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Hydrogen Bridge‐Mediated Efficient Electrooxidation of 5‐Hydroxymethylfurfural on Ni(OH)2─PO43−/Ni3(PO4)2 Heterojunctions.

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Title: Hydrogen Bridge‐Mediated Efficient Electrooxidation of 5‐Hydroxymethylfurfural on Ni(OH)2─PO43−/Ni3(PO4)2 Heterojunctions.
Authors: Liu, Xupo1,2 (AUTHOR), Zhang, Jingru1 (AUTHOR), Chen, Ye1 (AUTHOR), Wang, Gongke1,2 (AUTHOR) wanggongke@126.com, Qiu, Jiayao1 (AUTHOR), Sha, Xiaokang1 (AUTHOR), Liu, Yi3 (AUTHOR), Chang, Meinan2 (AUTHOR), Guo, Junpo2 (AUTHOR) guojunpo@htu.edu.cn, Wang, Deli3 (AUTHOR) wangdl81125@hust.edu.cn
Source: Angewandte Chemie International Edition. 10/13/2025, Vol. 64 Issue 42, p1-10. 10p.
Subject Terms: *HYDROXYMETHYLFURFURAL, *ELECTROLYTIC oxidation, *HYDROGEN bonding, *ORTHOPHOSPHATES, *CATALYSTS, *BIOMASS conversion, *NICKEL phosphates
Abstract: Accelerating proton deintercalation and transfer on the catalyst surface is crucial for the electrochemical oxidation of 5‐hydroxymethylfurfural (HMF) into the high‐value 2,5‐furanodicarboxylic acid (FDCA). Herein, we have constructed a Ni(OH)2─PO43−/Ni3(PO4)2 heterojunction catalyst that demonstrates exceptional selectivity (97.16%), yield (94.16%), and Faraday efficiency (94.31%) in the selective oxidation of HMF toward FDCA. The incorporation of PO43− groups triggers the formation of hydrogen bridges and reconfigures the interfacial charge distribution, facilitating the activation and subsequent proton deintercalation of lattice‐hydroxyl‐groups to generate active Ni3+─O catalytic sites (PO43−⋯H─O─Ni2+ → HPO42− + Ni3+─O). Both density functional theory calculations and pH‐dependent experiments emphasize the crucial function of these hydrogen bridges as proton ferries, effectively boosting the proton transfer efficiency during HMF oxidation. Theoretical studies unveil that the rate‐controlling step for OH adsorption on Ni(OH)2─PO43− occurs via the hydrogen bridge connecting the PO43− group with the α‐C atom in *HMF‐H intermediate (PO43−⋯H─O⋯COR → PO42−─H⋯O─COR), significantly reducing the energy barrier for HMF oxidation. This study introduces a novel hydrogen bridge‐mediated electrooxidation mechanism that holds great potential for advancing biomass conversion technologies. [ABSTRACT FROM AUTHOR]
Database: Academic Search Index
Description
Abstract:Accelerating proton deintercalation and transfer on the catalyst surface is crucial for the electrochemical oxidation of 5‐hydroxymethylfurfural (HMF) into the high‐value 2,5‐furanodicarboxylic acid (FDCA). Herein, we have constructed a Ni(OH)2─PO43−/Ni3(PO4)2 heterojunction catalyst that demonstrates exceptional selectivity (97.16%), yield (94.16%), and Faraday efficiency (94.31%) in the selective oxidation of HMF toward FDCA. The incorporation of PO43− groups triggers the formation of hydrogen bridges and reconfigures the interfacial charge distribution, facilitating the activation and subsequent proton deintercalation of lattice‐hydroxyl‐groups to generate active Ni3+─O catalytic sites (PO43−⋯H─O─Ni2+ → HPO42− + Ni3+─O). Both density functional theory calculations and pH‐dependent experiments emphasize the crucial function of these hydrogen bridges as proton ferries, effectively boosting the proton transfer efficiency during HMF oxidation. Theoretical studies unveil that the rate‐controlling step for OH adsorption on Ni(OH)2─PO43− occurs via the hydrogen bridge connecting the PO43− group with the α‐C atom in *HMF‐H intermediate (PO43−⋯H─O⋯COR → PO42−─H⋯O─COR), significantly reducing the energy barrier for HMF oxidation. This study introduces a novel hydrogen bridge‐mediated electrooxidation mechanism that holds great potential for advancing biomass conversion technologies. [ABSTRACT FROM AUTHOR]
ISSN:14337851
DOI:10.1002/anie.202509274