Engineering Cu/Ru Heterointerface-Shelled Nanocavities by the Kirkendall Effect for Highly Efficient Nitrate Electroreduction to Ammonia

作者：Shuangqun Chen, Zhouhao Zhu, Kepeng Song, Hengrui Zhang, Dan Luo, Tong Cao, Yongtu Zou, Changxu Liu, Li‐Yong Gan, Daliang Zhang, Yu Han, Jianfeng Huang · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c11097 · 被引用次数：48 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Caching and Content Delivery、Advanced Photocatalysis Techniques

Electrochemical nitrate (NO 3 – ) reduction to ammonia (NH 3 ) offers a sustainable approach for NH 3 synthesis while concurrently addressing NO 3 – pollution. However, achieving efficient NO 3 – -to-NH 3 conversion remains challenging due to sluggish multistep proton-coupled electron transfer processes and poor intermediate converison. Here, we present a nanocatalyst featuring a hollow nanocavity encased within a shell rich in Cu/Ru heterointerfaces, which synergistically leverages both interfacial and structural advantages to effectively lower energy barriers and accelerate intermediate conversion kinetics, thereby enhancing the overall catalytic performance for NH 3 production. Density functional theory (DFT) computations, supported by operando and control experiments, reveal that CuRu heterointerfaces with their optimized electronic structure act as the primary active sites, establishing a favorable NO 3 – -to-NH 3 reaction pathway. Simultaneously, the catalytic synergy between Cu and CuRu sites enables tandem catalysis, which is further amplified by nanocavity-induced spatial confinement of the key intermediate NO 2 – . This nanocatalyst is realized via a Kirkendall effect–driven strategy, with its structural features systematically optimized. The resulting catalyst demonstrates outstanding NH 3 production performance in a 0.1 M KNO 3 + 0.1 M KOH electrolyte, delivering a Faradaic efficiency of 97.4%, a yield of 152.6 mg h –1 mg metal –1, and an energy efficiency of 40% ...