Helmut Tributsch

Influence of selenium on the catalytic properties of ruthenium-based cluster catalysts for oxygen reduction

The favourable influence of selenium on the catalytic properties of Ru-based catalysts for the oxygen reduction reaction in acid electrolytes has been investigated by rotating disk electrode measurements. Compared to the oxygen reduction of selenium-free Ru-based catalysts, the overpotential at low current densities (ca. 10 μA cm−2) is not affected by the presence of selenium whereas selenium-containing catalysts show higher current densities under fuel cell relevant conditions. The kinetically controlled current density at 0.6 V versus SHE increases 4–5 fold with increasing selenium content. A maximum value is obtained at about 15 mol% Se. This effect is tentatively explained by a modification of the catalytic active centre, which is assumed to consist of Ruue5f8Cue5f8CO complexes. IR spectroscopic investigations indicate a reaction of selenium with these complexes. This model is also supported by the study of the electrooxidation of CO. In contrast to the selenium-free catalyst, no CO oxidation is observed on the selenium-containing catalyst. Additional effects of selenium are an enhanced stability towards electrochemical oxidation and a lower amount of Ru oxides formed during synthesis, as evidenced from XRD investigations. Direct four electron oxygen reduction to water is efficient and H2O2 production of these catalysts is small (about 5% at potentials <0.3 V vs. SHE ).

Carbon supported catalysts for oxygen reduction in acidic media prepared by thermolysis of Ru3(CO)12

Abstract Carbon supported catalysts for oxygen reduction in acidic media based on ruthenium and selenium have been prepared by thermolysis of Ru 3 (CO) 12 in organic solvents. The mass specific activity of these catalysts is higher than that of the unsupported samples. The optimum loading of the supporting carbon with catalyst has been found to be about 10%; higher loadings lead to only a slight increase in activity. As is evident from TEM, agglomeration of catalyst particles occurs, however, these agglomerates are homogeneously distributed over the supporting carbon. The activity is compared with commercial high surface area Pt/carbon and Ru/carbon catalysts. Characterisation of the catalyst with XPS and XRD indicates that it consists of a ruthenium core, which is surrounded by an amorphous shell containing Ru in various oxidation states, selenium and oxygen as well as high amounts of carbon. The real structure of the shell is unknown. After heat treatment, the activity of the catalyst towards oxygen reduction is slightly enhanced.

Thin film preparation of semiconducting iron pyrite

Pyrite (Fe52) has been investigated as a promising new absorber material for thin film solar cell applications because of its high optical absorption coefficient of 1OL cm1, and its bandgap of 0.9 to 1.0 eV. Thin layers have been prepared by Metal Organic Chemical Vapor Deposition, MOCVD, Chemical Spray Pyrolysis, CSP, Chemical Vapor Transport, CVT, and Sulfurization of Iron Oxide films, 510. It is postulated that for the material FeS2, if x is not zero, a high point defect concentration results from replacing 2 dipoles by single S atoms. This causes the observed photovoltages and solar conversion efficiencies to be lower than expected. Using the Fe-O-S ternary phase diagram and the related activity plots, a thermodynamic understanding is formulated for the resulting composition of each of these types of films. It is found that by operating in the oxide portion of the phase diagram, the resulting oxidation state favors pyrite formation over FeS. By proper orientation of the grains relative to the film surface, and by control of pinholes and stoichiometry, an efficient thin film photovolatic solar cell material could be achieved.

Metalorganic chemical vapor deposition of iron disulfide and its use for solar energy conversion

Thin polycrystalline films of iron disulfide have been grown on different substrates by chemical vapour deposition. The films were characterized using optical absorption and TEM. RBS and EDAX analysis has been used to explore the chemical stoichiometry. XRD and FTIR allowed the identification of both FeS2 phases pyrite and marcasite. A novel method for sensitization of highly porous Ti02 elecrodes with ultra thin (10-20 nm) polycrystalline films of FeS2 (pyrite) is presented. Photoelectrochemical solar cell using the above electrode generated high photovoltage of up to 600mV compared with single crystalline electrode (200 mV). In this device the semiconductor with a small band gap and high absorption coefficient (FeS2 pyrite; EG = 0.9 eV; a = 6 x 105 cm-1) absorbs the light and injects electrons into the conduction band the wide band gap semiconductor (Ti02 anatase; EG = 3.2 eV). Regeneration of holes is taking place by electron transfer from redox system in the electrolyte.