Operando Tracking of Hydrazine Intermediate Reveals the Gerischer–Marcus Pathway for Ammonia Electrooxidation on Oxygen‐Deficient CuO

作者：Yan Du, Hua Li, Yuhui Yin, Dina Sun, Ning Li, Baodui Wang · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202524377 · 被引用次数：6 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、CO2 Reduction Techniques and Catalysts、Electrocatalysts for Energy Conversion

Abstract The ammonia electrooxidation reaction (AOR) represents a pivotal process for sustainable energy technologies, yet its mechanism on non‐precious metal catalysts remains ambiguous, primarily due to the elusive nature of key reaction intermediates. Specifically, the role of oxygen vacancies (Ov) in steering the AOR pathway is not well understood. Herein, we directly captured the hydrazine (N 2 H 4 ) intermediate, which unequivocally confirms the operation of the Gerischer–Marcus (G–M) pathway on oxygen‐deficient copper oxide (CuO). This breakthrough was enabled by an aggregation‐induced emission electrochemiluminescence (AIE‐ECL) probe, which allows quantitative, real‐time detection of N 2 H 4 with ultrahigh sensitivity (0.163 nM). The direct visualization of probe consumption via fluorescence microscopy imaging provided orthogonal validation. Combined with in situ spectroscopy and DFT calculations, we establish that oxygen vacancies (Ov) act as a “steering wheel” to preferentially stabilize N 2 H 4 and channel the reaction preferentially along the G–M route. A direct correlation between Ov concentration and N 2 H 4 accumulation is demonstrated, linking atomic‐scale defect structure to macroscopic catalytic performance. This work not only presents a paradigm for probing elusive electrocatalytic intermediates but also delivers a fundamental principle for influencing reaction pathways through defect engineering.