Preparation and Study of Sulfonated Co-Polynaphthoyleneimide Proton-Exchange Membrane for a H2/Air Fuel Cell

The sulfonated polynaphthoyleneimide polymer (co-PNIS70/30) was prepared by copolymerization of 4,40 -diaminodiphenyl ether-2,20 -disulfonic acid (ODAS) and 4,4’-methylenebisanthranilic acid (MDAC) with ODAS/MDAC molar ratio 0.7/0.3. High molecular weight co-PNIS70/30 polymers were synthesized either in phenol or in DMSO by catalytic polyheterocyclization in the presence of benzoic acid and triethylamine. The titration reveals the ion-exchange capacity of the polymer equal to 2.13 meq/g. The membrane films were prepared by casting polymer solution. Conductivities of the polymer films were determined using both in- and through-plane geometries and reached ~96 and ~60 mS/cm, respectively. The anisotropy of the conductivity is ascribed to high hydration of the surface layer compared to the bulk. SFG NMR diffusometry shows that, in the temperature range from 213 to 353 K, the 1H self-diffusion coefficient of the co-PNIS70/30 membrane is about one third of the diffusion coefficient of Nafion® at the same humidity. However, temperature dependences of proton conductivities of Nafion® and of co-PNIS70/30 membranes are nearly identical. Membrane–electrode assemblies (MEAs) based on co-PNIS70/30 were fabricated by different procedures. The optimal MEAs with co-PNIS70/30 membranes are characterized by maximum output power of ~370 mW/cm² at 80 °C. It allows considering sulfonated co-PNIS70/30 polynaphthoyleneimides membrane attractive for practical applications

Graphite photoelectrochemistry 2. Photoelectrochemical studies of highly oriented pyrolitic graphite

Abstract Photoelectrochemical reduction of oxygen and other observations of sustained electrochemically generated photocurrents with graphitic (HOPG) electrodes in aqueous solutions are reported. The photocurrents were observed over a wide pH range: 0 (0.5 M H 2 SO 4 )-14 (1 M NaOH). Photocurrent-potential, capacitance-potential and photocurrent light action spectral measurements were performed with basal plane and edge plane HOPG electrodes in order to elucidate the origin of the observed photocurrent. The photocurrent is attributed to hot electron-hot hole pairs photogenerated by direct transition between p-electronic states of the valence and conduction bands of graphite. Photogenerated carriers, holes or electrons, are driven by the electric field in the space charge layer (scl) to the electrode electrolyte interface, where they react directly with species in the electrolyte inducing anodic or cathodic photocurrent. The potential corresponding to the change of the photocurrent sign from cathodic to anodic was attributed to the flat band potential (E FB ). The E FB of the basal plane electrode was 0 V versus SHE regardless of pH, while for the edge plane electrode E FB changed at a rate of 54 mV per unit of pH. The shift of E FB of the edge plane electrode with pH is ascribed to a change of the pH dependent surface dipole formed by oxygen containing surface redox groups

Graphite photoelectrochemistry Part 4. Photoelectrochemical studies of quinones in acetonitrile at HOPG electrodes

Abstract Stationary photocurrents for reduction of different quinone compounds (benzoquinone, 1,4-naphthoquinone, and 9,10-phenanthroquinone) at irradiated highly oriented pyrolytic graphite (HOPG) electrodes in CH 3 CN are reported. Excitation of hot electrons in a graphite electrode by UV-vis light absorption and subsequent hot electron transfer to an acceptor species (quinones) in the electrolyte is assumed to be the source of the photocurrent. This mechanism is supported by photocurrent-potential dependence and photocurrent light action spectra. The effect of the potential drop in the space charge layer of graphite electrodes on photocurrent generation was evaluated by the comparison of photocurrent generation at basal and edge plane HOPG orientations and glassy carbon (GC) electrodes

The incorporation of titania into modified silicates for solar photodegradation of aqueous species

A new class of sol-gel-derived photocatalytic materials has been synthesized and used in solar-assisted photodegradation studies. The materials are comprised of a homogeneous dispersion of commercial TiO2 powder into silica and organically modified silicate (Ormosil) hosts. The efficiency of the photocatalytic properties of these TiO2-containing materials was determined by their relative performance in the solar photodecomposition of aqueous rhodamine B. The improved adsorption properties of the modified materials compared to commercial TiO2 increase the photodecomposition rate and the buoyancy properties, although excess hydrophobicity decreases the wetted section of the catalyst and its photocatalytic performance. These materials can be used as floatable catalysts for solar-assisted water purification

