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The development of electrically conductive and high surface area carbon is important for the improvement of supercapacitor energy densities. Yttrium hydroxide microspindles were prepared and shown ...

Hierarchical porous carbons (HPCs) hold great promise in energy-related applications owing to their excellent chemical stability and well-developed porous structures. Attention has been drawn toward developing new synthetic strategies and precursor materials that permit greater control over composition, size, morphology, and pore structure. There is a growing trend of employing metal-organic frameworks (MOFs) as HPC precursors as their highly customizable characteristics favor new HPC syntheses. In this article, we report a biomimetically grown bacterial-templated MOF synthesis where the bacteria not only facilitate the formation of MOF nanocrystals but also provide morphology and porosity control. The resultant HPCs show improved electrochemical capacity behavior compared to pristine MOF-derived HPCs. Considering the broad availability of bacteria and ease of their production, in addition to significantly improved MOF growth efficiency on bacterial templates, we believe that the bacterial-templated MOF is a promising strategy to produce a new generation of HPCs.

A series of aromatic polyimides derived from 4,4′-hexafluoroisopropylidine diphthalic anhydride (6FDA), with different ratios of 2,4,6-trimethyl-1,3-phenylenediamine (DAM), and 3,5-diaminobenzoic a...

Lanthanum hydroxide nanorods were employed as both a template and catalyst for carbon synthesis by chemical vapor deposition. The resulting carbon possesses hollow nanorod shapes with graphitic walls. The hollow carbon nanorods were interconnected at some junctions forming a mazelike network, and the broken ends of the tubular carbon provide accessibility to the inner surface of the carbon, resulting in a surface area of 771 m2/g. The hollow carbon was tested as an electrode material for supercapacitors. A specific capacitance of 128 F/g, an energy density of 55 Wh/kg, and a power density of 1700 W/kg at 1 A/g were obtained using the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as the electrolyte.

Hierarchical porous carbons (HPCs) hold great promise in energy-related applications owing to their excellent chemical stability and well-developed porous structures. Attention has been drawn toward developing new synthetic strategies and precursor materials that permit greater control over composition, size, morphology, and pore structure. There is a growing trend of employing metal-organic frameworks (MOFs) as HPC precursors as their highly customizable characteristics favor new HPC syntheses. In this article, we report a biomimetically grown bacteria-templated MOF synthesis where the bacteria not only facilitate the formation of MOF nanocrystals, but also provides morphology and porosity control. The resultant HPCs show improved electrochemical capacity behavior compared to pristine MOF derived HPCs. Considering the broad availability of bacteria and ease of its production, in addition to significantly improved MOF growth efficiency on bacterial templates, we believe that bacteria-templated MOF is a promising strategy to produce a new generation of HPCs.

Hierarchical porous carbons (HPCs) hold great promise in energy-related applications owing to their excellent chemical stability and well-developed porous structures. Attention has been drawn toward developing new synthetic strategies and precursor materials that permit greater control over composition, size, morphology, and pore structure. There is a growing trend of employing metal-organic frameworks (MOFs) as HPC precursors as their highly customizable characteristics favor new HPC syntheses. In this article, we report a biomimetically grown bacteria-templated MOF synthesis where the bacteria not only facilitates the formation of MOF nanocrystals, but also provides morphology and porosity control. The resultant HPCs show improved electrochemical capacity behavior compared to pristine MOF derived HPCs. Considering the broad availability of bacteria and ease of its production, in addition to significantly improved MOF growth efficiency on bacterial templates, we believe that bacteria-templated MOF is a promising strategy to produce a new generation of HPCs.

An immiscible polymer blend comprised of high-performance copolyimide 6FDA-DAM:DABA(3:2) (6FDD) and polybenzimidazole (PBI) was compatibilized using 2-methylimidazole (2-MI), a commercially available small molecule. Membranes were fabricated from blends of 6FDD:PBI (50:50) with and without 2-MI for H2/CO2 separations. The membranes demonstrated a matrix-droplet type microstructure as evident with scanning electron microscopy (SEM) imaging where 6FDD is the dispersed phase and PBI is the continuous phase. In addition, membranes with 2-MI demonstrated a uniform microstructure as observed by smaller and more uniformly dispersed 6FDD domains in contrast to 6FDD:PBI (50:50) blend membranes without 2-MI. This compatibilization effect of 2-MI was attributed to interfacial localization of 2-MI that lowers the interfacial energy similar to a surfactant. Upon the incorporation of 2-MI, the H2/CO2 selectivity improved remarkably, compared to the pure blend, and surpassed the Robeson's upper bound. To our knowledge, this is the first report of the use of a small molecule to compatibilize a high-performance immiscible polymer blend. This approach could afford a novel class of membranes in which immiscible polymer blends can be compatibilized in an economical and convenient fashion.

