Insights into catalyst reconstruction: Towards rational design of advanced CO2 hydrogenation catalysts

Advancing the development of CO(2 )hydrogenation reaction to address the environmental challenges stemming from excessive CO2 emissions requires the rational design of outstanding catalysts. The severe conditions of CO2 hydrogenation reaction often result in the structural reconstruction of the catalyst. For catalysts, the identification of structural reconstructions, understanding the structure-performance relationships and the manipulation of reconstruction are critical issues. However, practical reactions often involve complex reconstructive behaviors (the dynamic changes of phase, morphology, interface, and chemical state) in catalysts. In this review, we discuss the fundamental types of catalyst reconstruction behavior and the correlation between reconstruction behavior and catalytic performance. Subsequently, in situ characterization techniques and theoretical simulation calculations for monitoring the reconstruction behavior under operational conditions were introduced. The external and internal triggers of catalyst structural reconstruction are further discussed. Finally, the strategies for manipulating catalyst reconstruction are proposed. From the perspective of active site evolution, it can stabilize the active site in the reaction and maintain high activity for a long time. From the point of view of electronic structure, the enhancement of electron transfer creates a prominent charge density gradient, resulting in a change in the adsorption site and capacity of the adsorbed species. This review provides new insights into the structural reconstruction and true active sites of CO2 hydrogenation catalysts, offering guidance for the rational design of advanced catalysts.