Pt-Mo/C, Pt-Fe/C and Pt-Mo-Sn/C Nanocatalysts Derived from Cluster Compounds for Proton Exchange Membrane Fuel Cells

Nanosized bimetallic PtMo, PtFe and trimetallic PtMoSn catalysts deposited on highly dispersed carbon black Vulcan XC-72 were synthesized from the cluster complex compounds PtCl(P(C6H5)3)(C3H2N2(CH3)2)Mo(C5H4CH3)(CO)3, Pt(P(C6H5)3)(C3N2H2(CH3)2)Fe(CO)3(COC6H5C2C6H5), and PtCl(P(C6H5)3)(C3N2H2(CH3)2)C5H4CH3Mo(CO)3SnCl2, respectively. Structural characteristics of these catalysts were studied using X-ray diffraction (XRD), microprobe energy dispersive spectroscopy (EDX), and transmission electron microscopy (TEM). The synthesized catalysts were tested in aqueous 0.5 M H2SO4 in a three-electrode electrochemical cells and in single fuel cells. Electrocatalytic activity of PtMo/C and PtFe/C in the oxygen reduction reaction (ORR) and the activity of PtMoSn/C in electrochemical oxidation of ethanol were evaluated. It was shown that specific characteristics of the synthesized catalysts are 1.5–2 times higher than those of a commercial Pt(20%)/C catalyst. The results of experiments indicate that PtFe/C, PtMo/C, and PtMoSn/C catalysts prepared from the corresponding complex precursors can be regarded as promising candidates for application in fuel cells due to their high specific activity

Cardo Polybenzimidazole (PBI-O-PhT) Based Membrane Reinforced with m-polybenzimidazole Electrospun Nanofiber Mat for HT-PEM Fuel Cell Applications

The further development of high temperature polymer electrolyte membrane (HT-PEM) fuel cells largely depends on the improvement of all components of the membrane–electrode assembly (MEA), especially membranes and electrodes. To improve the membrane characteristics, the cardo-polybenzimidazole (PBI-O-PhT)-based polymer electrolyte complex doped with phosphoric acid is reinforced using an electrospun m-PBI mat. As a result, the PBI-O-PhT/es-m-PBInet · nH3PO4 reinforced membrane is obtained with hydrogen crossover values (~0.2 mA cm−2 atm−1), one order of magnitude lower than the one of the initial PBI-O-PhT membrane (~3 mA cm−2 atm−1) during HT-PEM fuel cell operation with Celtec®P1000 electrodes at 180 °C. Just as importantly, the reinforced membrane resistance was very close to the original one (65–75 mΩ cm2 compared to ~60 mΩ cm2). A stress test that consisted of 20 start–stops, which included cooling to the room temperature and heating back to 180 °C, was applied to the MEAs with the reinforced membrane. More stable operation for the HT-PEM fuel cell was shown when the Celtec®P1000 cathode (based on carbon black) was replaced with the carbon nanofiber cathode (based on the pyrolyzed polyacrylonitrile electrospun nanofiber mat). The obtained data confirm the enhanced characteristics of the PBI-O-PhT/es-m-PBInet · nH3PO4 reinforced membrane

Sn-Doped Hematite Films as Photoanodes for Photoelectrochemical Alcohol Oxidation

Here, the modification of semiconductor thin film hematite photoanode by doping with Sn ions is reported. Undoped and Sn-doped hematite films are fabricated by the electrochemical deposition of FeOOH from aqueous alkaline electrolyte, followed by calcination in air. The photoanodes were tested in photoelectrocatalytic oxidation of water, methanol, ethylene glycol, and glycerol. It is shown that modification by tin dramatically increased the activity of hematite in the photoelectrochemical oxidation of alcohols upon visible light irradiation. The photoelectrocatalytic activity of Sn-modified hematite increased in the sequence of: H2O 2H2(OH)2 3H5(OH)3. The quantum yield of photocurrent in the oxidation of alcohols reached 10%. The relatively low photocurrent yield was ascribed to the recombination of photoexcited holes within the hematite layer and on surface states located at the hematite/electrolyte interface. Intensity-modulated photocurrent spectroscopy (IMPS) was used to quantify the recombination losses of holes via surface states. The IMPS results suggested that the hole acceptor in the electrolyte (alcohol) influences photocurrent both by changing the charge transfer rate in the photoelectrooxidation process and by the efficient suppression of the surface recombination of generated holes. Thin-film Sn-modified hematite photoanodes are promising instruments for the photoelectrochemical degradation of organic pollutants