Acid‐Catalyzed Dehydration of Fructose into 5‐Hydroxymethylfurfural by Cellulose‐Derived Amorphous Carbon

Abstract

Carbonaceous solid (CS) catalysts with --SO₃H, --COOH, and phenolic --OH groups were prepared by incomplete hydrothermal carbonization of cellulose followed by either sulfonation with H₂SO₄ to give carbonaceous sulfonated solid (CSS) material or by both chemical activation with KOH and sulfonation to give activated carbonaceous sulfonated solid (a-CSS) material. The obtained carbon products (CS, CSS, and a-CSS) were amorphous; the CSS material had a small surface area (<0.5 m² g⁻¹) and a high --SO₃H group concentration (0.953 mmol g⁻¹), whereas the a-CSS material had a large surface area (514 m² g ⁻¹) and a low --SO₃H group concentration (0.172 mmol g⁻¹). The prepared materials were evaluated as catalysts for the dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) in the ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]). Remarkably high 5-HMF yields (83 %) could be obtained efficiently (80 °C and 10 min reaction time). CSS and a-CSS catalysts had similar catalytic activities and efficiencies for the conversion of fructose to 5-HMF in [BMIM][Cl]; this could be explained by the trade-off between --SO₃H group concentration (high for CSS) and surface area (high for a-CSS). The cellulose-derived catalysts and ionic liquid exhibited constant activity for five successive recycles, and thus, the methods developed provide a renewable strategy for biomass conversion.

Production of 5-Hydroxymethylfurfural from Fructose Catalyzed by Sulfonated Bamboo-Derived Carbon Prepared by Simultaneous Carbonization and Sulfonation

“…1b) demonstrates bands at 1008 cm -1 , 1033 cm -1 , and 1173 cm -1 , which are consistent with SO3H groups Geng et al 2011). In addition, phenolic C-OH, C=C, C=O, OH stretching vibration, and carboxylic C-OH bending vibration bands appear at 1225 cm -1 , 1618 cm -1 , 1733 cm -1 , 2995 cm -1 , and 1430 cm -1 , respectively, demonstrating the presence of COOH (2) ( 1) and phenolic OH groups on the surface of the catalyst (Weng 2010;Fu et al 2012;Qi et al 2012). XPS analysis (Fig.…”

“…After each test cycle, the recovered catalyst was washed with ethanol and dried at 100 °C for 6 h before the next run. As is shown in Fig.7, a 92.1% HMF yield was achieved in the first run, demonstrating that SBC is more efficient than sulfonated carbon derived from cellulose with an 83% HMF yield in [BMIM][Cl] (Qi et al 2012), sulfonated carbon derived from lignin with an 84% HMF yield in DMSO-[BMIM][Cl] mixture and graphite oxide (GO) with a 60.8% HMF yield in DMSO (Nie et al 2014). It is also comparable with macroporous strong-acid resin D001-cc with a 93.0% HMF yield in [BMIM][Cl] .…”

Progress in the Development of Mesoporous Solid Acid and Base Catalysts for Converting Carbohydrates into Platform Chemicals

“…To further probe such effects, Qi et al [ 33 ] prepared two kinds of carbonaceous catalysts functionalized with -SO 3 H, -COOH, and phenolic -OH groups by incomplete hydrothermal carbonization of cellulose, followed either by sulfonation with H 2 SO 4 (CSS) or by chemical activation with KOH and subsequent sulfonation (A-CSS). Through pretreatment with KOH, the surface morphology of CS changes drastically, as shown in Fig.…”

Acid–Base Bifunctional Hf Nanohybrids Enable High Selectivity in the Catalytic Conversion of Ethyl Levulinate to γ-Valerolactone

“…In addition, it can be employed for producing biofuels and fuel additives (e.g., 2-methyltetrahydrofuran) [7], and as a key intermediate in the synthesis of fine chemicals (e.g., pentenoic acid and α-methylene-γ-valerolactone (MeGVL)), as shown in Scheme 1 [8,9]. Typically, GVL can be prepared from lignocellulose via sequential catalytic pathways involving various reactions such as hydrolysis, isomerization, dehydration, etherification, esterification, hydrogenation, and lactonization [10][11][12][13][14][15][16]. Amongst these conversion processes, cascade hydrogenation and cyclization were deemed in recent years as the key step in catalytically upgrading levulinic acid and its esters to GVL [17,18].…”