Interfacial Proton‐Coupled Electron Transfer Reverses Water Inhibition for Selective 5‐hydroxymethylfurfural Hydrogenation
Abstract
ABSTRACT The selective aqueous hydrogenation of 5‐hydroxymethylfurfural (HMF) to 2,5‐bis(hydroxymethyl)furan (BHMF) is pivotal for biomass valorization. While nanoscale zero‐valent iron (nZVI) offers a sustainable H 2 ‐free alternative, its efficiency is severely suppressed by a rigid interfacial water layer that impedes substrate access and drives non‐selective pathways. Herein, we surmount this limitation by engineering atomically dispersed Ni sites on nZVI to orchestrate a surface proton‐coupled electron transfer (PCET). Mechanistically, single Ni atoms in the electron‐deficient state (Ni δ+ ) function as “electron pumps”, establishing a direct longitudinal inner‐sphere channel for electron delivery towards the −CHO group of HMF. Concurrently, the Ni δ+ sites facilitate prompt proton release by weakening hydrogen binding on adjacent lattice oxygen. Ni δ+ ‐induced electronic modulation transforms proximal lattice Fe into strong Lewis acids to polarize bulk water, creating a continuous lateral proton shuttle to the adsorbed HMF. This orthogonal PCET system drastically boosts electron selectivity from 10.6% (pristine nZVI) to 81.6%, achieving >95% HMF conversion (20–150 mM) with >95% BHMF selectivity under ambient conditions, outperforming pristine nZVI (<10% conversion) by orders of magnitude. This work demonstrates that engineering interfacial PCET pathways can reverse classical solvent inhibition, opening a general route for efficient aqueous hydrogenation.
Article Details
Authors (13)
Haopeng Pei
State Key Laboratory of Green Papermaking and Resource Recycling, Shanghai Engineering Research Center of Solid Waste Treatment and Resource Recovery, School of Environmental Science and Engineering
Guangming Zhan
State Key Laboratory of Green Papermaking and Resource Recycling, School of Environmental Science and Engineering
Yinghao Li
Long Zhao
Key Laboratory of Evolution and Marine Biodiversity (Ministry of Education) and Institute of Evolution and Marine Biodiversity, Ocean University of China, Qingdao, China.
Weiwei Ma
Equine Infectious Diseases and Lentiviruses Division, State Key Laboratory for Animal Disease Control and Prevention, Harbin Veterinary Research Institute of Chinese Academy of Agricultural Sciences
Chenglin Hao
State Key Laboratory of Green Papermaking and Resource Recycling School of Environmental Science and Engineering Shanghai Jiao Tong University Shanghai P. R. China
Minzi Liao
School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Sicong Ma
State Key Laboratory of Green Pesticide, College of Chemistry
Bing Zhou
Yitao Pan
State Key Laboratory of Green Papermaking and Resource Recycling, Shanghai Engineering Research Center of Solid Waste Treatment and Resource Recovery, School of Environmental Science and Engineering
Jinming Luo
State Key Laboratory of Green Papermaking and Resource Recycling, Shanghai Engineering Research Center of Solid Waste Treatment and Resource Recovery, School of Environmental Science and Engineering
Hao Li
Lizhi Zhang
State Key Laboratory of Green Papermaking and Resource Recycling, Shanghai Engineering Research Center of Solid Waste Treatment and Resource Recovery, School of Environmental Science and Engineering