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1.
Two electroactive polymeric arylene bisimides, namely poly[(4,7,10-trioxatrideca-1,13-diyl)-(1,4,5,8-naphthalenetetracarboxylic bisimide-N,N′-diyl)] and its perylene analogue – poly[(4,7,10-trioxatrideca-1,13-diyl)-(3,4,9,10-perylenetetracarboxylic bisimide-N,N′-diyl)] have been synthesized and studied by cyclic voltammetry, UV–vis-NIR as well as Raman spectroeletrochemistry. Contrary to low molecular weight arylene bisimides, which show a clear two electron, double-step electrochemical reduction (neutral form to radical anion and from radical anion to dianion), in the synthesized polymers multielectron transfers are observed, accompanied with a strong electrochromic effect. However, as probed by cyclic voltammetry, their first reduction step is retarded and covers a wider potential range. We attribute this effect to macromolecular nature of the compounds being reduced and their structural inhomogeneity caused by π-stacking induced nanoaggregation of bisimide segments of the polymer chains. The second redox step seems unaffected by the polymeric nature of the electroactive compounds and yields a reduction peak similar to that registered for low molecular weight bisimides. Raman spectroelectrochemical data, combined with the established vibrational model of the perylene derivative – (poly[(4,7,10-trioxatrideca-1,13-diyl)-(3,4,9,10-perylenetetracarboxylic bisimide-N,N′-diyl)]) – enabled us to determine the mechanism of the first step of the electrochemical reduction process. The electrochemically induced shifts of the Raman bands unequivocally show that the reduction process results in the transformation of the carbonyl group into a radical anion. The surplus negative charge is delocalized on the six-member imide ring with the aromatic core very little affected.  相似文献   

2.
An electrically conducting copolymer film, poly(2-biphenyl-3-octylthiophene) (PBOT), was electropolymerized from the comonomer 2-biphenyl-3-octylthiophene (BOT) and characterized by both ex situ and in situ spectroelectrochemical techniques: UV-vis spectroscopy, FTIR spectroscopy and resonance Raman spectroscopy. The formed copolymer was compared with a copolymer synthesized from a mixture of 3-octylthiophene and biphenyl, poly(thienyl biphenyl) (PTB). All spectroscopic measurements gave evidence of formation of a conductive material with high content of short phenylene segments but with an effective conjugation length shorter than in the PTB copolymer film. The structure of PBOT was also less crosslinked having more para-substitution than the structure of PTB.  相似文献   

3.
In order to perform an in-depth study on the electropolymerization mechanism of bis(alkyl)-substituted bithiophenes, poly[4,4′-bis(metylbutylthio)-2,2′-bithiophene] (poly-MBTBT) has been electrogenerated by using both potentiodynamic and potentiostatic techniques under different experimental conditions. Bidimensional spectroelectrochemical data have allowed us to obtain valuable information about both the polymer and the soluble oligomers electrogenerated in the process. The same kind of oligomers has been observed in the potentiodynamic and potentiostatic polymerization.  相似文献   

4.
A new monomer; N-(2-(thiophen-3-yl)methylcarbonyloxyethyl) maleimide (NMT) was synthesized. The chemical structure of the monomer was characterized by Nuclear Magnetic Resonance (1H-NMR) and Fourier Transform Infrared (FTIR) Spectroscopy. Electrochemical polymerization of NMT was performed in acetonitrile (AN)/borontrifloride ethylether (BFEE) solvent mixture (1:1, v/v) where tetrabutylammonium tetrafluoroborate (TBAFB) was utilized as the supporting electrolyte. The resulting conducting polymer was characterized by Fourier Transform Infrared (FTIR) Spectroscopy, thermal analyses and Scanning Electron Microscopy (SEM). Electrical conductivity was measured by the four-probe technique. The spectroelectrochemical behavior and switching ability of P(NMT) film were investigated by UV–Vis spectrophotometry. P(NMT) revealed color changes between yellow and blue in the reduced and oxidized states respectively.  相似文献   

