Gradual internal reforming is based on local coupling between steam reforming of the fuel which occurs on a catalyst and hydrogen electrochemical oxidation which occurs at the electrode triple-phase perimeter. In order to demonstrate the feasibility of this strategy, the catalytic and electrochemical properties of lanthanum chromite, pure and impregnated with ruthenium, were investigated. Ruthenium supported on lanthanum chromite exhibits very good catalytic activity for the steam reforming of methane. Full conversion of steam is obtained for ratios H20/CH4 even lower than 1 at 700°C. No carbon deposition could be detected after 100 h of operation. Electrochemical measurements, carried out by impedance spectroscopy on cone-shaped microelectrodes of lanthanum chromite, show that the overpotential resistance under H2/H20 is lower than under CO/CO2 and much lower than under CH4/H20. In the presence of ruthenium, impedance diagrams under hydrogen and methane are fairly similar and gas analysis shows that some methane is reformed. This observation demonstrates that gradual internal reforming can be implemented. A detailed analysis of the electrode impedance diagrams shows that the so-called high-frequency semicircle is virtually independent of the nature of the atmosphere. This indicates that it is not directly related to any chemical or electrochemical step of the electrode reaction.

International audienceThis paper deals with the performance of anhydrous proton-conducting polymers obtained by blending modified Nafion^® membranes with proton conducting ionic liquids (PILs). It has been shown that the conductivities depend more on the PIL uptake than on its intrinsic conductivity. Conductivities at 130°C approaching those of current Nafion membranes at 80°C and 98% relative humidity were obtained with the best blends. These data allow considering MEA operating at 120-130°C based on membrane and electrodes incorporating these blends. This is clearly a positive feature for an implementation in hybrid vehicles powered by proton exchange membrane fuel cells (PEMFCs) operating above 100°C. Lastly, preliminary results for a PIL based on a half-neutralized diamine show an improvement in oxidation and, provided that the neutralization is optimized, a neat reinforcement of the Nafion membrane can be expected

In an attempt to establish comparison criteria for the electrocatalytical properties of electrode materials, systematic measurements were carried out on microelectrodes of simple shapes. The overpotential resistances were normalized with respect to the electrode triple‐phase boundary length and the electrode capacitances to the electrode interface area. Results obtained on metals such as Ag, Pt, Au, and Ni, and on some oxides, under either cathodic or anodic atmospheres, show marked differences which allow us to classify them. The positions of several materials in the cathode and anode material lists can be significantly different, indicating different electrocatalytical requirements under solid oxide fuel cell cathode and anode atmospheres. The clearest example is silver, which exhibits excellent electrocatalytical properties for the oxygen electrode reaction and very poor properties for hydrogen oxidation.

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A new type of Nafion/Fe structured membrane ensuring faster kinetics, higher efficiency, and mechanical properties has been prepared and will be compared in its performance with the Fe-exchanged commercial Dupont 117 Nafion/Fe membrane during the abatement of model organic compounds. During the casting of the laboratory Nafion sample, the iron ions were introduced directly into the Nafion oligomer solution. This novel laboratory Nafion/Fe was tested as an immobilized catalyst in the degradation of several toxic pollutants showing a faster photoassisted degradation kinetics and a wider effective photocatalytic pH range compared to the Fe-exchanged commercial Dupont 117 Nafion/Fe membrane. When carrying out Ar ion sputtering of the 50 topmost catalyst layers, evidence is presented by X-ray photoelectron spectroscopy that Fe ions are found in the inner Nafion layers and seem to be responsible for the immobilized photoassisted Fenton processes leading to the degradation of 4-chorophenol (4-CP) taken as a model organic pollutant for the degradation process reported in this study. In the laboratory sample, the iron oxy/hydroxy Nafion moiety undergoes a transition to a more stable Nafion/Fe species during 4-CP degradation as determined by X-ray diffraction. This more stable form shows a higher iron dispersion and crystallinity compared to the fresh sample and is stabilized by the Nafion matrix avoiding the formation of separate iron phases. By infrared absorption (Fourier transform infrared), evidence is presented for the band of akaganeite-like species at 870 cm(-1) on the laboratory Nafion/Fe sample. This band disappears after 4-CP degradation because of the formation of the more highly dispersed iron species. Sputtering experiments show a decrease of F-containing groups in the laboratory Nafion/Fe samples closer to the catalyst upper layer while the amounts of Fe, C, and in particular O species increase in the topmost layer(s). In particular, the oxygenated species develop in the Nafion/Fe up to approximately 50 A below the catalyst surface. These species remain stable during the long-term Nafion/Fe degradation of 4-CP. Dynamo-mechanical analysis performed on laboratory Nafion/ Fe membrane samples revealed that these membranes possessed a greater mechanical modulus and resistance than the commercial Dupont 117 Nafion membrane.

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