravimetry and FTIR anal. Supercapacitor measurements and electrochem. characterizations of the electrodes examd. by cyclic voltammetry and electrochem. impedance spectroscopy. Electrochem. measurements showed that the best current value was obtained from PAN and TiO2 coated DBC. The performances of both PAN and PAN+TiO2 coated DBC electrodes were investigated as supercapacitors. PAN+TiO2/DBC showed the best specific capacitance value of 156.00 F g-1 and PAN/DBC showed 74.93 F g-1. In addn., PAN+TiO2/DBC exhibited reliable stability performance over 2000.00 cycles.
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  23. 23
    Aslan, S. An Electrochemical Immunosensor Modified with Titanium IV Oxide/Polyacrylonitrile Nanofibers for the Determination of a Carcinoembryonic Antigen.. New J. Chem. 2021, 45 (12), 5391– 5398,  DOI: 10.1039/D0NJ05385F
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    23
    An electrochemical immunosensor modified with titanium IV oxide/polyacrylonitrile nanofibers for the determination of a carcinoembryonic antigen
    Aslan, Sema
    New Journal of Chemistry (2021), 45 (12), 5391-5398CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)
    Carcinoembryonic antigen (CEA) is considerably addressed for the clin. diagnosis of misc. tumor types. In this study, an electrochem. immunosensor for the detn. of the CEA biomarker was presented. Titanium(IV) oxide nanoparticle (TiO2np)-loaded polyacrylonitrile nanofibers (PANnf) were prepd. by electrospinning at the surface of the discharged battery coal electrode (DBC), and loaded with CEA antibodies (Anti-CEA) as the CEA biomarker receptor. Finally, DBC/PANnf + TiO2np/Anti-CEA was utilized for the CEA detection. Fabrication steps were characterized by cyclic voltammetry and electrochem. impedance spectroscopy in the presence of a [Fe(CN)6]3-/4- probe. Results demonstrated that PANnf and TiO2nps exhibited a very fine network for immunosensing. The usage of this composite system is a novel immunosensor development approach for the label-free detection of CEA. Under optimal conditions, the DBC/PANnf + TiO2np/Anti-CEA immunosensor exhibited high sensitivity toward the CEA biomarker in the low concn. range of 0.01-10 ng mL-1, with the detection limit of 0.01 ng mL-1 and relative std. deviation of 1.17 (n = 5). Results indicated that even very small changes in the CEA concn. can be sensed with the presented system. Also, the recovery of the immunosensor was found to be 99.42% ± 1.41 in real sera samples contg. dopamine and ascorbic acid. It has great potential in the clin. screening of divergent cancer biomarkers.
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  24. 24
    Wang, J.; Jákli, A.; West, J. L. Liquid Crystal/Polymer Fiber Mats as Sensitive Chemical Sensors.. J. Mol. Liq. 2018, 267, 490– 495,  DOI: 10.1016/j.molliq.2018.01.051
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    24
    Liquid crystal/polymer fiber mats as sensitive chemical sensors
    Wang, Junren; Jakli, Antal; West, John L.
    Journal of Molecular Liquids (2018), 267 (), 490-495CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
    We present quant. measurements of the optical response of liq. crystal (LC)/polymer composite fiber mats to toluene and acetone vapors. Our analyses in comparison with control measurements of pure LC film and polymer fiber mats show that the chems. can pass through the polymer sheath of the fibers and be absorbed by the LC in the core. This absorption changes the optical properties of the fiber mats which can be used to produce sensitive and reversible detection. The sensitive response at low concns. of both acetone and toluene demonstrates the feasibility of using these fibers for highly sensitive and specific sensors for volatile org. compd. detection.
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  25. 25
    Wang, J.; Jákli, A.; West, J. L. Morphology Tuning of Electrospun Liquid Crystal/Polymer Fibers.. ChemPhysChem 2016, 17 (19), 3080– 3085,  DOI: 10.1002/cphc.201600430
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    25
    Morphology Tuning of Electrospun Liquid Crystal/Polymer Fibers
    Wang, Junren; Jakli, Antal; West, John L.
    ChemPhysChem (2016), 17 (19), 3080-3085CODEN: CPCHFT; ISSN:1439-4235. (Wiley-VCH Verlag GmbH & Co. KGaA)
    This paper elucidates the means to control precisely the morphol. of electrospun liq. crystal/polymer fibers formed by phase sepn. The relative humidity, soln. parameters (concn., solvent), and the process parameter (feed rate) were varied systematically. We show that the morphol. of the phase-sepd. liq. crystal can be continuously tuned from capsules to uniform fibers with systematic formation of beads-on-a-string structured fibers in the intermediate ranges. In all cases, the polymer forms a sheath around a liq.-crystal (LC) core. The width of the polymer sheath and the diam. of the LC core increase with increasing feed rates. This is similar to the results obtained by coaxial electrospinning. Because these fibers retain the responsive properties of liq. crystals and because of their large surface area, they have potential applications as thermo-, chemo-, and biosensors. Because the size and shape of the liq.-crystal domains will have a profound effect on the performance of the fibers, our ability to precisely control morphol. will be crucial in developing these applications.
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    Buyuktanir, E. A.; Frey, M. W.; West, J. L. Self-Assembled, Optically Responsive Nematic Liquid Crystal/Polymer Core-Shell Fibers: Formation and Characterization.. Polymer (Guildf). 2010, 51 (21), 4823– 4830,  DOI: 10.1016/j.polymer.2010.08.011
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    There is no corresponding record for this reference.
  27. 27
    Aslan, S.; Bal Altuntaş, D.; Koçak, Ç.; Kara Subaşat, H. Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes.. Electroanalysis 2021, 33, 120– 128,  DOI: 10.1002/elan.202060239
    Google Scholar
    27
    Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes
    Aslan, Sema; Bal Altuntas, Derya; Kocak, Cagdas; Kara Subasat, Huelya
    Electroanalysis (2021), 33 (1), 120-128CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The TiO2 nanoparticles are electrospun with polyacrylonitrile (PAN) polymer soln. onto the discharged battery coal (DBC) electrode and the results are evaluated as a supercapacitor. The morphol. and chem. compn. of the synthesized TiO2 nanoparticles and PAN+TiO2 nanocomposite fibers were characterized by SEM, thermogravimetry and FTIR anal. Supercapacitor measurements and electrochem. characterizations of the electrodes examd. by cyclic voltammetry and electrochem. impedance spectroscopy. Electrochem. measurements showed that the best current value was obtained from PAN and TiO2 coated DBC. The performances of both PAN and PAN+TiO2 coated DBC electrodes were investigated as supercapacitors. PAN+TiO2/DBC showed the best specific capacitance value of 156.00 F g-1 and PAN/DBC showed 74.93 F g-1. In addn., PAN+TiO2/DBC exhibited reliable stability performance over 2000.00 cycles.
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  28. 28
    Tajik, S.; Dubal, D. P.; Gomez-Romero, P.; Yadegari, A.; Rashidi, A.; Nasernejad, B.; Inamuddin; Asiri, A. M. Nanostructured Mixed Transition Metal Oxides for High Performance Asymmetric Supercapacitors: Facile Synthetic Strategy.. Int. J. Hydrogen Energy 2017, 42 (17), 12384– 12395,  DOI: 10.1016/j.ijhydene.2017.03.117
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    28
    Nanostructured mixed transition metal oxides for high performance asymmetric supercapacitors: Facile synthetic strategy
    Tajik, Sanaz; Dubal, Deepak P.; Gomez-Romero, Pedro; Yadegari, Amir; Rashidi, Alimorad; Nasernejad, Bahram; Inamuddin; Asiri, Abdullah M.
    International Journal of Hydrogen Energy (2017), 42 (17), 12384-12395CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
    Exceptionally simple and cost-effective solid-state method is reported for the synthesis of different mixed transition metal oxides (MTMOs) including FeCo2O4, MnCo2O4 and ZnCo2O4 with unique nanostructures. The morphol. anal. show that MTMOs possess distinct nanostructures such as tetragonal, spherical nanoparticles and hexagonal nanosheets. Furthermore, these MTMOs showed excellent supercapacitive properties with specific capacitances of 660-1263 F/g at c.d. of 2 A/g. Asym. capacitor was fabricated with FeCo2O4 as pos. and activated carbon as neg. electrode which exhibits a specific capacitance of 88 F/g with energy d. of 24 Wh/kg (1.1 mWh/cm3) and cycle life (93%) over 5000 cycles.
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  29. 29
    Shiyanovskii, S. V.; Smalyukh, I. I.; Lavrentovich, O. D. Computer Simulations and Fluorescence Confocal Polarizing Microscopy of Structures in Cholesteric Liquid Crystals. Defects in Liquid Crystals: Computer Simulations, Theory and Experiments 2001, 229– 270,  DOI: 10.1007/978-94-010-0512-8_10
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    Zhang, W.; Zhang, L.; Liang, X.; Le Zhou; Xiao, J.; Yu, L.; Li, F.; Cao, H.; Li, K.; Yang, Z.; Yang, H. Unconventional High-Performance Laser Protection System Based on Dichroic Dye-Doped Cholesteric Liquid Crystals.. Sci. Rep. 2017, 7 (1), 42955,  DOI: 10.1038/srep42955
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    30
    Unconventional High-Performance Laser Protection System Based on Dichroic Dye-Doped Cholesteric Liquid Crystals
    Zhang, Wanshu; Zhang, Lanying; Liang, Xiao; Le Zhou; Xiao, Jiumei; Yu, Li; Li, Fasheng; Cao, Hui; Li, Kexuan; Yang, Zhou; Yang, Huai
    Scientific Reports (2017), 7 (), 42955CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
    High-performance and cost-effective laser protection system is of crucial importance for the rapid advance of lasers in military and civilian fields leading to severe damages of human eyes and sensitive optical devices. However, it is crucially hindered by the angle-dependent protective effect and the complex prepn. process. Here we demonstrate that angle-independence, good processibility, wavelength tunability, high optical d. and good visibility can be effectuated simultaneously, by embedding dichroic anthraquinone dyes in a cholesteric liq. crystal matrix. More significantly, unconventional two-dimensional parabolic protection behavior is reported for the first time that in stark contrast to the existing protection systems, the overall parabolic protection behavior enables protective effect to increase with incident angles, hence providing omnibearing high-performance protection. The protective effect is controllable by dye concn., LC cell thickness and CLC reflection efficiency, and the system can be made flexible enabling applications in flexible and even wearable protection devices. This research creates a promising avenue for the high-performance and cost-effective laser protection, and may foster the development of optical applications such as solar concentrators, car explosion-proof membrane, smart windows and polarizers.
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  31. 31
    Kumar, P.; Neeraj; Kang, S.; Lee, S. H.; Raina, K. K. Analysis of Dichroic Dye-Doped Polymer-Dispersed Liquid Crystal Materials for Display Devices.. Thin Solid Films 2011, 520 (1), 457– 463,  DOI: 10.1016/j.tsf.2011.06.038
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    31
    Analysis of dichroic dye-doped polymer-dispersed liquid crystal materials for display devices
    Kumar, Pankaj; Neeraj; Kang, Shin-Woong; Lee, Seung Hee; Raina, K. K.
    Thin Solid Films (2011), 520 (1), 457-463CODEN: THSFAP; ISSN:0040-6090. (Elsevier B.V.)
    Dichroic polymer-dispersed liq. crystals (DPDLCs) based on nematic liq. crystal materials with azo dye were investigated in detail for the application of display devices. Polarizing optical microscopy, differential scanning calorimeter and electro-optic expts. all have shown that the DPDLC contg. low concn. of dyes modifies the basic properties of these materials like optical transmission, threshold voltage, contrast ratio and absorbance factor. A min. amt. of dye needs to be added to the liq. crystal with the polymer matrix for its effective phase sepn. and to minimize the transmittance in the OFF state and therefore gives rise to an overall improvement in contrast ratio of the devices. Mol. orientation and dynamics in droplet sizes are readily controlled in these DPDLC materials. These findings imply that the value of the threshold elec. field Eth is approx. 8 V/μm for pure polymer-dispersed liq. crystal (without dye) where the threshold elec. field Eth values are approx. 4.0 V/μm, 2.0 V/μm, 1.7 V/μm 1.0 V/μm, for 0.0625%, 0.125%, 0.25% and 0.5% with azo dye in DPDLCs, resp. From the results we can also infer that the max. contrast is approx. 2.55 times the min. contrast obsd. in the expt. for DPDLCs. The results show that the DPDLC with proscribed dye concn. will be possibly suitable and promising functional electronic materials for green technol. flexible liq. crystal display.
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    Sheng, M.; Zhang, L.; West, J. L.; Fu, S. Multicolor Electrochromic Dye-Doped Liquid Crystal Yolk–Shell Microcapsules. ACS Appl. Mater. Interfaces 2020, 12, 29728,  DOI: 10.1021/acsami.0c09354
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    Multicolor Electrochromic Dye-Doped Liquid Crystal Yolk-Shell Microcapsules
    Sheng, Mingfei; Zhang, Liping; West, John Lawton; Fu, Shaohai
    ACS Applied Materials & Interfaces (2020), 12 (26), 29728-29736CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    A new system of yolk-shell microcapsules contg. two types of dye-doped liq. crystals was prepd. via seed emulsion polymn. in which the synthetic process was mimicking plant respiration. The resulting system demonstrated reversible low voltage-driven switching between multispectral colored and transparent states. Moreover, wearable multicolor electrochromic fibers based on calcium alginate were produced via wet spinning to expand the application of yolk-shell dye-doped liq. crystal microcapsules. In addn. to its long-term optical stability, the proposed cells and fibers also have satisfactory driving voltage values of color change (4.8 and 9.0 V), which are far lower than the human body safety voltage (12 V). We believe that the prepd. microcapsules and fibers are potentially widely applicable in smart windows, electronic paper, and military camouflage clothing.
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    Tajalli, H.; Gilani, A. G.; Zakerhamidi, M. S.; Tajalli, P. The Photophysical Properties of Nile Red and Nile Blue in Ordered Anisotropic Media.. Dye. Pigment. 2008, 78 (1), 15– 24,  DOI: 10.1016/j.dyepig.2007.10.002
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    The photophysical properties of Nile red and Nile blue in ordered anisotropic media
    Tajalli, H.; Gilani, A. Ghanadzadeh; Zakerhamidi, M. S.; Tajalli, P.
    Dyes and Pigments (2008), 78 (1), 15-24CODEN: DYPIDX; ISSN:0143-7208. (Elsevier Ltd.)
    The absorption and fluorescence spectra of a highly fluorescent laser dye, Nile red, were studied in nematic solvents and isotropic liqs. as a function of the solvent polarity and type. The interaction of the dye with the anisotropic surrounding and with that of the isotropic solvents was studied and compared using optical spectroscopy. The spectral behavior of the cationic oxazine dye, Nile blue, was also studied in anisotropic and isotropic environments for comparison. The spectral shifts were correlated by the solvent polarity and nature. The electrooptical effect of the guest-host systems was also studied in an electrooptical system using polarized spectroscopic method and the dichroic ratios R and degree of anisotropies S of these dyes in the liq. cryst. hosts were studied.
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    Zhang, X.; Liu, X.; Zhang, X.; Tian, Y.; Meng, Y. Ordering of the 7CB Liquid Crystal Induced by Nanoscale Confinement and Boundary Lubrication.. Liq. Cryst. 2012, 39 (11), 1305– 1313,  DOI: 10.1080/02678292.2012.715686
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    Ordering of the 7CB liquid crystal induced by nanoscale confinement and boundary lubrication
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    In this study, the thermodn. properties of nanoscale-thick 4-heptyl-4'-cyanobiphenyl (7CB) liq. crystals (LCs) confined in carbon nanotubes were investigated using differential scanning calorimetric methods. Both the isotropic-nematic phase transition temp. and the enthalpy increase decrease as the nanoscale confining size decreases, indicating the ordering effect of the 7CB mols. under nanoscale confinement. An av.-order parameter <S> is calcd. to quant. identify the ordering effect of LCs by utilizing a simple expression of the Landau-de Gennes (LdG) free energy. The av.-ordering parameter <S> of the 7CB LC can be 0.7 within a confinement thickness of ∼25 nm and above 0.5 within a film thickness of up to 100 nm. When lubricating the 7CB LC between a steel ball and chromium-coated glass disk at low speeds, a stable boundary layer with a thickness of 10 nm is formed that is independent of the entrainment speed. At higher speeds, the thickness of the 7CB lubrication film ranges from several tens of nanometers to 100 nm, resulting in a stable velocity-independent friction coeff. of approx. 0.03. The ordered microstructure of the 7CB mols. under confinement provides the underlay mechanism of its boundary lubrication property.
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    Ahn, W.; Kim, C. Y.; Kim, H.; Kim, S. C. Phase Behavior of Polymer/Liquid Crystal Blends.. Macromolecules 1992, 25 (19), 5002– 5007,  DOI: 10.1021/ma00045a028
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    Phase behavior of polymer/liquid crystal blends
    Ahn, W.; Kim, C. Y.; Kim, H.; Kim, S. C.
    Macromolecules (1992), 25 (19), 5002-7CODEN: MAMOBX; ISSN:0024-9297.
    The thermodn. phase behavior of blends of a low-mol.-wt. liq. crystal (LC), 4-cyano-4'-n-heptylbiphenyl (I), with each of 2 amorphous polymers, poly(Me methacrylate) (II) and polystyrene (III) was studied as a function of temp. or LC concn. Phase diagrams for both the binary I-II and I-III blends were constructed from DSC and optical microscopic observations showing that I was partially miscible in both II and III. There existed a polymer/isotropic LC 2-phase state at a given compn. besides the polymer/nematic LC 2-phase state and the polymer/solid cryst. LC 2-phase state. The polymer/isotropic LC 2-phase morphol. was clearly obsd. by the phase-contrast optical microscope in the temp. range between the homogeneous single-phase state and the polymer/nematic LC 2-phase state, while DSC or cross-polarized light microscopy failed to detect the existence of the polymer/isotropic LC 2-phase state. This was also confirmed by a light-scattering expt. At a low ratio of LC in both the blends, direct transformation between the homogeneous single-phase state and the polymer/nematic LC 2-phase state was obsd. without going through the polymer/isotropic LC 2-phase state.
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    Javadian, S.; Dalir, N.; Gilani, A. G.; Kakemam, J.; Yousefi, A. A New Approach to Study Interaction Parameters in Cyanobiphenyl Liquid Crystal Binary Systems.. J. Chem. Thermodyn. 2015, 80, 22– 29,  DOI: 10.1016/j.jct.2014.08.010
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    A new approach to study interaction parameters in cyanobiphenyl liquid crystal binary systems
    Javadian, Soheila; Dalir, Nima; Gilani, Ali Ghanadzadeh; Kakemam, Jamal; Yousefi, Ali
    Journal of Chemical Thermodynamics (2015), 80 (), 22-29CODEN: JCTDAF; ISSN:0021-9614. (Elsevier Ltd.)
    The phase transition of heptylcyanobiphenyl 7CB and pentylcyanobiphenyl 5CB liq. crystals was investigated using the differential scanning calorimetry DSC technique. Then, the phase transition of different compns. of 7CB/5CB binary mixt. was studied to det. the eutectic point. The phase diagram of mentioned binary system in 7CB mole fraction of 0.45 at T = 273.45 K is in good agreement with that of predicted from Schroder-van Laar equation. The thermodn. excess functions and interaction parameters were calcd. to describe the phase transition phys. using the non-random mixing for the first time. The P* randomicity parameter was used to describe the phase transitions of C-N and N-I in which a small amt. of P* shows a non-random identity of C-N phase transition. Contrarily, the P* is greater in N-I phase transition showing a random mixing process.
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    Sautter, B. P. Continuous Polymer Nanofibers Using Electrospinning , 2005.
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    Migliaresi, C.; Ruffo, G. A.; Zomer Volpato, F.; Zeni, D. Advanced Electrospinning Setups and Special Fibre and Mesh Morphologies. Electrospinning Adv. Biomed. Appl. Ther. 2012.
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    Huang, Z.-M.; Zhang, Y.-Z.; Kotaki, M.; Ramakrishna, S. A Review on Polymer Nanofibers by Electrospinning and Their Applications in Nanocomposites.. Compos. Sci. Technol. 2003, 63 (15), 2223– 2253,  DOI: 10.1016/S0266-3538(03)00178-7
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    A review on polymer nanofibers by electrospinning and their applications in nanocomposites
    Huang, Zheng-Ming; Zhang, Y.-Z.; Kotaki, M.; Ramakrishna, S.
    Composites Science and Technology (2003), 63 (15), 2223-2253CODEN: CSTCEH; ISSN:0266-3538. (Elsevier Science Ltd.)
    A review. A comprehensive review is presented on the researches and developments related to electrospun polymer nanofibers including processing, structure and property characterization, applications, and modeling and simulations. Information of those polymers together with their processing conditions for electrospinning of ultrafine fibers has been summarized in the paper. Other issues regarding the technol. limitations, research challenges, and future trends are also discussed.
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    Mu, X.; Du, J.; Zhang, Y.; Liang, Z.; Wang, H.; Huang, B.; Zhou, J.; Pan, X.; Zhang, Z.; Xie, E. Construction of Hierarchical CNT/RGO-Supported MnMoO 4 Nanosheets on Ni Foam for High-Performance Aqueous Hybrid Supercapacitors.. ACS Appl. Mater. Interfaces 2017, 9 (41), 35775– 35784,  DOI: 10.1021/acsami.7b09005
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    Construction of Hierarchical CNT/rGO-Supported MnMoO4 Nanosheets on Ni Foam for High-Performance Aqueous Hybrid Supercapacitors
    Mu, Xuemei; Du, Jingwei; Zhang, Yaxiong; Liang, Zhilin; Wang, Huan; Huang, Baoyu; Zhou, Jinyuan; Pan, Xiaojun; Zhang, Zhenxing; Xie, Erqing
    ACS Applied Materials & Interfaces (2017), 9 (41), 35775-35784CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Rationally designed conductive hierarchical nanostructures are highly desirable for supporting pseudocapacitive materials to achieve high-performance electrodes for supercapacitors. Herein, manganese molybdate nanosheets were hydrothermally grown with graphene oxide (GO) on three-dimensional nickel foam-supported carbon nanotube structures. Under the optimal graphene oxide concn., the obtained carbon nanotubes/reduced graphene oxide/MnMoO4 composites (CNT/rGO/MnMoO4) as binder-free supercapacitor cathodes perform with a high specific capacitance of 2374.9 F g-1 at the scan rate of 2 mV s-1 and good long-term stability (97.1% of the initial specific capacitance can be maintained after 3000 charge/discharge cycles). The asym. device with CNT/rGO/MnMoO4 as the cathode electrode and the carbon nanotubes/activated carbon on nickel foam (CNT-AC) as the anode electrode can deliver an energy d. of 59.4 Wh kg-1 at the power d. of 1367.9 W kg-1. These superior performances can be attributed to the synergistic effects from each component of the composite electrodes: highly pseudocapacitive MnMoO4 nanosheets and three-dimensional conductive Ni foam/CNTs/rGO networks. These results suggest that the fabricated asym. supercapacitor can be a promising candidate for energy storage devices.
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    Reneker, D. H.; Chun, I. Nanometre Diameter Fibres of Polymer, Produced by Electrospinning.. Nanotechnology 1996, 7 (3), 216– 223,  DOI: 10.1088/0957-4484/7/3/009
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    Nanometer diameter fibers of polymer, produced by electrospinning
    Reneker, Darrell H.; Chun, Iksoo
    Nanotechnology (1996), 7 (3), 216-223CODEN: NNOTER; ISSN:0957-4484. (Institute of Physics Publishing)
    The electrospinning process for the prepn. of polymer fibers with diams. of 40-2000 nm is reviewed with 41 refs. Electrospinning uses elec. forces to produce polymer fibers with nanometer-scale diams. Electrospinning occurs when the elec. forces at the surface of a polymer soln. or melt overcome the surface tension and cause an elec. charged jet to be ejected. When the jet dries or solidifies, an elec. charged fiber remains. This charged fiber can be directed or accelerated by elec. forces and then collected in sheets or other useful geometrical forms. More than 20 polymers, including poly(ethylene oxide), nylon, polyimide, DNA, polyaramid, and polyaniline, have been electrospun in the lab. Most were spun from soln., although spinning from the melt in vacuum and air was also demonstrated. Electrospinning from polymer melts in a vacuum is advantageous because higher fields and higher temps. can be used than in air.
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    Beachley, V.; Wen, X. Effect of Electrospinning Parameters on the Nanofiber Diameter and Length.. Mater. Sci. Eng., C 2009, 29 (3), 663– 668,  DOI: 10.1016/j.msec.2008.10.037
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    Effect of electrospinning parameters on the nanofiber diameter and length
    Beachley, Vince; Wen, Xuejun
    Materials Science & Engineering, C: Materials for Biological Applications (2009), 29 (3), 663-668CODEN: MSCEEE; ISSN:0928-4931. (Elsevier B.V.)
