Impact of Design on the Activity of ZrO2 Catalysts in Cellulose Hydrolysis-Dehydration to Glucose and 5-Hydroxymethylfurfural

Abstract

The one-pot hydrolysis-dehydration of activated microcrystalline cellulose was studied in pure hydrothermal water at 453 K over ZrO2 catalysts produced by thermodegradation, microwave treatment, mechanical activation, and sol–gel methods and spent without any co-catalyst. ZrO2 prepared by microwave treatment was more active compared to ones derived by other methods. The catalyst calcination temperature also impacted reactivity. The cellulose conversion increased simultaneously with acidity and SBET, which in turn were set by the preparation method and calcination temperature. Phase composition did not affect the activity. Yields of glucose and 5-HMF reaching 18 and 15%, respectively, were over the most promising ZrO2 prepared by microwave treatment at 593 K. To our knowledge, this ZrO2 sample provided the highest activity in terms of TOF values (15.1 mmol g−1 h−1) compared to the pure ZrO2 systems reported elsewhere. High stability of ZrO2 derived by microwave irradiation was shown in five reaction runs.

Hydrolysis–Dehydration of Cellulose: Efficiency of NbZr Catalysts under Batch and Flow Conditions

“…At the same time, mesoporous materials with high specific surface area can be obtained by the method of the joint microwave heating of niobia and zirconia precursors. Previously, we reported textural data on pure ZrO2 samples [36]. It was found that oxide catalysts prepared by microwave heating, similar to the present work, had a higher specific surface area compared to catalysts produced by a combination of mechanical activation and microwave.…”

“…The chromatograph was equipped by a RI detector and Rezex ROA-Organic Acids column (Phenomenex, 300 × 5.0 mm, Torrance, CA, USA). Additional information on catalyst testing techniques can be found in our previous papers [27,36,55].…”

TiO2/g-C3N4/SO3H(IL): Unique Usage of Ionic Liquid-Based Sulfonic Acid as an Efficient Photocatalyst for Visible-Light-Driven Preparation of 5-HMF from Cellulose and Glucose

“…45,46 The solubility constraints of polysaccharides and disaccharides render these carbohydrates unsolvable in traditional solvents, thus making them undesirable feed stocks. 47 Although cellulose and its building unit glucose are the most recognized precursors for the generation of 5-HMF, 48,49 the stout structure of cellulose and the questionable stability of 5-HMF under punitive reaction conditions have been lingering challenges in the conversion of cellulose/glucose to 5-HMF, culminating in poor yields, with acid catalyst-promoted degradation of cellulose/glucose being the norm. 50−52 Heterogeneous acidic catalysts are endowed with several favorable attributes such as lower costs and ease of separation and recycling.…”

“…One of the most significant building components based on biomass is 5-hydroxymethylfurfural (5-HMF), which is an important precursor in view of the presence of hydroxymethyl and aldehyde functional groups, and hence is very valuable in the manufacture of polymers, pharmaceuticals, fine chemicals, and related organics. − Acid-catalyzed dehydration of polysaccharides, disaccharides, and monosaccharides to furan derivatives is one of the significant pathways. , The solubility constraints of polysaccharides and disaccharides render these carbohydrates unsolvable in traditional solvents, thus making them undesirable feed stocks . Although cellulose and its building unit glucose are the most recognized precursors for the generation of 5-HMF, , the stout structure of cellulose and the questionable stability of 5-HMF under punitive reaction conditions have been lingering challenges in the conversion of cellulose/glucose to 5-HMF, culminating in poor yields, with acid catalyst-promoted degradation of cellulose/glucose being the norm. − …”