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.