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

作者：Yandong Wu, Yimin Jiang, Wei Chen, Yue Xu, Chung‐Li Dong, Mengyi Qiu, Ta Thi Thuy Nga, Ming Yang, Zhongcheng Xia, Chao Xie, Leitao Xu, Ruiqi Wang, Shuangyin Wang, Yuqin Zou · 发表于：Advanced Materials · 年份：2023 · DOI：10.1002/adma.202307799 · 被引用次数：69 · 研究领域：Catalysis for Biomass Conversion、Ammonia Synthesis and Nitrogen Reduction、Electrocatalysts for Energy Conversion

Abstract 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/TiO 2 ) 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 C═O bond; thus the selectivity of DMF on Pd SA/TiO 2 increases 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). This work provides a promising approach for modifying electrocatalysts to realize the selective electroreduction of HMF to value‐added products.