5-Hydroxymethylfurfural (5-HMF) is an important bio-sourced intermediate, formed from carbohydrates such as glucose or fructose. The treatment at 150–250 °C of glucose or fructose in pure water and batch conditions, with catalytic amounts of most of the usual acid-basic solid catalysts, gave limited yields in 5-HMF, due mainly to the fast formation of soluble oligomers. Niobic acid, which possesses both Lewis and Brønsted acid sites, gave the highest 5-HMF yield, 28%, when high catalyst/glucose ratio is used. By contrast, we disclose in this work that the reaction of fructose in concentrated aqueous solutions of carboxylic acids, formic, acetic or lactic acids, used as reactive solvent media, leads to the selective dehydration of fructose in 5-HMF with yields up to 64% after 2 hours at 150 °C. This shows the potential of such solvent systems for the clean and easy production of 5-HMF from carbohydrates. The influence of adding solid catalysts to the carboxylic acid media was also reported, starting from glucose.

Hydrothermal dissolution and/or conversion of cellulose Avicel^® occurred at 190 °C under 5 MPa of H₂ in the absence of catalyst. This reaction is temperature and time dependent. A dissolution–conversion ratio of 35% was obtained after 24 h of reaction and glucose and HMF were detected as monomeric products in a global yield of less than 5%, indicating that the majority of the products are composed of soluble oligo- and polysaccharides. The unreacted cellulose was analyzed using XRD, ¹³C solid state NMR, TGA-DTA and SEM and compared to the initial cellulose. We showed that although morphology changes occurred during the reaction, no modification of the crystallinity was observed and that hydrothermal treatment did not affect a specific part of the cellulose polymer. The presence of Pt/γ-Al₂O₃ increased the initial rate of dissolution–conversion significantly as well as the distribution of the monomeric products. Pt and H₂ atmosphere were seen to increase the dissolution–conversion ratio however their role has not been yet well established.

Graphene oxide addresses increasing interests as a solid acid catalyst working in water for carbohydrate conversion. If there is a general agreement to correlate its unique catalytic performances to its ability to adsorb sugars, the origin of its acidity remains controversial. In this article, we study the acid strength of graphene oxide (GO) prepared by modified Hummers method and that of reduced GO by calorimetry of NH₃ adsorption and by FTIR of pyridine adsorption. Very strong acid sites are detected on GO by calorimetry, while reduced graphene oxide (reGO) is not very acidic. The FTIR of pyridine adsorption shows the prevailing presence of Br∅nsted acid sites and a unique feature, the presence of pyridine coordinated by hydrogen bonds. This exceptionally strong Br∅nsted acidity is tentatively explained by the presence of graphene domains decorated by hydroxyl, carboxylic, or sulfonated groups within the GO sheet, resulting in a high mobility of the negative charges which makes the proton free and explains its strong acidity. Accordingly, only GO is active and selective for native cellulose hydrolysis, leading to 27% yield in glucose. Finally, we show that sugar alcohols cannot be formed directly from cellulose using GO combined with Pt/re-GO under hydrogen, explained by the reduction of oxygenated functions of GO. The instability of the functional groups of GO in a reducing atmosphere is the weak point of this peculiar solid acid.

In this paper, evidence is provided that the model reaction of aqueous dihydroxyacetone (DHA) conversion is as sensitive to the TiO₂ catalysts’ basicity as to their acidity. Two parallel pathways transformed DHA: while the pathway catalyzed by Lewis acid sites gave pyruvaldehyde (PA) and lactic acid (LA), the base-catalyzed route afforded fructose. This is demonstrated on a series of six commercial TiO₂ samples and further confirmed by using two reference catalysts: niobic acid (NbOH), an acid catalyst, and a hydrotalcite (MgAlO), a basic catalyst. The original acid-base properties of the six commercial TiO₂ with variable structure and texture were investigated first by conventional methods in gas phase (FTIR or microcalorimetry of pyridine, NH₃ and CO₂ adsorption). A linear relationship between the initial rates of DHA condensation into hexoses and the total basic sites densities is highlighted accounting for the water tolerance of the TiO₂ basic sites whatever their strength. Rutile TiO₂ samples were the most basic ones. Besides, only the strongest TiO₂ Lewis acid sites were shown to be water tolerant and efficient for PA and LA formation.