The demand for cost-efficient separations requires membranes with high gas flux and high selectivity which opens the path for further improvements. Mixed matrix membranes (MMMs) made from 33.3 wt % ZIF-8 in 6FDA-durene were tested at 35 °C and 3.5 atm. At 33.3 wt % loading of ZIF-8, H2, N2, O2, and CH4 gas permeabilities increased approximately 400%. Cross-linking the surface of this MMM, by reacting with ethylenediamine vapor, yielded a 10-fold increase in H2/CO2, H2/N2, and H2/CH4 selectivities with respect to 6FDA-durene, preserving 55% of the H2 permeability of 6FDA-durene. The permselective properties of the cross-linked skin of the MMM fall above the most recent permeability–selectivity trade-off lines (2008 Robeson upper bounds) for H2/CO2, H2/N2, and H2/CH4 separations. To the best of our knowledge, this is the first example of a cross-linked ZIF/polymer MMM for gas separation.

A novel symmetrical alkylsulfonyl-substituted poly(phenylenevinylene) derivative, poly [2,5-bis-(2'-ethylhexylsulfonyl)-1,4-phenylene)vinylene] (SO2EH-PPV), was synthesized via palladium-catalyzed Stille coupling, and its electronic and optical properties were investigated. The novel PPV derivative was characterized by NMR, UV-visible absorption, photoluminescence, gel permeation chromatography, infrared spectroscopy, and cyclic voltammetry (CV). The polymer with Mw of 27,800 and a polydispersity index of 2.6 is readily soluble in common organic solvents, such as THF, chloroform, and toluene. The fluorescence quantum yield of the polymer, determined against rhodamine 6G in dilute aqueous solutions, was 0.95. The HOMO and LUMO levels of SO2EH-PPV were calculated to be -6.0 and -3.61 eV, respectively. The results obtained by CV suggest that SO2EH-PPV is a strong electron acceptor polymer. Single layer stable polymer light-emitting diode devices with the configuration of (ITO/PEDOT:PSS/SO2EH-PPV polymer/Al) were fabricated exhibiting a green light emission.

In this study, we explore the effect of the dialkoxy and dithioalkoxy side chains on the benzo [1,2-b:4,5-b′]dithiophene (BDT) unit by comparing the O-BDT homopolymer (O-PBDT), S-BDT homopolymer (S-PBDT), and S-BDT-alt-O-BDT copolymer (SO-PBDT) by computational calculations and experimental results. The polymers were prepared by Pd-catalyzed Stille coupling. Additionally, hole mobility and film morphology were studied by fabricating organic field effect transistors (OFETs) and using TappingMode AFM, respectively. The photovoltaic properties of the polymers were measured from fabricated PSC devices. The replacement of the alkoxy (−OR) groups with thioalkoxy (−SR) groups lowered the HOMO energy level of the conjugated polymers from 5.31 to 5.41 eV, and consequently enhanced Voc, while still preserving the excellent properties offered by the BDT-based polymers. Especially, high Voc of 0.99 V was achieved from S-PBDT polymer based PSC with up to 4.0% of PCE, which is one of the highest efficiencies reported f...

Low efficiencies and costly electrode materials have limited harvesting of thermal energy as electrical energy using thermo- electrochemical cells (or "thermocells"). We demonstrate thermocells, in practical configurations (from coin cells to cells that can be wrapped around exhaust pipes), that harvest low-grade thermal energy using relatively inexpensive carbon multiwalled nanotube (MWNT) electrodes. These electrodes provide high electrochemically accessible surface areas and fast redox-mediated electron transfer, which significantly enhances thermocell current generation capacity and overall efficiency. Thermocell efficiency is further improved by directly synthesizing MWNTs as vertical forests that reduce electrical and thermal resistance at electrode/substrate junctions. The efficiency of thermocells with MWNT electrodes is shown to be as high as 1.4% of Carnot efficiency, which is 3-fold higher than for previously demonstrated thermocells. With the cost of MWNTs decreasing, MWNT-based thermocells may become commercially viable for harvesting low-grade thermal energy.

