Liu Tianfu, Song Guohui, Liu Xiaoju, Chen Zhou, Shen Yu, Wang Qi, Peng Zhangquan, Wang Guoxiong
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.
University of Chinese Academy of Sciences, Beijing 100039, China.
iScience. 2023 Sep 19;26(10):107953. doi: 10.1016/j.isci.2023.107953. eCollection 2023 Oct 20.
Copper single-atom alloy catalysts (M@Cu SAAs) have shown great promise for electrochemical CO reduction reaction (CORR). However, a clear understanding of the CORR process on M@Cu SAAs is still lacking. This study uses density functional theoretical (DFT) calculations to obtain a comprehensive mechanism and the origin of activity of M@Cu SAAs. The importance of the adsorption mode of M@Cu is revealed: key intermediates either adsorbed in the adjacent hollow site around Cu atoms (AD mode) or adsorbed directly on the top site of M (SE mode). AD mode generally exhibits finely tuned binding strengths of key intermediates, which significantly enhances the activity of the catalysts. Increasing the coverage of ∗CO on the M@Cu with SE mode leads to relocation of the active site, resulting in improved activity of C products. The insights gained in this work have significant implications for rational design strategy toward efficient CORR electrocatalysts.
铜单原子合金催化剂（M@Cu SAA）在电化学CO还原反应（CORR）中展现出了巨大的潜力。然而，目前仍缺乏对M@Cu SAA上CORR过程的清晰理解。本研究采用密度泛函理论（DFT）计算来获得M@Cu SAA的全面反应机理和活性来源。揭示了M@Cu吸附模式的重要性：关键中间体要么吸附在Cu原子周围的相邻空心位点（AD模式），要么直接吸附在M的顶部位点（SE模式）。AD模式通常表现出对关键中间体的精细调节结合强度，这显著提高了催化剂的活性。增加SE模式下M@Cu上*CO的覆盖度会导致活性位点的重新定位，从而提高C产物的活性。这项工作中获得的见解对高效CORR电催化剂的合理设计策略具有重要意义。
