# Greener catalytic oxidation of furan derivatives with the help of new catalytic systems made through a bottom-up approach

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

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Lénaïck Hervé, Franck Rataboul, Amandine Cabiac, Maria Fernandez Espada, Catherine Pinel, et al.. Greener catalytic oxidation of furan derivatives with the help of new catalytic systems made through a bottom-up approach. International Symposium on Green Chemistry 2025, Centre National de la Recherche Scientifique; International Consortium on Eco-conception and renewable resources; WildEvents, May 2025, La Rochelle, France. hal-05106860

HAL Id: hal-05106860

https://hal.science/hal-05106860v1

Submitted on 11 Jun 2025

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Distributed under a Creative Commons Attribution 4.0 International License
Greener catalytic oxidation of furan derivatives with the help of new
catalytic systems made through a bottom-up approach

AUTHORS

Lénaïck Hervé / IRCELYON

Franck Rataboul / IRCELYON

Amandine Cabiac / IFPEN

Maria Fernandez Espada Pastor / IFPEN

Catherine Pinel / IRCELYON

Laurent Djakovitch / IRCELYON

PURPOSE OF THE ABSTRACT

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) used as monomers or for pharmaceutical syntheses, which can be produced through the
catalytic oxidation of 5-hydroxymethylfurfural (5-HMF).

Since 2010, many studies have investigated the selective oxidation of 5-HMF, primarily using noble metal-
supported catalysts (Au, Pd, Pt, Ru) in the presence of an excess 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 by stable metallic colloids in solutions can
be an effective means of optimizing the reaction parameters towards greener processes. Moreover, this method
has been relatively underexplored for 5-HMF oxidation. Few systems, such as core-shell Pt-Fe3O4 nanoparticles,
have been applied to FDCA formation(2), 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 furans
valorizations, we will present in this communication our strategy for developing an “ideal” catalytic system following
a bottom-up approach: discovering a stable and efficient heterogeneous catalysts from a "quasi-homogeneous"
colloidal phase able to work in the absence of soluble bases (Figure 1). We will detail our work from the synthesis of
stable metal colloids in aqueous media to support palladium nanoparticles on carriers for the selective oxidation of
HMF into DFF or FDCA under mild reaction conditions.

Materials & Methods

PVP-stabilized palladium colloids (Pd NPs) were prepared 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 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

We previously reported the use of palladium based catalysts for the catalytic oxidation of carbonyl compounds4, and we present here our initial results on “quasi-homogeneous” catalysis using palladium colloids. The results observed will serve as a baseline for further development of catalysts based on non-critical metals like Cu, Ag or Au. First studies focused on particle size and stability of Pd NPs aqueous solutions, as well as the effect of the palladium colloids on the activity and selectivity of 5-HMF oxidation. Parameters like base concentration, temperature, and air/O₂ flow rate were evaluated to clarify their roles in the reaction pathways, comparing our results to those of existing literature.

TEM analyses revealed uniform particles size of around 3.5 nm with a narrow distribution showing also that, colloidal solutions are stable for at least one month. As an example of catalytic conditions variations, under air bubbling, the temperature of the reaction affects the selectivity. While at 25°C, HMF conversion reaches 60% with 80-90% selectivity to HMFCA, at 80°C, HMF is fully converted with a selectivity up to 70% to FDCA.

## FIGURES

<figure><img src="image_2.png" /><figcaption>**FIGURE 1**
TEM analysis and size distribution of palladium nanoparticles</figcaption></figure>

<figure><img src="image_3.png" /><figcaption>**FIGURE 2**
Sketch of the reaction pathway and the bottom-up approach</figcaption></figure>

## KEYWORDS

HMF Catalytic Selective Oxidation | Colloidal Catalyst | Mild Conditions | Green Catalysis
BIBLIOGRAPHY

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

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

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

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