Nicholas M Bedford

Ni‐based hydroxides are promising electrocatalysts for biomass oxidation reactions, supplanting the oxygen evolution reaction (OER) due to lower overpotentials while producing value‐added chemicals. The identification and subsequent engineering of their catalytically active sites are essential to facilitate these anodic reactions. Herein, the proportional relationship between catalysts’ deprotonation propensity and Faradic efficiency of 5‐hydroxymethylfurfural (5‐HMF)‐to‐2,5 furandicarboxylic acid (FDCA, FE FDCA ) is revealed by thorough density functional theory (DFT) simulations and atomic‐scale characterizations, including in situ synchrotron diffraction and spectroscopy methods. The deprotonation capability of ultrathin layer‐double hydroxides (UT‐LDHs) is regulated by tuning the covalency of metal (M)‐oxygen (O) motifs through defect site engineering and selection of M 3+ co‐chemistry. NiMn UT‐LDHs show an ultrahigh FE FDCA of 99% at 1.37 V versus reversible hydrogen electrode (RHE) and retain a high FE FDCA of 92.7% in the OER‐operating window at 1.52 V, about 2× that of NiFe UT‐LDHs (49.5%) at 1.52 V. Ni–O and Mn–O motifs function as dual active sites for HMF electrooxidation, where the continuous deprotonation of Mn–OH sites plays a dominant role in achieving high selectivity while suppressing OER at high potentials. The results showcase a universal concept of modulating competing anodic reactions in aqueous biomass electrolysis by electronically engineering the deprotonation behavior of metal hydroxides, anticipated to be translatable across various biomass substrates.