Highly efficient binary copper-iron catalyst for photoelectrochemical carbon dioxide reduction toward methane

A rational design of an electrocatalyst presents a promising avenue for solar fuels synthesis from carbon dioxide (CO2) fixation but is extremely challenging. Herein, we use density functional theory calculations to study an inexpensive binary copper-iron catalyst for photoelectrochemical CO2 reduction toward methane. The calculations of reaction energetics suggest that Cu and Fe in the binary system can work in synergy to significantly deform the linear configuration of CO2 and reduce the high energy barrier by stabilizing the reaction intermediates, thus spontaneously favoring CO2 activation and conversion for methane synthesis. Experimentally, the designed CuFe catalyst exhibits a high current density of -38.3 mA.cm(-2) using industry-ready silicon photoelectrodes with an impressive methane Faradaic efficiency of up to 51%, leading to a distinct turnover frequency of 2,176 h(-1) under air mass 1.5 global (AM 1.5G) one-sun illumination.