    Polymer nanofibers exhibit properties that make them a favorable material for the development of tissue engineering scaffolds, filtration devices, sensors, and high strength lightwt. materials. Electrospinning is a versatile method commonly used to manuf. polymer nanofibers. Collection of electrospun nanofibers across two parallel plates is a technique useful for creating nanofiber structures because it allows for the collection of linearly oriented individual nanofiber arrays and these arrays can be easily transferred to other substrates or structures. It is of importance to have some understanding of the capabilities of this collection method, such as the max. length of fibers that can be collected across two parallel plates. The effect of different electrospinning parameters on max. fiber length, av. fiber diam., diam. uniformity, and fiber quality was explored. It was shown that relatively long continuous polycaprolactone (PCL) nanofibers with av. diams. from approx. 350 nm to 1 μm could be collected across parallel plates at lengths up to 35-50 cm. Exptl. results lead to the hypothesis that even longer continuous nanofibers over 50 cm could be collected if the size of the parallel plates were increased. Extending the max. fiber length that can be collected across parallel plates could expand the applications of electrospinning. Polymer soln. concn., plate size, and applied voltage were all shown to have varying effects on max. fiber length, fiber diam., and fiber uniformity.
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    Yördem, O. S.; Papila, M.; Menceloǧlu, Y. Z. Effects of Electrospinning Parameters on Polyacrylonitrile Nanofiber Diameter: An Investigation by Response Surface Methodology.. Mater. Des. 2008, 29 (1), 34– 44,  DOI: 10.1016/j.matdes.2006.12.013
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    Okutan, N.; Terzi, P.; Altay, F. Affecting Parameters on Electrospinning Process and Characterization of Electrospun Gelatin Nanofibers. Food Hydrocoll. 2014, 39, 19– 26,  DOI: 10.1016/j.foodhyd.2013.12.022
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    Jacobs, V.; Anandjiwala, R. D.; Maaza, M. The Influence of Electrospinning Parameters on the Structural Morphology and Diameter of Electrospun Nanofibers.. J. Appl. Polym. Sci. 2010, 115 (5), 3130– 3136,  DOI: 10.1002/app.31396
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    The influence of electrospinning parameters on the structural morphology and diameter of electrospun nanofibers
    Jacobs, Valencia; Anandjiwala, Rajesh D.; Maaza, Malik
    Journal of Applied Polymer Science (2010), 115 (5), 3130-3136CODEN: JAPNAB; ISSN:0021-8995. (John Wiley & Sons, Inc.)
    Electrospinning is a simple method of producing nanofibers by introducing elec. field into the polymer solns. We report an exptl. investigation on the influence of processing parameters and soln. properties on the structural morphol. and av. fiber diam. of electrospun poly ethylene oxide (PEO) polymer soln. Exptl. trials have been conducted to investigate the effect of soln. parameters, such as concn., mol. wt., addn. of polyelectrolyte in PEO soln., solvent effect, as well as governing parameter, such as applied voltage. The concn. of the aq. PEO soln. has shown noteworthy influence on the fiber diam. and structural morphol. of electrospun nanofibers. At lower concns. of PEO polymer soln., the fibers showed irregular morphol. with large variations in fiber diam., whereas at higher concns., the nanofibers with regular morphol. and on av. uniform fiber diam. were obtained. We find that the addn. of polyelectrolytes, such as sodium salt of Poly acrylic acid (PAA) and Poly allylamine hydrochloride (PAH), increases the cond. of PEO solns. and thereby decreases the bead formation in electrospun nanofibers. The increase in applied voltage has been found to affect the structural morphol. of nanofiber while the addn. of ethanol in PEO soln. diminishes the bead defects.
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    Fong, H.; Chun, I.; Reneker, D. Beaded Nanofibers Formed during Electrospinning.. Polymer (Guildf). 1999, 40 (16), 4585– 4592,  DOI: 10.1016/S0032-3861(99)00068-3
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    Beaded nanofibers formed during electrospinning
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    Polymer (1999), 40 (16), 4585-4592CODEN: POLMAG; ISSN:0032-3861. (Elsevier Science Ltd.)
    Electrospinning is a straightforward method to produce polymer fibers with diams. in the range of 100 nm. from polymer solns. Electrospun fibers often have beads in regular arrays. The viscoelasticity of the soln., charge d. carried by the jet, and the surface tension of the soln. are the key factors that influence the formation of the beaded fibers.
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    Cramariuc, B.; Cramariuc, R.; Scarlet, R.; Manea, L. R.; Lupu, I. G.; Cramariuc, O. Fiber Diameter in Electrospinning Process.. J. Electrostat. 2013, 71 (3), 189– 198,  DOI: 10.1016/j.elstat.2012.12.018
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    Fiber diameter in electrospinning process
    Cramariuc, Bogdan; Cramariuc, Radu; Scarlet, Roxana; Manea, Liliana Rozemarie; Lupu, Iuliana G.; Cramariuc, Oana
    Journal of Electrostatics (2013), 71 (3), 189-198CODEN: JOELDH; ISSN:0304-3886. (Elsevier B.V.)
    In order to increase the control on the fiber diam. we propose in this paper a methodol. to det. stability domains of the process in which the electrospun fiber diam. can be predetd. and also controlled by means of the polymer soln. flow and the applied voltage. To define these stability domains we employ a combination of anal. expressions depending on the location along the traveling jet. In the vicinity of the nozzle we employ the expression which links the fiber diam. with the kinematic viscosity of the polymer soln., nozzle-collector distance, soln. d., liq. flow, elec. current and intensity of the electrostatic field. At larger distances from the nozzle, the fiber diam. can be expressed as a function of soln. d., liq. flow, intensity of the applied electrostatic field and distance from the nozzle. Close to the collector the fiber diam. can be expressed with respect to the superficial tension of the polymer soln., dielec. permittivity, liq. flow and intensity of the elec. current. Under specific constrains, the superposition of the plots obtained from these math. expressions will be used to det. the stability domain for the fiber diam. in which the diam. can be controlled by two process parameters, namely applied voltage and polymer soln. flow. Through this approach the present paper can contribute to increased control of the electrospinning process and thus enhanced applicability.
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    An, N.; Xu, Q.; Xu, L. H.; Wu, S. Z. Orientation Structure and Mechanical Properties of Polyacrylonitrile Precursors.. Adv. Mater. Res. 2006, 11–12, 383– 386,  DOI: 10.4028/www.scientific.net/AMR.11-12.383
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    Orientation structure and mechanical properties of polyacrylonitrile precursors
    An, Na; Xu, Qiang; Xu, Lianghua; Wu, Sizhu
    Advanced Materials Research (Zuerich, Switzerland) (2006), 11-12 (AICAM 2005), 383-386CODEN: AMREFI; ISSN:1022-6680. (Trans Tech Publications Ltd.)
    The microstructure of the polyacrylonitrile (PAN) precursors can strongly affect the structure of the carbon fibers which dets. the final mech. properties of the fibers. The orientation factors (fΔn) of PAN precursors under different draw ratios were characterized by the birefringence (Δnf), which was obtained through polarized microscopy. The results show that the increasing of the draw ratio may enhance the degree of orientation, which can correspondingly improve the mech. properties. However the increasing speed of the orientation factor slows down as the draw ratio reached to 8.
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    Kityk, A. V.; Wolff, M.; Knorr, K.; Morineau, D.; Lefort, R.; Huber, P. Continuous Paranematic-to-Nematic Ordering Transitions of Liquid Crystals in Tubular Silica Nanochannels.. Phys. Rev. Lett. 2008, 101 (18), 187801,  DOI: 10.1103/PhysRevLett.101.187801
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    Continuous Paranematic-to-Nematic Ordering Transitions of Liquid Crystals in Tubular Silica Nanochannels
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    Physical Review Letters (2008), 101 (18), 187801/1-187801/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
    The optical birefringence of rodlike nematogens (7CB, 8CB), imbibed in parallel SiO2 channels with 10 nm diam. and 300 μm length, is measured and compared to the thermotropic bulk behavior. The orientational order of the confined liq. crystals, quantified by the uniaxial nematic ordering parameter, evolves continuously between paranematic and nematic states, in contrast to the discontinuous isotropic-to-nematic bulk phase transitions. A Landau-de Gennes model reveals that the strength of the orientational ordering fields, imposed by the SiO2 walls, is beyond a crit. threshold, that separates discontinuous from continuous paranematic-to-nematic behavior. Quenched disorder effects, attributable to wall irregularities, leave the transition temps. affected only marginally, despite the strong ordering fields in the channels.
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    Jasiurkowska-Delaporte, M.; Juszyńska-Gałązka, E.; Sas, W.; Zieliński, P. M.; Baranowska-Korczyc, A. Soft versus Hard Confinement Effects on the Phase Transitions, and Intra- and Inter- Molecular Dynamics of 6BT Liquid Crystal Constrained in Electrospun Polymer Fibers and in Nanopores.. J. Mol. Liq. 2021, 331, 115817,  DOI: 10.1016/j.molliq.2021.115817
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    Soft versus hard confinement effects on the phase transitions, and intra- and inter- molecular dynamics of 6BT liquid crystal constrained in electrospun polymer fibers and in nanopores
    Jasiurkowska-Delaporte, Malgorzata; Juszynska-Galazka, Ewa; Sas, Wojciech; Zielinski, Piotr M.; Baranowska-Korczyc, Anna
    Journal of Molecular Liquids (2021), 331 (), 115817CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
    This work examines the behavior of a liq. crystal (LC) under soft confinement, resulting from interactions between polymer and guest liq. cryst. mols., and under hard confinement, imposed by rigid pore walls. It studies the confinement effects for electrospun fibers composed of poly(ε-caprolactone) (PCL) and different wt. content of 4-hexyl-4'-isothiocyanatobiphenyl (6BT) liq. crystal, and 6BT enclosed in nanoporous alumina, with pore diams. of 200 nm, 120 nm, 80 nm and 40 nm. Differential scanning calorimetry, broadband dielec. and Fourier-transform IR spectroscopy were employed to gain detailed insights into the effects of both forms of confinement on 6BT. The crystn. process of 6BT was found to be enhanced in the composite fibers, but fully suppressed for the material confined in pores. The relaxation rates of the rotational motion of the LC mols. around their short axis in the 25.6 wt% 6BT and 17 wt% 6BT PCL/6BT fibers are in line with those found for 6BT in the 200 nm and 80 nm pores. Two-dimensional correlation spectroscopy (2D-COS) anal. of IR spectra confirmed that soft and hard confinement have different impacts on the intramol. dynamics of 6BT. The study also discusses the influence of guest mols. on the intramol. potentials of PCL.
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    Özgan, Ş.; Okumuş, M. Thermal and Spectrophotometric Analysis of Liquid Crystal 8CB/8OCB Mixtures.. Brazilian J. Phys. 2011, 41 (2–3), 118– 122,  DOI: 10.1007/s13538-011-0034-1
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    Thermal and spectrophotometric analysis of liquid crystal 8CB/8OCB mixtures
    Ozgan, Sukru; Okumus, Mustafa
    Brazilian Journal of Physics (2011), 41 (2-3), 118-122CODEN: BJPHE6; ISSN:0103-9733. (Springer)
    The binary system of 4-octyl-4'-cyanobiphenyl (8CB) and 4-octyloxy-4'-cyanobiphenyl (8OCB) was studied by differential scanning calorimetry (DSC) and UV absorption spectrophotometry (UV). The phase-transition temps., enthalpies, and entropies were detd. by calorimetric methods on DSC. The results indicate clearly the existence of 3-phase regions across the cryst.-to-smectic A, smectic A-to-nematic, and nematic-to-isotropic transitions in the 8CB/8OCB mixts. The obtained phase-transition temps. of the 8CB/8OCB mixts. are between the data for 8CB and 8OCB. A few of the phase transitions cannot be obsd. at high heating rates. The phase-transition temps. of the 8CB/8OCB mixts. rise with the heating rate between 2 K/min and 15 K/min. the activation energies were calcd. by the Ozawa method for the phase transitions of 25% 8CB and 75% 8OCB liq. crystal mixts. UV expts. were carried out to characterize the absorptivity consts. of liq. crystal and their mixts. The molar absorptivity and max. absorption wavelengths were measured in chloroform soln. by UV spectrophotometry. The max. absorption wavelength of the 8CB/8OCB mixts. increases with decreasing percent wt. of 8CB in 8OCB, a result assocd. with the different lengths of the alkyl chain.
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    Oweimreen, G. A.; Morsy, M. A. DSC Studies on P-Cyanophenyl p-(n-Alkyl)Benzoate Liquid Crystals: Evidence for Polymorphism and Conformational Change.. Thermochim. Acta 1999, 325 (2), 111– 118,  DOI: 10.1016/S0040-6031(98)00572-3
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    DSC studies on p-cyanophenyl p-(n-alkyl)benzoate liquid crystals: evidence for polymorphism and conformational change
    Oweimreen, G. A.; Morsy, M. A.
    Thermochimica Acta (1999), 325 (2), 111-118CODEN: THACAS; ISSN:0040-6031. (Elsevier Science B.V.)
    Temps. and enthalpy changes are reported for the melting, clearing, and nematic-to-solid transition of the p-cyanophenyl p-(alkyl)benzoate (RCBz) liq. crystals. Several solid structures exist for the RCBzs. Evidence that the transitions between the various solid forms involve conformational changes is provided by exotherms and endotherms appearing in heating and cooling cycles, resp. Also as long as melted RCBzs are not allowed to solidify they undergo repeated, reversible nematic-to-isotropic and isotropic-to-nematic transitions making them suitable for use in liq. crystal displays (LCD).
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    Mamuk, A. E.; Nesrullajev, A.; Mukherjee, P. K. Refractive and Birefringent Properties of 4-Alkyl-4′-Oxycyanobiphenyls at Direct and Reverse Phase Transitions.. Mol. Cryst. Liq. Cryst. 2017, 648 (1), 168– 181,  DOI: 10.1080/15421406.2017.1307499
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    Refractive and birefringent properties of 4-alkyl-4'-oxycyanobiphenyls at direct and reverse phase transitions
    Mamuk, Atilla Eren; Nesrullajev, Arif; Mukherjee, Prabir K.
    Molecular Crystals and Liquid Crystals (2017), 648 (1), 168-181CODEN: MCLCD8; ISSN:1542-1406. (Taylor & Francis, Inc.)
    Studies of temp. behavior of the mean refractive index, ordinary and extraordinary refractive indexes, and birefringence have been carried out for three nematogens. The thermo-morphol. properties of the biphasic regions of the direct nematic-isotropic liq. and reverse isotropic liq.-nematic phase transitions have been investigated. The 4-n-alkyl-4'-oxycyanobiphenyls (n = 5, 6, 7) were objects of our study. Studies have been carried out for the circular cycle as the heating-cooling. Temp. behavior of the order parameter in nematic mesophase and at the nematic-isotropic liq. and isotropic liq.-nematic phase transition is discussed.
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    Hosaka, S.; Tozaki, K.; Hayashi, H.; Inaba, H. Effect of Magnetic Field on the Phase Transitions of EBBA by Means of a High-Resolution and Super-Sensitive DSC.. Phys. B Condens. Matter 2003, 337 (1–4), 138– 146,  DOI: 10.1016/S0921-4526(03)00389-2
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    Effect of magnetic field on the phase transitions of EBBA by means of a high-resolution and super-sensitive DSC
    Hosaka, Shotaro; Tozaki, Ken-ichi; Hayashi, Hideko; Inaba, Hideaki
    Physica B: Condensed Matter (Amsterdam, Netherlands) (2003), 337 (1-4), 138-146CODEN: PHYBE3; ISSN:0921-4526. (Elsevier Science B.V.)
    Phase transitions of the N-p-ethoxybenzylidene-p'-butylaniline (EBBA) were measured by a high-resoln. and super-sensitive DSC. The crystal to liq. crystal transition and liq. crystal to isotropic liq. transition was obsd. at 305.8 and 352.4 K at a heating rate of 1 mK s-1, resp. The crystal to liq. crystal transition has fine structures resulting from different cryst. states of the sample which depended on the sample prepn. and on the heating rate of the measurement. The temp. due to liq. crystal to isotropic liq. transition was raised by 34 mK by applying a magnetic field of 5 T. The magnetic effect is discussed based on the extension of the Clapeyron equation.
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    Mukherjee, P. K. Isotropic to Smectic-A Phase Transition: A Review.. J. Mol. Liq. 2014, 190, 99– 111,  DOI: 10.1016/j.molliq.2013.11.001
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    Isotropic to smectic-A phase transition: A review
    Mukherjee, Prabir K.
    Journal of Molecular Liquids (2014), 190 (), 99-111CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
    A review. An attempt towards a unified picture of the direct transition from the isotropic to smectic-A phase is presented. The isotropic to smectic-A phase transition is described in detail, including structure and nature revealed by expts., mol. models and Landau-de Gennes theory. The wide variety of phenomena including effects of nonmesogenic impurities and elec. field, hydrodynamics, fluctuations, and elastic theory of liq. cryst. elastomers is discussed. A brief review on the general information about the isotropic to lamellar phase transition in lyotropic liq. crystals was given. The various predictions are compared with the available exptl. results. Open questions and possible approaches to finding answers are discussed.
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    Avci, N.; Nesrullajev, A.; Oktik, Ş. Nonlinear Thermotropic and Thermo-Optical Behaviour of Planar Oriented Textures in Nematic Liquid Crystals at Phase Transitions. Brazilian J. Phys. 2010, 40 (2), 224– 227
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    Nonlinear thermotropic and thermo-optical behaviour of planar oriented textures in nematic liquid crystals at phase transitions
    Avci, Nejmettin; Nesrullajev, Arif; Oktik, Sener
    Brazilian Journal of Physics (2010), 40 (2), 224-227CODEN: BJPHE6; ISSN:0103-9733. (Sociedade Brasileira de Fisica)
    Thermotropic, thermo-morphol. and thermo-optical properties of the planar oriented nematic liq. crystals have been investigated for large temp. interval and esp. for the direct nematic - isotropic liq. and the reverse isotropic liq. - nematic phase transition regions. Temp. dependences of the optical transmission, absorption coeff. and optical birefringence for both heating and cooling processes were obtained. Nonlinear thermotropic and thermo-optical behavior and temp. hysteresis for the optical transmission, absorption coeff. and optical birefringence at the phase transitions has been found.
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    Abeykoon, N. C.; Bonso, J. S.; Ferraris, J. P. Supercapacitor Performance of Carbon Nanofiber Electrodes Derived from Immiscible PAN/PMMA Polymer Blends.. RSC Adv. 2015, 5 (26), 19865– 19873,  DOI: 10.1039/C4RA16594B
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    59
    Supercapacitor performance of carbon nanofiber electrodes derived from immiscible PAN/PMMA polymer blends
    Abeykoon, Nimali C.; Bonso, Jeliza S.; Ferraris, John P.
    RSC Advances (2015), 5 (26), 19865-19873CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    Polymer blends yield carbon materials with superior performances for supercapacitor applications since blending can lead to controlled and fine pore architectures. In this study, a supercapacitor electrode material derived from an immiscible polymer blend comprising polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) was investigated. PAN was used as the carbonizing polymer while PMMA was used as the sacrificial polymer. The polymer blend solns. in DMF were electrospun to obtain freestanding nanofiber mats. The resulting mat was carbonized and activated by CO2 at 1000 °C to obtain porous carbon nanofibers (CNFs), as PAN converts to carbon and the sacrificial polymer decomps. creating pores. We demonstrated that the pore sizes can be tuned by varying the amt. of PMMA loading in the blend compns. PAN : PMMA (95 : 5), was found to be the optimum blend compn., affording the highest surface area of 2419 m2 g-1, higher degree of graphitization, higher carbon yield and lower charge transfer resistance among the blend compns. studied. Furthermore, the PAN : PMMA (95 : 5) CNFs showed the highest capacitance of 140 F g-1 and energy densities of 67 W h kg-1 at 3.5 V and 101 W h kg-1 at 4 V in an ionic electrolyte (EMITFSI) and also showed good cycling stability with 85% capacitance retention after 1000 cycles.
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    Geng, P.; Wang, L.; Du, M.; Bai, Y.; Li, W.; Liu, Y.; Chen, S.; Braunstein, P.; Xu, Q.; Pang, H. MIL-96-Al for Li–S Batteries: Shape or Size?. Adv. Mater. 2022, 34 (4), 2107836,  DOI: 10.1002/adma.202107836
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    MIL-96-Al for Li-S Batteries: Shape or Size
    Geng, Pengbiao; Wang, Lei; Du, Meng; Bai, Yang; Li, Wenting; Liu, Yanfang; Chen, Shuangqiang; Braunstein, Pierre; Xu, Qiang; Pang, Huan
    Advanced Materials (Weinheim, Germany) (2022), 34 (4), 2107836CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Metal-org. frameworks (MOFs) with controllable shapes and sizes show a great potential in Li-S batteries. However, neither the relationship between shape and specific capacity nor the influence of MOF particle size on cyclic stability have been fully established yet. Herein, MIL-96-Al with various shapes, forming hexagonal platelet crystals (HPC), hexagonal bipyramidal crystals (HBC), and hexagonal prismatic bipyramidal crystals (HPBC) are successfully prepd. via cosolvent methods. D. functional theory (DFT) calcns. demonstrate that the HBC shape with highly exposed planes can effectively adsorb lithium polysulfides (LPS) during the charge/discharge process. By changing the relative proportion of the cosolvents, HBC samples with different particle sizes are prepd. When these MIL-96-Al crystals are used as sulfur host materials, it is found that those with a smaller size of the HBC shape deliver higher initial capacity. These investigations establish that different crystal planes have different adsorption abilities for LPS, and that the MOF particle size should be considered for a suitable sulfur host. More broadly, this work provides a strategy for designing sulfur hosts in Li-S batteries.
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    Bai, Y.; Liu, C.; Chen, T.; Li, W.; Zheng, S.; Pi, Y.; Luo, Y.; Pang, H. MXene-Copper/Cobalt Hybrids via Lewis Acidic Molten Salts Etching for High Performance Symmetric Supercapacitors. Angew. Chem Int. Ed. 2021, 60 (48), 25318– 25322,  DOI: 10.1002/anie.202112381
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    MXene-Copper/Cobalt Hybrids via Lewis Acidic Molten Salts Etching for High Performance Symmetric Supercapacitors
    Bai, Yang; Liu, Chunli; Chen, Tingting; Li, Wenting; Zheng, Shasha; Pi, Yecan; Luo, Yongsong; Pang, Huan
    Angewandte Chemie, International Edition (2021), 60 (48), 25318-25322CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    MXenes have attracted great interests as supercapacitors due to their metallic cond., high d., and hydrophilic nature. Herein we report Ti3C2-Cu/Co hybrids via molten salt etching in which the existence of metal atoms and their interactions with MXene via surficial O atoms were elucidated by XAFS for the first time. The electrochem. investigation of Ti3C2-Cu electrode demonstrated the pseudocapacitive contribution of Cu and a splendid specific capacitance of 885.0 F g-1 at 0.5 A g-1 in 1.0 M H2SO4. Sym. supercapacitor Ti3C2-Cu//Ti3C2-Cu was demonstrated with operating voltage of 1.6 V, areal capacitance of 290.5 mF cm-2 at 1 mA cm-2, and stability over 10 000 cycles. It delivered an areal energy d. of 103.3μWh cm-2 at power d. of 0.8 mW cm-2, based on which a supercapacitor pouch was fabricated. It provides deeper insights into the molten salt mechanism and strategies for designing MXene-based materials for electrochem. energy storage.
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    Li, W.; Guo, X.; Geng, P.; Du, M.; Jing, Q.; Chen, X.; Zhang, G.; Li, H.; Xu, Q.; Braunstein, P.; Pang, H. Rational Design and General Synthesis of Multimetallic Metal–Organic Framework Nano-Octahedra for Enhanced Li–S Battery. Adv. Mater. 2021, 33 (45), 2105163,  DOI: 10.1002/adma.202105163
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    Rational Design and General Synthesis of Multimetallic Metal-Organic Framework Nano-Octahedra for Enhanced Li-S Battery
    Li, Wenting; Guo, Xiaotian; Geng, Pengbiao; Du, Meng; Jing, Qingling; Chen, Xudong; Zhang, Guangxun; Li, Hongpeng; Xu, Qiang; Braunstein, Pierre; Pang, Huan
    Advanced Materials (Weinheim, Germany) (2021), 33 (45), 2105163CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Metal-org. frameworks (MOFs), which consist of central metal nodes and org. linkers, constitute a fast growing class of cryst. porous materials with excellent application potential. Herein, a series of Mn-based multimetallic MOF (bimetallic and trimetallic MIL-100) nano-octahedra are prepd. by a facile one-pot synthetic strategy. The types and proportions of the incorporated elements can be tuned while retaining the original topol. structure. The introduction of other metal ions is verified at the at. level by combining X-ray absorption fine structure expts. and theor. calcns. Furthermore, these multimetallic Mn-based MIL-100 nano-octahedra are utilized as sulfur hosts to prep. cathodes for Li-S batteries. The MnNi-MIL-100@S cathode exhibits the best Li-S battery performance among all reported MIL-100@S composite cathode materials, with a reversible capacity of ≈708.8 mAh g-1 after 200 cycles. The synthetic strategy described herein is utilized to incorporate metal ions into the MOF architecture, of which the parent monometallic MOF nano-octahedra cannot be prepd. directly, thus rationally generating novel multimetallic MOFs. Importantly, the strategy also allows for the general synthesis and study of various micro-/nanoscale MOFs in the energy storage field.
