QUANTUM-CHEMICAL STUDY OF CATALYSTS BASED ON OXIDES OF TRANSITION-METALS

Catalysts based on oxides of transition metals were studied by xalpha-DV calculations. The chemical composition and electronic structure of surface layers for platinum(IV) oxide catalysts modified under percompound electrosynthesis were determined by X-ray photoelectron spectroscopic, quantum chemical, and electrochemical data. The main regularities in electronic structure change under the transition from solid pure oxide PtO2 to its, in part, N-substituted PtO2-xNx were analyzed. Then, we looked for perspective catalysts, calculating the electronic structure for analogous compounds of Ir(III), Ir(IV), Rh(III), and Pd(II). We found that the changes in electronic structure of rhodium oxide under 0 -N-substitution allowed us to predict the excellent properties of its compound as a catalyst for percompound electrosynthesis reactions. (C) 1994 John Wiley & Sons, Inc.