Nanostructured core-shell metal borides-oxides as highly efficient electrocatalysts for photoelectrochemical water oxidation

Oxygen evolution reaction (OER) catalysts are critical components of photoanodes for photoelectrochemical (PEC) water oxidation. Herein, nanostructured metal boride MB (M = Co, Fe) electrocatalysts, which have been synthesized by a Sn/SnCl₂ redox assisted solid-state method, were integrated with WO₃ thin films to build heterojunction photoanodes. As-obtained MB modified WO₃ photoanodes exhibit enhanced charge carrier transport, amended separation of photogenerated electrons and holes, prolonged hole lifetime and increased charge carrier density. Surface modification of CoB and FeB significantly enhances the photocurrent density of WO₃ photoanodes from 0.53 to 0.83 and 0.85 mA cm^-2, respectively, in transient chronoamperometry (CA) at 1.23 V vs. RHE (V_RHE) under interrupted illumination in 0.1 M Na₂SO₄ electrolyte (pH 7), corresponding to an increase of 1.6 relative to pristine WO₃. In contrast, the pristine MB thin film electrodes do not produce noticeable photocurrent during water oxidation. The metal boride catalysts transform in situ to a core-shell structure with a metal boride core and a metal oxide (MO, M = Co, Fe) surface layer. When coupled to WO₃ thin films, the CoB@CoO_x nanostructures exhibit a higher catalytic enhancement than corresponding pure cobalt borate (Co-B_i) and cobalt hydroxide (Co(OH)_x) electrocatalysts. Our results emphasize the role of the semiconductor-electrocatalyst interface for photoelectrodes and their high dependency on materials combination.