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    Hang, X.; Xue, Y.; Cheng, Y.; Du, M.; Du, L.; Pang, H. From Co-MOF to CoNi-MOF to Ni-MOF: A Facile Synthesis of 1D Micro-/Nanomaterials. Inorg. Chem. 2021, 60 (17), 13168– 13176,  DOI: 10.1021/acs.inorgchem.1c01561
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    From Co-MOF to CoNi-MOF to Ni-MOF: A Facile Synthesis of 1D Micro-/Nanomaterials
    Hang, Xinxin; Xue, Yadan; Cheng, Yan; Du, Meng; Du, Liting; Pang, Huan
    Inorganic Chemistry (2021), 60 (17), 13168-13176CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
    Controlling the growth of metal-org. frameworks (MOFs) at the micro-/nanoscopic scale will result in new phys. properties and novel functions into the materials without changing the chem. identities and the characteristic features of the MOFs themselves. Herein, the authors report a facile approach to synthesize 3,5-pyridinedicarboxylic acid MOFs [Co-MOF, CoxNiy-MOFs (x and y represent the molar ratio of Co2+ and Ni2+ and x/y = 1:1, 1:5, 1:10, 1:15, and 1:20), and Ni-MOF] with a 1-dimensional micro-/nanoscaled rod-like architecture. From Co-MOF to CoxNiy-MOFs to Ni-MOF, the diams. of the rods turn to be spindly with the increase of Ni2+ content which will facilitate the supercapacitor performances. Co1Ni20-MOF exhibits a highest specific capacity of 597 F g-1 at 0.5 A g-1 and excellent cycle performance (retained 93.59% after 4000 cycles) among these MOF materials owing to its micro-/nanorod structure with a smaller diam. and the synergy effect between the optimum molar ratio of Co2+ and Ni2+.
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    Yates, N. D. J.; Fascione, M. A.; Parkin, A. Methodologies for “Wiring” Redox Proteins/Enzymes to Electrode Surfaces. Chem. Eur. J. 2018, 24 (47), 12164– 12182,  DOI: 10.1002/chem.201800750
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    Methodologies for "Wiring" Redox Proteins/Enzymes to Electrode Surfaces
    Yates, Nicholas D. J.; Fascione, Martin A.; Parkin, Alison
    Chemistry - A European Journal (2018), 24 (47), 12164-12182CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. The immobilization of redox proteins or enzymes onto conductive surfaces has application in the anal. of biol. processes, the fabrication of biosensors, and in the development of green technologies and biochem. synthetic approaches. This review evaluates the methods through which redox proteins can be attached to electrode surfaces in a "wired" configuration, i.e., one that facilitates direct electron transfer. The feasibility of simple electroactive adsorption onto a range of electrode surfaces is illustrated, with a highlight on the recent advances that have been achieved in biotechnol. device construction using carbon materials and metal oxides. The covalent crosslinking strategies commonly used for the modification and biofunctionalization of electrode surfaces are also evaluated. Recent innovations in harnessing chem. biol. methods for elec. wiring redox biol. to surfaces are emphasized.
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    Mazloum-Ardakani, M.; Khoshroo, A. Nano Composite System Based on Coumarin Derivative-Titanium Dioxide Nanoparticles and Ionic Liquid: Determination of Levodopa and Carbidopa in Human Serum and Pharmaceutical Formulations.. Anal. Chim. Acta 2013, 798, 25– 32,  DOI: 10.1016/j.aca.2013.08.045
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    65
    Nano composite system based on coumarin derivative-titanium dioxide nanoparticles and ionic liquid: Determination of levodopa and carbidopa in human serum and pharmaceutical formulations
    Mazloum-Ardakani, Mohammad; Khoshroo, Alireza
    Analytica Chimica Acta (2013), 798 (), 25-32CODEN: ACACAM; ISSN:0003-2670. (Elsevier B.V.)
    The combination of coumarin deriv. (7-(1,3-dithiolan-2-yl)-9,10-dihydroxy-6H-benzofuro[3,2-c]chromen-6-on), (DC)-titanium dioxide nanoparticles (TiO2) and ionic liq. (IL) yields nanostructured electrochem. sensor, formed a novel kind of structurally uniform and electrocatalytic activity material. This new ionic liq.-TiO2 nanoparticles modified carbon paste electrode (IL-CTP) due to its enhanced cond. presented very large current response from electroactive substrates. The modified electrode was characterized by different methods including a scanning electron microscope (SEM), electrochem. impedance spectroscopy (EIS) and voltammetry. A pair of well-defined quasi reversible redox peaks of coumarin deriv. was obtained at the modified carbon paste electrode (DC/IL-CTP) by direct electron transfer between the coumarin deriv. and the CP electrode. Dramatically enhanced electrocatalytic activity was exemplified at the DC/IL-CTP electrode, as an electrochem. sensor to study the electro oxidn. of levodopa (LD) and carbidopa (CD). Based on differential pulse voltammetry (DPV), the oxidn. of LD and CD exhibited the dynamic range between 0.10- 900.0 μM and 20.0-900.0 μM resp., and the detection limit (3σ) for LD and CD were 41 nM and 0.38 μM, resp. DPV was used for simultaneous detn. of LD and CD at the DC/IL-CTP electrode, and quantitation of LD and CD in some real samples (such as tablets of Parkin-C Fort and Madopar, Sinemet, water, urine, and human blood serum) by the std. addn. method.
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    Xia, X. H.; Tu, J. P.; Zhang, Y. Q.; Mai, Y. J.; Wang, X. L.; Gu, C. D.; Zhao, X. B. Freestanding Co 3O 4 Nanowire Array for High Performance Supercapacitors. RSC Adv. 2012, 2 (5), 1835– 1841,  DOI: 10.1039/c1ra00771h
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    Freestanding Co3O4 nanowire array for high performance supercapacitors
    Xia, Xin-hui; Tu, Jiang-ping; Zhang, Yong-qi; Mai, Yong-jin; Wang, Xiu-li; Gu, Chang-dong; Zhao, Xin-bing
    RSC Advances (2012), 2 (5), 1835-1841CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    We report a single-cryst. Co3O4 nanowire array grown on a nickel foam prepd. by a hydrothermal synthesis method for supercapacitor application. The Co3O4 nanowires show sharp tips and have an av. diam. of 70 nm, and a length up to 25 μm. Impressively, the as-prepd. single-cryst. Co3O4 nanowire array exhibits noticeable pseudocapacitive performance with a high capacitance of 754 F g-1 at 2 A g-1 and 610 F g-1 at 40 A g-1 as well as excellent cycling stability. The enhanced supercapacitor performance is due to the unique one-dimensional (1D) architecture, which provides fast diffusion paths for ions and facilitates the electron and ion transfer on the Co3O4/electrolyte interfaces. Moreover, the 1D nanowire array can accommodate the vol. expansion and restrain the pulverization and deterioration of Co3O4 during the repeated cycling process, resulting in enhanced cycling stability.
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    Li, B.; Lopez-Beltran, H.; Siu, C.; Skorenko, K. H.; Zhou, H.; Bernier, W. E.; Whittingham, M. S.; Jones, W. E. Vaper Phase Polymerized PEDOT/Cellulose Paper Composite for Flexible Solid-State Supercapacitor.. ACS Appl. Energy Mater. 2020, 3 (2), 1559– 1568,  DOI: 10.1021/acsaem.9b02044
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    67
    Vaper Phase Polymerized PEDOT/Cellulose Paper Composite for Flexible Solid-State Supercapacitor
    Li, Boxiao; Lopez-Beltran, Hendrick; Siu, Carrie; Skorenko, Kenneth H.; Zhou, Hui; Bernier, William E.; Whittingham, M. Stanley; Jones, Wayne E., Jr.
    ACS Applied Energy Materials (2020), 3 (2), 1559-1568CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    A flexible solid-state supercapacitor based on vapor phase polymd. (VPP) PEDOT into cellulose paper matrix (PEDOT/CP) was successfully fabricated. The PEDOT/CP composite material worked as both current collector and electrode in constructed test cells. It had a low sheet resistance of 14 Ω/square and survived the Scotch tape test for adhesion. It also showed excellent stability with no significant cond. drop after 1000 cycles of bending. The PEDOT from electrode obtained the mass specific capacitance of 179 F/g at scan rate of 10 mV/s, which was among the highest specific capacitances ever reported. This high capacitance was attributed to the combination of the VPP technique and the porous fibrous structure of the cellulose matrix. The EDOT vapor penetrated and polymd. through the CP matrix made of nanometer to micrometer level CP fibers. The highest electrode volumetric capacitance achieved was 13.7 F/cm3. The whole device achieved an energy d. of 0.76 mWh/cm3 and a power d. of 0.01 W/cm3. Bending the supercapacitor to 90° or rotating to 45° caused no major change in capacitance. Owing to the all nonmetallic materials used to construct the supercapacitor, it can be easily disposed. The incineration of the supercapacitor does not release significant hazardous exhaust.
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    Aydın, H.; Kurtan, U.; Demir, M.; Karakuş, S. Synthesis and Application of a Self-Standing Zirconia-Based Carbon Nanofiber in a Supercapacitor.. Energy Fuels 2022, 36 (4), 2212– 2219,  DOI: 10.1021/acs.energyfuels.1c04208
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    68
    Synthesis and Application of a Self-Standing Zirconia-Based Carbon Nanofiber in a Supercapacitor
    Aydin, Hamide; Kurtan, Umran; Demir, Muslum; Karakus, Selcan
    Energy & Fuels (2022), 36 (4), 2212-2219CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)
    Electrospun metal oxide-embedded carbon nanofibers have attracted considerable attention in energy storage applications for the development and fabrication of supercapacitors owing to their unique properties such as flexibility, high capacitance, large sp. surface areas, and morphol. and cond. properties. Herein, a novel zirconia-based carbon nanofiber (referred to as CNF-20ZrO2) was fabricated using a simple electrospinning method and applied to a supercapacitor as the electroactive material for the first time. The optimal electrode (CNF-20ZrO2) demonstrates a high specific capacitance of 140 F/g at 1 A/g. In addn., the assembled supercapacitor delivers max. specific energy of 4.86 Wh/kg at a specific power of 250 W/kg and shows excellent cycling stability of 82.6% after 10 000 cycles at 1 A/g. The electrochem. performance of the electrode originates from the high content of nitrogen and oxygen species, abundant electrochem. active sites, and high ionic cond.
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    Zhang, Q.; Chen, C.; Chen, W.; Pastel, G.; Guo, X.; Liu, S.; Wang, Q.; Liu, Y.; Li, J.; Yu, H.; Hu, L. Nanocellulose-Enabled, All-Nanofiber, High-Performance Supercapacitor.. ACS Appl. Mater. Interfaces 2019, 11, 5919,  DOI: 10.1021/acsami.8b17414
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    Nanocellulose-Enabled, All-Nanofiber, High-Performance Supercapacitor
    Zhang, Qi; Chen, Chaoji; Chen, Wenshuai; Pastel, Glenn; Guo, Xiaoyu; Liu, Shouxin; Wang, Qingwen; Liu, Yixing; Li, Jian; Yu, Haipeng; Hu, Liangbing
    ACS Applied Materials & Interfaces (2019), 11 (6), 5919-5927CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Nanocellulose has been used as a sustainable nanomaterial for constructing advanced electrochem. energy-storage systems with renewability, lightwt., flexibility, high performance, and satisfying safety. Here, we demonstrate a high-performance all-nanofiber asym. supercapacitor (ASC) assembled using a forest-based, nanocellulose-derived hierarchical porous carbon (nanocellulose carbon, HPC) anode, a mesoporous nanocellulose membrane separator (nanocellulose separator), and a NiCo2O4 cathode with nanocellulose carbon as the support matrix (nanocellulose cathode, HPC/NiCo2O4). HPC has a three-dimensional porous structure comprising interconnected nanofibers with an ultrahigh surface area of 2046 m2 g-1. When integrated with the mesoporous feature of the nanocellulose membrane separator, these properties facilitate the quick delivery of both ions and electrons even with a thick (up to several hundreds of micrometers) and highly loaded (5.8 mg cm-2) ASC design. Consequently, the all-nanofiber ASC demonstrates a high electrochem. performance (64.83 F g-1 (10.84 F cm-3) at 0.25 A g-1 and 32.78 F g-1 or 5.48 F cm-3 at 4 A g-1) that surpasses most cellulose-based ASCs ever reported. Moreover, the nanocellulose components promise renewability, low cost, and biodegradability, thereby presenting a promising direction toward high-power, environmentally friendly, and renewable energy-storage devices.
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    Lee, K. H.; Oh, J.; Son, J. G.; Kim, H.; Lee, S. S. Nitrogen-Doped Graphene Nanosheets from Bulk Graphite Using Microwave Irradiation.. ACS Appl. Mater. Interfaces 2014, 6 (9), 6361– 6368,  DOI: 10.1021/am405735c
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    Nitrogen-Doped Graphene Nanosheets from Bulk Graphite using Microwave Irradiation
    Lee, Kwang Hoon; Oh, Jinwoo; Son, Jeong Gon; Kim, Heesuk; Lee, Sang-Soo
    ACS Applied Materials & Interfaces (2014), 6 (9), 6361-6368CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Using simple microwave irradn. under the presence of Na amide as a N source, prepn. of N-doped graphene nanosheets was successfully demonstrated. It is notable that exfoliation and N doping of graphite to N-doped graphene simultaneously occurred during the microwave irradn. within a minute, and N content of the doped graphene could reach up to 8.1%. Also the binding configuration of N atom on graphitic layer consisted of various N-contg. moieties such as pyridine-N, pyrrolic-N, and quaternary-N, and their compn. was changed as a function of irradn. power. Although formation of undoped reduced graphene oxide by microwave irradn. resulted in slight increase of elec. cond. because of the reductive recovery of oxidized graphite to graphene, N doping involved during irradn. induced much more notable increase of elec. cond. >300 S cm-1. Also, N-doped graphene showed highly enhanced capacitive performance than that of undoped reduced graphene oxide, the specific capacitance of 200 F/g (c.d. of 0.5 A/g), which ascribes the pseudocapacitive effect from the incorporation of N atom on graphitic layer.
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    Ferhi, N.; Desalegn Assresahegn, B.; Ardila-Suarez, C.; Dissem, N.; Guay, D.; Duong, A. Defective Metal-Organic Framework-808@Polyaniline Composite Materials for High Capacitance Retention Supercapacitor Electrodes.. ACS Appl. Energy Mater. 2022, 5 (1), 1235– 1243,  DOI: 10.1021/acsaem.1c03649
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    Defective Metal-Organic Framework-808@Polyaniline Composite Materials for High Capacitance Retention Supercapacitor Electrodes
    Ferhi, Najmeddine; Desalegn Assresahegn, Birhanu; Ardila-Suarez, Carolina; Dissem, Nour; Guay, Daniel; Duong, Adam
    ACS Applied Energy Materials (2022), 5 (1), 1235-1243CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Among their potential applications, metal-org. frameworks (MOFs) emerge as promising alternative electrode materials to overcome the disadvantages of low energy d. supercapacitors. Although the potential of MOFs lies in their adjustable pore structure and high surface areas, they possess poor cond. In this context, composites with conductive matrixes, including org. conductive polymers, have proved to enhance the electrochem. properties of MOFs and their structural stability in the long-term cycling process compared to the pristine MOF. In this study, we have chosen defective zirconium MOF-808 (d-MOF-808) as a porous material because of its resistance to strong acidic media in a postsynthetic modification process. As a conductive agent, polyaniline (PANI) was selected due to its high stability and facile synthesis. The obtained composites of d-MOF-808@PANI at d-MOF/PANI ratios of 15:1, 30:1, and 60:1 increase the charge transport properties compared to the pristine d-MOF-808 and PANI. Electrochem. evaluation of the new hybrid electrode materials was made to demonstrate the capacitance retention. Among the series of materials prepd., the 60:1 composite shows the highest capacitance (188 F/g at 30 mV s-1) in 1 M KOH and a notable capacitance retention of 99.8% for up to 10,000 cycles with 99.7% coulombic efficiency.
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    Zhang, F.; Liu, H.; Wu, Z.; Zhang, J.; Cui, E.; Yue, L.; Hou, G. Polyacrylamide Gel-Derived Nitrogen-Doped Carbon Foam Yields High Performance in Supercapacitor Electrodes.. ACS Appl. Energy Mater. 2021, 4 (7), 6719– 6729,  DOI: 10.1021/acsaem.1c00777
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    Polyacrylamide Gel-Derived Nitrogen-Doped Carbon Foam Yields High Performance in Supercapacitor Electrodes
    Zhang, Feng; Liu, Huachen; Wu, Zhaofeng; Zhang, Junhao; Cui, Entian; Yue, Lu; Hou, Guihua
    ACS Applied Energy Materials (2021), 4 (7), 6719-6729CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Porous carbons play a vital role in supercapacitor electrodes. The capacitive performance of porous carbons depends mostly on the pore structure and surface chem. It is highly desirable to develop robust methods to prep. porous carbons with controlled structures and compns. Herein, a nitrogen-doped carbon foam was prepd. on the basis of polyacrylamide gel with K2CO3 and K2B4O7 as the activating agent and salt template, resp. Due to the constraint effect of the cross-linked polyacrylamide network, K2CO3 and K2B4O7 can be homogeneously embedded in the polymer matrix. The subsequent carbonization results in the nitrogen-doped carbon foam (PACF) with a hierarchically porous structure and high sp. surface area (~ 3404.8 m2 g-1). K2B4O7 not only serves as the sol. salt template but can also reinforce the carbonaceous skeleton during carbonization. PACF yields an outstanding specific capacitance (346.9 F g-1 at 0.5 A g-1), good rate performance (224.4 F g-1 at 50 A g-1), and excellent cycle capability (retaining 97.2% of the initial capacitance after 10,000 consecutive charge-discharge cycles). This study demonstrates the potential of polyacrylamide gel as a promising carbon precursor and enriches the tool box for the prepn. of porous carbons.
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    Zhu, Y. P.; Xia, C.; Lei, Y.; Singh, N.; Schwingenschlögl, U.; Alshareef, H. N. Solubility Contrast Strategy for Enhancing Intercalation Pseudocapacitance in Layered MnO2 Electrodes.. Nano Energy 2019, 56, 357– 364,  DOI: 10.1016/j.nanoen.2018.11.063
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    Solubility contrast strategy for enhancing intercalation pseudocapacitance in layered MnO2 electrodes
    Zhu, Yun-Pei; Xia, Chuan; Lei, Yongjiu; Singh, Nirpendra; Schwingenschlogl, Udo; Alshareef, Husam N.
    Nano Energy (2019), 56 (), 357-364CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
    Pseudocapacitance is generally assocd. with either surface redox reactions or ion intercalation processes without a phase transition. Typically, these two mechanisms have been independently studied, and most works have focused on optimizing one or the other in different material systems. Here we have developed a strategy based on soly. contrast, in which the contribution from the two capacitive mechanisms is simultaneously optimized. Taking layered birnessite MnO2 as a model, controllable nanostructures and oxygen vacancies are achieved through a simple copptn. process. Simultaneously controlling crystallite size and defect concn. is shown to enhance the charging-discharging kinetics together with both redox and intercalation capacitances. This synergistic effect results from enhanced ionic diffusion, electronic cond., and large surface-to-vol. ratio. In addn., considerable cycling durability is achieved, resulting from improved framework strength by defect creation and the absence of proton (de)intercalation during discharge/charge. This work underscores the importance of synergistically regulating nanostructure and defects in redox-active materials to improve pseudocapacitive charge storage.
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    Wang, P.; Wen, Y.; Lu, J.; Yin, S.; Key, J.; Wang, N.; Shen, P. K. Manganese Oxide(III)/Carbon Hybrids with Interesting Morphologies as Improved Active Materials for Supercapacitors.. Int. J. Hydrogen Energy 2019, 44 (26), 13623– 13631,  DOI: 10.1016/j.ijhydene.2019.03.240
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    Manganese(III) oxide/carbon hybrids with interesting morphologies as improved active materials for supercapacitors
    Wang, Peng; Wen, Ying; Lu, Jiajia; Yin, Shibin; Key, Julian; Wang, Ningzhang; Shen, Pei Kang
    International Journal of Hydrogen Energy (2019), 44 (26), 13623-13631CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
    Mn2O3/C hybrids with almond-like, peach-like and peanut-like morphologies are fabricated via hydrothermal method followed by annealing in air at ambient pressure. Their phys. properties and morphologies are characterized by XRD, Raman scattering spectroscopy (Raman), XPS, Brunauer-Emmett-Teller (BET), SEM and scanning TEM (STEM). Almond-like Mn2O3/C (Mn2O3/C-ALL) and peach-like Mn2O3/C (Mn2O3/C-PCL) hybrids are highly porous with large-sized mesopores. But peanut-like Mn2O3/C (Mn2O3/C-PNL) is composed of densely packed slender nanofibers. The results show Mn2O3 and C have homogeneous contact accounting for high cond. In 1.0M Na2SO4 aq. electrolyte, Mn2O3/C-PCL has the highest specific capacitance of 158.8 F g-1 at 1.0 A g-1, compared to Mn2O3/C-ALL (105.1 F g-1) and Mn2O3/C-PNL (77.5 F g-1). Also, the capacitance retention of Mn2O3/C-PCL achieves 48.8% upon a 50-fold increase in c.d. Finally, the Mn2O3/C-PCL displays an impressive long-term cycle stability of 90.6% specific capacitance retention after 10,000 cycles at 1.0 A g-1. Therefore, this work highlights the importance of morphol. in Mn2O3/C hybrids design to obtain high performance supercapacitor materials.
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    Lu, W.; Li, Y.; Yang, M.; Jiang, X.; Zhang, Y.; Xing, Y. Construction of Hierarchical Mn2O3@MnO2Core-Shell Nanofibers for Enhanced Performance Supercapacitor Electrodes.. ACS Appl. Energy Mater. 2020, 3 (9), 8190– 8197,  DOI: 10.1021/acsaem.0c00392
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    Construction of Hierarchical Mn2O3@MnO2 Core-Shell Nanofibers for Enhanced Performance Supercapacitor Electrodes
    Lu, Wei; Li, Yuan; Yang, Man; Jiang, Xin; Zhang, Yanxia; Xing, Yan
    ACS Applied Energy Materials (2020), 3 (9), 8190-8197CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Manganese oxide (MnOx) is a considerable candidate for supercapacitor electrode materials owing to its large theor. capacitance and low price, but its performance is generally limited by unsatisfactory cycle performance and poor cond. Herein, Mn2O3@MnO2 composite nanofibers have been prepd. via electrospinning and hydrothermal methods. Adjusting the KMnO4 precursor concn. during the hydrothermal process, Mn2O3@MnO2 core-shell nanofibers with variable compositional ratios of MnO2 to Mn2O3 have been obtained. The hierarchically core-shell structure and the synergistic effect between the two oxides enable the as-prepd. Mn2O3@MnO2 nanocomposite electrode to achieve a desirable elec. cond. and cycle stability. Consequently, [email protected] nanofiber electrodes display an enhanced specific capacitance of 225.0 F g-1 (0.2 A g-1) along with a pretty cycling stability (86.5% after 5000 cycles) at 5 A g-1. These results demonstrate the substantial prospects of the as-prepd. Mn2O3@MnO2 nanofibers for enhanced performance supercapacitors.
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    Wang, T.; Guo, J.; Guo, Y.; Feng, J.; Wu, D. Nitrogen-Doped Carbon Derived from Deep Eutectic Solvent as a High-Performance Supercapacitor.. ACS Appl. Energy Mater. 2021, 4 (3), 2190– 2200,  DOI: 10.1021/acsaem.0c02703
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    Nitrogen-Doped Carbon Derived from Deep Eutectic Solvent as a High-Performance Supercapacitor
    Wang, Tao; Guo, Jia; Guo, Yao; Feng, Jing; Wu, Dongling
    ACS Applied Energy Materials (2021), 4 (3), 2190-2200CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    As a kind of ionic fluid, deep-eutectic solvent (DES) has been used not only as a solvent but also as a precursor for carbon prepn. in recent years. Herein, porous nitrogen-doped carbon (NC) has been prepd. via simple pyrolysis of L-tyrosine-based DES. The effects of the proportion of the components in DES and the carbonization temp. on the morphol., pore structure, chem. compn., and the performance for supercapacitor application have been investigated. The as-prepd. NCs show large surface areas, high nitrogen contents, hierarchical porous structures, and excellent capacitive performances. Specifically, the optimized sample exhibits a higher specific capacitance (306.5 F g-1), better rate capability (70.3% at 50 A g-1), and also shows high area capacitance (7.1 F cm-2) and specific capacitance (235.8 F g-1) when 30 mg/cm2 of the sample is loaded. The constructed sym. supercapacitor attains a high energy d. of 16.9 W h kg-1 (at 450 W kg-1) in the neutral electrolyte and outstanding cycling stability of 100% retention after 50,000 cycles. Moreover, the fabricated sym. solid KOH/poly(vinyl alc.) supercapacitor displays a superior energy d. of 15.2 W h kg-1 at 700 W kg-1 and can retain 8.8 W h kg-1 at 14 kW kg-1. Our work presents a route for the synthesis of porous carbon using DES as the carbonaceous precursor and also demonstrates its possible application in energy storage.
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    Bal Altuntaş, D.; Aslan, S.; Akyol, Y.; Nevruzoǧlu, V. Synthesis of New Carbon Material Produced from Human Hair and Its Evaluation as Electrochemical Supercapacitor.. Energy Sources, Part A Recover. Util. Environ. Eff. 2020, 42 (19), 2346– 2356,  DOI: 10.1080/15567036.2020.1782536
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This article is cited by 2 publications.

