Theoretical prediction of the reaction mechanism underlying the active phase of Bn (n = 3–5) and Cu-doped electron deficient Bn-1 clusters: Reduction of CO2

Abstract

In this work, we use density functional theory (DFT) method to study the catalytic role of Bn (n = 3–5) and Cu-doped B clusters in CO2 hydrogenation reduction reaction. The results show that CuBn-1 reduces the adsorption capacity of reactants and intermediates compared with Bn clusters, indicating that the catalytic performance of electron-deficient clusters is better. The energy barrier of CO2 reduction to CO on Bn and CuBn-1 clusters is 0.65 eV and 0.58 eV, respectively. Cu doping reduces the CO2 catalytic reduction ability of Bn clusters. In addition, our results show that the rate of CO2 catalytic reduction reaction is directly proportional to temperature, and the reaction is rapid under high temperature conditions. In summary, the theoretical results support the mechanism of CO2 reduction reaction, that is, the key role of promoting CO2 hydrogenation through formic acid intermediates.