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

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

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. Graphical Abstract

As the demand for renewable chemicals grows, selective conversion of biomass-derived platform molecules has become a key challenge. 5-Hydroxymethylfurfural (HMF), a promising biomass-derived intermediate, can be hydrogenated into valuable products such as 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-dimethylfuran (DMF). However, achieving high selectivity toward specific products remains difficult. Now, researchers from the Chinese Academy of Forestry and China University of Petroleum, led by Prof. Jianchun Jiang and Prof. Kui Wang, have developed a porous carbon-supported Ni-ZnO nanoparticle catalyst (Ni-ZnO/AC) that enables solvent-regulated selective hydrogenation of HMF with exceptional efficiency.

Why This Matters

  • Tunable Product Selectivity: By simply switching solvents, the catalyst can selectively produce BHMF (97.5% selectivity in 1,4-dioxane) or DMF (99.5% selectivity in isopropanol).
  • Green and Scalable: The catalyst is synthesized via low-temperature coprecipitation using coconut shell-derived activated carbon, offering a sustainable and cost-effective approach.
  • Mechanistic Insight: The study reveals that solvent polarity and proton-donating ability jointly regulate the reaction pathway, with protic solvents enabling a hydrogen shuttle mechanism that facilitates hydrodeoxygenation.

Innovative Design and Features

  • Ni-ZnO/AC Catalyst: A semi-core–shell structure with strong Ni-ZnO interfacial interaction enhances charge transfer and catalytic activity.
  • Solvent Effect: Solvent polarity correlates linearly with product selectivity. Protic solvents like isopropanol lower activation energy (0.60 eV vs. 1.07 eV in 1,4-dioxane) by promoting proton-coupled hydroxyl removal.
  • Stability: The catalyst maintains high activity and selectivity over five cycles with minimal metal leaching.

Applications and Future Outlook

  • Biomass Valorization: This solvent-tuned strategy provides a practical route for converting HMF into high-value chemicals for pharmaceuticals, biofuels, and bioplastics.
  • Reaction Control: The work highlights the decisive role of solvent–catalyst–substrate interactions in directing reaction pathways, offering a new lever for reaction design in biomass conversion.
  • Industrial Potential: The simplicity of product control via solvent change makes this approach highly attractive for scalable, selective biomass upgrading.

This study not only advances our understanding of solvent effects in catalysis but also offers a promising and flexible strategy for the sustainable production of biomass-derived chemicals. Stay tuned for more innovations from Prof. Jianchun Jiang and Prof. Kui Wang’s teams!

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Nanoparticle Synthesis
Physical Sciences > Chemistry > Chemical Synthesis > Nanoparticle Synthesis
Nanoparticles
Physical Sciences > Materials Science > Nanotechnology > Nanobiotechnology > Nanomaterial > Nanoparticles
Materials for Energy and Catalysis
Physical Sciences > Materials Science > Materials for Energy and Catalysis
Catalyst Synthesis
Physical Sciences > Chemistry > Chemical Synthesis > Catalyst Synthesis
Reaction Mechanisms
Physical Sciences > Chemistry > Physical Chemistry > Reaction Mechanisms
  • Nano-Micro Letters Nano-Micro Letters

    Nano-Micro Letters is a peer-reviewed, international, interdisciplinary and open-access journal that focus on science, experiments, engineering, technologies and applications of nano- or microscale structure and system in physics, chemistry, biology, material science, and pharmacy.