MOF Encapsulating N‐Heterocyclic Carbene‐Ligated Copper Single‐Atom Site Catalyst towards Efficient Methane Electrosynthesis

Abstract

The exploitation of highly efficient carbon dioxide reduction (CO₂ RR) electrocatalyst for methane (CH₄ ) electrosynthesis has attracted great attention for the intermittent renewable electricity storage but remains challenging. Here, N-heterocyclic carbene (NHC)-ligated copper single atom site (Cu SAS) embedded in metal-organic framework is reported (2Bn-Cu@UiO-67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO₂ reduction to CH₄ at -1.5 V vs. RHE with a current density of 420 mA cm^-2 . The CH₄ FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s^-1 . The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO₂ to 2Bn-Cu, significantly increasing the availability of each catalytic center.