Regulating the Rate-Determining Step of Urea Oxidation Over a Vanadium Single Atom Incorporated Co Hydroxide Electrocatalyst

Urea oxidation reaction (UOR) has emerged as a competitive approach for many energy-related technologies due to the low overpotential and fast reaction dynamics. The main challenge lies in fabricating high-efficient catalysts with optimized electronic structure and understanding the intrinsic structure-related mechanisms. Here, we report a feasible strategy of regulating the rate-determining step (RDS) of UOR via an electrochemical reconstructed Co hydroxide catalyst incorporated with V single atoms. The optimal catalysts exhibit an enhanced UOR performance after V incorporation while remarkably suppressed the competitive oxygen evolution. Operando synchrotron-radiation Fourier transform infrared spectroscopy (SR-FTIR) combining density functional theory (DFT) calculations reveal that enabled by single atom V incorporation, the RDS of UOR has been changed from the first deprotonation step to the second one with a lower energy barrier, which is thermodynamically favorable for the overall reaction process