Hollow structured Cu@ZrO2 derived from Zr-MOF for selective hydrogenation of CO2 to methanol

Abstract

The development of a highly efficient catalyst for CO2 activation and selective conversion to methanol is critical to address the issues associated with the high thermal stability of CO2 and controllable synthesis of methanol. Cu-based catalysts have been widely studied because of the low cost and excellent performance in mild conditions. However, the improvement of catalytic activity and selectivity remains challenging. Herein, we prepared hollow Cu@ZrO2 catalysts through pyrolysis of Cu-loaded Zr-MOF for CO2 hydrogenation to methanol. Low-temperature pyrolysis generated highly dispersed Cu nanoparticles with balanced Cu0/Cu+ sites, larger amounts of surface basic sites and abundant Cu-ZrO2 interface in the hollow structure, contributing to enhanced catalytic capacity for adsorption/activation of CO2 and selective hydrogenation to methanol. In situ Fourier Transform Infrared Spectroscopy revealed the methanol formation followed the formate-intermediated pathway. This work would provide a guideline for the design of high-performance catalysts and the understanding of the mechanism and active sites for CO2 hydrogenation to methanol.