Zn-Doped RuO₂ electrocatalyts for Selective Oxygen Evolution: Relationship between Local Structure and Electrocatalytic Behavior in Chloride Containing Media

Nanocrystalline electrocatalytically active materials of chemical composition Ru1−xZnxO2 (0< x < 0.3) were synthesized by freeze-drying technique. The diffraction patterns of the prepared samples corresponded to single-phase rutile type oxides. Local structure of the Ru1−x ZnxO2 based on refinement of Ru K and Zn K edge EXAFS functions shows clustering of the Zn ions in the blocks with ilmenite structure intergrowing with Ru-rich rutile blocks. Ru1−xZnxO2 oxides are selective catalysts for anodic oxygen evolution. The selectivity toward oxygen evolution in the presence of chlorides is affected by the actual Zn content and can be ascribed to structural hindrance of the formation of the surface peroxo group based active sites for chlorine evolution. The selectivity toward oxygen evolution in presence of chlorides is accompanied by the drop of the total activity, which gets more pronounced with increasing Zn content.