Tailoring the selective adsorption sites of NiMoO by Ni particles for biomass upgrading assisted hydrogen production

5-Hydroxymethylfurfural electrooxidation reaction (HMFOR) is a promising route to produce value-added chemicals from biomass. Since it involves HMF adsorption and C–H/O–H cleavage, understanding the adsorption behavior and catalytic process of organic molecules on catalysts is important. Herein, the selective adsorption sites of NiMoO are tuned by Ni particles for HMFOR-assisted H2 production. Experimental and theoretical calculation results indicate that the synergistic interaction between Ni and NiMoO optimizes the adsorption/desorption of HMF/intermediates/2,5-furandicarboxylic acid (FDCA) and promotes the C–H/O–H bond cleavage, thereby improving the HMFOR kinetics (kNiMoO-Ni/kNiMoO = 1.97) and FDCA selectivity (99.3%). When coupled as a two-electrode system, it can drive efficient HMF conversion (FDCA yield: 98.5%) and H2 production (Faradaic efficiency: 99.1%) at 1.45 V. This work thus offers a strategy to tune the adsorption sites of catalyst for efficient HMFOR-assisted H2 production.