Highly Selective Ammonia Oxidation on BiVO₄ Photoanodes Co-catalyzed by Trace Amounts of Copper Ions

High-efficient photoelectrocatalytic direct ammonia oxidation reaction (AOR) conducted on semiconductor photoanodes remains a substantial challenge. Herein, we develop a strategy of simply introducing ppm levels of Cu ions (0.5-10 mg/L) into NH3 solutions to significantly improve the AOR photocurrent of bare BiVO4 photoanodes from 3.4 to 6.3 mA cm(-2) at 1.23 V-RHE, being close to the theoretical maximum photocurrent of BiVO4 (7.5 mA cm(-2)). The surface charge-separation efficiency has reached 90 % under a low bias of 0.8 V-RHE. This AOR exhibits a high Faradaic efficiency (FE) of 93.8 % with the water oxidation reaction (WOR) being greatly suppressed. N-2 is the main AOR product with FEs of 71.1 % in aqueous solutions and FEs of 100 % in non-aqueous solutions. Through mechanistic studies, we find that the formation of Cu-NH3 complexes possesses preferential adsorption on BiVO4 surfaces and efficiently competes with WOR. Meanwhile, the cooperation of BiVO4 surface effect and Cu-induced coordination effect activates N-H bonds and accelerates the first rate-limiting proton-coupled electron transfer for AOR. This simple strategy is further extended to other photoanodes and electrocatalysts.