Composition-Dependent Functionality of Copper Vanadate Photoanodes.

To understand functional roles of constituent elements in ternary metal oxide photoanodes, essential photoelectrochemical (PEC) properties are systematically analyzed on a series of copper vanadate compounds with different Cu:V elemental ratios. Homogeneous and highly continuous thin films of ß-Cu2V2O7, γ-Cu3V2O8, Cu11V6O26, and Cu5V2O10 are grown via reactive co-sputtering and their performance characteristics for the light-driven oxygen evolution reaction are evaluated. All four compounds have similar bandgaps in the range of 1.83-2.03 eV, though Cu-rich phases exhibit stronger optical absorption and higher charge separation efficiencies. Transient photocurrent analysis reveals a reduction of surface catalytic activity with increasing Cu:V elemental ratio due to competitive charge recombination at Cu-related surface states. This comprehensive analysis of PEC functionalities-including photon absorption, carrier separation, and heterogeneous charge transfer-informs strategies for improving PEC activity in the copper vanadate materials system and provides insights that may aid discovery, design, and engineering of new photoelectrode materials.