5.
Conjugated polymers were synthesized and used for polymer solar cells with new electron-rich units, 6-(2-thienyl)-4H-thieno[2,3-b]indole (2-TTI). 2-TTI was coupled with electron-pulling units, including benzothiadiazole and benzimidazole derivatives, to provide push–pull types of conjugated polymers (poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(2-methyl-5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)-2-(trifluoromethyl)-2H-benzimidazole) (PTTIDOCF3), poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole) (PTTIDOBT), poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(2,2-dimethyl-4,7-di(thiophen-2-yl)-2H-benzimidazole) (PTTIMBI), and poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(2,2-dimethyl-5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)-2H-benzimidazole) (PTTIDOMBI)). The synthesized conjugated polymers provided deep highest occupied molecular orbital energy levels for higher open-circuit voltages (VOC). The device composed of PTTIDOMBI and [6,6]-Phenyl C71 butyric acid methyl ester PC71BM (1:2) with chloronaphthalene additive showed a VOC of 0.72 V, a short-circuit current (JSC) of 9.16 mA/cm2, and a fill factor of 0.43; this gave a power conversion efficiency (PCE) of 2.84%. The PTTIDOMBI provided better morphology for enhanced charge transport, and this led to the higher JSC and PCE of the organic solar cells. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47624.  相似文献   

6.
Poly(o‐anisidine) (POA) counter electrodes (CEs) were fabricated by potentiodynamic deposition and incorporated into platinum (Pt)‐free dye‐sensitized solar cells (DSSCs). A different sweep number had great impact on the morphology and electrocatalytic activity of the POA films. The POA film fabricated by 25 sweep cycles was observed to have a highly porous morphology, and this resulted in a lower charge‐transfer resistance of 57 cm2 in comparison with the Pt CE. The DSSC assembled with the POA CE showed a higher photovoltaic conversion efficiency of 1.67% compared to 1.2% for the DSSC with the Pt CE under full sunlight illumination. Therefore, the high active surface area of the 25‐sweep‐segmented POA film could be considered a promising alternative CE for use in DSSCs because of its high electrocatalytic performance and electrochemical stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42041.  相似文献   

7.
New π‐conjugated polymers containing dithieno(3,2‐b:2′,3′‐d)pyrrole (DTP) were successfully synthesized via electropolymerization. The effect of structural differences on the electrochemical and optoelectronic properties of the 4‐[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl]aniline (DTP–aryl–NH2), 10‐[4H‐dithiyeno(3,2‐b:2′,3′‐d)pirol‐4‐il]dekan‐1‐amine (DTP–alkyl–NH2), and 1,10‐bis[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl] decane (DTP–alkyl–DTP) were investigated. The corresponding polymers were characterized by cyclic voltammetry, NMR (1H‐NMR and 13C‐NMR), and ultraviolet–visible spectroscopy. Changes in the electronic nature of the functional groups led to variations in the electrochemical properties of the π‐conjugated systems. The electroactive polymer films revealed redox couples and exhibited electrochromic behavior. The replacement of the DTP–alkyl–DTP unit with DTP–aryl–NH2 and DTP–alkyl–NH2 resulted in a lower oxidation potential. Both the poly(10‐(4H‐Dithiyeno[3,2‐b:2′,3′‐d]pirol‐4‐il)dekan‐1‐amin) (poly(DTP–alkyl–NH2)) and poly(1,10‐bis(4H‐dithieno[3,2‐b:2′,3′‐d]pyrrol‐4‐yl) decane) (poly(DTP–alkyl–DTP)) films showed multicolor electrochromism and also fast switching times (<1 s) in the visible and near infrared regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40701.  相似文献   

8.
Electron transfer mechanism during redox process of Pt(LSB)2, a derivative of S-benzyl-N-(ferrocenyl-1-methyl-metylidene)-dithiocarbazate (HLSB), is studied by cyclic voltammetry, differential pulse voltammetry, digitally simulation and in situ FTIR spectroelectrochemistry. Electrochemistry results indicated the redox process of Pt(LSB)2 involves two consecutive one-electron steps. Coordination of Pt to HLSB resulted in the increase of electron-withdrawing of the dithiocarbazate group, which is demonstrated by the positive shift of redox potentials of Pt(LSB)2 compared with those of HLSB. The peak-peak separation of 129 mV revealed a strong degree of electronic communication between the two-ferrocene moieties in Pt(LSB)2. The results of in situ FTIR indicated that electronic communication takes place through the skeleton chain of HLSB due to the extensive electron delocalization in the whole molecule.  相似文献   