  1. Melissa W. Williams, James Aaron Wimberly, Ratib M. Stwodah, Jimmy Nguyen, Paola A. D’Angelo, Christina Tang. Temperature-Responsive Structurally Colored Fibers via Blend Electrospinning. ACS Applied Polymer Materials 2023, 5 (4) , 3065-3078. https://doi.org/10.1021/acsapm.3c00222
  2. Zhibo Zhang, Andrey Bolshakov, Jiecai Han, Jiaqi Zhu, Kun-Lin Yang. Electrospun Core-Sheath Fibers with a Uniformly Aligned Polymer Network Liquid Crystal (PNLC). ACS Applied Materials & Interfaces 2023, 15 (11) , 14800-14809. https://doi.org/10.1021/acsami.2c23065
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  • Abstract

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    Figure 1

    Figure 1. Chemical structure of (a) 7cb and (b) c500. (c) Schematic diagram of the electrospinning diagram. (d) A picture of the nanofiber-coated electrode.

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    Figure 2

    Figure 2. Electrochemical evaluation of the c500 amount in the composite electrode structure. Cyclic voltammograms of (a) 0.27, (b) 0.37, (c) 0.56, (d) 0.65, and (e) 0.75%-added electrodes.

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    Figure 3

    Figure 3. SEM images of fibers which belong to (a) PAN, (b) PAN/7CB, and (c) PAN/7CB/C500; the thickness distribution of the fibers of (d) PAN, (e) PAN/7CB, and (f) PAN/7CB/C500.

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    Figure 4

    Figure 4. POM images of fibers cumulated on microscope slides are presented in (a,c,e) between crossed polarizers with a 137 nm optical retarder and in (b,d,f) without any retarder. (a,b), (c,d), and (e,f) are associated with PAN, PAN/7CB, and PAN/7CB/C500, respectively. Fibers were electrospun at a 12.0 kV application voltage and a 23.0 cm needle-to-collector distance. The scale bar represents 100 μm.

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    Figure 5

    Figure 5. DSC thermographs of bulk 7cb, bulk polyacrylonitrile, and the PAN/7CB fiber.

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    Figure 6

    Figure 6. FTIR spectra of PAN, 7cb, c500, and their nanofiber composites.

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    Figure 7

    Figure 7. Electrochemical characterizations of developed electrodes. (a) Cyclic voltammogram of (a) all nanofiber modified PGE electrodes, (b) detailed CV presentation of the PGE/PAN and PGE/PAN/7CB electrodes, (c) Nyquist plot of the nanofiber modified PGE electrodes, and (d) Nyquist plot of the 7cb-c500 nanofiber modified PGE electrode and its equivalent circuit.

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    Figure 8

    Figure 8. Cyclic voltammograms of (a) PGE/PAN, (b) PGE/PAN/7CB, and (c) PGE/PAN/7CB/C500 electrodes at scan rate from 5 to 100 mV/s.

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    Figure 9

    Figure 9. Cyclic stability of the PGE/PAN/7CB/C500 electrode. (a) Plots of 1st and 2500th cycles, and (b) Cs values of each 100th measurement and their correlation.

