Effect of copper cluster on reaction pathways of carbon dioxide hydrogenation on magnesium hydride surface

Abstract

Understanding the reaction mechanism of CO2 hydrogenation to produce value-added chemicals is essential for the rational design of catalysts to improve reaction activity and product selectivity. In this work, the first-principles calculations based on density functional theory were employed to study the effect of copper cluster on product selectivity in CO2 hydrogenation utilizing magnesium hydride as hydrogen source. The results show that on pristine MgH2 (0 0 1), CO2 molecule adsorbs on the surface with an O atom close to Mg atom, and the hydrogenation reaction follows formate pathway to yield CH3OH with an energy barrier only 1.09 eV for the rate-limiting step; however, the production of the most accessible C2-based product (CH2OH)2 needs to overcome an energy barrier up to 1.94 eV. On MgH2 (0 0 1) with Cu7 cluster, the C atom of CO2 molecule can strongly adsorb on a Cu atom of Cu7 cluster, and the hydrogenation more likely proceeds through reverse water-gas shift pathway, in which it is easy to generate C2 product C2H4 by the coupling of intermediate H2C*, with an energy barrier only 1.53 eV for the rate-limiting step. The findings utilizing transition metal cluster to change the reaction pathway and product selectivity of CO2 hydrogenation on magnesium hydride can provide novel perspectives for the design of catalysts.