Chen Jin-You, Liu Yi, Ma Tong-Mei, Li Zi-Yu, Li Xiao-Na
China School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Tianhe District, Guangzhou 510641, P. R. China.
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, P. R. China.
Inorg Chem. 2024 Oct 14;63(41):19179-19187. doi: 10.1021/acs.inorgchem.4c02767. Epub 2024 Oct 3.
Catalytic NO reduction by CO into N and CO is imperative owing to the increasingly rigorous emission regulation. Identifying the nature of active sites that govern the reactivity and selectivity of NO reduction is pivotal to tailor catalysts, while it is extremely challenging because of the complexity of real-life systems. Guided by our newly discovered triatomic Lewis acid-base-acid (LABA, Ce-Rh-Ce) site that accounts for the selective reduction of NO into N catalyzed by the RhCeO cluster in gas-phase experiments, the reactivity of the RhMO (M = Ta, V, and Al) clusters in catalytic NO reduction by CO was explored. We determined theoretically that the LABA site still prevails to reduce NO to N mediated by RhTaO and RhVO, and the strong M-oxygen affinity was emphasized to construct the LABA site. An overall assessment highlights that RhVO functions as a more promising catalyst because the well-fitting V-O bonding strength facilitates both elementary reactions of NO reduction and CO oxidation.
由于排放法规日益严格，通过一氧化碳将催化还原一氧化氮生成氮气和二氧化碳势在必行。确定控制一氧化氮还原反应活性和选择性的活性位点的性质对于定制催化剂至关重要，然而由于实际系统的复杂性，这极具挑战性。在我们新发现的三原子路易斯酸碱酸（LABA，铈-铑-铈）位点的指导下（该位点在气相实验中解释了由RhCeO簇催化的一氧化氮选择性还原为氮气的过程），我们探索了RhMO（M = 钽、钒和铝）簇在一氧化碳催化还原一氧化氮中的反应活性。我们从理论上确定，LABA位点在由RhTaO和RhVO介导的将一氧化氮还原为氮气的过程中仍然占主导地位，并且强调了强的M-氧亲和力对于构建LABA位点的作用。全面评估突出表明，RhVO是一种更有前景的催化剂，因为拟合良好的V-O键强度有利于一氧化氮还原和一氧化碳氧化的基本反应。
