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

Zhang, Bingxing; Zhang, Jianling; Shi, Jinbiao; Tan, Dongxing; Liu, Lifei; Zhang, Fanyu; Lu, Cheng; Su, Zhuizhui et al. · Nat Commun · 2019

basic_science · Level V

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Abstract

Developing highly efficient electrocatalysts based on cheap and earth-abundant metals for CO<sub>2</sub> 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 CO<sub>2</sub> reduction exhibits a maximum CO faradaic efficiency of 97% and high current density of ~10 mA cm<sup>-2</sup> at a low overpotential of 0.49 V. Moreover, the turnover frequency can reach 38347 h<sup>-1</sup> at overpotential of 0.49 V, which is the highest among the reported heterogeneous electrocatalysts for CO<sub>2</sub> 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 CO<sub>2</sub> reduction performance.