Deciphering Atomic Structure of Active Sites on ZnO-ZrO ₂ Solid Solution for CO ₂ Hydrogenation to Liquid Sunshine Methanol

Abstract

The Hydrogenation of CO₂ with renewable H₂ to produce Liquid Sunshine methanol is one of the most attractive pathways to achieve carbon neutrality. The reaction to CO₂ hydrogenation to methanol is a typical reaction requiring simultaneous activation of CO₂ and H₂. ZnO-ZrO₂ solid solution catalyst has been demonstrated to be an excellent catalyst. However, it is not clear the actual surface configuration of Zn and Zr in the lattice and how CO₂ and H₂ are activated on the active sites. Here, the fine structure of ZnO-ZrO₂ catalyst characterized by neutron diffraction together with STEM and DFT indicates the coordination environment changes from isolated Zn dopant to (Zn)-O-Zr-O-(Zn), which acts as the active sites for efficient activation of H₂ and CO₂, leading to the superior catalytic activity of the ZnO-ZrO₂ catalyst. This work sheds light on the rational design of multi-site catalysts for multi-molecule reactions.

Keywords: CO2 hydrogenation, Methanol synthesis, ZnO-ZrO2, Solid solution catalyst, Liquid Sunshine