9.
Poly(N‐methylpyrrole) (PNMPy), poly(N‐methylpyrrole‐TiO2) (PNMPy‐TiO2), and poly (N‐methylpyrrole‐ZnO) (PNMPy‐ZnO) nanocomposites were synthesized by in situ electropolymerization for cathode active material of lithium secondary batteries. The charge–discharging behavior of a Li/LiClO4/PNMPy battery was studied and compared with Li/LiClO4/PNMPy‐nanocomposite batteries. The nanocomposites and PNMPy films were characterized by cyclic voltammetry, in situ resistivity measurements, in situ UV–visible, and Fourier transform infra‐red (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The differences between redox couples (ΔE) were obtained for polymer nanocomposites and PNMPy films. During redox scan, a negative shift of potential was observed for polymer nanocomposite films. Significant differences from in situ resistivity of nanocomposites and PNMPy films were obtained. The in situ UV–visible spectra for PNMPy and polymer nanocomposite films show the intermediate spectroscopic behavior between polymer nanocomposites and PNMPy films. The FTIR peaks of polymer nanocomposite films were found to shift to higher wavelengths in PNMPy films. The SEM and TEM micrographs of nanocomposite films show the presence of nanoparticle in PNMPy backbone clearly. The result suggests that the inorganic semiconductor particles were incorporated in organic conducting PNMPy, which consequently modifies the properties and morphology of the film significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41526.  相似文献   

10.
作者自行合成了离子液体[BMIM]BF4,用循环伏安法(CV)、计时电量法(CA)和电化学原位红外反射光谱(in situFTIR),从分子水平考察了离子液体中马来酸在玻碳(GC)电极上的电化学还原过程。结果表明,[BMIM]BF4中马来酸在GC电极上的还原为不可逆过程,测得扩散系数D=9.62×10-8cm2/s;in situFTIRS研究发现,马来酸在离子液体[BMIM]BF4和水溶液中的电还原生成丁二酸的机理不同。在[BMIM]BF4中马来酸还原发生在其中的一个羧基上,即马来酸首先获得一个电子生成阴离子自由基,随后可能获得一个电子生成二价阴离子,或者获得一个电子并在2个H+的作用下生成醛类物质和水。  相似文献   

11.
In this study; poly (o-amino benzyl alcohol) and poly (o-amino benzyl alcohol-co-o-anisidine) copolymer films were electrochemically synthesized by cyclic voltammetry technique on the platinum electrode. The synthesis of copolymer films was achieved in various monomers feed ratio (o-amino benzyl alcohol: o-anisidine; 8:2, 1:1, 2:8) of o-amino benzyl alcohol and o-anisidine. Different solution types were tested in aqueous and non-aqueous media, especially during the synthesis process, as the electrolyte medium. As a result of the experiments, it was determined that sulfuric acid solution was the most suitable solution for both homopolymer and copolymer film growth. Homopolymer and copolymer samples were characterized by FT-IR, cyclic voltammetry (CV), SEM, digital images and TGA/DTA techniques. The CV, SEM and digital images results indicated that the solution which has high ratio of monomer is more effective in copolymer film synthesis mechanism. TGA results showed that the 1:1 copolymer film had higher thermal stability than the films at other monomer ratios. Also, electrochemical studies exhibited that the copolymer film in 1:1 ratio is partially more electrochemically stable than other copolymer films.  相似文献   

12.
Plenty of oily wastewater discharged from industrial and domestic sewage has deteriorated the environment severely, so stimuli-responsive membranes with switchable wettability have been of considerable attraction for its potential application in oil/water separation. In this work, a novel pH-dependent thermoresponsive membrane fabricated by grafting the poly[2-(diethylamino)ethyl acrylamide] (PDEAEAM) from the poly(vinylidene fluoride) (PVDF) membrane via surface-initiated atom transfer radical polymerization is explored to achieve the oil/water separation. The PDEAEAM-g-PVDF membrane shows hydrophilicity at room temperature under neutral condition while hydrophobicity at 50°C under alkaline condition. Wettability of the membrane at different temperatures is dominated by the lower critical solution temperature (LCST) of PDEAEAM, and the LCST of PDEAEAM is pH dependent. Due to the LCST of PDEAEAM, the membrane shows a variation of separation efficiency for separating hexadecane/water emulsion with temperature and pH. Typical separation efficiencies are 97.10% at 25°C under neutral condition and 30.26% at 50°C under alkaline condition.  相似文献   

