Integrating Host Design and Tailored Electronic Effects of Yolk–Shell Zn−Mn Diatomic Sites for Efficient CO₂ Electroreduction

Abstract Modulating the surface and spatial structure of the host is associated with the reactivity of the active site, and also enhances the mass transfer effect of the CO 2 electroreduction process (CO 2 RR). Herein, we describe the development of two‐step ligand etch–pyrolysis to access an asymmetric dual‐atomic‐site catalyst (DASC) composed of a yolk–shell carbon framework (Zn 1 Mn 1 ‐SNC) derived from S,N‐coordinated Zn−Mn dimers anchored on a metal–organic framework (MOF). In Zn 1 Mn 1 ‐SNC, the electronic effects of the S/N−Zn−Mn−S/N configuration are tailored by strong interactions between Zn−Mn dual sites and co‐coordination with S/N atoms, rendering structural stability and atomic distribution. In an H‐cell, the Zn 1 Mn 1 ‐SNC DASC shows a low onset overpotential of 50 mV and high CO Faraday efficiency of 97 % with a low applied overpotential of 343 mV, thus outperforming counterparts, and in a flow cell, it also reaches a high current density of 500 mA cm −2 at −0.85 V, benefitting from the high structure accessibility and active dual sites. DFT simulations showed that the S,N‐coordinated Zn−Mn diatomic site with optimal adsorption strength of COOH* lowers the reaction energy barrier, thus boosting the intrinsic CO 2 RR activity on DASC. The structure‐property correlation found in this study suggests new ideas for the development of highly accessible atomic catalysts.

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