Understanding the role of Cu+/Cu0 sites at Cu2O based catalysts in ethanol production from CO2 electroreduction -A DFT study

Abstract

Cu₂O based electrocatalysts generally exhibit better selectivity for C₂ products (ethylene or ethanol) in electrochemical carbon dioxide reduction. The surface characteristic of the mixed Cu⁺ and Cu⁰ chemical state is believed to play an essential role that is still unclear. In the present study, density functional theory (DFT) calculations have been performed to understand the role of copper chemical states in selective ethanol formation using a partially reduced Cu₂O surface model consisting of adjacent Cu⁺/Cu⁰ sites. We mapped out the free energy diagram of the reaction pathway from CO intermediate to ethanol and discussed the relation between the formation of critical reduction intermediates and the configuration of Cu⁺/Cu⁰ sites. The results showed that Cu⁺ sites facilitate the adsorption and stabilization of *CO, as well as its further hydrogenation to *CHO. More importantly, as compared to the high reaction energy (1.23 eV) of the dimerization of two *CO on Cu⁺/Cu⁰ sites, the preferable formation of *CHO on the Cu⁺ site makes the C–C coupling reaction with *CO on the Cu⁰ site happen under a relatively lower energy barrier of 0.58 eV. Furthermore, the post C–C coupling steps leading to the formation of the key intermediate *OCHCH₂ to C₂ compound are all thermodynamically favoured. Noteworthily, it is found that *OCHCH₂ inclines to the ethanol formation because the coordinatively unsaturated Cu⁺ site could maintain the C–O bond of *OCHCH₂, and the weak binding between *O and Cu⁺/Cu⁰ sites helps inhibit the pathway toward ethylene. These findings may provide guidelines for the design of CO and CO₂ reduction active sites with enhanced ethanol selectivity.