Nonequilibrium Laser Regulation of the Electronic Structure of the Ni‐Based Electrode for Boosting Nucleophilic Electrooxidation of Alcohols

Replacing the traditional oxygen evolution reaction with the alcohol oxidation reaction (AOR) can significantly reduce anodic overpotential and offer high‐value chemicals simultaneously. However, its progress is severely hampered by the intricate catalyst synthesis and inadequate control over the electronic structure of active sites. Here, we propose a strategy for nonequilibrium regulation of catalyst electronic structures via laser irradiation. By precisely modulating the number of laser pulses, the Ni 2+ /Ni 3+ ratio can be effectively tailored. The NiL‐100 electrode demonstrates excellent performance for the electrooxidation of multiple alcohols. Specifically, the current density of ethanol oxidation exceeds most of the Ni‐based catalysts reported so far, with 92.66% FE for acetic acid. Combining the first‐principles calculations, we establish the structure–activity relationship of catalysts: the laser‐tuned electronic structure optimizes the adsorption energy of reaction intermediates, then improves the catalytic activity. This work introduces an efficient, simple, green, and low‐cost method for the efficient manufacturing of self‐supporting electrodes that enables precise regulation of electronic structures, which will provide new insights for the large‐scale manufacturing of high‐performance catalysts.