Selective Electroreduction of 5-Hydroxymethylfurfural to Dimethylfuran in Neutral Electrolytes via Hydrogen Spillover and Adsorption Configuration Adjustment

5-Hydroxymethylfurfural (HMF), one of the essential C6 biomass derivatives, has been deeply investigated in electrocatalytic reduction upgrading. Nevertheless, the high product selectivity and rational design strategy of electrocatalysts for electrocatalytic HMF reduction is still a challenge. Here, a high selective electro-reduction of HMF to dimethylfuran (DMF) on palladium (Pd) single atom loaded on titanium dioxide (Pd SA/TiO2) via hydrogen spillover and adsorption configuration adjustment in neutral electrolytes is achieved. Combining density functional theory calculations and in situ characterization, it is revealed that Pd single atom could weaken the interaction between Pd atoms and adsorbed hydrogen (*H) to promote the *H spillover for increasing *H coverage on the surface and maintain the tilted adsorption configuration to activate CO bond; thus the selectivity of DMF on Pd SA/TiO2 increases to 90.33%. Besides, it is elaborated that low *H coverage on TiO2 favors the formation of bis(hydroxymethyl)hydro-furoin (BHH), and the flat adsorption configuration of HMF on Pd nanoparticles benefits to form 2,5-dihydroxymethylfuran (DHMF). This work provides a promising approach for modifying electrocatalysts to realize the selective electroreduction of HMF to value-added products. Selective electrocatalytic 5-hydroxymethylfurfural reduction reaction in neutral electrolytes to 2,5-dihydroxymethylfuran is a challenging reaction. Loaded palladium (Pd) single atoms enable the adsorbed hydrogen (*H) spillover to increase the *H coverage on titanium dioxide (TiO2) and maintain the tilted configuration to activate the CO bond, thus promoting selective electro-reduction to 2,5-dihydroxymethylfuran. Besides, the selective electro-reduction to bis(hydroxymethyl)hydro-furoin or 2,5-dihydroxymethylfuran can also be achieved on TiO2 or Pd nanoparticles loaded on Vulcan-XC72.image