Tuning the local electronic structure of Co15V-ZIF through bimetallic synergies as a bifunctional electrocatalyst for overall water splitting

Co-based bimetallic zeolite imidazolate frameworks (ZIFs) have been shown as promising electrocatalysts for the oxygen evolution reaction, but their electronic structure's influence on the catalytic performance for overall water splitting still needs further investigation. In this study, Co₁₅V-ZIF, structured as two-dimensional (2D) nanosheet arrays, are grown on nickel foam using one-step co-precipitation strategy. Owing to the synergistic effects of vanadium (V) and cobalt (Co) reasonably regulating the electronic structure, the synthesized bimetallic ZIFs demonstrate superior catalytic performance, which required the overpotentials of only 227 and 68 mV to achieve a current density of 10 mA cm^-2 in 1 M KOH for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. Furthermore, the water electrolyzer assembled with bimetallic ZIF as cathode and anode exhibits the capability to achieve 10 mA cm^-2 at a low cell voltage of 1.57 V. In situ Raman spectroscopy reveals that the introduction of V facilitates the formation of V-CoOOH, the real active site for OER, at lower applied potentials. Besides, it induces a local acidic environment on V-Co(OH)₂, the real active sites, thereby enhancing the HER performance of the sample. Density Functional Theory (DFT) calculations further show that the synergistic effects of V and Co induce electron redistribution, thereby improving electrical conductivity, reducing the energy barrier for water dissociation and hydrogen adsorption, which promotes the formation of H₃O⁺ and triggering H₃O⁺-induced water reduction in alkaline media. This work provides new insight into tailoring electronic structures to rationally design highly efficient ZIF electrocatalysts.