Tuning interfacial electronic coupling at Ni–Zn dual-atom sites for efficient CO₂ electroreduction

Rational design of catalytic interfaces at the atomic level is crucial for enhancing electrocatalytic CO₂ reduction. In this study, a Zeolite imidazolate frameworks-8 derived catalyst is developed, featuring atomically dispersed Ni–Zn dual-atom sites (NiZnN₆) coexisting with Ni₃ZnC_0.7 nanoparticles on nitrogen-doped carbon nanotubes. Strong interaction between the NiZnN₆ moieties and Ni₃ZnC_0.7 nanoparticle induces charge redistribution, enhancing the electron-donating ability of Ni active sites. Simultaneously, the dual-atom configuration creates an asymmetric electronic environment, where interfacial electronic coupling facilitates partial electron transfer from Zn to Ni, leading to electron enrichment at the Ni center. Consequently, Ni sites preferentially donate electrons to active CO₂ molecules, lowering the *COOH formation energy, while Zn sites promote *CO desorption, thus achieving high CO selectivity (99.6 %@−0.7 V vs. Reversible Hydrogen Electrode (RHE)). The in-depth investigation in this work provides guidance for establishing the relationship between structure and electrocatalytic activity, holding significant implications for fundamental research on the CO₂ reduction mechanism.