Constructing Asymmetric Charge Polarized NiCo Prussian Blue Analogue for Promoted Electrocatalytic Methanol to Formate Conversion

Abstract The highly selective electrochemical conversion of methanol to formate is of great significance for various clean energy devices, but understanding the structure‐to‐property relationship remains unclear. Here, the asymmetric charge polarized NiCo prussian blue analogue (NiCo PBA‐100) is reported to exhibit remarkable catalytic performance with high current density (210 mA cm−2 @1.65 V vs RHE) and Faraday efficiency (over 90%). Meanwhile, the hybrid water splitting and Zinc–methanol‐battery assembled by NiCo PBA‐100 display the promoted performance with decent stability. X‐ray absorption spectroscopy (XAS) and operando Raman spectroscopy indicate that the asymmetric charge polarization in NiCo PBA leads to more unoccupied states of Ni and occupied states of Co, thereby facilitating the rapid transformation of the high‐active catalytic centers. Density functional theory calculations combining operando Fourier transform infrared spectroscopy demonstrate that the final reconstructed catalyst derived by NiCo PBA‐100 exhibits rearranged d band properties along with a lowered energy barrier of the rate‐determining step and favors the desired formate production.