Promoted hydrogenation of CO2 to methanol over single-atom Cu sites with Na+ decorated microenvironment

Abstract Although single-atom Cu sites exhibit high efficiency in CO2 hydrogenation to methanol, they are prone to form Cu nanoparticles due to reduction and aggregation under reaction conditions, especially at high temperatures. Herein, single-atom Cu sites stabilized by adjacent Na+ ions have been successfully constructed within a metal-organic framework (MOF)-based catalyst, namely MOF-808-NaCu. It is found that the electrostatic interaction between the Na+ and Hδ− species plays a pivotal role in upholding the atomic dispersion of Cu in MOF-808-NaCu during CO2 hydrogenation, even at temperatures up to 275°C. This exceptional stabilization effect endows the catalyst with excellent activity (306 g·kgcat−1·h−1), high selectivity to methanol (93%), and long-term stability at elevated reaction temperatures, far surpassing the counterpart in the absence of Na+ (denoted as MOF-808-Cu). This work develops an effective strategy to the fabrication of stable single-atom sites for advanced catalysis by creating alkali-decorated microenvironment in close proximity.