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  • References

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      Yiǧit, D.; Udum, Y. A.; Güllü, M.; Toppare, L. Electrochemical and Spectroelectrochemical Studies of Poly(2,5-Di-2,3-Dihydrothieno[3,4-b][1,4]Dioxin-5-Ylthienyl) Derivatives Bearing Azobenzene, Coumarine and Fluorescein Dyes: Effect of Chromophore Groups on Electrochromic Properties.. Electrochim. Acta 2014, 147, 669– 677,  DOI: 10.1016/j.electacta.2014.09.053
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      Electrochemical and spectroelectrochemical studies of poly(2,5-di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylthienyl) derivatives bearing azobenzene, coumarine and fluorescein dyes: Effect of chromophore groups on electrochromic properties
      Yigit, Deniz; Udum, Yasemin Arslan; Gullu, Mustafa; Toppare, Levent
      Electrochimica Acta (2014), 147 (), 669-677CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
      Three novel thiophene based monomers, 2,5-di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylthienyl derivs., 1-4-[(2,5-Di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl-3-thienyl)](methoxy phenyl-2-phenyldiazene) (ETEAz), 4-2,5-[Di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl-3-thienyl methoxy]-2H-chromen-2-one (ETECo) and Me 2-{6-[(2,5-Di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl-3-thienyl) methoxy]-3-oxo-3H-xanthen -9-yl}benzoate (ETEFlo), were synthesized and their conducting polymers were electrochem. prepd. on ITO glass electrodes for the 1st time. The electroactive monomers were functionalized with strong chromophore groups such as azobenzene, coumarine and fluorescein to study the effect of chromophore units on electrochem. and spectroelectrochem. characteristics of corresponding conducting polymers. Spectroelectrochem. studies demonstrated that combination of a strong chromophore group with polymer backbone leads to significant changes in electronic and optoelectronic behaviors of resulting conducting polymers. PETEAz, PETECo and PETEFlo exhibited multicolored electrochromism with three distinct states. PETEAz revealed 33% (565 nm) and 52% (1270 nm) transmittance changes (ΔT%), while PETECo exhibited 40% (535 nm) and 64% (1245 nm) at their dominant wavelenghts. The optical contrasts of PETEFlo were measured as 15% (495 nm), 28% (560 nm) and 43% (1345 nm), which were lower than those of PETEAz and PETEFlo. All conducting polymer films could be very quickly switched between their neutral and oxidized states in both visible and NIR regions. Switching times values are 0.3 s at 565 nm and 0.4 s at 1270 nm for PETEAz, 0.4 s at 535 nm and 0.5 s at 1245 nm for PETECo, 0.4 s at 495 nm, 0.4 s at 560 nm and 0.7 s at 1345 nm. Also, the optical band gap values for PETEAz, PETECo and PETEFlo were calcd. as 1.6 eV, 1.4 eV and 1.55 eV, resp., from the onset of π-π* transition in polymer films' neutral states.
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      Bye, A.; King, H. K. The Biosynthesis of 4-Hydroxycoumarin and Dicoumarol by Aspergillus Fumigatus Fresenius.. Biochem. J. 1970, 117 (2), 237– 245,  DOI: 10.1042/bj1170237
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      Biosynthesis of 4-hydroxycoumarin and dicoumarol by Aspergillus fumigatus Fresenius
      Bye, Alan; King, Hugh Kirkman
      Biochemical Journal (1970), 117 (2), 237-45CODEN: BIJOAK; ISSN:0264-6021.
      A strain of A. fumigatus, isolated from spoiled hay, converts melilotic acid (o-hydroxyphenylpropionic acid) and o-coumaric acid into 4-hydroxycoumarin and dicoumarol. The sequence is melilotic acid -2H-→ o-coumaric acid +H2O-→ β-hydroxymelilotic acid -2H-→ β-oxomelilotic acid → 4-hydroxycoumarin, on the basis of (1) studies on the formation of postulated intermediates, (2) expts. with isotopically labeled materials and (3) sequential enzyme induction. In the presence of semicarbazide, o-coumaraldehyde is formed from o-coumaric acid: there is no evidence, however, that this lies on the normal metabolic pathway.
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    5. 5
      Wang, Y.-H.; Avula, B.; Nanayakkara, N. P. D.; Zhao, J.; Khan, I. A. Cassia Cinnamon as a Source of Coumarin in Cinnamon-Flavored Food and Food Supplements in the United States.. J. Agric. Food Chem. 2013, 61 (18), 4470– 4476,  DOI: 10.1021/jf4005862
      5
      Cassia Cinnamon as a Source of Coumarin in Cinnamon-Flavored Food and Food Supplements in the United States
      Wang, Yan-Hong; Avula, Bharathi; Nanayakkara, N. P. Dhammika; Zhao, Jianping; Khan, Ikhlas A.
      Journal of Agricultural and Food Chemistry (2013), 61 (18), 4470-4476CODEN: JAFCAU; ISSN:0021-8561. (American Chemical Society)
      Coumarin and other marker compds. were analyzed in authenticated cinnamon bark samples as well as locally bought cinnamon samples, cinnamon-flavored foods, and cinnamon-based food supplements using a validated UPLC-UV/MS method. The exptl. results indicated that C. verum bark contained only traces of coumarin, whereas barks from all three cassia species, esp. C. loureiroi and C. burmannii, contained substantial amts. of coumarin. These species could be potential sources of coumarin in cinnamon-flavored food in the U.S. Coumarin was detected in all locally bought cinnamon, cinnamon-flavored foods, and cinnamon food supplements. Their chem. profiles indicated that the cinnamon samples and the cinnamon in food supplements and flavored foods were probably Indonesian cassia, C. burmannii.
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    6. 6
      Leal, L. K. A.; Ferreira, A. A.; Bezerra, G.; Matos, F. J.; Viana, G. S. Antinociceptive, Anti-Inflammatory and Bronchodilator Activities of Brazilian Medicinal Plants Containing Coumarin: A Comparative Study.. J. Ethnopharmacol. 2000, 70 (2), 151– 159,  DOI: 10.1016/S0378-8741(99)00165-8
      6
      Antinociceptive, anti-inflammatory and bronchodilator activities of Brazilian medicinal plants containing coumarin: a comparative study
      Leal L K; Ferreira A A; Bezerra G A; Matos F J; Viana G S
      Journal of ethnopharmacology (2000), 70 (2), 151-9 ISSN:0378-8741.
      This work studied the antinociceptive, antiinflammatory and bronchodilator activities of hydroalcoholic extracts (HAEs) from Torresea cearensis, Justicia pectoralis, Eclipta alba, Pterodon polygaliflorus and Hybanthus ipecacuanha. These plants are largely used in north-eastern Brazil for respiratory tract diseases, and have in common coumarin, one of their active principles. The antinociceptive effects of all HAEs in mice were similar, and the inhibition of the acetic acid-induced writhing was 35-55% with 200 mg/kg, p.o. At this dose, the effect ranged from 41-77% with the formalin test in mice, and all the HAEs inhibited preferentially the 2nd phase of the response. In one case (P. polygaliflorus), the effect was partially reversed by naloxone. Except for the HAE from T. cearensis (200 mg/kg, p.o.) which inhibited carrageenan-induced edema by 47%, the others presented no effect orally but showed a significant activity intraperitoneally. On the other hand, T. cearensis was not active in the dextran model, while inhibitions with the other ones were lower than 30%. The bronchodilator activities of J. pectoralis and P. polygaliflorus HAEs as determined in isolated guinea-pig trachea were the most active.
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    7. 7
      Born, S. L.; Api, A. M.; Ford, R. A.; Lefever, F. R.; Hawkins, D. R. Comparative Metabolism and Kinetics of Coumarin in Mice and Rats.. Food Chem. Toxicol. 2003, 41 (2), 247– 258,  DOI: 10.1016/S0278-6915(02)00227-2
      7
      Comparative metabolism and kinetics of coumarin in mice and rats
      Born, S. L.; Api, A. M.; Ford, R. A.; Lefever, F. R.; Hawkins, D. R.
      Food and Chemical Toxicology (2003), 41 (2), 247-258CODEN: FCTOD7; ISSN:0278-6915. (Elsevier Science Ltd.)
      Coumarin, a well recognized rat hepatotoxicant, also causes acute, selective necrosis of terminal bronchiolar Clara cells in the mouse lung. Further, chronic oral gavage administration of coumarin at 200 mg/kg, a dose that causes Clara cell death, resulted in a statistically significant increased incidence of alveolar/bronchiolar adenomas and carcinomas in B6C3F1 mice. In contrast, mouse lung tumors were not obsd. at the 100 and 50 mg/kg dose levels in the oral gavage study, or in CD-1 mice following chronic intake of coumarin at levels equiv. to 276 mg/kg in diet. The current studies were designed to det. the impact of oral gavage vs. dietary administration on the pharmacokinetics and metab. of coumarin in CD-1 and B6C3F1 mice and F344 rats. Following the administration of 200 mg/kg 14C-coumarin via oral gavage, lung Cmax values (total 14C-assocd. radioactivity) were five- and 37-fold greater than those resulting from a 50 mg/kg oral gavage dose or 1000 ppm in diet, resp. Coumarin (200 mg/kg) pharmacokinetics and metab. was also examd. in F344 rats following oral gavage dosing. Total 14C-coumarin assocd. radioactivity in plasma was 3.5-fold lower than in the mouse, and the plasma half-life in rats was five-times longer than in mice. Using non-radiolabeled compd. (200 mg/kg), coumarin and products of the coumarin 3,4-epoxidn. pathway were quantitated in plasma and urine after oral gavage administration to mice and rats. 7-Hydroxycoumarin (7-HC) was quantitated in mouse plasma and urine. o-Hydroxyphenylacetic acid (o-HPAA) reached a concn. of 37 g/mL in plasma, and accounted for 41% of the dose in the urine, whereas the C for 7-hydroxycoumarin was 3 g/mL, and represented 7% of the administered dose. In the rat, the plasma Cmax for o-HPAA was 6 μg/mL, and accounted for 12% of the dose. The coumarin Cmax in rat plasma was comparable to that in mouse. Coumarin 3,4-epoxide (CE) and its rearrangement product o-hydroxyphenylacetaldehyde (o-HPA) and o-hydroxyphenylethanol (o-HPE), were not detected at any time point in plasma or urine. This anal. of coumarin and CE pharmacokinetics in rodents suggests that the differential tumor response in the mouse oral gavage and dietary bioassays is a function of the route of exposure, whereas species differences in lung toxicity between mice and rats result from heightened local bioactivation in the mouse lung.
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    8. 8
      Marles, R. J.; Compadre, Cé. M.; Farnsworth, N. R. Coumarin in Vanilla Extracts: Its Detection and Significance.. Econ. Bot. 1987, 41 (1), 41– 47,  DOI: 10.1007/BF02859345
      8
      Coumarin in vanilla extracts: its detection and significance
      Marles, Robin J.; Compadre, Cesar M.; Farnsworth, Norman R.
      Economic Botany (1987), 41 (1), 41-7CODEN: ECBOA5; ISSN:0013-0001.
      A vanilla ext. sample was dissolved in 10 mL aq. EtOH and coumarin was extd. with three 20-mL portions of CH2Cl2. The combined exts. were evapd. and coumarin was detd. by capillary gas chromatog. on a DB-1 coated column and identified by mass spectrometry. The method was used to detect coumarin in vanilla exts. brought into the US from Mexico.
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    9. 9
      Wesseling, J.; Van Driel, D.; Smrkovsky, M.; Van der Veer, E.; Geven-Boere, L.; Sauer, P. J.; Touwen, B. C. Neurological Outcome in School-Age Children after in Utero Exposure to Coumarins.. Early Hum. Dev. 2001, 63 (2), 83– 95,  DOI: 10.1016/S0378-3782(01)00140-2
      9
      Neurological outcome in school-age children after in utero exposure to coumarins
      Wesseling, J.; Van Driel, D.; Smrkovsky, M.; Van der Veer, E.; Geven-Boere, L. M.; Sauer, P. J. J.; Touwen, B. C. L.
      Early Human Development (2001), 63 (2), 83-95CODEN: EHDEDN; ISSN:0378-3782. (Elsevier Science Ltd.)
      The effect of prenatal exposure to coumarins (acenocoumarol, phenprocoumon) on neurol. outcome was assessed in a cohort of 306 children aged 7-15 yr. The findings were compared with those in a nonexposed cohort of 267 children, matched for sex, age, and demog. region. A neurol. examn. technique was used which pays special attention to minor neurol. dysfunction (MND). None of the children was neurol. abnormal. However, exposure to coumarins during gestation increased the risk of MND in children of school age, odds ratio 1.9, predominantly after exposure in the 2nd or 3rd trimester of pregnancy, odds ratio 2.1. A dose-response relationship was found, with an odds ratio of 1.2 per mg coumarin deriv. prescribed per day. The results suggest that coumarins have an influence on the development of the brain which can lead to MND in children of school age.
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    10. 10
      Costela, A.; Garcia-Moreno, I.; Figuera, J. M.; Amat-Guerri, F.; Barroso, J.; Sastre, R. Solid-State Dye Laser Based on Coumarin 540A-Doped Polymeric Matrices.. Opt. Commun. 1996, 130 (1–3), 44– 50,  DOI: 10.1016/0030-4018(96)00220-9
      10
      Solid-state dye laser based on Coumarin 540A-doped polymeric matrixes
      Costela, A.; Garcia-Moreno, I.; Figuera, J. M.; Amat-Guerri, F.; Barroso, J.; Sastre, R.
      Optics Communications (1996), 130 (1,2,3), 44-50CODEN: OPCOB8; ISSN:0030-4018. (Elsevier)
      Coumarin 540-A was dissolved in a copolymer of 2-hydroxyethyl methacrylate (HEMA) and Me methacrylate (MMA) 1:1 vol./vol. and in a pure poly(Me methacrylate) homopolymer (PMMA). Laser action was induced in the resulting solid-state solns. pumped with 1.2 mJ pulses at 337 nm from a nitrogen laser. The effects on the laser performance of different polymn. methods, dye concn. and polymeric matrix compn. were evaluated. Energy conversion efficiencies of 11% and lifetimes of ∼2000 pulses at 2 Hz repetition rate were demonstrated.
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    11. 11
      Sarmah, M.; Chutia, K.; Dutta, D.; Gogoi, P. Overview of Coumarin-Fused-Coumarins: Synthesis, Photophysical Properties and Their Applications.. Org. Biomol. Chem. 2021, 20 (1), 55– 72,  DOI: 10.1039/D1OB01876K
      11
      Overview of coumarin-fused-coumarins: synthesis, photophysical properties and their applications
      Sarmah Manashi; Chutia Kangkana; Dutta Dhiraj; Gogoi Pranjal; Dutta Dhiraj; Gogoi Pranjal
      Organic & biomolecular chemistry (2021), 20 (1), 55-72 ISSN:.
      Coumarin-fused-coumarins have attracted significant attention in the scientific world owing to their boundless applications in interdisciplinary areas. Various synthetic pathways have been developed to construct novel coumarin-fused-coumarin analogues by the fusion of modern methodologies with a classical Pechmann reaction or Knoevenagel condensation. Owing to their extended molecular framework, they possess interesting photophysical properties depending on the fused coumarin ring systems. This review highlights previously published reports on the synthetic strategies for structurally diverse coumarin-fused-coumarins. Furthermore, the scope of the synthesized biscoumarin-fused entities is described by highlighting their photophysical properties and applications.
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    12. 12
      Kalay, H.; Yiǧit, D.; Hizalan, G.; Güllü, M.; Depci, T.; Cirpan, A.; Toppare, L.; Hacioglu, S. O. Synthesis, Electrochromic Characterization and Solar Cell Application of Thiophene Bearing Alternating Copolymers with Azobenzene and Coumarin Subunits.. J. Macromol. Sci. Part A 2020, 57 (8), 589– 599,  DOI: 10.1080/10601325.2020.1740598
      12
      Synthesis, electrochromic characterization and solar cell application of thiophene bearing alternating copolymers with azobenzene and coumarin subunits
      Kalay, Huseyin; Yigit, Deniz; Hizalan, Gonul; Gullu, Mustafa; Depci, Tolga; Cirpan, Ali; Toppare, Levent; Hacioglu, Serife O.
      Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (2020), 57 (8), 589-599CODEN: JSPCE6; ISSN:1060-1325. (Taylor & Francis, Inc.)
      In this study, azobenzene and coumarin functionalized thiophene comprising two copolymers (poly (4-((3'''-hexyl-[2,2':5',2'':5'',2'''-tetrathiophene] - 3'-yl)methoxy) - 2H-chromen-2-one) (P1) and poly (1-(4-((4'''-hexyl-[2,2': 5', 2'': 5'', 2''' - tetrathiophene] - 3'-yl) methoxy) phenyl) -2-phenyldiazene) (P2)), were designed and synthesized according to the donor-acceptor (D-A) approach to investigate their electrochem., optical and photovoltaic behaviors. Among the various copolymn. methods to obtain P1 and P2, Stille copolymn. reaction was preferred. The optical band gaps of the polymers were calcd. as 1.88 eV and 1.64 eV using UV-VIS spectrophotometer for P1 and P2. Electrochem. and spectroelectrochem. studies for synthesized copolymers support their usage in org. solar cell applications. The org. solar cells (OSCs) were designed using polymer as an electron donor group and PC60BM as an electron acceptor group. Performances of OSCs based on P1 and P2 were investigated with the device structure of ITO/PEDOT:PSS/Polymer(P1/P2):PC60BM/LiF/Al. The highest power conversion efficiency was obtained as 0.81% for P1 based device with 0.47 V open-circuit voltage (Voc) and 4.92 mA/cm2 c.d. (Jsc) values. The highest efficiency for P2 comprising device was found to be 0.96% under optimum conditions with 0.60 V and 4.98 mA/cm2, Voc and Jsc values, resp.
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    13. 13
      Demus, D.; Goodby, J.; Gray, G. W.; Spiess, H. -W.; Vill, V. Handbook of Liquid Crystals; Wiley, 1998.
      There is no corresponding record for this reference.
    14. 14
      Chipot, C.; Shell, M. S.; Pohorille, A. Thermotropic Liquid Crystals, Fundamentals.. Springer Series in Chemical Physics 2007, 86, 1– 31,  DOI: 10.1007/978-3-540-38448-9_1
      14
      Introduction
      Chipot, Christophe; Shell, M. Scott; Pohorille, Andrew
      Springer Series in Chemical Physics (2007), 86 (Free Energy Calculations), 1-31CODEN: SSCPDA; ISSN:0172-6218. (Springer GmbH)
      A review on free energy calcns. To understand fully the vast majority of chem. processes, it is often necessary to examine their underlying free energy behavior. This is the case, for instance, in protein-ligand binding and drug partitioning across the cell membrane. These processes, which are of paramount importance in the field of computer-aided, rational drug design, cannot be predicted reliably without knowledge of the assocd. free energy changes. The reliable detn. of free energy changes using numerical simulations based on the fundamental principles of statistical mechanics is now within reach. Developments on the methodol. front in conjunction with the continuous increase in computational power have contributed to bringing free energy calcns. to the level of robust and well-characterized modeling tools, while widening their field of applications.
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    15. 15
      Al-Ahmed, A.; Sarı, A.; Mazumder, M. A. J.; Hekimoǧlu, G.; Al-Sulaiman, F. A.; Inamuddin Thermal Energy Storage and Thermal Conductivity Properties of Octadecanol-MWCNT Composite PCMs as Promising Organic Heat Storage Materials. Sci. Reports 2020, 10, 9168,  DOI: 10.1038/s41598-020-64149-3
      15
      Thermal energy storage and thermal conductivity properties of Octadecanol-MWCNT composite PCMs as promising organic heat storage materials
      Al-Ahmed, Amir; Sari, Ahmet; Mazumder, Mohammad Abu Jafar; Hekimoglu, Gokhan; Al-Sulaiman, Fahad A.; Inamuddin
      Scientific Reports (2020), 10 (1), 9168CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)
      Fatty alcs. have been identified as promising org. phase change materials (PCMs) for thermal energy storage, because of their suitable temp. range, nontoxicity and can be obtained from both natural and synthetic sources. Like all other org. PCMs, octadecanol (OD) as PCM suffers from low thermal cond. (TC). In this work, to enhance its TC, it was grafted on the functionalized MWCNT and were used as a conductive filler to enhance overall thermal properties of OD in a composite PCM (CPCMs) structure. The OD/OD-g-MWCNT sample showed better dispersion within the composites and the presence of addnl. OD boosted the overall heat storage enthalpy compared to that of plane composite sample with OD/MWCNT. In a non-quant. approach, it was obsd. that, any increase in grafting ratio of OD increases the heat storage enthalpy of the composites. The heat storage enthalpy of (267.7 J/g) OD/OD-g-MWCNT(4:1)-5wt% composite PCM had reached very close to the heat storage enthalpy value of pure OD (269.3 J/g), and much higher than that of OD/MWCNT-5wt% (234.5 J/g). Champion sample i.e.OD/OD-g-MWCNT (4:1)-5wt%, showed good heat storage enthalpy, cycling performance, thermal stability and TC enhancement by 262.5%.
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    16. 16
      Lagerwall, J. P. F.; McCann, J. T.; Formo, E.; Scalia, G.; Xia, Y. Coaxial Electrospinning of Microfibres with Liquid Crystal in the Core.. Chem. Commun. 2008, 42, 5420,  DOI: 10.1039/b810450f
      There is no corresponding record for this reference.
    17. 17
      Reyes, C. G.; Sharma, A.; Lagerwall, J. P. F. Non-Electronic Gas Sensors from Electrospun Mats of Liquid Crystal Core Fibres for Detecting Volatile Organic Compounds at Room Temperature.. Liq. Cryst. 2016, 43 (13–15), 1986– 2001,  DOI: 10.1080/02678292.2016.1212287
      17
      Non-electronic gas sensors from electrospun mats of liquid crystal core fibres for detecting volatile organic compounds at room temperature
      Reyes, Catherine G.; Sharma, Anshul; Lagerwall, Jan P. F.
      Liquid Crystals (2016), 43 (13-15), 1986-2001CODEN: LICRE6; ISSN:0267-8292. (Taylor & Francis Ltd.)
      Non-woven mats comprised of liq. crystal-functionalized fibers are coaxially electrospun to create soft gas sensors that function non-electronically, thus requiring no power supply, detecting org. vapors at room temp. The fibers consist of a poly(vinylpyrrolidone) (PVP) sheath surrounding a core of nematic 4-cyano-4'pentylbiphenyl (5CB) liq. crystal. Several types of mats, contg. uniformly cylindrical or irregular beaded fibers, in uniform or random orientations, are exposed to toluene vapor as a representative volatile org. compd. Between crossed polarizers all mats respond with a fast (response time on the order of a second or faster) redn. in brightness during gas exposure, and they return to the original state upon removal of the gas almost as quickly. With beaded fibers, the response of the mats is visible even without polarizers. We discuss how variations in fiber spinning conditions such as humidity level and the ratio of core-sheath fluid flow rates can be used to tune fiber morphol. and thereby the response. Considering future development perspectives, we argue that fibers turned responsive through the incorporation of a liq. crystal core show promise as a new generation of sensors with textile form factor, ideal for wearable technol. applications.
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    18. 18
      Schelski, K.; Reyes, C. G.; Pschyklenk, L.; Kaul, P.-M.; Lagerwall, J. Quantitative Volatile Organic Compound (VOC) Sensing with Liquid Crystal Core Fibers.. Cell Reports Phy. Sci. 2021, 2, 100661,  DOI: 10.1016/j.xcrp.2021.100661
      18
      Quantitative volatile organic compound sensing with liquid crystal core fibers
      Schelski, Katrin; Reyes, Catherine G.; Pschyklenk, Lukas; Kaul, Peter-Michael; Lagerwall, Jan P. F.
      Cell Reports Physical Science (2021), 2 (12), 100661CODEN: CRPSF5; ISSN:2666-3864. (Elsevier Inc.)
      Polymer fibers with liq. crystals (LCs) in the core have potential as autonomous sensors of airborne volatile org. compds. (VOCs), with a high surface-to-vol. ratio enabling fast and sensitive response and an attractive non-woven textile form factor. We demonstrate their ability to continuously and quant. measure the concn. of toluene, cyclohexane, and isopropanol as representative VOCs, via the impact of each VOC on the LC birefringence. The response is fully reversible and repeatable over several cycles, the response time can be as low as seconds, and high sensitivity is achieved when the operating temp. is near the LC-isotropic transition temp. We propose that a broad operating temp. range can be realized by combining fibers with different LC mixts., yielding autonomous VOC sensors suitable for integration in apparel or in furniture that can compete with existing consumer-grade electronic VOC sensors in terms of sensitivity and response speed.
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    19. 19
      Reyes, C.; Lagerwall, J. P.; Muševič, I.; Chien, L.-C.; Broer, D. J.; Chigrinov, V. G. Advancing Flexible Volatile Compound Sensors Using Liquid Crystals Encapsulated in Polymer Fibers. SPIE 10555, Emerging Liquid Crystal Technologies XIII 2018, 105550O,  DOI: 10.1117/12.2292533
      There is no corresponding record for this reference.
    20. 20
      Mamuk, A. E.; Koçak, Ç.; Demirci Dönmez, Ç. E. Production and Characterization of Liquid Crystal/Polyacrylonitrile Nano-Fibers by Electrospinning Method.. Colloid Polym. Sci. 2021, 299 (7), 1209– 1221,  DOI: 10.1007/s00396-021-04842-5
      20
      Production and characterization of liquid crystal/polyacrylonitrile nano-fibers by electrospinning method
      Mamuk, Atilla Eren; Kocak, Cagdas; Demirci Donmez, Cigdem Elif
      Colloid and Polymer Science (2021), 299 (7), 1209-1221CODEN: CPMSB6; ISSN:0303-402X. (Springer)
      We present that high birefringent nematic liq. crystal, 4-n-pentyl-4'-cyanobiphenyl, was incorporated into the polyacrylonitrile precursor which has a strong polar cyano group so as to produce electrospun nano-fibers, as the first time. Optical textures of nano-fibers were taken by polarized optical microscopy with different angles to det. the orientation degree of liq. crystal mols. in the center of the fiber. The mols. of liq. crystal self-ordered within the core of the fiber. Variation in morphol. of liq. crystal/polymer nano-fibers were examd. by utilizing both SEM and polarized optical microscopy depending on liq. crystal concn. in precursor and application voltage during electrospinning. Morphol. of nano-fibers was significantly affected by electrospinning parameters and liq. crystal/polymer ratio. To understand phase sepn. and thermal stability of nano-fibers, calorimetric and thermogravimetric analyzes were performed.
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    21. 21
      Koçak, Ç.; Mamuk, A. E.; Demirci Dönmez, E. Ç.; Poyraz, M. Electrospun Fibers of Liquid Crystal Mixtures.. J. Mater. Sci. Mater. Electron. 2022, 33, 15209– 15221,  DOI: 10.1007/s10854-022-08439-8
      21
      Electrospun fibers of liquid crystal mixtures
      Kocak, Cagdas; Mamuk, Atilla Eren; Demirci Donmez, Cigdem Elif; Poyraz, Mehmet
      Journal of Materials Science: Materials in Electronics (2022), 33 (18), 15209-15221CODEN: JSMEEV; ISSN:0957-4522. (Springer)
