Manganese acting as a high-performance heterogeneous electrocatalyst in carbon dioxide reduction

Developing highly efficient electrocatalysts based on cheap and earth-abundant metals for CO₂ reduction is of great importance. Here we demonstrate that the electrocatalytic activity of manganese-based heterogeneous catalyst can be significantly improved through halogen and nitrogen dual-coordination to modulate the electronic structure of manganese atom. Such an electrocatalyst for CO₂ reduction exhibits a maximum CO faradaic efficiency of 97% and high current density of ~10 mA cm^-2 at a low overpotential of 0.49 V. Moreover, the turnover frequency can reach 38347 h^-1 at overpotential of 0.49 V, which is the highest among the reported heterogeneous electrocatalysts for CO₂ reduction. In situ X-ray absorption experiment and density-functional theory calculation reveal the modified electronic structure of the active manganese site, on which the free energy barrier for intermediate formation is greatly reduced, thus resulting in a great improvement of CO₂ reduction performance.