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Vol. 18 (2026)

A Promising Strategy for Solvent-Regulated Selective Hydrogenation of 5-Hydroxymethylfurfural over Porous Carbon-Supported Ni-ZnO Nanoparticles

https://doi.org/10.1007/s40820-025-01847-5
Rulu Huang
National Key Laboratory for Development and Utilization of Forest Food Resources, Biomass Energy and Material Key Laboratory of Jiangsu Province, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, People’s Republic of China
Chao Liu
School of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, People’s Republic of China
Kaili Zhang
Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, People’s Republic of China
Jianchun Jiang
National Key Laboratory for Development and Utilization of Forest Food Resources, Biomass Energy and Material Key Laboratory of Jiangsu Province, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, People’s Republic of China
Ziqi Tian
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, People’s Republic of China
Yongming Chai
State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, People’s Republic of China
Kui Wang
National Key Laboratory for Development and Utilization of Forest Food Resources, Biomass Energy and Material Key Laboratory of Jiangsu Province, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, People’s Republic of China

Corresponding Author: Kui Wang

wangkui@caf.ac.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 5

Abstract

Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization. Herein, we report porous carbon-supported Ni-ZnO nanoparticles catalyst (Ni-ZnO/AC) synthesized via low-temperature coprecipitation, exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural (HMF). A linear correlation is first observed between solvent polarity (ET(30)) and product selectivity within both polar aprotic and protic solvent classes, suggesting that solvent properties play a vital role in directing reaction pathways. Among these, 1,4-dioxane (aprotic) favors the formation of 2,5-bis(hydroxymethyl)furan (BHMF) with 97.5% selectivity, while isopropanol (iPrOH, protic) promotes 2,5-dimethylfuran production with up to 99.5% selectivity. Mechanistic investigations further reveal that beyond polarity, proton-donating ability is critical in facilitating hydrodeoxygenation. iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal, lowering the activation barrier. In contrast, 1,4-dioxane, lacking hydrogen bond donors, stabilizes BHMF and hinders further conversion. Density functional theory calculations confirm a lower activation energy in iPrOH (0.60 eV) compared to 1,4-dioxane (1.07 eV). This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation, highlighting the decisive role of solvent-catalyst-substrate interactions.


Highlights:
1 A porous carbon-supported Ni-ZnO nanoparticles catalyst (Ni-ZnO/AC) was synthesized by low-temperature coprecipitation, demonstrating exceptional catalytic activity and stability.
2 Selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (97.5%) or 2,5-dimethylfuran (99.5%) is achieved over Ni-ZnO/AC catalyst by solvent-tuning.
3 Solvent-catalyst interaction jointly regulates hydrodeoxygenation behavior in HMF hydrogenation by modulating rate and pathway via a hydrogen shuttle mechanism.

Keywords

Porous carbon-supported Ni-ZnO nanoparticles catalyst Selective hydrogenation 5-Hydroxymethylfurfural Solvent Proton-donating ability
Huang, Rulu, Chao Liu, Kaili Zhang, Jianchun Jiang, Ziqi Tian, Yongming Chai, and Kui Wang. 2025. “A Promising Strategy for Solvent-Regulated Selective Hydrogenation of 5-Hydroxymethylfurfural over Porous Carbon-Supported Ni-ZnO Nanoparticles”. Nano-Micro Letters 18 (July):5. https://doi.org/10.1007/s40820-025-01847-5.
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