      Electrospinning is a powerful and promising technique in prodn. of nano-materials namely nano-fibers. Nano-sized materials show properties apart from their macroscopic/bulk sizes, and enable us to fabricate materials that could be designed as functional composites of different kinds of materials. We electrospun to form core-sheath nanofibers composed of polyacrylonitrile (PAN) sheath with a core of widely used nematic liq. crystals (6CB and 8CB) by blending them in various ratios. The nano-fibers were fabricated in different conditions regarding the feeding rate and electrospinning voltage. The phys. properties were investigated. Optical properties revealed the birefringence of the nano-fibers which is an important property for the light modulating devices. The thicknesses of the nano-fibers were detd. from SEM images and the distribution of the thickness was shown in a histogram. The thermal studies put forward the N-I transition temps. of the liq. crystal/PAN nano-fibers, that the temps. were in compliance with that of liq. crystals. It can control light modulation by tuning such liq. crystal/fiber material known to be usable in optoelectronics.
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    22. 22
      Aslan, S.; Bal Altuntaş, D.; Koçak, Ç.; Kara Subaşat, H. Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes.. Electroanalysis 2021, 33 (1), 120– 128,  DOI: 10.1002/elan.202060239
      22
      Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes
      Aslan, Sema; Bal Altuntas, Derya; Kocak, Cagdas; Kara Subasat, Huelya
      Electroanalysis (2021), 33 (1), 120-128CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The TiO2 nanoparticles are electrospun with polyacrylonitrile (PAN) polymer soln. onto the discharged battery coal (DBC) electrode and the results are evaluated as a supercapacitor. The morphol. and chem. compn. of the synthesized TiO2 nanoparticles and PAN+TiO2 nanocomposite fibers were characterized by SEM, thermogravimetry and FTIR anal. Supercapacitor measurements and electrochem. characterizations of the electrodes examd. by cyclic voltammetry and electrochem. impedance spectroscopy. Electrochem. measurements showed that the best current value was obtained from PAN and TiO2 coated DBC. The performances of both PAN and PAN+TiO2 coated DBC electrodes were investigated as supercapacitors. PAN+TiO2/DBC showed the best specific capacitance value of 156.00 F g-1 and PAN/DBC showed 74.93 F g-1. In addn., PAN+TiO2/DBC exhibited reliable stability performance over 2000.00 cycles.
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    23. 23
      Aslan, S. An Electrochemical Immunosensor Modified with Titanium IV Oxide/Polyacrylonitrile Nanofibers for the Determination of a Carcinoembryonic Antigen.. New J. Chem. 2021, 45 (12), 5391– 5398,  DOI: 10.1039/D0NJ05385F
      23
      An electrochemical immunosensor modified with titanium IV oxide/polyacrylonitrile nanofibers for the determination of a carcinoembryonic antigen
      Aslan, Sema
      New Journal of Chemistry (2021), 45 (12), 5391-5398CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)
      Carcinoembryonic antigen (CEA) is considerably addressed for the clin. diagnosis of misc. tumor types. In this study, an electrochem. immunosensor for the detn. of the CEA biomarker was presented. Titanium(IV) oxide nanoparticle (TiO2np)-loaded polyacrylonitrile nanofibers (PANnf) were prepd. by electrospinning at the surface of the discharged battery coal electrode (DBC), and loaded with CEA antibodies (Anti-CEA) as the CEA biomarker receptor. Finally, DBC/PANnf + TiO2np/Anti-CEA was utilized for the CEA detection. Fabrication steps were characterized by cyclic voltammetry and electrochem. impedance spectroscopy in the presence of a [Fe(CN)6]3-/4- probe. Results demonstrated that PANnf and TiO2nps exhibited a very fine network for immunosensing. The usage of this composite system is a novel immunosensor development approach for the label-free detection of CEA. Under optimal conditions, the DBC/PANnf + TiO2np/Anti-CEA immunosensor exhibited high sensitivity toward the CEA biomarker in the low concn. range of 0.01-10 ng mL-1, with the detection limit of 0.01 ng mL-1 and relative std. deviation of 1.17 (n = 5). Results indicated that even very small changes in the CEA concn. can be sensed with the presented system. Also, the recovery of the immunosensor was found to be 99.42% ± 1.41 in real sera samples contg. dopamine and ascorbic acid. It has great potential in the clin. screening of divergent cancer biomarkers.
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    24. 24
      Wang, J.; Jákli, A.; West, J. L. Liquid Crystal/Polymer Fiber Mats as Sensitive Chemical Sensors.. J. Mol. Liq. 2018, 267, 490– 495,  DOI: 10.1016/j.molliq.2018.01.051
      24
      Liquid crystal/polymer fiber mats as sensitive chemical sensors
      Wang, Junren; Jakli, Antal; West, John L.
      Journal of Molecular Liquids (2018), 267 (), 490-495CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
      We present quant. measurements of the optical response of liq. crystal (LC)/polymer composite fiber mats to toluene and acetone vapors. Our analyses in comparison with control measurements of pure LC film and polymer fiber mats show that the chems. can pass through the polymer sheath of the fibers and be absorbed by the LC in the core. This absorption changes the optical properties of the fiber mats which can be used to produce sensitive and reversible detection. The sensitive response at low concns. of both acetone and toluene demonstrates the feasibility of using these fibers for highly sensitive and specific sensors for volatile org. compd. detection.
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    25. 25
      Wang, J.; Jákli, A.; West, J. L. Morphology Tuning of Electrospun Liquid Crystal/Polymer Fibers.. ChemPhysChem 2016, 17 (19), 3080– 3085,  DOI: 10.1002/cphc.201600430
      25
      Morphology Tuning of Electrospun Liquid Crystal/Polymer Fibers
      Wang, Junren; Jakli, Antal; West, John L.
      ChemPhysChem (2016), 17 (19), 3080-3085CODEN: CPCHFT; ISSN:1439-4235. (Wiley-VCH Verlag GmbH & Co. KGaA)
      This paper elucidates the means to control precisely the morphol. of electrospun liq. crystal/polymer fibers formed by phase sepn. The relative humidity, soln. parameters (concn., solvent), and the process parameter (feed rate) were varied systematically. We show that the morphol. of the phase-sepd. liq. crystal can be continuously tuned from capsules to uniform fibers with systematic formation of beads-on-a-string structured fibers in the intermediate ranges. In all cases, the polymer forms a sheath around a liq.-crystal (LC) core. The width of the polymer sheath and the diam. of the LC core increase with increasing feed rates. This is similar to the results obtained by coaxial electrospinning. Because these fibers retain the responsive properties of liq. crystals and because of their large surface area, they have potential applications as thermo-, chemo-, and biosensors. Because the size and shape of the liq.-crystal domains will have a profound effect on the performance of the fibers, our ability to precisely control morphol. will be crucial in developing these applications.
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    26. 26
      Buyuktanir, E. A.; Frey, M. W.; West, J. L. Self-Assembled, Optically Responsive Nematic Liquid Crystal/Polymer Core-Shell Fibers: Formation and Characterization.. Polymer (Guildf). 2010, 51 (21), 4823– 4830,  DOI: 10.1016/j.polymer.2010.08.011
      There is no corresponding record for this reference.
    27. 27
      Aslan, S.; Bal Altuntaş, D.; Koçak, Ç.; Kara Subaşat, H. Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes.. Electroanalysis 2021, 33, 120– 128,  DOI: 10.1002/elan.202060239
      27
      Electrochemical Evaluation of Titanium (IV) Oxide/Polyacrylonitrile Electrospun Discharged Battery Coals as Supercapacitor Electrodes
      Aslan, Sema; Bal Altuntas, Derya; Kocak, Cagdas; Kara Subasat, Huelya
      Electroanalysis (2021), 33 (1), 120-128CODEN: ELANEU; ISSN:1040-0397. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The TiO2 nanoparticles are electrospun with polyacrylonitrile (PAN) polymer soln. onto the discharged battery coal (DBC) electrode and the results are evaluated as a supercapacitor. The morphol. and chem. compn. of the synthesized TiO2 nanoparticles and PAN+TiO2 nanocomposite fibers were characterized by SEM, thermogravimetry and FTIR anal. Supercapacitor measurements and electrochem. characterizations of the electrodes examd. by cyclic voltammetry and electrochem. impedance spectroscopy. Electrochem. measurements showed that the best current value was obtained from PAN and TiO2 coated DBC. The performances of both PAN and PAN+TiO2 coated DBC electrodes were investigated as supercapacitors. PAN+TiO2/DBC showed the best specific capacitance value of 156.00 F g-1 and PAN/DBC showed 74.93 F g-1. In addn., PAN+TiO2/DBC exhibited reliable stability performance over 2000.00 cycles.
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    28. 28
      Tajik, S.; Dubal, D. P.; Gomez-Romero, P.; Yadegari, A.; Rashidi, A.; Nasernejad, B.; Inamuddin; Asiri, A. M. Nanostructured Mixed Transition Metal Oxides for High Performance Asymmetric Supercapacitors: Facile Synthetic Strategy.. Int. J. Hydrogen Energy 2017, 42 (17), 12384– 12395,  DOI: 10.1016/j.ijhydene.2017.03.117
      28
      Nanostructured mixed transition metal oxides for high performance asymmetric supercapacitors: Facile synthetic strategy
      Tajik, Sanaz; Dubal, Deepak P.; Gomez-Romero, Pedro; Yadegari, Amir; Rashidi, Alimorad; Nasernejad, Bahram; Inamuddin; Asiri, Abdullah M.
      International Journal of Hydrogen Energy (2017), 42 (17), 12384-12395CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
      Exceptionally simple and cost-effective solid-state method is reported for the synthesis of different mixed transition metal oxides (MTMOs) including FeCo2O4, MnCo2O4 and ZnCo2O4 with unique nanostructures. The morphol. anal. show that MTMOs possess distinct nanostructures such as tetragonal, spherical nanoparticles and hexagonal nanosheets. Furthermore, these MTMOs showed excellent supercapacitive properties with specific capacitances of 660-1263 F/g at c.d. of 2 A/g. Asym. capacitor was fabricated with FeCo2O4 as pos. and activated carbon as neg. electrode which exhibits a specific capacitance of 88 F/g with energy d. of 24 Wh/kg (1.1 mWh/cm3) and cycle life (93%) over 5000 cycles.
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    29. 29
      Shiyanovskii, S. V.; Smalyukh, I. I.; Lavrentovich, O. D. Computer Simulations and Fluorescence Confocal Polarizing Microscopy of Structures in Cholesteric Liquid Crystals. Defects in Liquid Crystals: Computer Simulations, Theory and Experiments 2001, 229– 270,  DOI: 10.1007/978-94-010-0512-8_10
      There is no corresponding record for this reference.
    30. 30
      Zhang, W.; Zhang, L.; Liang, X.; Le Zhou; Xiao, J.; Yu, L.; Li, F.; Cao, H.; Li, K.; Yang, Z.; Yang, H. Unconventional High-Performance Laser Protection System Based on Dichroic Dye-Doped Cholesteric Liquid Crystals.. Sci. Rep. 2017, 7 (1), 42955,  DOI: 10.1038/srep42955
      30
      Unconventional High-Performance Laser Protection System Based on Dichroic Dye-Doped Cholesteric Liquid Crystals
      Zhang, Wanshu; Zhang, Lanying; Liang, Xiao; Le Zhou; Xiao, Jiumei; Yu, Li; Li, Fasheng; Cao, Hui; Li, Kexuan; Yang, Zhou; Yang, Huai
      Scientific Reports (2017), 7 (), 42955CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)
      High-performance and cost-effective laser protection system is of crucial importance for the rapid advance of lasers in military and civilian fields leading to severe damages of human eyes and sensitive optical devices. However, it is crucially hindered by the angle-dependent protective effect and the complex prepn. process. Here we demonstrate that angle-independence, good processibility, wavelength tunability, high optical d. and good visibility can be effectuated simultaneously, by embedding dichroic anthraquinone dyes in a cholesteric liq. crystal matrix. More significantly, unconventional two-dimensional parabolic protection behavior is reported for the first time that in stark contrast to the existing protection systems, the overall parabolic protection behavior enables protective effect to increase with incident angles, hence providing omnibearing high-performance protection. The protective effect is controllable by dye concn., LC cell thickness and CLC reflection efficiency, and the system can be made flexible enabling applications in flexible and even wearable protection devices. This research creates a promising avenue for the high-performance and cost-effective laser protection, and may foster the development of optical applications such as solar concentrators, car explosion-proof membrane, smart windows and polarizers.
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    31. 31
      Kumar, P.; Neeraj; Kang, S.; Lee, S. H.; Raina, K. K. Analysis of Dichroic Dye-Doped Polymer-Dispersed Liquid Crystal Materials for Display Devices.. Thin Solid Films 2011, 520 (1), 457– 463,  DOI: 10.1016/j.tsf.2011.06.038
      31
      Analysis of dichroic dye-doped polymer-dispersed liquid crystal materials for display devices
      Kumar, Pankaj; Neeraj; Kang, Shin-Woong; Lee, Seung Hee; Raina, K. K.
      Thin Solid Films (2011), 520 (1), 457-463CODEN: THSFAP; ISSN:0040-6090. (Elsevier B.V.)
      Dichroic polymer-dispersed liq. crystals (DPDLCs) based on nematic liq. crystal materials with azo dye were investigated in detail for the application of display devices. Polarizing optical microscopy, differential scanning calorimeter and electro-optic expts. all have shown that the DPDLC contg. low concn. of dyes modifies the basic properties of these materials like optical transmission, threshold voltage, contrast ratio and absorbance factor. A min. amt. of dye needs to be added to the liq. crystal with the polymer matrix for its effective phase sepn. and to minimize the transmittance in the OFF state and therefore gives rise to an overall improvement in contrast ratio of the devices. Mol. orientation and dynamics in droplet sizes are readily controlled in these DPDLC materials. These findings imply that the value of the threshold elec. field Eth is approx. 8 V/μm for pure polymer-dispersed liq. crystal (without dye) where the threshold elec. field Eth values are approx. 4.0 V/μm, 2.0 V/μm, 1.7 V/μm 1.0 V/μm, for 0.0625%, 0.125%, 0.25% and 0.5% with azo dye in DPDLCs, resp. From the results we can also infer that the max. contrast is approx. 2.55 times the min. contrast obsd. in the expt. for DPDLCs. The results show that the DPDLC with proscribed dye concn. will be possibly suitable and promising functional electronic materials for green technol. flexible liq. crystal display.
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    32. 32
      Sheng, M.; Zhang, L.; West, J. L.; Fu, S. Multicolor Electrochromic Dye-Doped Liquid Crystal Yolk–Shell Microcapsules. ACS Appl. Mater. Interfaces 2020, 12, 29728,  DOI: 10.1021/acsami.0c09354
      32
      Multicolor Electrochromic Dye-Doped Liquid Crystal Yolk-Shell Microcapsules
      Sheng, Mingfei; Zhang, Liping; West, John Lawton; Fu, Shaohai
      ACS Applied Materials & Interfaces (2020), 12 (26), 29728-29736CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      A new system of yolk-shell microcapsules contg. two types of dye-doped liq. crystals was prepd. via seed emulsion polymn. in which the synthetic process was mimicking plant respiration. The resulting system demonstrated reversible low voltage-driven switching between multispectral colored and transparent states. Moreover, wearable multicolor electrochromic fibers based on calcium alginate were produced via wet spinning to expand the application of yolk-shell dye-doped liq. crystal microcapsules. In addn. to its long-term optical stability, the proposed cells and fibers also have satisfactory driving voltage values of color change (4.8 and 9.0 V), which are far lower than the human body safety voltage (12 V). We believe that the prepd. microcapsules and fibers are potentially widely applicable in smart windows, electronic paper, and military camouflage clothing.
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    33. 33
      Tajalli, H.; Gilani, A. G.; Zakerhamidi, M. S.; Tajalli, P. The Photophysical Properties of Nile Red and Nile Blue in Ordered Anisotropic Media.. Dye. Pigment. 2008, 78 (1), 15– 24,  DOI: 10.1016/j.dyepig.2007.10.002
      33
      The photophysical properties of Nile red and Nile blue in ordered anisotropic media
      Tajalli, H.; Gilani, A. Ghanadzadeh; Zakerhamidi, M. S.; Tajalli, P.
      Dyes and Pigments (2008), 78 (1), 15-24CODEN: DYPIDX; ISSN:0143-7208. (Elsevier Ltd.)
      The absorption and fluorescence spectra of a highly fluorescent laser dye, Nile red, were studied in nematic solvents and isotropic liqs. as a function of the solvent polarity and type. The interaction of the dye with the anisotropic surrounding and with that of the isotropic solvents was studied and compared using optical spectroscopy. The spectral behavior of the cationic oxazine dye, Nile blue, was also studied in anisotropic and isotropic environments for comparison. The spectral shifts were correlated by the solvent polarity and nature. The electrooptical effect of the guest-host systems was also studied in an electrooptical system using polarized spectroscopic method and the dichroic ratios R and degree of anisotropies S of these dyes in the liq. cryst. hosts were studied.
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    34. 34
      Zhang, X.; Liu, X.; Zhang, X.; Tian, Y.; Meng, Y. Ordering of the 7CB Liquid Crystal Induced by Nanoscale Confinement and Boundary Lubrication.. Liq. Cryst. 2012, 39 (11), 1305– 1313,  DOI: 10.1080/02678292.2012.715686
      34
      Ordering of the 7CB liquid crystal induced by nanoscale confinement and boundary lubrication
      Zhang, Xiangjun; Liu, Xiaoxiang; Zhang, Xiaohao; Tian, Yu; Meng, Yonggang
      Liquid Crystals (2012), 39 (11), 1305-1313CODEN: LICRE6; ISSN:0267-8292. (Taylor & Francis Ltd.)
      In this study, the thermodn. properties of nanoscale-thick 4-heptyl-4'-cyanobiphenyl (7CB) liq. crystals (LCs) confined in carbon nanotubes were investigated using differential scanning calorimetric methods. Both the isotropic-nematic phase transition temp. and the enthalpy increase decrease as the nanoscale confining size decreases, indicating the ordering effect of the 7CB mols. under nanoscale confinement. An av.-order parameter <S> is calcd. to quant. identify the ordering effect of LCs by utilizing a simple expression of the Landau-de Gennes (LdG) free energy. The av.-ordering parameter <S> of the 7CB LC can be 0.7 within a confinement thickness of ∼25 nm and above 0.5 within a film thickness of up to 100 nm. When lubricating the 7CB LC between a steel ball and chromium-coated glass disk at low speeds, a stable boundary layer with a thickness of 10 nm is formed that is independent of the entrainment speed. At higher speeds, the thickness of the 7CB lubrication film ranges from several tens of nanometers to 100 nm, resulting in a stable velocity-independent friction coeff. of approx. 0.03. The ordered microstructure of the 7CB mols. under confinement provides the underlay mechanism of its boundary lubrication property.
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    35. 35
      Ahn, W.; Kim, C. Y.; Kim, H.; Kim, S. C. Phase Behavior of Polymer/Liquid Crystal Blends.. Macromolecules 1992, 25 (19), 5002– 5007,  DOI: 10.1021/ma00045a028
      35
      Phase behavior of polymer/liquid crystal blends
      Ahn, W.; Kim, C. Y.; Kim, H.; Kim, S. C.
      Macromolecules (1992), 25 (19), 5002-7CODEN: MAMOBX; ISSN:0024-9297.
      The thermodn. phase behavior of blends of a low-mol.-wt. liq. crystal (LC), 4-cyano-4'-n-heptylbiphenyl (I), with each of 2 amorphous polymers, poly(Me methacrylate) (II) and polystyrene (III) was studied as a function of temp. or LC concn. Phase diagrams for both the binary I-II and I-III blends were constructed from DSC and optical microscopic observations showing that I was partially miscible in both II and III. There existed a polymer/isotropic LC 2-phase state at a given compn. besides the polymer/nematic LC 2-phase state and the polymer/solid cryst. LC 2-phase state. The polymer/isotropic LC 2-phase morphol. was clearly obsd. by the phase-contrast optical microscope in the temp. range between the homogeneous single-phase state and the polymer/nematic LC 2-phase state, while DSC or cross-polarized light microscopy failed to detect the existence of the polymer/isotropic LC 2-phase state. This was also confirmed by a light-scattering expt. At a low ratio of LC in both the blends, direct transformation between the homogeneous single-phase state and the polymer/nematic LC 2-phase state was obsd. without going through the polymer/isotropic LC 2-phase state.
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    36. 36
      Javadian, S.; Dalir, N.; Gilani, A. G.; Kakemam, J.; Yousefi, A. A New Approach to Study Interaction Parameters in Cyanobiphenyl Liquid Crystal Binary Systems.. J. Chem. Thermodyn. 2015, 80, 22– 29,  DOI: 10.1016/j.jct.2014.08.010
      36
      A new approach to study interaction parameters in cyanobiphenyl liquid crystal binary systems
      Javadian, Soheila; Dalir, Nima; Gilani, Ali Ghanadzadeh; Kakemam, Jamal; Yousefi, Ali
      Journal of Chemical Thermodynamics (2015), 80 (), 22-29CODEN: JCTDAF; ISSN:0021-9614. (Elsevier Ltd.)
      The phase transition of heptylcyanobiphenyl 7CB and pentylcyanobiphenyl 5CB liq. crystals was investigated using the differential scanning calorimetry DSC technique. Then, the phase transition of different compns. of 7CB/5CB binary mixt. was studied to det. the eutectic point. The phase diagram of mentioned binary system in 7CB mole fraction of 0.45 at T = 273.45 K is in good agreement with that of predicted from Schroder-van Laar equation. The thermodn. excess functions and interaction parameters were calcd. to describe the phase transition phys. using the non-random mixing for the first time. The P* randomicity parameter was used to describe the phase transitions of C-N and N-I in which a small amt. of P* shows a non-random identity of C-N phase transition. Contrarily, the P* is greater in N-I phase transition showing a random mixing process.
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    37. 37
      Sautter, B. P. Continuous Polymer Nanofibers Using Electrospinning , 2005.
      There is no corresponding record for this reference.
    38. 38
      Migliaresi, C.; Ruffo, G. A.; Zomer Volpato, F.; Zeni, D. Advanced Electrospinning Setups and Special Fibre and Mesh Morphologies. Electrospinning Adv. Biomed. Appl. Ther. 2012.
      There is no corresponding record for this reference.
    39. 39
      Huang, Z.-M.; Zhang, Y.-Z.; Kotaki, M.; Ramakrishna, S. A Review on Polymer Nanofibers by Electrospinning and Their Applications in Nanocomposites.. Compos. Sci. Technol. 2003, 63 (15), 2223– 2253,  DOI: 10.1016/S0266-3538(03)00178-7
      39
      A review on polymer nanofibers by electrospinning and their applications in nanocomposites
      Huang, Zheng-Ming; Zhang, Y.-Z.; Kotaki, M.; Ramakrishna, S.
      Composites Science and Technology (2003), 63 (15), 2223-2253CODEN: CSTCEH; ISSN:0266-3538. (Elsevier Science Ltd.)
      A review. A comprehensive review is presented on the researches and developments related to electrospun polymer nanofibers including processing, structure and property characterization, applications, and modeling and simulations. Information of those polymers together with their processing conditions for electrospinning of ultrafine fibers has been summarized in the paper. Other issues regarding the technol. limitations, research challenges, and future trends are also discussed.
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    40. 40
      Mu, X.; Du, J.; Zhang, Y.; Liang, Z.; Wang, H.; Huang, B.; Zhou, J.; Pan, X.; Zhang, Z.; Xie, E. Construction of Hierarchical CNT/RGO-Supported MnMoO 4 Nanosheets on Ni Foam for High-Performance Aqueous Hybrid Supercapacitors.. ACS Appl. Mater. Interfaces 2017, 9 (41), 35775– 35784,  DOI: 10.1021/acsami.7b09005
      40
      Construction of Hierarchical CNT/rGO-Supported MnMoO4 Nanosheets on Ni Foam for High-Performance Aqueous Hybrid Supercapacitors
      Mu, Xuemei; Du, Jingwei; Zhang, Yaxiong; Liang, Zhilin; Wang, Huan; Huang, Baoyu; Zhou, Jinyuan; Pan, Xiaojun; Zhang, Zhenxing; Xie, Erqing
      ACS Applied Materials & Interfaces (2017), 9 (41), 35775-35784CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Rationally designed conductive hierarchical nanostructures are highly desirable for supporting pseudocapacitive materials to achieve high-performance electrodes for supercapacitors. Herein, manganese molybdate nanosheets were hydrothermally grown with graphene oxide (GO) on three-dimensional nickel foam-supported carbon nanotube structures. Under the optimal graphene oxide concn., the obtained carbon nanotubes/reduced graphene oxide/MnMoO4 composites (CNT/rGO/MnMoO4) as binder-free supercapacitor cathodes perform with a high specific capacitance of 2374.9 F g-1 at the scan rate of 2 mV s-1 and good long-term stability (97.1% of the initial specific capacitance can be maintained after 3000 charge/discharge cycles). The asym. device with CNT/rGO/MnMoO4 as the cathode electrode and the carbon nanotubes/activated carbon on nickel foam (CNT-AC) as the anode electrode can deliver an energy d. of 59.4 Wh kg-1 at the power d. of 1367.9 W kg-1. These superior performances can be attributed to the synergistic effects from each component of the composite electrodes: highly pseudocapacitive MnMoO4 nanosheets and three-dimensional conductive Ni foam/CNTs/rGO networks. These results suggest that the fabricated asym. supercapacitor can be a promising candidate for energy storage devices.
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    41. 41
      Reneker, D. H.; Chun, I. Nanometre Diameter Fibres of Polymer, Produced by Electrospinning.. Nanotechnology 1996, 7 (3), 216– 223,  DOI: 10.1088/0957-4484/7/3/009
      41
      Nanometer diameter fibers of polymer, produced by electrospinning
      Reneker, Darrell H.; Chun, Iksoo
      Nanotechnology (1996), 7 (3), 216-223CODEN: NNOTER; ISSN:0957-4484. (Institute of Physics Publishing)
      The electrospinning process for the prepn. of polymer fibers with diams. of 40-2000 nm is reviewed with 41 refs. Electrospinning uses elec. forces to produce polymer fibers with nanometer-scale diams. Electrospinning occurs when the elec. forces at the surface of a polymer soln. or melt overcome the surface tension and cause an elec. charged jet to be ejected. When the jet dries or solidifies, an elec. charged fiber remains. This charged fiber can be directed or accelerated by elec. forces and then collected in sheets or other useful geometrical forms. More than 20 polymers, including poly(ethylene oxide), nylon, polyimide, DNA, polyaramid, and polyaniline, have been electrospun in the lab. Most were spun from soln., although spinning from the melt in vacuum and air was also demonstrated. Electrospinning from polymer melts in a vacuum is advantageous because higher fields and higher temps. can be used than in air.
