Bioinspired Catalyst Design Accelerated Proton Transfer Kinetics for 1,4‐Butanediol Electrooxidation in Flow‐Cell Electrolyzer

ABSTRACT The 1,4‐butanediol oxidation reaction (BDOR) provides a sustainable platform for producing valuable chemicals, yet its reaction kinetics remain constrained by inefficient proton transfer. Inspired by nature's enzymatic proton transfer systems, we report a bioinspired terephthalate‐modified NiFe‐catalyst (NiFe‐TPA) for efficient BDOR in a flow‐cell electrolyzer. Spectroscopic and mechanistic analyses revealed that TPA modification tailored the electronic and coordination environments and enhanced proton transfer kinetics during BDOR. As a result, NiFe‐TPA produced 100 mA cm −2 current density at 1.40 V vs. RHE for BDOR and 1.51 V vs. RHE for the oxygen evolution reaction (OER). When integrated into a flow cell, NiFe‐TPA required a cell voltage of 2.1 V, reaching 1 A current for BDOR‐assisted water electrolysis. Electrochemical analysis with in situ Raman spectroscopy indicated that NiFe‐TPA involved γ‐Ni(O)OH phase for OER while TPA mediated proton transfer enhancement for BDOR. Our findings establish a broadly applicable design strategy for developing high‐performance bioinspired catalysts for electrocatalytic oxidation reactions.