Zheng Yajun, Yao Hedan, Di Ruinan, Xiang Zhicheng, Wang Qiang, Lu Fangfang, Li Yu, Yang Guangxing, Ma Qiang, Zhang Zhiping
School of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an, 710065, China.
School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, 211816, China.
Nat Commun. 2022 May 11;13(1):2577. doi: 10.1038/s41467-022-30289-5.
Catalytic reduction of CO over Cu-based catalysts can produce various carbon-based products such as the critical intermediate CO, yet significant challenges remain in shedding light on the underlying mechanisms. Here, we develop a modified triple-stage quadrupole mass spectrometer to monitor the reduction of CO to CO in the gas phase online. Our experimental observations reveal that the coordinated HO on Cu(I)-based catalysts promotes CO adsorption and reduction to CO, and the resulting efficiencies are two orders of magnitude higher than those without HO. Isotope-labeling studies render compelling evidence that the O atom in produced CO originates from the coordinated HO on catalysts, rather than CO itself. Combining experimental observations and computational calculations with density functional theory, we propose a detailed reaction mechanism of CO reduction to CO over Cu(I)-based catalysts with coordinated HO. This study offers an effective method to reveal the vital roles of HO in promoting metal catalysts to CO reduction.
在铜基催化剂上催化还原一氧化碳可生成各种碳基产物，如关键中间体一氧化碳，但要阐明其潜在机制仍面临重大挑战。在此，我们开发了一种改进的三级四极杆质谱仪，用于在线监测气相中一氧化碳还原为一氧化碳的过程。我们的实验观察结果表明，基于Cu(I)的催化剂上配位的羟基促进了一氧化碳的吸附和还原为一氧化碳，其产生的效率比没有羟基时高出两个数量级。同位素标记研究提供了令人信服的证据，表明生成的一氧化碳中的氧原子源自催化剂上配位的羟基，而非一氧化碳本身。结合实验观察结果以及基于密度泛函理论的计算，我们提出了在具有配位羟基的Cu(I)基催化剂上一氧化碳还原为一氧化碳的详细反应机理。这项研究提供了一种有效的方法来揭示羟基在促进金属催化剂还原一氧化碳中的重要作用。
