Selective Electrochemical Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran with NiAl Layered Double Hydroxide Nanosheet Catalysts

The selective oxidative transformation of 5-hydroxymethylfurfural (HMF) is a key route toward producing a wide variety of chemicals in the biorefinery industry. Herein, we report a NiAl layered double hydroxide (NiAl-LDH) catalyst as a highly effective electrocatalytic oxidation catalyst for the transformation of HMF into 2,5-diformylfuran (DFF), a valuable furan-based chemical, with about 75.53% DFF selectivity under neutral conditions. It demonstrated good stability without deactivation after 9 cycles of repeated electrolysis. The NiAl-LDH electrocatalyst was deposited on a nickel foam support via a hydrothermal method, and its structural properties and surface morphology were extensively investigated. Systematic studies of reaction temperature, current intensity, and electrolyte concentration revealed that the neutral electrolyte plays a critical role in achieving high DFF selectivity by suppressing aldehyde over-oxidation. Mechanistic investigations with electrochemically active surface area (ECSA), electrochemical impedance spectroscopy (EIS), Tafel slope and density functional theory (DFT) calculations revealed that the reversible transformation between Ni(OH)2 and active NiOOH species in the NiAl-LDH electrocatalyst was the main reason for the oxidation of HMF, while the incorporation of Al provided structural support to the electrode, enabling the catalyst to exhibit excellent stability during electrolysis. Overall, this work demonstrates an active, earth-abundant metal electrocatalyst for the valorization of biomass-derived 5-HMF to DFF.