Single-particle fluorescence spectroelectrochemistry was used to investigate the electrochemical oxidation of isolated, immobilized particles of the conjugated polymers BEH-PPV and MEH-PPV at an indium tin oxide (ITO) electrode immersed in an electrolyte solution. Two types of particles were investigated: (i) polymer single molecules (SM) and (ii) nanoparticle (NP) aggregates of multiple polymer single molecules. For the BEH-PPV polymer, the observation of nearly identical lowest oxidation potentials for different SM in the ensemble is evidence for effective electrostatic screening by the surrounding electrolyte solution. A combination of Monte Carlo simulations and application of Poisson-Boltzmann solvers were used to model the charging of polymer single molecules and nanoparticles in the electrochemical environment. The results indicate that the penetration of electrolyte anions into the polymer nanoparticles is necessary to produce the observed narrow fluorescence quenching vs oxidation potential curves. Finally, fluorescence-lifetime single-molecule spectroelectrochemical (SMS-EC) data revealed that at low potential an excited state reduction process (i.e., electron transfer from ITO to the polymer) is probably the dominant fluorescence quenching process.

Poly(p-phenylenevinylene) (PPV) derivatives have long been studied because of their attractive opto- and electroluminescent properties and have potential applications for devices such as light-emitting diodes and photovoltaics. The ability to induce alignment of these PPV derivatives may lead to the enhancement of charge mobility and their efficiency. In this study, uniform nanofibers of poly[2,5-(2'-ethylhexyloxy)]-1,4-phenylenevinylene (BEH-PPV) have been fabricated through the method of electrospinning, and an induced alignment of the polymer fibers was observed through photoluminescence data. This study also focuses on the doping of these fibers with the fullerene derivative, 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)-C(61) (PCBM), to induce more incidence of donor/acceptor junctions. Composite fibers with up to a 1:2 weight ratio of PCBM/BEH-PPV have been fabricated and exhibited an ability to quench the photoluminescence of BEH-PPV, indicative of charge transfer.

The polymerization to polyaniline nanofibers was carried out in an aqueous system using aniline, 1 M HCl. and ammonium peroxydisulfate (APS) with additional use of sodium hypochlorite solution as a co-oxidant. The addition of sodium hypochlorite solution was made either before or after the addition of APS. This new method always produces polyaniline nanofibers with long length. Additional advantages of this new method are discussed. The effect of aniline concentration, hypochlorite concentration, different acid use, reaction temperature, and both aniline and hypochlorite purity on morphology and electrical property of the nanofibers synthesized by this new method was investigated.

A carbon aerogel was prepared by carbonizing a resorcinol−formaldehyde polymer gel at 800 °C. Nitrogen adsorption shows the obtained carbon aerogel has both micropores (0.54 nm) and mesopores (2.14 nm). Matrimid mixed-matrix membranes containing the carbon aerogels were successfully prepared and evaluated for the permeation of H2, N2, O2, CH4, CO2, and gas mixtures. The ideal selectivity of H2/N2, CO2/CH4, and O2/N2 gas pairs increased from 79.6, 34.5, and 6.6 for pure Matrimid to 111, 47.8, and 9.1 at 20% loading, respectively. These results suggest that the polymer chains can penetrate the carbon mesopores to achieve good contact between the carbon aerogel and Matrimid, while the micropores may provide size and shape selectivity.

The process of electrospinning, which produces fibers in the nanometer to micron range under the influence of high voltages, has been widely studied to produce polymer and textile fibers. Mesoporous molecular sieve fibers have been produced in our lab, and this technique was extended to produce an interwoven mesh of polymer-molecular sieve composite fibers. The electroluminescent polymer MEH-PPV and molecular sieve SBA-15 were used to produce the composite fibers. An interesting aspect of these composites is that the fluorescence of MEH-PPV is blue shifted in the composites. The composites have been characterized by microscopy, vibrational spectroscopy, and fluorescence measurements.

