# Keggin Heteropolyacid Immobilized on Nanosilica as a Heterogeneous Catalyst for Sugar Dehydration in an Aqueous Medium

## TL;DR

This paper presents a new heterogeneous catalyst for converting sugars into 5-hydroxymethylfurfural in water, with good activity and reusability.

## Contribution

A novel method to immobilize Keggin heteropolyacid on nanosilica for sugar dehydration in aqueous media is developed.

## Key findings

- Fructose conversion to 5-HMF was more effective than glucose under the tested conditions.
- The immobilized catalysts showed activity comparable to the homogeneous PW12 but with easier separation.
- The catalyst retained activity over three cycles but failed to effectively convert glucose in brewing wastewater.

## Abstract

The dehydration of fructose and glucose to 5-hydroxymethylfurfural (HMF) in water solution was carried out in the presence of functionalized heteropolyanion-based heterogeneous catalysts. Two catalysts were prepared by immobilizing the Keggin polyoxometalate H3PW12O40 (PW12) onto nanoSiO2 by the use of imidazoline and -SO3− surface species through acid–base reactions. The catalysts were characterized by N2 adsorption–desorption isotherms, XRD, TGA, FTIR, solid-state NMR, SEM, and acidity–basicity measurements. Catalytic reactions in batch conditions were performed at 165 °C in the presence of suspended catalysts, and the yield of furfural and 5-hydroxymethylfurfural (5-HMF) was determined. The catalytic activity of the materials was tested for sugars at 1M concentration in a water solution. The valorization of sugars (fructose and glucose) was found to be more effective in the case of fructose. Furthermore, the two catalysts in which the heteropolyacid was immobilized showed activity similar to that observed for naked PW12 (reaction in homogeneous phase), despite the heterogeneous nature of the process, but with the advantage of easier separation at the end of the reaction by simple filtration. The material’s substantial stability was demonstrated through three consecutive catalytic test cycles, in which the same catalyst was recovered after each experiment and washed several times with hot water. Finally, tests devoted to the valorization of sugars contained in wastewater from the brewing industry provided a poor yield in 5-HMF, indicating that the catalysts prepared here were, unfortunately, not suitable for this transformation under the conditions tested. This was because the catalysts prepared in this work showed a low capacity to transform glucose (the most present sugar in the carbohydrate fraction of this biomass) into furans.