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    42. 42
      Beachley, V.; Wen, X. Effect of Electrospinning Parameters on the Nanofiber Diameter and Length.. Mater. Sci. Eng., C 2009, 29 (3), 663– 668,  DOI: 10.1016/j.msec.2008.10.037
      42
      Effect of electrospinning parameters on the nanofiber diameter and length
      Beachley, Vince; Wen, Xuejun
      Materials Science & Engineering, C: Materials for Biological Applications (2009), 29 (3), 663-668CODEN: MSCEEE; ISSN:0928-4931. (Elsevier B.V.)
      Polymer nanofibers exhibit properties that make them a favorable material for the development of tissue engineering scaffolds, filtration devices, sensors, and high strength lightwt. materials. Electrospinning is a versatile method commonly used to manuf. polymer nanofibers. Collection of electrospun nanofibers across two parallel plates is a technique useful for creating nanofiber structures because it allows for the collection of linearly oriented individual nanofiber arrays and these arrays can be easily transferred to other substrates or structures. It is of importance to have some understanding of the capabilities of this collection method, such as the max. length of fibers that can be collected across two parallel plates. The effect of different electrospinning parameters on max. fiber length, av. fiber diam., diam. uniformity, and fiber quality was explored. It was shown that relatively long continuous polycaprolactone (PCL) nanofibers with av. diams. from approx. 350 nm to 1 μm could be collected across parallel plates at lengths up to 35-50 cm. Exptl. results lead to the hypothesis that even longer continuous nanofibers over 50 cm could be collected if the size of the parallel plates were increased. Extending the max. fiber length that can be collected across parallel plates could expand the applications of electrospinning. Polymer soln. concn., plate size, and applied voltage were all shown to have varying effects on max. fiber length, fiber diam., and fiber uniformity.
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    43. 43
      Yördem, O. S.; Papila, M.; Menceloǧlu, Y. Z. Effects of Electrospinning Parameters on Polyacrylonitrile Nanofiber Diameter: An Investigation by Response Surface Methodology.. Mater. Des. 2008, 29 (1), 34– 44,  DOI: 10.1016/j.matdes.2006.12.013
      There is no corresponding record for this reference.
    44. 44
      Okutan, N.; Terzi, P.; Altay, F. Affecting Parameters on Electrospinning Process and Characterization of Electrospun Gelatin Nanofibers. Food Hydrocoll. 2014, 39, 19– 26,  DOI: 10.1016/j.foodhyd.2013.12.022
      There is no corresponding record for this reference.
    45. 45
      Jacobs, V.; Anandjiwala, R. D.; Maaza, M. The Influence of Electrospinning Parameters on the Structural Morphology and Diameter of Electrospun Nanofibers.. J. Appl. Polym. Sci. 2010, 115 (5), 3130– 3136,  DOI: 10.1002/app.31396
      45
      The influence of electrospinning parameters on the structural morphology and diameter of electrospun nanofibers
      Jacobs, Valencia; Anandjiwala, Rajesh D.; Maaza, Malik
      Journal of Applied Polymer Science (2010), 115 (5), 3130-3136CODEN: JAPNAB; ISSN:0021-8995. (John Wiley & Sons, Inc.)
      Electrospinning is a simple method of producing nanofibers by introducing elec. field into the polymer solns. We report an exptl. investigation on the influence of processing parameters and soln. properties on the structural morphol. and av. fiber diam. of electrospun poly ethylene oxide (PEO) polymer soln. Exptl. trials have been conducted to investigate the effect of soln. parameters, such as concn., mol. wt., addn. of polyelectrolyte in PEO soln., solvent effect, as well as governing parameter, such as applied voltage. The concn. of the aq. PEO soln. has shown noteworthy influence on the fiber diam. and structural morphol. of electrospun nanofibers. At lower concns. of PEO polymer soln., the fibers showed irregular morphol. with large variations in fiber diam., whereas at higher concns., the nanofibers with regular morphol. and on av. uniform fiber diam. were obtained. We find that the addn. of polyelectrolytes, such as sodium salt of Poly acrylic acid (PAA) and Poly allylamine hydrochloride (PAH), increases the cond. of PEO solns. and thereby decreases the bead formation in electrospun nanofibers. The increase in applied voltage has been found to affect the structural morphol. of nanofiber while the addn. of ethanol in PEO soln. diminishes the bead defects.
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    46. 46
      Sirin, S.; Cetiner, S.; Sarac, A. S. Polymer Nanofibers Via Electrospinning: Factors Affecting Nanofiber Quality. KSU. J. Eng. Sci. 2013, 16 (2), 1– 12
      There is no corresponding record for this reference.
    47. 47
      Fong, H.; Chun, I.; Reneker, D. Beaded Nanofibers Formed during Electrospinning.. Polymer (Guildf). 1999, 40 (16), 4585– 4592,  DOI: 10.1016/S0032-3861(99)00068-3
      47
      Beaded nanofibers formed during electrospinning
      Fong, H.; Chun, I.; Reneker, D. H.
      Polymer (1999), 40 (16), 4585-4592CODEN: POLMAG; ISSN:0032-3861. (Elsevier Science Ltd.)
      Electrospinning is a straightforward method to produce polymer fibers with diams. in the range of 100 nm. from polymer solns. Electrospun fibers often have beads in regular arrays. The viscoelasticity of the soln., charge d. carried by the jet, and the surface tension of the soln. are the key factors that influence the formation of the beaded fibers.
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    48. 48
      Cramariuc, B.; Cramariuc, R.; Scarlet, R.; Manea, L. R.; Lupu, I. G.; Cramariuc, O. Fiber Diameter in Electrospinning Process.. J. Electrostat. 2013, 71 (3), 189– 198,  DOI: 10.1016/j.elstat.2012.12.018
      48
      Fiber diameter in electrospinning process
      Cramariuc, Bogdan; Cramariuc, Radu; Scarlet, Roxana; Manea, Liliana Rozemarie; Lupu, Iuliana G.; Cramariuc, Oana
      Journal of Electrostatics (2013), 71 (3), 189-198CODEN: JOELDH; ISSN:0304-3886. (Elsevier B.V.)
      In order to increase the control on the fiber diam. we propose in this paper a methodol. to det. stability domains of the process in which the electrospun fiber diam. can be predetd. and also controlled by means of the polymer soln. flow and the applied voltage. To define these stability domains we employ a combination of anal. expressions depending on the location along the traveling jet. In the vicinity of the nozzle we employ the expression which links the fiber diam. with the kinematic viscosity of the polymer soln., nozzle-collector distance, soln. d., liq. flow, elec. current and intensity of the electrostatic field. At larger distances from the nozzle, the fiber diam. can be expressed as a function of soln. d., liq. flow, intensity of the applied electrostatic field and distance from the nozzle. Close to the collector the fiber diam. can be expressed with respect to the superficial tension of the polymer soln., dielec. permittivity, liq. flow and intensity of the elec. current. Under specific constrains, the superposition of the plots obtained from these math. expressions will be used to det. the stability domain for the fiber diam. in which the diam. can be controlled by two process parameters, namely applied voltage and polymer soln. flow. Through this approach the present paper can contribute to increased control of the electrospinning process and thus enhanced applicability.
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    49. 49
      An, N.; Xu, Q.; Xu, L. H.; Wu, S. Z. Orientation Structure and Mechanical Properties of Polyacrylonitrile Precursors.. Adv. Mater. Res. 2006, 11–12, 383– 386,  DOI: 10.4028/www.scientific.net/AMR.11-12.383
      49
      Orientation structure and mechanical properties of polyacrylonitrile precursors
      An, Na; Xu, Qiang; Xu, Lianghua; Wu, Sizhu
      Advanced Materials Research (Zuerich, Switzerland) (2006), 11-12 (AICAM 2005), 383-386CODEN: AMREFI; ISSN:1022-6680. (Trans Tech Publications Ltd.)
      The microstructure of the polyacrylonitrile (PAN) precursors can strongly affect the structure of the carbon fibers which dets. the final mech. properties of the fibers. The orientation factors (fΔn) of PAN precursors under different draw ratios were characterized by the birefringence (Δnf), which was obtained through polarized microscopy. The results show that the increasing of the draw ratio may enhance the degree of orientation, which can correspondingly improve the mech. properties. However the increasing speed of the orientation factor slows down as the draw ratio reached to 8.
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    50. 50
      Kityk, A. V.; Wolff, M.; Knorr, K.; Morineau, D.; Lefort, R.; Huber, P. Continuous Paranematic-to-Nematic Ordering Transitions of Liquid Crystals in Tubular Silica Nanochannels.. Phys. Rev. Lett. 2008, 101 (18), 187801,  DOI: 10.1103/PhysRevLett.101.187801
      50
      Continuous Paranematic-to-Nematic Ordering Transitions of Liquid Crystals in Tubular Silica Nanochannels
      Kityk, Andriy V.; Wolff, Matthias; Knorr, Klaus; Morineau, Denis; Lefort, Ronan; Huber, Patrick
      Physical Review Letters (2008), 101 (18), 187801/1-187801/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      The optical birefringence of rodlike nematogens (7CB, 8CB), imbibed in parallel SiO2 channels with 10 nm diam. and 300 μm length, is measured and compared to the thermotropic bulk behavior. The orientational order of the confined liq. crystals, quantified by the uniaxial nematic ordering parameter, evolves continuously between paranematic and nematic states, in contrast to the discontinuous isotropic-to-nematic bulk phase transitions. A Landau-de Gennes model reveals that the strength of the orientational ordering fields, imposed by the SiO2 walls, is beyond a crit. threshold, that separates discontinuous from continuous paranematic-to-nematic behavior. Quenched disorder effects, attributable to wall irregularities, leave the transition temps. affected only marginally, despite the strong ordering fields in the channels.
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    51. 51
      Dierking, I. Textures of Liquid Crystals; Wiley, 2003.
      There is no corresponding record for this reference.
    52. 52
      Jasiurkowska-Delaporte, M.; Juszyńska-Gałązka, E.; Sas, W.; Zieliński, P. M.; Baranowska-Korczyc, A. Soft versus Hard Confinement Effects on the Phase Transitions, and Intra- and Inter- Molecular Dynamics of 6BT Liquid Crystal Constrained in Electrospun Polymer Fibers and in Nanopores.. J. Mol. Liq. 2021, 331, 115817,  DOI: 10.1016/j.molliq.2021.115817
      52
      Soft versus hard confinement effects on the phase transitions, and intra- and inter- molecular dynamics of 6BT liquid crystal constrained in electrospun polymer fibers and in nanopores
      Jasiurkowska-Delaporte, Malgorzata; Juszynska-Galazka, Ewa; Sas, Wojciech; Zielinski, Piotr M.; Baranowska-Korczyc, Anna
      Journal of Molecular Liquids (2021), 331 (), 115817CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
      This work examines the behavior of a liq. crystal (LC) under soft confinement, resulting from interactions between polymer and guest liq. cryst. mols., and under hard confinement, imposed by rigid pore walls. It studies the confinement effects for electrospun fibers composed of poly(ε-caprolactone) (PCL) and different wt. content of 4-hexyl-4'-isothiocyanatobiphenyl (6BT) liq. crystal, and 6BT enclosed in nanoporous alumina, with pore diams. of 200 nm, 120 nm, 80 nm and 40 nm. Differential scanning calorimetry, broadband dielec. and Fourier-transform IR spectroscopy were employed to gain detailed insights into the effects of both forms of confinement on 6BT. The crystn. process of 6BT was found to be enhanced in the composite fibers, but fully suppressed for the material confined in pores. The relaxation rates of the rotational motion of the LC mols. around their short axis in the 25.6 wt% 6BT and 17 wt% 6BT PCL/6BT fibers are in line with those found for 6BT in the 200 nm and 80 nm pores. Two-dimensional correlation spectroscopy (2D-COS) anal. of IR spectra confirmed that soft and hard confinement have different impacts on the intramol. dynamics of 6BT. The study also discusses the influence of guest mols. on the intramol. potentials of PCL.
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    53. 53
      Özgan, Ş.; Okumuş, M. Thermal and Spectrophotometric Analysis of Liquid Crystal 8CB/8OCB Mixtures.. Brazilian J. Phys. 2011, 41 (2–3), 118– 122,  DOI: 10.1007/s13538-011-0034-1
      53
      Thermal and spectrophotometric analysis of liquid crystal 8CB/8OCB mixtures
      Ozgan, Sukru; Okumus, Mustafa
      Brazilian Journal of Physics (2011), 41 (2-3), 118-122CODEN: BJPHE6; ISSN:0103-9733. (Springer)
      The binary system of 4-octyl-4'-cyanobiphenyl (8CB) and 4-octyloxy-4'-cyanobiphenyl (8OCB) was studied by differential scanning calorimetry (DSC) and UV absorption spectrophotometry (UV). The phase-transition temps., enthalpies, and entropies were detd. by calorimetric methods on DSC. The results indicate clearly the existence of 3-phase regions across the cryst.-to-smectic A, smectic A-to-nematic, and nematic-to-isotropic transitions in the 8CB/8OCB mixts. The obtained phase-transition temps. of the 8CB/8OCB mixts. are between the data for 8CB and 8OCB. A few of the phase transitions cannot be obsd. at high heating rates. The phase-transition temps. of the 8CB/8OCB mixts. rise with the heating rate between 2 K/min and 15 K/min. the activation energies were calcd. by the Ozawa method for the phase transitions of 25% 8CB and 75% 8OCB liq. crystal mixts. UV expts. were carried out to characterize the absorptivity consts. of liq. crystal and their mixts. The molar absorptivity and max. absorption wavelengths were measured in chloroform soln. by UV spectrophotometry. The max. absorption wavelength of the 8CB/8OCB mixts. increases with decreasing percent wt. of 8CB in 8OCB, a result assocd. with the different lengths of the alkyl chain.
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    54. 54
      Oweimreen, G. A.; Morsy, M. A. DSC Studies on P-Cyanophenyl p-(n-Alkyl)Benzoate Liquid Crystals: Evidence for Polymorphism and Conformational Change.. Thermochim. Acta 1999, 325 (2), 111– 118,  DOI: 10.1016/S0040-6031(98)00572-3
      54
      DSC studies on p-cyanophenyl p-(n-alkyl)benzoate liquid crystals: evidence for polymorphism and conformational change
      Oweimreen, G. A.; Morsy, M. A.
      Thermochimica Acta (1999), 325 (2), 111-118CODEN: THACAS; ISSN:0040-6031. (Elsevier Science B.V.)
      Temps. and enthalpy changes are reported for the melting, clearing, and nematic-to-solid transition of the p-cyanophenyl p-(alkyl)benzoate (RCBz) liq. crystals. Several solid structures exist for the RCBzs. Evidence that the transitions between the various solid forms involve conformational changes is provided by exotherms and endotherms appearing in heating and cooling cycles, resp. Also as long as melted RCBzs are not allowed to solidify they undergo repeated, reversible nematic-to-isotropic and isotropic-to-nematic transitions making them suitable for use in liq. crystal displays (LCD).
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    55. 55
      Mamuk, A. E.; Nesrullajev, A.; Mukherjee, P. K. Refractive and Birefringent Properties of 4-Alkyl-4′-Oxycyanobiphenyls at Direct and Reverse Phase Transitions.. Mol. Cryst. Liq. Cryst. 2017, 648 (1), 168– 181,  DOI: 10.1080/15421406.2017.1307499
      55
      Refractive and birefringent properties of 4-alkyl-4'-oxycyanobiphenyls at direct and reverse phase transitions
      Mamuk, Atilla Eren; Nesrullajev, Arif; Mukherjee, Prabir K.
      Molecular Crystals and Liquid Crystals (2017), 648 (1), 168-181CODEN: MCLCD8; ISSN:1542-1406. (Taylor & Francis, Inc.)
      Studies of temp. behavior of the mean refractive index, ordinary and extraordinary refractive indexes, and birefringence have been carried out for three nematogens. The thermo-morphol. properties of the biphasic regions of the direct nematic-isotropic liq. and reverse isotropic liq.-nematic phase transitions have been investigated. The 4-n-alkyl-4'-oxycyanobiphenyls (n = 5, 6, 7) were objects of our study. Studies have been carried out for the circular cycle as the heating-cooling. Temp. behavior of the order parameter in nematic mesophase and at the nematic-isotropic liq. and isotropic liq.-nematic phase transition is discussed.
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    56. 56
      Hosaka, S.; Tozaki, K.; Hayashi, H.; Inaba, H. Effect of Magnetic Field on the Phase Transitions of EBBA by Means of a High-Resolution and Super-Sensitive DSC.. Phys. B Condens. Matter 2003, 337 (1–4), 138– 146,  DOI: 10.1016/S0921-4526(03)00389-2
      56
      Effect of magnetic field on the phase transitions of EBBA by means of a high-resolution and super-sensitive DSC
      Hosaka, Shotaro; Tozaki, Ken-ichi; Hayashi, Hideko; Inaba, Hideaki
      Physica B: Condensed Matter (Amsterdam, Netherlands) (2003), 337 (1-4), 138-146CODEN: PHYBE3; ISSN:0921-4526. (Elsevier Science B.V.)
      Phase transitions of the N-p-ethoxybenzylidene-p'-butylaniline (EBBA) were measured by a high-resoln. and super-sensitive DSC. The crystal to liq. crystal transition and liq. crystal to isotropic liq. transition was obsd. at 305.8 and 352.4 K at a heating rate of 1 mK s-1, resp. The crystal to liq. crystal transition has fine structures resulting from different cryst. states of the sample which depended on the sample prepn. and on the heating rate of the measurement. The temp. due to liq. crystal to isotropic liq. transition was raised by 34 mK by applying a magnetic field of 5 T. The magnetic effect is discussed based on the extension of the Clapeyron equation.
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    57. 57
      Mukherjee, P. K. Isotropic to Smectic-A Phase Transition: A Review.. J. Mol. Liq. 2014, 190, 99– 111,  DOI: 10.1016/j.molliq.2013.11.001
      57
      Isotropic to smectic-A phase transition: A review
      Mukherjee, Prabir K.
      Journal of Molecular Liquids (2014), 190 (), 99-111CODEN: JMLIDT; ISSN:0167-7322. (Elsevier B.V.)
      A review. An attempt towards a unified picture of the direct transition from the isotropic to smectic-A phase is presented. The isotropic to smectic-A phase transition is described in detail, including structure and nature revealed by expts., mol. models and Landau-de Gennes theory. The wide variety of phenomena including effects of nonmesogenic impurities and elec. field, hydrodynamics, fluctuations, and elastic theory of liq. cryst. elastomers is discussed. A brief review on the general information about the isotropic to lamellar phase transition in lyotropic liq. crystals was given. The various predictions are compared with the available exptl. results. Open questions and possible approaches to finding answers are discussed.
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    58. 58
      Avci, N.; Nesrullajev, A.; Oktik, Ş. Nonlinear Thermotropic and Thermo-Optical Behaviour of Planar Oriented Textures in Nematic Liquid Crystals at Phase Transitions. Brazilian J. Phys. 2010, 40 (2), 224– 227
      58
      Nonlinear thermotropic and thermo-optical behaviour of planar oriented textures in nematic liquid crystals at phase transitions
      Avci, Nejmettin; Nesrullajev, Arif; Oktik, Sener
      Brazilian Journal of Physics (2010), 40 (2), 224-227CODEN: BJPHE6; ISSN:0103-9733. (Sociedade Brasileira de Fisica)
      Thermotropic, thermo-morphol. and thermo-optical properties of the planar oriented nematic liq. crystals have been investigated for large temp. interval and esp. for the direct nematic - isotropic liq. and the reverse isotropic liq. - nematic phase transition regions. Temp. dependences of the optical transmission, absorption coeff. and optical birefringence for both heating and cooling processes were obtained. Nonlinear thermotropic and thermo-optical behavior and temp. hysteresis for the optical transmission, absorption coeff. and optical birefringence at the phase transitions has been found.
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    59. 59
      Abeykoon, N. C.; Bonso, J. S.; Ferraris, J. P. Supercapacitor Performance of Carbon Nanofiber Electrodes Derived from Immiscible PAN/PMMA Polymer Blends.. RSC Adv. 2015, 5 (26), 19865– 19873,  DOI: 10.1039/C4RA16594B
      59
      Supercapacitor performance of carbon nanofiber electrodes derived from immiscible PAN/PMMA polymer blends
      Abeykoon, Nimali C.; Bonso, Jeliza S.; Ferraris, John P.
      RSC Advances (2015), 5 (26), 19865-19873CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      Polymer blends yield carbon materials with superior performances for supercapacitor applications since blending can lead to controlled and fine pore architectures. In this study, a supercapacitor electrode material derived from an immiscible polymer blend comprising polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) was investigated. PAN was used as the carbonizing polymer while PMMA was used as the sacrificial polymer. The polymer blend solns. in DMF were electrospun to obtain freestanding nanofiber mats. The resulting mat was carbonized and activated by CO2 at 1000 °C to obtain porous carbon nanofibers (CNFs), as PAN converts to carbon and the sacrificial polymer decomps. creating pores. We demonstrated that the pore sizes can be tuned by varying the amt. of PMMA loading in the blend compns. PAN : PMMA (95 : 5), was found to be the optimum blend compn., affording the highest surface area of 2419 m2 g-1, higher degree of graphitization, higher carbon yield and lower charge transfer resistance among the blend compns. studied. Furthermore, the PAN : PMMA (95 : 5) CNFs showed the highest capacitance of 140 F g-1 and energy densities of 67 W h kg-1 at 3.5 V and 101 W h kg-1 at 4 V in an ionic electrolyte (EMITFSI) and also showed good cycling stability with 85% capacitance retention after 1000 cycles.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitlamt7w%253D&md5=539974852cb5c49e5d35dc22a0d6a67f
    60. 60
      Geng, P.; Wang, L.; Du, M.; Bai, Y.; Li, W.; Liu, Y.; Chen, S.; Braunstein, P.; Xu, Q.; Pang, H. MIL-96-Al for Li–S Batteries: Shape or Size?. Adv. Mater. 2022, 34 (4), 2107836,  DOI: 10.1002/adma.202107836
      60
      MIL-96-Al for Li-S Batteries: Shape or Size
      Geng, Pengbiao; Wang, Lei; Du, Meng; Bai, Yang; Li, Wenting; Liu, Yanfang; Chen, Shuangqiang; Braunstein, Pierre; Xu, Qiang; Pang, Huan
      Advanced Materials (Weinheim, Germany) (2022), 34 (4), 2107836CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Metal-org. frameworks (MOFs) with controllable shapes and sizes show a great potential in Li-S batteries. However, neither the relationship between shape and specific capacity nor the influence of MOF particle size on cyclic stability have been fully established yet. Herein, MIL-96-Al with various shapes, forming hexagonal platelet crystals (HPC), hexagonal bipyramidal crystals (HBC), and hexagonal prismatic bipyramidal crystals (HPBC) are successfully prepd. via cosolvent methods. D. functional theory (DFT) calcns. demonstrate that the HBC shape with highly exposed planes can effectively adsorb lithium polysulfides (LPS) during the charge/discharge process. By changing the relative proportion of the cosolvents, HBC samples with different particle sizes are prepd. When these MIL-96-Al crystals are used as sulfur host materials, it is found that those with a smaller size of the HBC shape deliver higher initial capacity. These investigations establish that different crystal planes have different adsorption abilities for LPS, and that the MOF particle size should be considered for a suitable sulfur host. More broadly, this work provides a strategy for designing sulfur hosts in Li-S batteries.
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    61. 61
      Bai, Y.; Liu, C.; Chen, T.; Li, W.; Zheng, S.; Pi, Y.; Luo, Y.; Pang, H. MXene-Copper/Cobalt Hybrids via Lewis Acidic Molten Salts Etching for High Performance Symmetric Supercapacitors. Angew. Chem Int. Ed. 2021, 60 (48), 25318– 25322,  DOI: 10.1002/anie.202112381
      61
      MXene-Copper/Cobalt Hybrids via Lewis Acidic Molten Salts Etching for High Performance Symmetric Supercapacitors
      Bai, Yang; Liu, Chunli; Chen, Tingting; Li, Wenting; Zheng, Shasha; Pi, Yecan; Luo, Yongsong; Pang, Huan
      Angewandte Chemie, International Edition (2021), 60 (48), 25318-25322CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      MXenes have attracted great interests as supercapacitors due to their metallic cond., high d., and hydrophilic nature. Herein we report Ti3C2-Cu/Co hybrids via molten salt etching in which the existence of metal atoms and their interactions with MXene via surficial O atoms were elucidated by XAFS for the first time. The electrochem. investigation of Ti3C2-Cu electrode demonstrated the pseudocapacitive contribution of Cu and a splendid specific capacitance of 885.0 F g-1 at 0.5 A g-1 in 1.0 M H2SO4. Sym. supercapacitor Ti3C2-Cu//Ti3C2-Cu was demonstrated with operating voltage of 1.6 V, areal capacitance of 290.5 mF cm-2 at 1 mA cm-2, and stability over 10 000 cycles. It delivered an areal energy d. of 103.3μWh cm-2 at power d. of 0.8 mW cm-2, based on which a supercapacitor pouch was fabricated. It provides deeper insights into the molten salt mechanism and strategies for designing MXene-based materials for electrochem. energy storage.
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    62. 62
      Li, W.; Guo, X.; Geng, P.; Du, M.; Jing, Q.; Chen, X.; Zhang, G.; Li, H.; Xu, Q.; Braunstein, P.; Pang, H. Rational Design and General Synthesis of Multimetallic Metal–Organic Framework Nano-Octahedra for Enhanced Li–S Battery. Adv. Mater. 2021, 33 (45), 2105163,  DOI: 10.1002/adma.202105163
      62
      Rational Design and General Synthesis of Multimetallic Metal-Organic Framework Nano-Octahedra for Enhanced Li-S Battery
      Li, Wenting; Guo, Xiaotian; Geng, Pengbiao; Du, Meng; Jing, Qingling; Chen, Xudong; Zhang, Guangxun; Li, Hongpeng; Xu, Qiang; Braunstein, Pierre; Pang, Huan
