Liang Haojie, Zhang Bin, Hong Mei, Yang Xinchun, Zhu Ling, Liu Xingchen, Qi Yuntao, Zhao Shichao, Wang Guofu, van Bavel Alexander P, Wen Xiaodong, Qin Yong
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, 030001, Taiyuan, China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China.
Angew Chem Int Ed Engl. 2024 Mar 18;63(12):e202318747. doi: 10.1002/anie.202318747. Epub 2024 Feb 12.
Metal atoms on the support serve as active sites for many heterogeneous catalysts. However, the active metal sites on the support are conventionally described as static, and the intermediates adsorbed on the support far away from the active metal sites cannot be transformed. Herein, we report the first example of operando mobile catalysis to promote catalytic efficiency by enhancing the collision probability between active sites and reactants or reaction intermediates. Specifically, ligand-coordinated Pt single atoms (isolated MeCpPt- species) are bonded on CeO and transformed into mobile MeCpPt(H)CO complexes during the reverse water gas shift reaction for operando mobile catalysis. This strategy enables the conversion of inert carbonate intermediates on the CeO support. A turnover frequency (TOF) of 6358 mol CO mol ⋅ h and 99 % CO selectivity at 300 °C is obtained for reverse water gas shift reaction, dramatically higher than those of Pt catalysts reported in the literature. Operando mobile catalysis presents a promising strategy for designing high-efficiency heterogeneous catalysts for various chemical reactions and applications.
载体上的金属原子是许多多相催化剂的活性位点。然而，传统上认为载体上的活性金属位点是静态的，吸附在远离活性金属位点的载体上的中间体无法发生转化。在此，我们报道了首例通过提高活性位点与反应物或反应中间体之间的碰撞概率来促进催化效率的原位动态催化实例。具体而言，配体配位的铂单原子（孤立的MeCpPt-物种）键合在CeO上，并在逆水煤气变换反应过程中转化为可移动的MeCpPt(H)CO配合物，用于原位动态催化。该策略能够实现CeO载体上惰性碳酸盐中间体的转化。对于逆水煤气变换反应，在300 °C时获得了6358 mol CO mol ⋅ h的周转频率（TOF）和99 %的CO选择性，显著高于文献报道的铂催化剂。原位动态催化为设计用于各种化学反应和应用的高效多相催化剂提供了一种有前景的策略。
