Well-Defined Cu Precatalysts Indicate Design Rules for Reactivity in Nitrate Electroreduction

作者：Jiahui Du, Anna Loiudice, Krishna Kumar, Ludovic Zaza, Raffaella Buonsanti · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c09246 · 被引用次数：20 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Caching and Content Delivery、Advanced Photocatalysis Techniques

High Resolution Image Download MS PowerPoint Slide The electrochemical nitrate reduction reaction (NO 3 RR) to ammonia (NH 3 ) is a promising route for sustainable NH 3 synthesis. Cu-based materials are the most used and promising catalysts for this reaction. However, Cu undergoes uncontrollable compositional and structural changes under NO 3 RR conditions, necessitating a deeper understanding of the relationship between precatalyst features, structural evolution, and catalytic performance for the advancement of current catalyst design rules. Here, we exploit well-defined Cu and Cu oxide nanocrystals (NCs) as precatalysts to elucidate these correlations. We find that the size, shape, and oxide content of the Cu precatalysts all play a role in driving structural evolution and, thus, the catalytic behavior during NO 3 RR. In particular, a higher oxide content, an optimized {111}/{100} facet ratio, and the spatial proximity of these facets forming grain boundaries within the active catalysts emerge as key factors to enhance NH 3 selectivity. Among the studied Cu precatalysts, 10 nm Cu spheres integrate these key features, achieving a competitive NH 3 production rate compared to the state of the art. This work links pre- and in situ-formed catalyst features to catalytic performance, offering insights into the morphological dynamics of Cu catalysts under NO 3 RR conditions.