Chang Xiaowei, Yu Chengying, Yang Chen, Xie Huizhi, Xia Shucai, Fang Zihao, Li Junhao, Zhang Sijia, Liu Fangfang, Wang Tianjun, Tan Yuan, Chen Xingkun, Shi Song, Guo Qing, Xu Qian, Hu Jun, Ding Honghe, Huang Chuanqi, Zhou Chuanyao, Zhu Junfa, Yang Xueming, Yang Wenshao
Hangzhou Institute of Advanced Studies, Zhejiang Normal University, Hangzhou 311231, China.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
J Am Chem Soc. 2025 May 14;147(19):16164-16170. doi: 10.1021/jacs.5c00807. Epub 2025 Apr 30.
CO activation is of great significance for resource utilization and environmental protection, but remains a major challenge. Here, we present a study of CO activation and dissociation on a single crystal Co(101̅0) surface below 150 K via combined surface techniques and DFT calculations. Our study reveals that the groove site of the Co(101̅0) surface provides an ideal anchor for a surface-confined bent CO, showing tridentate coordination with the surface. With this understanding, a cobalt nanocrystal catalyst containing groove sites was developed, high activity and high selectivity for conversion of CO to CO by the reverse water-gas shift reaction were acquired. The nanocrystal catalyst with these groove sites appears to be much more active in comparison to the catalysts without such sites. This study provides key insights into the active sites and activation configuration for moderate-condition CO activation and precise atomic-level design of confinement-controlled heterogeneous catalysts.
一氧化碳（CO）活化对于资源利用和环境保护具有重要意义，但仍然是一个重大挑战。在此，我们通过结合表面技术和密度泛函理论（DFT）计算，对150 K以下单晶Co(101̅0)表面上的CO活化和解离进行了研究。我们的研究表明，Co(101̅0)表面的沟槽位点为表面受限的弯曲CO提供了理想的锚定位置，显示出与表面的三齿配位。基于这一认识，开发了一种含有沟槽位点的钴纳米晶催化剂，通过逆水煤气变换反应将CO转化为CO₂时获得了高活性和高选择性。与没有这些位点的催化剂相比，具有这些沟槽位点的纳米晶催化剂似乎活性更高。这项研究为温和条件下CO活化的活性位点和活化构型以及限域控制的多相催化剂的精确原子级设计提供了关键见解。