Electrochromic devices composed of laminated polymer layers, as the working electrode, and vanadium pentoxide, as the counter electrode, were prepared and evaluated. Three different laminate systems were investigated using various combinations of poly(3,4-ethylenedioxythiophene), poly(N-methylpyrrole), and polyaniline as the active electrochromes. The color change of the laminate devices was measured using spectrocolorimetric techniques and analyzed using Commission Internationale de l'Eclairage 1931 (x, y)-chromaticity coordinates. The device's observed colors in their fully doped and dedoped states are found to be linearly dependent on the color coordinates of the two individual polymers that comprise the laminate.

In this study, we have explored the first use of the siliceous MCM-41 molecular sieve as an additive to enhance the gas permeability characteristics of a high-performance polysulfone. For all gases...

Mechanistic studies on the polymerization of α,α‘-dibromo-2-methoxy-5-(2-ethylhexyloxy)xylene have been performed. Polymerizations were initially carried out by adding potassium tert-butoxide to monomer in the presence of a chain transfer agent, anthracene. Anthracene showed little effect on the molecular weight of the resulting polymer, suggesting that the major polymerization route was not radically initiated. Polymerizations were also carried out by adding monomer to potassium tert-butoxide in the presence of a nucleophile, 4-methoxyphenol. The molecular weight of the resulting polymer scaled linearly with the amount of 4-methoxyphenol, suggesting an anionic mechanism. In addition, each polymerization was monitored by in-situ torque measurements to further elucidate the polymerization mechanism and optimize polymerization conditions.

Self-assembled multilayers of the three modified cyclodextrins (hexakis(2,3-O-hexyl-6-deoxy-6-amino)-α-cyclodextrin (1), heptakis(2,3-O-hexyl-6-deoxy-6-amino)-β-cyclodextrin (2), and octakis(2,3-O-hexyl-6-deoxy-6-amino)-γ-cyclodextrin (3)) on bare gold, as well as on gold surfaces modified with mercaptopropionic (4) and mercaptooctanoic (5) acid, were investigated by cyclic voltammetric, contact angle, FT-IR, and quartz crystal microbalance measurements in neutral aqueous media. The level of organization of the aggregates formed by the three CD derivatives (1−3) on the negatively charged surface of the mercaptopropionic and mercaptooctanoic acid modified gold electrodes proved to be substantially better than that on bare gold electrodes. This finding suggests that although the amphiphilic character of compounds 1−3 can induce aggregation on a gold surface, the electrostatic interaction between the carboxylic acid groups and the positively charged cyclodextrins is the primary force leading to the formation...

The use of an alkanethiol-based self-assembled mixed monolayer as an electronic relay system effecting mediated electron transfer between immobilized glucose oxidase (GOx) and a gold electrode is reported. We compare the behavior of mixed monolayers of various compositions of 16-ferrocenylhexadecanethiol (16FAT) and aminoethanethiol, to which GOx is attached, as biosensors for glucose. The amperometric response of such electrodes in the presence of glucose in solution depends on the mole ratio between the 16FAT molecules and the attached protein molecules. The most sensitive system is a mixed monolayer that contains 7% 16FAT. For higher 16FAT concentrations, both a catalytic response and a wave corresponding to reversible 16FAT voltammetry are observed in the presence of glucose. This suggests that there are separate domains of 16FAT and of aminoethanethiol in such a mixed monolayer. When the mixed monolayer contains more than 7% 16FAT, a portion of the 16FAT molecules cannot “feel” the GOx and does not f...

A linear polythiophene, poly[bis(5‘,2‘-bithiophene-2-yl)]dimethylsilane, which incorporates silyl bridges in the backbone was synthesized to tailor the electrochromic properties. Solid-state electrochromic devices comprised of this polymer as the active material were fabricated and were analyzed following CIE L*a*b* formalism. By limiting the effective conjugation in the polymer, its electrochromic properties were deliberately altered to produce a yellow to green color change from its neutral to oxidized state.

The synthesis of 2-phenylthieno[3,4-b]thiophene was carried out in two steps from 3,4-dibromothiophene and phenylacetylene. Electropolymerization of this monomer affords a novel low band gap (Egap) polymer that was characterized by cyclic voltammetry and electrochemistry. An Egap of ca. 0.85 eV was observed, which is among the lowest reported to date for any conductive polymer.

The authors report a differential scanning calorimetric method for the study of Co(II) phthalocyanine formation in zeolite NaY.

Das cyclische Voltammogramm der Titelverbindung (I) zeigt Einelektronen-Reduktionsstufen bei 0.79 und 0.14 V (gegen die SCE).