Dual-Vacancy Engineering in Amorphous NiCo Oxyhydroxide Enables Selective Glycerol Electrooxidation to Formic Acid

Electrocatalytic glycerol oxidation to formic acid (FA) offers a sustainable route for biomass valorization, yet non-noble metal catalysts generally suffer from sluggish C-C bond cleavage and poor product selectivity. Here we report an amorphous nickel–cobalt oxyhydroxide bearing both metal and oxygen vacancies (D-NiCoOxHy-VCr,O), grown on nickel foam via one-step electrodeposition followed by electrochemical activation with Cr doping. The coexistence of the dual vacancies is experimentally confirmed by X-ray photoelectron spectroscopy (XPS), which reveals elevated Ni3+/Co3+ ratios and reduced lattice oxygen, and by electron paramagnetic resonance (EPR), which shows a markedly enhanced signal at g = 2.003. Building on prior Cr-leaching approaches in single-metal nickel oxides, this work extends dual-vacancy engineering to an amorphous bimetallic NiCo oxyhydroxide and correlates the defect structure with glycerol-induced interfacial responses, charge-transfer behavior, and product selectivity. The catalyst delivers 200 mA cm−2 at 1.31 V vs. RHE and achieves 100% Faradaic efficiency for formate at 1.32 V vs. RHE. In situ electrochemical impedance spectroscopy further reveals a significantly reduced charge-transfer resistance. These results establish Cr-assisted dual-vacancy engineering in amorphous bimetallic oxyhydroxides as a promising strategy for selective biomass electrooxidation.