Highly Selective Ammonia Oxidation on BiVO 4 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 NH ₃ solutions to significantly improve the AOR photocurrent of bare BiVO ₄ photoanodes from 3.4 to 6.3 mA cm ^-2 at 1.23 V _RHE , being close to the theoretical maximum photocurrent of BiVO ₄ (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-NH ₃ complexes possesses preferential adsorption on BiVO ₄ surfaces and efficiently competes with WOR. Meanwhile, the cooperation of BiVO ₄ 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.
(© 2023 Wiley-VCH GmbH.)