Enhancing the Electrocatalytic Oxidation of 5-Hydroxymethylfurfural Through Cascade Structure Tuning for Highly...

Electrocatalytic 5-hydroxymethylfurfural oxidation reaction (HMFOR) provides a promising strategy to convert biomass derivative to high-value-added chemicals. Herein, a cascade strategy is proposed to construct Pd-NiCo₂O₄ electrocatalyst by Pd loading on Ni-doped Co₃O₄ and for highly active and stable synergistic HMF oxidation. An elevated current density of 800 mA cm^-2 can be achieved at 1.5 V, and both Faradaic efficiency and yield of 2,5-furandicarboxylic acid remained close to 100% over 10 consecutive electrolysis. Experimental and theoretical results unveil that the introduction of Pd atoms can modulate the local electronic structure of Ni/Co, which not only balances the competitive adsorption of HMF and OH^- species, but also promote the active Ni³⁺ species formation, inducing high indirect oxidation activity. We have also discovered that Ni incorporation facilitates the Co²⁺ pre-oxidation and electrophilic OH* generation to contribute direct oxidation process. This work provides a new approach to design advanced electrocatalyst for biomass upgrading.