Selective methanol production via CO2 reduction on Cu2O revealed by micro-kinetic study combined with constant potential model

High efficiency electrocatalysis of greenhouse gas CO2 2 to liquid fuel methanol attracts great attentions that allows energy transformation from renewable electric energy to storable chemical energy. Catalytically converting CO2 2 to methanol using green hydrogen is a promising pathway to achieve carbon neutrality. In this work, the catalytic activity and product selectivity of the electrochemical CO2 2 reduction reaction on Cu2O 2 O were studied using a micro-kinetic model based on Marcus charge transfer theory. The constant potential model under the grand-canonical ensemble enables the accurate description of binding energies and ground-state charge transfer upon surface adsorption as a function of electrode potential. Firstly, the potential-dependent activation energies and rate constants of all possible elementary reactions involved in CO2 2 reduction are calculated. Then, the surface coverage and its derivative can be obtained in a steady-state approximation. Finally, the total reaction rate and partial reaction rate can be deduced, allowing for direct comparison with catalytic activity (current density) and product selectivity (Faradaic efficiency). It is found that CH3OH 3 OH is the dominant product on the Cu2O(111) 2 O(111) surface, while CO is the main product on the Cu2O(110) 2 O(110) surface. Based on the derived total and partial reaction rates under the steady-state approximation, it is demonstrated that Cu2O(111) 2 O(111) exhibits the highest electrocatalytic activity and methanol selectivity at U =-0.6 V vs. SHE. This research presents a methodology for predicting apparent electrocatalytic performance from microscopic reaction energy calculations, which can be applied to other important electrocatalytic reaction mechanisms and performance predictions.