Wang Si-Dun, Chen Jiao-Jiao, Ma Tong-Mei, Li Xiao-Na, He Sheng-Gui
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Tianhe District, Guangzhou 510641, P. R. China.
J Phys Chem Lett. 2023 May 18;14(19):4388-4393. doi: 10.1021/acs.jpclett.3c00767. Epub 2023 May 4.
By using state-of-the-art mass spectrometry and guided by the newly discovered single-electron mechanism (SEM; e.g., Ti + 2NO → Ti-O + NO), we determined experimentally that the vanadium-aluminum oxide clusters VAlO ( = 1-3) can catalyze the reduction of NO by CO and substantiated theoretically that the SEM still prevails in driving the catalysis. This finding marks an important step in cluster science in which a noble metal had been demonstrated to be indispensable in NO activation mediated by heteronuclear metal clusters. The results provide new insights into the SEM in which active V-Al cooperative communication favors the transfer of an unpaired electron from the V atom to NO attached to the Al atom on which the reduction reaction actually takes place. This study provides a clear picture for improving our understanding of related heterogeneous catalysis, and the electron hopping behavior induced by NO adsorption could be a fundamental chemistry for driving NO reduction.
通过使用最先进的质谱技术，并以新发现的单电子机制（SEM；例如，Ti + 2NO → Ti-O + NO）为指导，我们通过实验确定钒铝氧化物簇VAlO（ = 1-3）可以催化CO还原NO，并从理论上证实SEM在驱动催化过程中仍然占主导地位。这一发现标志着簇科学迈出了重要一步，此前已证明在异核金属簇介导的NO活化中贵金属是不可或缺的。结果为SEM提供了新的见解，其中活性V-Al协同通讯有利于未配对电子从V原子转移到附着在Al原子上的NO，还原反应实际上在Al原子上发生。这项研究为增进我们对相关多相催化的理解提供了清晰的图景，并且NO吸附诱导的电子跳跃行为可能是驱动NO还原的基础化学。
