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

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 CO₂ electroreduction process (CO₂ 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 (Zn₁ Mn₁ -SNC) derived from S,N-coordinated Zn-Mn dimers anchored on a metal-organic framework (MOF). In Zn₁ Mn₁ -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 Zn₁ Mn₁ -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 CO₂ RR activity on DASC. The structure-property correlation found in this study suggests new ideas for the development of highly accessible atomic catalysts.