Vibronic Coupling of Adjacent Single-Atom Co and Zn Sites for Bifunctional Electrocatalysis of Oxygen Reduction and Evolution Reactions

With the goal of improving the activity of single-atom catalysts, in-depth investigations were performed to design adjacent single-metal sites to produce a modulation effect by using symmetry breaking as an indicator of tuning the electronic structure. A CoN4-ZnN4/C catalyst composed of adjacent Co and Zn sites anchoredon nitrogen-doped graphene was predicted by first-principle calculations to exhibitpromising bifunctional electrocatalytic activity for oxygen reduction and evolution reactions with an overpotential of 0.225 and 0.264 V, respectively, which is superior toCoN4/C catalysts and outperforms commercial Pt/C and IrO2benchmarks. Theimpressive catalytic activity originates from the remarkable asymmetric deformation and strong pseudo-Jahn-Teller vibronic coupling effect, through which the Zn siteacts as a modulator to induce the symmetry-breaking phenomenon and tune the d-band structure and binding strength between key intermediates and the Co site. It provides mechanism-based insight for applying diatomic site catalysts for catalytic reactions and further understanding of the modulation effect

Automated summary

This study investigates the use of adjacent single-metal sites as a way to improve the activity of single-atom catalysts through a modulation effect. By using first-principle calculations, a CoN4-ZnN4/C catalyst anchored on nitrogen-doped graphene is predicted to show promising electrocatalytic activity for oxygen reduction and evolution reactions, outperforming commercial benchmarks. The enhanced catalytic activity is attributed to the asymmetric deformation and pseudo-Jahn-Teller vibronic coupling effect induced by the Zn site.