# A bottom-up approach to design new catalytic systems for the mild oxidation of furan derivatives

Lénaïck Hervé, Franck Rataboul, Catherine Pinel, Amandine Cabiac, Maria Fernandez Espada Pastor, Laurent Djakovitch

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Lénaïck Hervé, Franck Rataboul, Catherine Pinel, Amandine Cabiac, Maria Fernandez Espada Pastor, et al.. A bottom-up approach to design new catalytic systems for the mild oxidation of furan derivatives. French Conference on Catalysis 2025, Groupe d'Etude en Catalyse; Catalysis Division of the French Chemical Society, May 2025, La Tremblade, France. hal-05106159

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Submitted on 10 Jun 2025

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# A bottom-up approach to design new catalytic systems for the mild oxidation of furan derivatives

Lénaick Hervé¹*, Franck Rataboul¹, Catherine Pinel¹, Amandine Cabiac², Maria Fernandez Espada Pastor², Laurent Djakovitch¹*

²IRCELYON, CNRS, 69626 Villeurbanne, France

²IFP Energies nouvelles, 69320 Solaize, France

* laurent.djakovitch@ircelyon.univ-lyon1.fr

¹lenaick.herve@ircelyon.univ-lyon1.fr

## Introduction

To reduce our dependence on fossil resources and promote sustainability, biomass is a key carbon source. Carbohydrate-rich biomass yields a variety of valuable molecules, including 2,5-furandicarboxylic acid (FDCA) and 2,5-diformylfuran (DFF), which can be produced through the catalytic oxidation of 5-hydroxymethylfurfural (5-HMF) for applications as monomers or pharmaceuticals.

Since 2010, many studies have investigated the selective oxidation of 5-HMF, primarily using noble metal-supported catalysts (Au, Pd, Pt, Ru) and several equivalents of soluble base.¹ However, the high cost of these metals, combined with wastewater treatment issues, highlight the need for new approaches. In this context, a bottom-up strategy appears promising. “Quasi-homogeneous” catalysis through metallic colloids stable in solutions may provide an effective way to identify the most suitable metal(s) for the catalytic system. This method has been relatively underexplored for 5-HMF oxidation. Some systems, such as core-shell Pt-Fe₃O₄ nanoparticles, have been applied to FDCA formation², while NH₄·V₃O₈-Fe₃O₄ nanoparticles have been used for DFF.³

In the context of a project funded by PEPR BBEST-FURFUN (2023-2026) focused on bio-sourced furan valorization, we will present in this communication our strategy for developing an “ideal” catalytic system through a bottom-up approach: this is the creation of a "quasi-homogeneous" colloidal phase and then the progression to stable and efficient heterogeneous catalysts (Figure 1). We will detail here our developments for the synthesis of stable palladium colloids in aqueous media for the selective oxidation of HMF to either DFF or FDCA under mild conditions.

## Materials & Methods

We prepared PVP-stabilized palladium colloids (Pd NPs) through a reliable method.⁴ Na₂PdCl₄ and PVP (10 eq.) were separately dissolved in water, combined, and stirred vigorously for 0.5 hours. Pd NPs were then formed by reduction with NaBH₄ (2.5 eq.) at room temperature and stirring for 1 day. The Pd NPs were characterized by ICP and TEM, and the colloidal solution has shown to be stable over weeks.

For catalytic experiments, 40 mL of a 0.5 wt% HMF solution in water, Na₂CO₃ (≤1.2 eq./HMF) and palladium colloidal solution (0.55 mol.%), were placed in a three-neck flask, exposed to a flow of wet air, and stirred at 1000 rpm at 25 or 80°C for 48 hours. Reaction mixtures were analyzed via HPLC.

## Results & Discussion

Palladium is renowned for the catalytic oxidation of carbonyl compounds, and we present initial results on “quasi-homogeneous” catalysis using palladium colloids, that will serve as a baseline for comparison with non-critical metals (e.g., Cu, Ag, Au). First analysis focused on particle size and stability of Pd NP solutions in aqueous media, as well as the effect of palladium colloids on the activity and

selectivity for 5-HMF oxidation. Various catalytic tests examined parameters like base concentration, temperature, and air/O₂ flow rate to clarify their roles in the reaction pathway, with the support of existing literature.

TEM analysis revealed uniform particles of around 3.5 nm with a narrow size distribution and stable, as colloidal solution for at least one month. As an example of catalytic conditions variations, temperature effect showed that at 25°C, HMF conversion reached 70% with 80% selectivity into HMFCA, while at 80°C, HMF was fully converted with 100% selectivity into FDCA.

<figure><img src="image_2.png" /><figcaption>**Figure 1.** TEM analysis (a) and distribution of the particles size (b) of the Pd colloid; (c) sketch of the reaction mechanism and the bottom-up strategy.</figcaption></figure>

## Significance

This study participates to the advances towards the implementation of robust routes for the very important reaction of oxidation of 5-HMF into DFF or FDCA, particularly by using more eco-friendly procedures limiting the use of oxygen pressure, as well as expensive reagents and solvents.

## References

1. Z. Zhang, K. Deng, ACS Catal., **2015**, *5*, 11.

2. Y. Zhang, Z. Xue, J. Wang, X. Zhao, Y. Deng, W. Zhao, T. Mu, RSC Adv., **2016**, *6*, 56.

3. J. Lai, S. Zhou, F. Cheng, D. Guo, X. Liu, Q. Xu, D. Yin, Catal. Lett., **2020**, *150*, 1301.

4. D. Bourbiaux, S. Mangematin, L. Djakovitch, F. Rataboul, Catal. Lett., **2021**, *151*, 3239.