Dynamic Surface Restructuring Driven Formation of a Highly Polarized CO Species on a Defected Copper Surface

作者：Jun Cai, Jiayu Lv, Kai Zhou, Shui Lin, Xinyi Zhang, Yijing Zang, Lu Wang, Yang Gu, Tao Zhang, Hui Zhang, Zhu‐Jun Wang, Bo Yang, Mingshu Chen, Fan Yang, Yimin Li, Zhi Liu · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c12851 · 被引用次数：4 · 研究领域：CO2 Reduction Techniques and Catalysts、Catalysts for Methane Reforming、Ammonia Synthesis and Nitrogen Reduction

High Resolution Image Download MS PowerPoint Slide The catalytic versatility of the copper surface calls for a fundamental understanding of the formation and reactivity of key intermediates in various C 1 catalytic conversions such as water–gas shift reaction, CO/CO 2 hydrogenation, and electrochemical reduction reactions. Here, based on in situ spectroscopic and morphological evidence, we demonstrate the formation of a bridge CO* species through the adsorption-induced restructuring of a defect-rich Cu surface and its reactivity toward C–O bond dissociation and C–C coupling under hydrogenation reaction conditions. In corroboration with computational simulations, we attribute the unexpected reactivity to its enhanced adsorption strength and polarity with respect to commonly observed on-top CO* species. Our findings provide new insights into the strong correlation between the surface defect density and the selectivity toward methane, C 2 hydrocarbons, and oxygenates over Cu-based catalysts. The marked impact on reactivity highlights the crucial role of dynamic surface restructuring in determining the reaction selectivity over copper-based catalysts.