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

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.