Rational Pathways Tuning Facilitates Photoelectrochemical Upcycling of Nitrite to Ammonia Using CuPd Nanoalloy on GaN/Si Photocathode

作者：Kejian Li, Tianyin Qiu, Bingxing Zhang, Zhengwei Ye, Jan Paul Menzel, Wan Jae Dong, Yuyang Pan, Songtao Tang, Zhuoran Long, Víctor S. Batista, Zetian Mi · 发表于：Environmental Science & Technology · 年份：2025 · DOI：10.1021/acs.est.5c04038 · 被引用次数：6 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Advanced Photocatalysis Techniques、Caching and Content Delivery

Solar-driven photoelectrochemical conversion of nitrite to ammonia represents a sustainable yet unexplored approach for environmental remediation and resource recovery. Here, we demonstrate that Cu 5 Pd 1 alloy nanoparticles, integrated with vertically grown GaN nanowires on an n + -p Si photocathode (Cu 5 Pd 1 /GaN/Si), enable highly efficient and selective nitrite reduction to ammonia. This photoelectrode achieves a Faradaic efficiency of 99.7% for NH 3, with a yield rate of 162.2 μmol h –1 cm –2 and a nearly 100% selectivity. Additionally, the Cu 5 Pd 1 /GaN/Si photoelectrode maintains robust performance in the presence of various anions and can effectively remove ∼98% of nitrite even at low concentrations. Density functional theory calculations, supported by in situ spectroscopic techniques, reveal that Cu–Pd alloying fundamentally alters the nitrite reduction mechanisms. Unlike the *NOH-mediated pathway on Cu and Pd, which can lead to competing N 2 formation, the CuPd alloy preferentially stabilizes the *NHO intermediate, making NH 3 production thermodynamically preferred and highly selective. These findings highlight that a rational electrocatalyst design can effectively tune reaction pathways to enhance both the efficiency and selectivity of photoelectrocatalytic nitrite upcycling.