13.
Hydroxyapatite (HAp) crystals were prepared via an in situ biomimetic process in the presence of poly(vinyl alcohol) (PVA). The effect of polymer amount and its molecular weight on the physical properties of the HAp crystals were investigated. X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR) analysis, confirmed the formation of the crystalline HAp at room temperature. Microstructural features such as size and morphology of the resulting HAp samples were characterized using BET, scanning and transmission electron microscopy. The results indicate that the development (size and shape) of the HAp nanocrystals precipitated in an aqueous solution of PVA was influenced by the molecular weight of the polymer in such a way that smallest crystallite size was observed in the case of PVA with the highest molecular weight. It is believed that the HAp formation was initiated through the interaction of Ca2+ ions with the negative side groups on the polymer surface. The larger number of reaction sites in the PVA polymer with higher molecular weight led to a higher number of HAp nuclei and therefore smaller crystallite size.  相似文献   

14.
Poly(m‐aminophenyl acetic acid) was synthesized under different conditions from the respective monomer, using ammonium persulfate as oxidizing agent in both the presence and the absence of CuCl2 in HCl(aq). Moreover, the copolymers between aniline and m‐aminophenyl acetic acid were prepared at several feed mol ratios (f1) of aniline. Copper was introduced by the Batch method in the homo‐ and copolymers of different compositions. The polymers were characterized by FTIR and UV‐vis spectroscopy, elemental analysis, thermal analysis, and electrical conductivity. The thermal stability and the content of copper increased as the content of aniline was increased in the copolymers. Moreover, the copolymers showed a high thermal stability; at 400°C a weight loss < 10% was observed. The electrical conductivity was increased with a higher content of aniline in the copolymers, achieving semiconduction values. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1484–1492, 2003  相似文献   

15.
Summary By Schotten-Baumann's esterification of poly(2-hydroxyethyl methacrylate) with 10-undecenoyl chloride a new multimonomer - poly[2-(10-undecenoyloxy)ethyl methacrylate] was prepared. Based on the results of elemental analysis, FTIR, 1H-NMR and 13C-NMR spectra, the structure of the multimonomer was proposed. The thermal properties of the multimonomer were studied by DSC and TG. The rate of disappearance of double bonds in the multimonomer during UV irradiation was examined in the solid state to obtain a crosslinked product. Received: 17 September 2001/Revised version: 5 February 2002/ Accepted: 7 March 2002  相似文献   

16.
The temperature–conductivity characteristics of poly(3‐hexylthiophene) (P3HT) composites filled with P3HT‐grafted indium tin oxide (ITO) particles were investigated in this work. The ITO particles were first treated with a silane coupling reagent of 3‐aminopropyltriethoxysilane (APS), and then thiophene rings were introduced through a condensation reaction between the ending amino groups of APS and the carboxylic groups of thiophene‐3‐acetic acid. The composites were prepared by the polymerization filling of the 3‐hexylthiophene (3HT) monomer with the thiophene‐ring‐introduced ITO particles. Elemental analysis, Fourier transform infrared, and X‐ray photoelectron spectroscopy were used to confirm the grafting reaction on the ITO surface. The longer the polymerization time was or the higher the 3HT/ITO feeding ratio was, the more P3HT was grafted. The influence of the grafted amount on the electrical properties of ITO particles was attributed to the wrapping effect formed by the grafted P3HT on the surface of the ITO particles. The conductivity change of the P3HT‐grafted ITO/P3HT composites was proved to be subject to the change in the average gap width of ITO interparticles, which was determined by the filling ratio of P3HT to ITO in the polymerization and the volume expansion effect of a P3HT thin film between neighboring ITO particles during the heating process. In comparison with the ungrafted ITO/P3HT composites, the grafting treatment enhanced the interaction between the particles and polymer matrix, and this was helpful for obtaining a more homogeneous dispersion structure for the composites and thus afforded a higher positive temperature coefficient intensity and better reproducibility. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1881–1888, 2006  相似文献   

17.
The water-soluble polypyrrole, poly[4-(3-pyrrolyl)butanesulfonic acid] (P3PyBSH), in which the β-position of pyrrole ring is substituted with n-butanesulfonic acid group, is synthesized by oxidation polymerization of 3PyBSNa followed with an ion-exchange of Na+ with H+. It can be cast into free-standing film from its aqueous solution and has a conductivity of 4.0×10−4 S/cm, higher than that of its sodium salt (5.5× 10−6 S/cm) by about 2 orders. The increase in conductivity is attributed to the self-doping by the protons originally on the side chains as supported by the absence of the anion FeCl4 (which generates during the polymerization) and the presence of polaron and bipolaron characteristics in its UV-Vis and IR spectra.  相似文献   

