Cheng Dongfang, Nguyen Khanh-Ly C, Sumaria Vaidish, Wei Ziyang, Zhang Zisheng, Gee Winston, Li Yichen, Morales-Guio Carlos G, Heyde Markus, Roldan Cuenya Beatriz, Alexandrova Anastassia N, Sautet Philippe
Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA, USA.
Department of Interface Science, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, Berlin, Germany.
Nat Commun. 2025 Apr 30;16(1):4064. doi: 10.1038/s41467-025-59267-3.
Cu is the most promising metal catalyst for CO electroreduction (CORR) to multi-carbon products, yet the structure sensitivity of the reaction and the stability versus restructuring of the catalyst surface under reaction conditions remain controversial. Here, atomic scale simulations of surface energies and reaction pathway kinetics supported by experimental evidence unveil that CORR does not take place on perfect planar Cu(111) and Cu(100) surfaces but rather on steps or kinks. These planar surfaces tend to restructure in reaction conditions to the active stepped surfaces, with the strong binding of CO on defective sites acting as a thermodynamic driving force. Notably, we identify that the square motifs adjacent to defects, not the defects themselves, as the active sites for CORR via synergistic effect. We evaluate these mechanisms against experiments of CORR on ultra-high vacuum-prepared ultraclean Cu surfaces, uncovering the crucial role of step-edge orientation in steering selectivity. Overall, our study refines the structural sensitivity of CORR on Cu at the atomic level, highlights the self-activation mechanism and elucidates the origin of in situ restructuring of Cu surfaces during the reaction.
铜是将CO电还原（CORR）为多碳产物最具前景的金属催化剂，但该反应的结构敏感性以及在反应条件下催化剂表面相对于重构的稳定性仍存在争议。在此，由实验证据支持的表面能和反应路径动力学的原子尺度模拟揭示，CORR并非发生在完美的平面Cu(111)和Cu(100)表面，而是发生在台阶或扭结处。这些平面表面在反应条件下倾向于重构为活性台阶表面，CO在缺陷位点上的强吸附作为热力学驱动力。值得注意的是，我们通过协同效应确定，与缺陷相邻的方形图案而非缺陷本身是CORR的活性位点。我们根据在超高真空制备的超清洁Cu表面上进行的CORR实验评估了这些机制，揭示了台阶边缘取向在控制选择性方面的关键作用。总体而言，我们的研究在原子水平上细化了CORR在Cu上的结构敏感性，突出了自激活机制，并阐明了反应过程中Cu表面原位重构的起源。
