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, we achieve a high selective electro-reduction of HMF to dimethylfuran (DMF) on Pd single atom loaded on TiO 2 via hydrogen spillover and adsorption configuration adjustment in neutral electrolytes. Combining the density functional theory calculation and in-situ characterization, it was revealed that Pd single atom could weaken the interaction between the Pd atom and adsorbed hydrogen (*H) to promote the *H spillover for increasing *H coverage on the surface and maintain the tilted adsorption configuration to activate C = O bond; thus the selectivity of DMF on Pd single atom loaded on TiO 2 increased to 90.33%. Besides, it is elaborated that low *H coverage on TiO 2 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); thus the selectivity of BHH on TiO 2 and that of DHMF on Pd nanoparticles loaded on Vulcan-XC72 can reach 70.16% and 89.63%. This work provides a promising approach for modifying electrocatalysts to realize the selective electroreduction of HMF to value-added products. This article is protected by copyright. All rights reserved.