18.
Pressure-composition (p, x) isotherms were obtained for the carbon dioxide + 2-(2-ethoxyethoxy)ethyl acrylate [2-(2-EE)EA] system at five temperatures (313.2 K, 333.2 K, 353.2 K, 373.2 K, and 393.2 K) and pressure up to 22.86 MPa. The carbon dioxide + 2-(2-EE)EA system exhibits type-I phase behavior with a continuous mixture critical curve. The experimental results for carbon dioxide + 2-(2-EE)EA mixtures are correlated using the Peng–Robinson equation of state (PR-EOS) using mixing rule including two adjustable parameters. The critical property of 2-(2-EE)EA is estimated with the Joback–Lyderson method.Experimental data up to 485 K and 206.6 MPa are reported for binary and ternary mixtures of poly(2-(2-ethoxyethoxy)ethyl acrylate) [P(2-(2-EE)EA)] + carbon dioxide + 2-(2-EE)EA, P(2-(2-EE)EA) + carbon dioxide + dimethyl ether (DME), P(2-(2-EE)EA) + carbon dioxide + propylene and P(2-(2-EE)EA) + carbon dioxide + 1-butene systems. High-pressure cloud-point data are also reported for P(2-(2-EE)EA) in supercritical carbon dioxide, propane, propylene, butane, 1-butene, and DME at temperature to 474 K and a pressure range of (8.45–206.6) MPa. Cloud-point behavior for the P(2-(2-EE)EA) + carbon dioxide + 2-(2-EE)EA system were measured in changes of the pressure–temperature (p, T) slope and with 2-(2-EE)EA mass fraction of 0.0 wt%, 5.9 wt%, 14.9 wt%, 30.3 wt% and 60.2 wt%. With 0.650 2-(2-EE)EA to the P(2-(2-EE)EA) + carbon dioxide solution, the cloud point curves take on the appearance of a typical lower critical solution temperature boundary. The P(2-(2-EE)EA) + carbon dioxide + (0.0–46.6) wt% DME systems change the (p, T) curve from upper critical solution temperature region to lower critical solution temperature region as the DME mass fraction increases. Also, the impact by propylene and 1-butene mass fraction for the P(2-(2-EE)EA) + carbon dioxide + propylene and 1-butene system is measured at temperatures to 454 K and a pressure range of (75.7 to 119.6) MPa.  相似文献   

19.
Conductive homopolymers and composites of poly(2‐chloroaniline) (P2ClAn) and polyfuran (PFu) were synthesized chemically in hydrous and anhydrous media, and their properties were investigated. The polymers and composites were characterized by Fourier infrared spectroscopy, ultraviolet‐visible absorption spectroscopy, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, magnetic susceptibility, and conductivity measurements. It was found that the PFu/P2ClAn composite is thermally more stable than both the P2ClAn/PFu composite and the homopolymers. It was determined from Gouy scale measurements that conducting mechanisms of homopolymers and composites are polaron and bipolaron in nature. It was observed that the conductivity and magnetic susceptibility values changed with a changing amount of the guest polymer in the prepared composites. The conductivity (3.21 × 10?2 S/cm) of the P2ClAn/PFu (55.8% m/m) composite was found to be higher than the conductivities of both homopolymers (σPFu = 1.44 × 10?5 S/cm; σP2ClAn = 1.32 × 10?3 S/cm). It was determined that the composites synthesized had different conductivities and morphological and thermal properties from changing synthesis order. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2924–2931, 2003  相似文献   

20.
Poly(2‐iodoaniline) (PIANI) and poly(aniline‐co‐2‐iodoaniline) [P(An‐co‐2‐IAn)] were synthesized by electrochemical methods in acetonitrile solution containing tetrabutylammonium perchlorate (TBAP) and perchloric acid (HClO4). The voltametry of the copolymer shows characteristics similar to those of conventional polyaniline (PANI), and it exhibits higher dry electrical conductivity than PIANI and lower than PANI. The observed decrease in the conductivity of the copolymer relative to PANI is attributed to the incorporation of the iodine moieties into the PANI chain. The structure and properties of these conducting films were characterized by FTIR and UV‐Vis spectroscopy and by an electrochemical method (cyclic voltametry). Conductivity values, FTIR and UV‐Vis spectra of the PIANI and copolymer were compared with those of PANI and the relative solubility of the PIANI and the copolymer powders was determined in various organic solvents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1652–1658, 2003  相似文献   

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