      Advanced Materials (Weinheim, Germany) (2021), 33 (45), 2105163CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Metal-org. frameworks (MOFs), which consist of central metal nodes and org. linkers, constitute a fast growing class of cryst. porous materials with excellent application potential. Herein, a series of Mn-based multimetallic MOF (bimetallic and trimetallic MIL-100) nano-octahedra are prepd. by a facile one-pot synthetic strategy. The types and proportions of the incorporated elements can be tuned while retaining the original topol. structure. The introduction of other metal ions is verified at the at. level by combining X-ray absorption fine structure expts. and theor. calcns. Furthermore, these multimetallic Mn-based MIL-100 nano-octahedra are utilized as sulfur hosts to prep. cathodes for Li-S batteries. The MnNi-MIL-100@S cathode exhibits the best Li-S battery performance among all reported MIL-100@S composite cathode materials, with a reversible capacity of ≈708.8 mAh g-1 after 200 cycles. The synthetic strategy described herein is utilized to incorporate metal ions into the MOF architecture, of which the parent monometallic MOF nano-octahedra cannot be prepd. directly, thus rationally generating novel multimetallic MOFs. Importantly, the strategy also allows for the general synthesis and study of various micro-/nanoscale MOFs in the energy storage field.
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    63. 63
      Hang, X.; Xue, Y.; Cheng, Y.; Du, M.; Du, L.; Pang, H. From Co-MOF to CoNi-MOF to Ni-MOF: A Facile Synthesis of 1D Micro-/Nanomaterials. Inorg. Chem. 2021, 60 (17), 13168– 13176,  DOI: 10.1021/acs.inorgchem.1c01561
      63
      From Co-MOF to CoNi-MOF to Ni-MOF: A Facile Synthesis of 1D Micro-/Nanomaterials
      Hang, Xinxin; Xue, Yadan; Cheng, Yan; Du, Meng; Du, Liting; Pang, Huan
      Inorganic Chemistry (2021), 60 (17), 13168-13176CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      Controlling the growth of metal-org. frameworks (MOFs) at the micro-/nanoscopic scale will result in new phys. properties and novel functions into the materials without changing the chem. identities and the characteristic features of the MOFs themselves. Herein, the authors report a facile approach to synthesize 3,5-pyridinedicarboxylic acid MOFs [Co-MOF, CoxNiy-MOFs (x and y represent the molar ratio of Co2+ and Ni2+ and x/y = 1:1, 1:5, 1:10, 1:15, and 1:20), and Ni-MOF] with a 1-dimensional micro-/nanoscaled rod-like architecture. From Co-MOF to CoxNiy-MOFs to Ni-MOF, the diams. of the rods turn to be spindly with the increase of Ni2+ content which will facilitate the supercapacitor performances. Co1Ni20-MOF exhibits a highest specific capacity of 597 F g-1 at 0.5 A g-1 and excellent cycle performance (retained 93.59% after 4000 cycles) among these MOF materials owing to its micro-/nanorod structure with a smaller diam. and the synergy effect between the optimum molar ratio of Co2+ and Ni2+.
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    64. 64
      Yates, N. D. J.; Fascione, M. A.; Parkin, A. Methodologies for “Wiring” Redox Proteins/Enzymes to Electrode Surfaces. Chem. Eur. J. 2018, 24 (47), 12164– 12182,  DOI: 10.1002/chem.201800750
      64
      Methodologies for "Wiring" Redox Proteins/Enzymes to Electrode Surfaces
      Yates, Nicholas D. J.; Fascione, Martin A.; Parkin, Alison
      Chemistry - A European Journal (2018), 24 (47), 12164-12182CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. The immobilization of redox proteins or enzymes onto conductive surfaces has application in the anal. of biol. processes, the fabrication of biosensors, and in the development of green technologies and biochem. synthetic approaches. This review evaluates the methods through which redox proteins can be attached to electrode surfaces in a "wired" configuration, i.e., one that facilitates direct electron transfer. The feasibility of simple electroactive adsorption onto a range of electrode surfaces is illustrated, with a highlight on the recent advances that have been achieved in biotechnol. device construction using carbon materials and metal oxides. The covalent crosslinking strategies commonly used for the modification and biofunctionalization of electrode surfaces are also evaluated. Recent innovations in harnessing chem. biol. methods for elec. wiring redox biol. to surfaces are emphasized.
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    65. 65
      Mazloum-Ardakani, M.; Khoshroo, A. Nano Composite System Based on Coumarin Derivative-Titanium Dioxide Nanoparticles and Ionic Liquid: Determination of Levodopa and Carbidopa in Human Serum and Pharmaceutical Formulations.. Anal. Chim. Acta 2013, 798, 25– 32,  DOI: 10.1016/j.aca.2013.08.045
      65
      Nano composite system based on coumarin derivative-titanium dioxide nanoparticles and ionic liquid: Determination of levodopa and carbidopa in human serum and pharmaceutical formulations
      Mazloum-Ardakani, Mohammad; Khoshroo, Alireza
      Analytica Chimica Acta (2013), 798 (), 25-32CODEN: ACACAM; ISSN:0003-2670. (Elsevier B.V.)
      The combination of coumarin deriv. (7-(1,3-dithiolan-2-yl)-9,10-dihydroxy-6H-benzofuro[3,2-c]chromen-6-on), (DC)-titanium dioxide nanoparticles (TiO2) and ionic liq. (IL) yields nanostructured electrochem. sensor, formed a novel kind of structurally uniform and electrocatalytic activity material. This new ionic liq.-TiO2 nanoparticles modified carbon paste electrode (IL-CTP) due to its enhanced cond. presented very large current response from electroactive substrates. The modified electrode was characterized by different methods including a scanning electron microscope (SEM), electrochem. impedance spectroscopy (EIS) and voltammetry. A pair of well-defined quasi reversible redox peaks of coumarin deriv. was obtained at the modified carbon paste electrode (DC/IL-CTP) by direct electron transfer between the coumarin deriv. and the CP electrode. Dramatically enhanced electrocatalytic activity was exemplified at the DC/IL-CTP electrode, as an electrochem. sensor to study the electro oxidn. of levodopa (LD) and carbidopa (CD). Based on differential pulse voltammetry (DPV), the oxidn. of LD and CD exhibited the dynamic range between 0.10- 900.0 μM and 20.0-900.0 μM resp., and the detection limit (3σ) for LD and CD were 41 nM and 0.38 μM, resp. DPV was used for simultaneous detn. of LD and CD at the DC/IL-CTP electrode, and quantitation of LD and CD in some real samples (such as tablets of Parkin-C Fort and Madopar, Sinemet, water, urine, and human blood serum) by the std. addn. method.
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    66. 66
      Xia, X. H.; Tu, J. P.; Zhang, Y. Q.; Mai, Y. J.; Wang, X. L.; Gu, C. D.; Zhao, X. B. Freestanding Co 3O 4 Nanowire Array for High Performance Supercapacitors. RSC Adv. 2012, 2 (5), 1835– 1841,  DOI: 10.1039/c1ra00771h
      66
      Freestanding Co3O4 nanowire array for high performance supercapacitors
      Xia, Xin-hui; Tu, Jiang-ping; Zhang, Yong-qi; Mai, Yong-jin; Wang, Xiu-li; Gu, Chang-dong; Zhao, Xin-bing
      RSC Advances (2012), 2 (5), 1835-1841CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      We report a single-cryst. Co3O4 nanowire array grown on a nickel foam prepd. by a hydrothermal synthesis method for supercapacitor application. The Co3O4 nanowires show sharp tips and have an av. diam. of 70 nm, and a length up to 25 μm. Impressively, the as-prepd. single-cryst. Co3O4 nanowire array exhibits noticeable pseudocapacitive performance with a high capacitance of 754 F g-1 at 2 A g-1 and 610 F g-1 at 40 A g-1 as well as excellent cycling stability. The enhanced supercapacitor performance is due to the unique one-dimensional (1D) architecture, which provides fast diffusion paths for ions and facilitates the electron and ion transfer on the Co3O4/electrolyte interfaces. Moreover, the 1D nanowire array can accommodate the vol. expansion and restrain the pulverization and deterioration of Co3O4 during the repeated cycling process, resulting in enhanced cycling stability.
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    67. 67
      Li, B.; Lopez-Beltran, H.; Siu, C.; Skorenko, K. H.; Zhou, H.; Bernier, W. E.; Whittingham, M. S.; Jones, W. E. Vaper Phase Polymerized PEDOT/Cellulose Paper Composite for Flexible Solid-State Supercapacitor.. ACS Appl. Energy Mater. 2020, 3 (2), 1559– 1568,  DOI: 10.1021/acsaem.9b02044
      67
      Vaper Phase Polymerized PEDOT/Cellulose Paper Composite for Flexible Solid-State Supercapacitor
      Li, Boxiao; Lopez-Beltran, Hendrick; Siu, Carrie; Skorenko, Kenneth H.; Zhou, Hui; Bernier, William E.; Whittingham, M. Stanley; Jones, Wayne E., Jr.
      ACS Applied Energy Materials (2020), 3 (2), 1559-1568CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      A flexible solid-state supercapacitor based on vapor phase polymd. (VPP) PEDOT into cellulose paper matrix (PEDOT/CP) was successfully fabricated. The PEDOT/CP composite material worked as both current collector and electrode in constructed test cells. It had a low sheet resistance of 14 Ω/square and survived the Scotch tape test for adhesion. It also showed excellent stability with no significant cond. drop after 1000 cycles of bending. The PEDOT from electrode obtained the mass specific capacitance of 179 F/g at scan rate of 10 mV/s, which was among the highest specific capacitances ever reported. This high capacitance was attributed to the combination of the VPP technique and the porous fibrous structure of the cellulose matrix. The EDOT vapor penetrated and polymd. through the CP matrix made of nanometer to micrometer level CP fibers. The highest electrode volumetric capacitance achieved was 13.7 F/cm3. The whole device achieved an energy d. of 0.76 mWh/cm3 and a power d. of 0.01 W/cm3. Bending the supercapacitor to 90° or rotating to 45° caused no major change in capacitance. Owing to the all nonmetallic materials used to construct the supercapacitor, it can be easily disposed. The incineration of the supercapacitor does not release significant hazardous exhaust.
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    68. 68
      Aydın, H.; Kurtan, U.; Demir, M.; Karakuş, S. Synthesis and Application of a Self-Standing Zirconia-Based Carbon Nanofiber in a Supercapacitor.. Energy Fuels 2022, 36 (4), 2212– 2219,  DOI: 10.1021/acs.energyfuels.1c04208
      68
      Synthesis and Application of a Self-Standing Zirconia-Based Carbon Nanofiber in a Supercapacitor
      Aydin, Hamide; Kurtan, Umran; Demir, Muslum; Karakus, Selcan
      Energy & Fuels (2022), 36 (4), 2212-2219CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)
      Electrospun metal oxide-embedded carbon nanofibers have attracted considerable attention in energy storage applications for the development and fabrication of supercapacitors owing to their unique properties such as flexibility, high capacitance, large sp. surface areas, and morphol. and cond. properties. Herein, a novel zirconia-based carbon nanofiber (referred to as CNF-20ZrO2) was fabricated using a simple electrospinning method and applied to a supercapacitor as the electroactive material for the first time. The optimal electrode (CNF-20ZrO2) demonstrates a high specific capacitance of 140 F/g at 1 A/g. In addn., the assembled supercapacitor delivers max. specific energy of 4.86 Wh/kg at a specific power of 250 W/kg and shows excellent cycling stability of 82.6% after 10 000 cycles at 1 A/g. The electrochem. performance of the electrode originates from the high content of nitrogen and oxygen species, abundant electrochem. active sites, and high ionic cond.
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    69. 69
      Zhang, Q.; Chen, C.; Chen, W.; Pastel, G.; Guo, X.; Liu, S.; Wang, Q.; Liu, Y.; Li, J.; Yu, H.; Hu, L. Nanocellulose-Enabled, All-Nanofiber, High-Performance Supercapacitor.. ACS Appl. Mater. Interfaces 2019, 11, 5919,  DOI: 10.1021/acsami.8b17414
      69
      Nanocellulose-Enabled, All-Nanofiber, High-Performance Supercapacitor
      Zhang, Qi; Chen, Chaoji; Chen, Wenshuai; Pastel, Glenn; Guo, Xiaoyu; Liu, Shouxin; Wang, Qingwen; Liu, Yixing; Li, Jian; Yu, Haipeng; Hu, Liangbing
      ACS Applied Materials & Interfaces (2019), 11 (6), 5919-5927CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Nanocellulose has been used as a sustainable nanomaterial for constructing advanced electrochem. energy-storage systems with renewability, lightwt., flexibility, high performance, and satisfying safety. Here, we demonstrate a high-performance all-nanofiber asym. supercapacitor (ASC) assembled using a forest-based, nanocellulose-derived hierarchical porous carbon (nanocellulose carbon, HPC) anode, a mesoporous nanocellulose membrane separator (nanocellulose separator), and a NiCo2O4 cathode with nanocellulose carbon as the support matrix (nanocellulose cathode, HPC/NiCo2O4). HPC has a three-dimensional porous structure comprising interconnected nanofibers with an ultrahigh surface area of 2046 m2 g-1. When integrated with the mesoporous feature of the nanocellulose membrane separator, these properties facilitate the quick delivery of both ions and electrons even with a thick (up to several hundreds of micrometers) and highly loaded (5.8 mg cm-2) ASC design. Consequently, the all-nanofiber ASC demonstrates a high electrochem. performance (64.83 F g-1 (10.84 F cm-3) at 0.25 A g-1 and 32.78 F g-1 or 5.48 F cm-3 at 4 A g-1) that surpasses most cellulose-based ASCs ever reported. Moreover, the nanocellulose components promise renewability, low cost, and biodegradability, thereby presenting a promising direction toward high-power, environmentally friendly, and renewable energy-storage devices.
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    70. 70
      Lee, K. H.; Oh, J.; Son, J. G.; Kim, H.; Lee, S. S. Nitrogen-Doped Graphene Nanosheets from Bulk Graphite Using Microwave Irradiation.. ACS Appl. Mater. Interfaces 2014, 6 (9), 6361– 6368,  DOI: 10.1021/am405735c
      70
      Nitrogen-Doped Graphene Nanosheets from Bulk Graphite using Microwave Irradiation
      Lee, Kwang Hoon; Oh, Jinwoo; Son, Jeong Gon; Kim, Heesuk; Lee, Sang-Soo
      ACS Applied Materials & Interfaces (2014), 6 (9), 6361-6368CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Using simple microwave irradn. under the presence of Na amide as a N source, prepn. of N-doped graphene nanosheets was successfully demonstrated. It is notable that exfoliation and N doping of graphite to N-doped graphene simultaneously occurred during the microwave irradn. within a minute, and N content of the doped graphene could reach up to 8.1%. Also the binding configuration of N atom on graphitic layer consisted of various N-contg. moieties such as pyridine-N, pyrrolic-N, and quaternary-N, and their compn. was changed as a function of irradn. power. Although formation of undoped reduced graphene oxide by microwave irradn. resulted in slight increase of elec. cond. because of the reductive recovery of oxidized graphite to graphene, N doping involved during irradn. induced much more notable increase of elec. cond. >300 S cm-1. Also, N-doped graphene showed highly enhanced capacitive performance than that of undoped reduced graphene oxide, the specific capacitance of 200 F/g (c.d. of 0.5 A/g), which ascribes the pseudocapacitive effect from the incorporation of N atom on graphitic layer.
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    71. 71
      Ferhi, N.; Desalegn Assresahegn, B.; Ardila-Suarez, C.; Dissem, N.; Guay, D.; Duong, A. Defective Metal-Organic Framework-808@Polyaniline Composite Materials for High Capacitance Retention Supercapacitor Electrodes.. ACS Appl. Energy Mater. 2022, 5 (1), 1235– 1243,  DOI: 10.1021/acsaem.1c03649
      71
      Defective Metal-Organic Framework-808@Polyaniline Composite Materials for High Capacitance Retention Supercapacitor Electrodes
      Ferhi, Najmeddine; Desalegn Assresahegn, Birhanu; Ardila-Suarez, Carolina; Dissem, Nour; Guay, Daniel; Duong, Adam
      ACS Applied Energy Materials (2022), 5 (1), 1235-1243CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Among their potential applications, metal-org. frameworks (MOFs) emerge as promising alternative electrode materials to overcome the disadvantages of low energy d. supercapacitors. Although the potential of MOFs lies in their adjustable pore structure and high surface areas, they possess poor cond. In this context, composites with conductive matrixes, including org. conductive polymers, have proved to enhance the electrochem. properties of MOFs and their structural stability in the long-term cycling process compared to the pristine MOF. In this study, we have chosen defective zirconium MOF-808 (d-MOF-808) as a porous material because of its resistance to strong acidic media in a postsynthetic modification process. As a conductive agent, polyaniline (PANI) was selected due to its high stability and facile synthesis. The obtained composites of d-MOF-808@PANI at d-MOF/PANI ratios of 15:1, 30:1, and 60:1 increase the charge transport properties compared to the pristine d-MOF-808 and PANI. Electrochem. evaluation of the new hybrid electrode materials was made to demonstrate the capacitance retention. Among the series of materials prepd., the 60:1 composite shows the highest capacitance (188 F/g at 30 mV s-1) in 1 M KOH and a notable capacitance retention of 99.8% for up to 10,000 cycles with 99.7% coulombic efficiency.
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    72. 72
      Zhang, F.; Liu, H.; Wu, Z.; Zhang, J.; Cui, E.; Yue, L.; Hou, G. Polyacrylamide Gel-Derived Nitrogen-Doped Carbon Foam Yields High Performance in Supercapacitor Electrodes.. ACS Appl. Energy Mater. 2021, 4 (7), 6719– 6729,  DOI: 10.1021/acsaem.1c00777
      72
      Polyacrylamide Gel-Derived Nitrogen-Doped Carbon Foam Yields High Performance in Supercapacitor Electrodes
      Zhang, Feng; Liu, Huachen; Wu, Zhaofeng; Zhang, Junhao; Cui, Entian; Yue, Lu; Hou, Guihua
      ACS Applied Energy Materials (2021), 4 (7), 6719-6729CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Porous carbons play a vital role in supercapacitor electrodes. The capacitive performance of porous carbons depends mostly on the pore structure and surface chem. It is highly desirable to develop robust methods to prep. porous carbons with controlled structures and compns. Herein, a nitrogen-doped carbon foam was prepd. on the basis of polyacrylamide gel with K2CO3 and K2B4O7 as the activating agent and salt template, resp. Due to the constraint effect of the cross-linked polyacrylamide network, K2CO3 and K2B4O7 can be homogeneously embedded in the polymer matrix. The subsequent carbonization results in the nitrogen-doped carbon foam (PACF) with a hierarchically porous structure and high sp. surface area (~ 3404.8 m2 g-1). K2B4O7 not only serves as the sol. salt template but can also reinforce the carbonaceous skeleton during carbonization. PACF yields an outstanding specific capacitance (346.9 F g-1 at 0.5 A g-1), good rate performance (224.4 F g-1 at 50 A g-1), and excellent cycle capability (retaining 97.2% of the initial capacitance after 10,000 consecutive charge-discharge cycles). This study demonstrates the potential of polyacrylamide gel as a promising carbon precursor and enriches the tool box for the prepn. of porous carbons.
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    73. 73
      Zhu, Y. P.; Xia, C.; Lei, Y.; Singh, N.; Schwingenschlögl, U.; Alshareef, H. N. Solubility Contrast Strategy for Enhancing Intercalation Pseudocapacitance in Layered MnO2 Electrodes.. Nano Energy 2019, 56, 357– 364,  DOI: 10.1016/j.nanoen.2018.11.063
      73
      Solubility contrast strategy for enhancing intercalation pseudocapacitance in layered MnO2 electrodes
      Zhu, Yun-Pei; Xia, Chuan; Lei, Yongjiu; Singh, Nirpendra; Schwingenschlogl, Udo; Alshareef, Husam N.
      Nano Energy (2019), 56 (), 357-364CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
      Pseudocapacitance is generally assocd. with either surface redox reactions or ion intercalation processes without a phase transition. Typically, these two mechanisms have been independently studied, and most works have focused on optimizing one or the other in different material systems. Here we have developed a strategy based on soly. contrast, in which the contribution from the two capacitive mechanisms is simultaneously optimized. Taking layered birnessite MnO2 as a model, controllable nanostructures and oxygen vacancies are achieved through a simple copptn. process. Simultaneously controlling crystallite size and defect concn. is shown to enhance the charging-discharging kinetics together with both redox and intercalation capacitances. This synergistic effect results from enhanced ionic diffusion, electronic cond., and large surface-to-vol. ratio. In addn., considerable cycling durability is achieved, resulting from improved framework strength by defect creation and the absence of proton (de)intercalation during discharge/charge. This work underscores the importance of synergistically regulating nanostructure and defects in redox-active materials to improve pseudocapacitive charge storage.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisVWksL%252FK&md5=304a0cf5331538b1497553ef4e5457e6
    74. 74
      Wang, P.; Wen, Y.; Lu, J.; Yin, S.; Key, J.; Wang, N.; Shen, P. K. Manganese Oxide(III)/Carbon Hybrids with Interesting Morphologies as Improved Active Materials for Supercapacitors.. Int. J. Hydrogen Energy 2019, 44 (26), 13623– 13631,  DOI: 10.1016/j.ijhydene.2019.03.240
      74
      Manganese(III) oxide/carbon hybrids with interesting morphologies as improved active materials for supercapacitors
      Wang, Peng; Wen, Ying; Lu, Jiajia; Yin, Shibin; Key, Julian; Wang, Ningzhang; Shen, Pei Kang
      International Journal of Hydrogen Energy (2019), 44 (26), 13623-13631CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
      Mn2O3/C hybrids with almond-like, peach-like and peanut-like morphologies are fabricated via hydrothermal method followed by annealing in air at ambient pressure. Their phys. properties and morphologies are characterized by XRD, Raman scattering spectroscopy (Raman), XPS, Brunauer-Emmett-Teller (BET), SEM and scanning TEM (STEM). Almond-like Mn2O3/C (Mn2O3/C-ALL) and peach-like Mn2O3/C (Mn2O3/C-PCL) hybrids are highly porous with large-sized mesopores. But peanut-like Mn2O3/C (Mn2O3/C-PNL) is composed of densely packed slender nanofibers. The results show Mn2O3 and C have homogeneous contact accounting for high cond. In 1.0M Na2SO4 aq. electrolyte, Mn2O3/C-PCL has the highest specific capacitance of 158.8 F g-1 at 1.0 A g-1, compared to Mn2O3/C-ALL (105.1 F g-1) and Mn2O3/C-PNL (77.5 F g-1). Also, the capacitance retention of Mn2O3/C-PCL achieves 48.8% upon a 50-fold increase in c.d. Finally, the Mn2O3/C-PCL displays an impressive long-term cycle stability of 90.6% specific capacitance retention after 10,000 cycles at 1.0 A g-1. Therefore, this work highlights the importance of morphol. in Mn2O3/C hybrids design to obtain high performance supercapacitor materials.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXns1yhtr0%253D&md5=ea1a269f2f34dc3cadb8f93629433530
    75. 75
      Lu, W.; Li, Y.; Yang, M.; Jiang, X.; Zhang, Y.; Xing, Y. Construction of Hierarchical Mn2O3@MnO2Core-Shell Nanofibers for Enhanced Performance Supercapacitor Electrodes.. ACS Appl. Energy Mater. 2020, 3 (9), 8190– 8197,  DOI: 10.1021/acsaem.0c00392
      75
      Construction of Hierarchical Mn2O3@MnO2 Core-Shell Nanofibers for Enhanced Performance Supercapacitor Electrodes
      Lu, Wei; Li, Yuan; Yang, Man; Jiang, Xin; Zhang, Yanxia; Xing, Yan
      ACS Applied Energy Materials (2020), 3 (9), 8190-8197CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Manganese oxide (MnOx) is a considerable candidate for supercapacitor electrode materials owing to its large theor. capacitance and low price, but its performance is generally limited by unsatisfactory cycle performance and poor cond. Herein, Mn2O3@MnO2 composite nanofibers have been prepd. via electrospinning and hydrothermal methods. Adjusting the KMnO4 precursor concn. during the hydrothermal process, Mn2O3@MnO2 core-shell nanofibers with variable compositional ratios of MnO2 to Mn2O3 have been obtained. The hierarchically core-shell structure and the synergistic effect between the two oxides enable the as-prepd. Mn2O3@MnO2 nanocomposite electrode to achieve a desirable elec. cond. and cycle stability. Consequently, [email protected] nanofiber electrodes display an enhanced specific capacitance of 225.0 F g-1 (0.2 A g-1) along with a pretty cycling stability (86.5% after 5000 cycles) at 5 A g-1. These results demonstrate the substantial prospects of the as-prepd. Mn2O3@MnO2 nanofibers for enhanced performance supercapacitors.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhs1CktrnP&md5=6baec37277f2c490d56a2b6d3f280f3b
    76. 76
      Wang, T.; Guo, J.; Guo, Y.; Feng, J.; Wu, D. Nitrogen-Doped Carbon Derived from Deep Eutectic Solvent as a High-Performance Supercapacitor.. ACS Appl. Energy Mater. 2021, 4 (3), 2190– 2200,  DOI: 10.1021/acsaem.0c02703
      76
      Nitrogen-Doped Carbon Derived from Deep Eutectic Solvent as a High-Performance Supercapacitor
      Wang, Tao; Guo, Jia; Guo, Yao; Feng, Jing; Wu, Dongling
      ACS Applied Energy Materials (2021), 4 (3), 2190-2200CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      As a kind of ionic fluid, deep-eutectic solvent (DES) has been used not only as a solvent but also as a precursor for carbon prepn. in recent years. Herein, porous nitrogen-doped carbon (NC) has been prepd. via simple pyrolysis of L-tyrosine-based DES. The effects of the proportion of the components in DES and the carbonization temp. on the morphol., pore structure, chem. compn., and the performance for supercapacitor application have been investigated. The as-prepd. NCs show large surface areas, high nitrogen contents, hierarchical porous structures, and excellent capacitive performances. Specifically, the optimized sample exhibits a higher specific capacitance (306.5 F g-1), better rate capability (70.3% at 50 A g-1), and also shows high area capacitance (7.1 F cm-2) and specific capacitance (235.8 F g-1) when 30 mg/cm2 of the sample is loaded. The constructed sym. supercapacitor attains a high energy d. of 16.9 W h kg-1 (at 450 W kg-1) in the neutral electrolyte and outstanding cycling stability of 100% retention after 50,000 cycles. Moreover, the fabricated sym. solid KOH/poly(vinyl alc.) supercapacitor displays a superior energy d. of 15.2 W h kg-1 at 700 W kg-1 and can retain 8.8 W h kg-1 at 14 kW kg-1. Our work presents a route for the synthesis of porous carbon using DES as the carbonaceous precursor and also demonstrates its possible application in energy storage.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXktFemur8%253D&md5=c11de33e6b396fe5dd9fd5bc0044d6d1
    77. 77
      Bal Altuntaş, D.; Aslan, S.; Nevruzoǧlu, V. Carbon Microrod Material Derived From Human Hair and Its Electrochemical Supercapacitor Application.. Gazi Univ. J. Sci. 2021, 34 (3), 1– 1,  DOI: 10.35378/gujs.712032
      There is no corresponding record for this reference.
    78. 78
      Bal Altuntaş, D.; Aslan, S.; Akyol, Y.; Nevruzoǧlu, V. Synthesis of New Carbon Material Produced from Human Hair and Its Evaluation as Electrochemical Supercapacitor.. Energy Sources, Part A Recover. Util. Environ. Eff. 2020, 42 (19), 2346– 2356,  DOI: 10.1080/15567036.2020.1782536
      There is no corresponding record for this reference.
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