Overcoming dual dehydrogenation barriers in the oxidation of 1-methoxy-2-propanol on the electronically modulated Mn–Ni(OH)2/NF electrode for efficient production 1-methoxy-2-propanone

Ni(OH) 2 /NF demonstrates strong electrocatalytic performance in the oxidation of 1-methoxy-2-propanol (MOP) to 1-methoxy-2-propanone (MOA). However, its catalytic efficiency is restricted by two sluggish dehydrogenation stages: the oxidation of Ni 2 + –OH to generate the active Ni 3+ –O intermediate, and the abstraction of the α-hydrogen from the MOP molecule. To address these limitations, the present study introduces a strategy centered on tuning the electronic structure. By incorporating manganese (Mn) into the coordination structure of Ni(OH) 2 /NF nanosheets in a controlled manner, both reaction steps are effectively enhanced through synergistic effects. X-ray photoelectron spectroscopy (XPS) and synchrotron-based X-ray absorption fine structure (XAFS) analyses reveal that Mn incorporation modifies the local electronic environment of Ni through electronic interactions. This adjustment decreases the d -orbital electron density of Ni, thereby facilitating the oxidation of Ni 2+ to the catalytically active Ni 3+ species during MOP conversion. Electrochemical measurements combined with density functional theory (DFT) calculations indicate that Mn incorporation markedly enhances the adsorption of MOP molecules on the catalyst surface, which thereby promotes more efficient reaction kinetics. This synergistic regulation effectively lowers the energy barrier associated with the dual dehydrogenation steps, resulting in markedly improved catalytic performance of Mn–Ni(OH) 2 /NF for MOP oxidation, with the product Faradaic efficiency reaching around 90 %.