Xindong Mu

A novel approach for the preparation of nanocrystalline cellulose by using phosphotungstic acid

In this work, a sustainable and green process to prepare nanocrystalline cellulose (NCC) from bleached hardwood pulp was demonstrated. Rod-like nanocrystalline cellulose with the size of 15-40 nm in width and hundreds of nanometers in length was obtained through H3PW12O40 (HPW)-catalyzed hydrolysis of bleached pulp fibers under the mild reaction conditions. Thermogravimetric analysis revealed that the resulting NCC exhibited much higher thermal stability than the partially sulfated NCC (prepared by sulfuric acid). In addition, the concentrated HPW could be easily recovered and recycled through the extraction with diethyl ether, and the recovered HPW could be reused for several rounds of cellulose hydrolysis without activity lost. These fundamental studies are of crucial importance for the development and application of NCC products/NCC-based biomaterials with good thermal stability.

Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst.

Conversion of fructose and glucose into 5-hydroxymethylfurfural (HMF) was investigated in various imidazolium ionic liquids, including 1-butyl-3-methylimidazolium chloride (BmimCl), 1-hexyl-3-methylimidazolium chloride (HmimCl), 1-octyl-3-methylimidazolium chloride (OmimCl), 1-benzyl-3-methylimidazolium chloride (BemimCl), 1-Butyl-2,3-dimethylimidazolium chloride (BdmimCl), and 1-butyl-3-methylimidazolium p-toluenesulfonate (BmimPS). The acidic C-2 hydrogen of imidazolium cations was shown to play a major role in the dehydration of fructose in the absence of a catalyst, such as sulfuric acid or CrCl(3). Both the alkyl groups of imidazolium cations and the type of anions affected the reactivity of the carbohydrates. Although, except BmimCl and BemimCl, other four ionic liquids could only achieve not more than 25% HMF yields without an additional catalyst, 60-80% HMF yields were achieved in HmimCl, BdmimCl, and BmimPS in the presence of sulfuric acid or CrCl(3) in sufficient quantities.

Comparison of different alkali-based pretreatments of corn stover for improving enzymatic saccharification

Corn stover was treated with NaOH, NaOH+anthraquinone (AQ), NaOH+Na(2)SO(3) (alkaline), NaOH+Na(2)SO(3) (neutral), and NaOH+Na(2)S, respectively. The treated corn stover was subjected to hydrolysis with cellulase (20 FPU/g dry biomass) and β-glucosidase (10I U/g dry biomass). Compared with other pretreatment methods, alkaline sodium sulfite pretreatment (ASSP) at a relatively low temperature of 140°C provided for the best lignin removal of about 92%. After ASSP with 10 wt.% of the total alkali charge (Na(2)SO(3):NaOH=1:1) at 140°C for 30 min and subsequent enzymatic hydrolysis, a total sugar yield of 78.2% was obtained on the basis of the amount of glucose and xylose released from raw corn stover. This yield was 24.0% higher than that achieved with NaOH only under the same conditions. Therefore, the supplement of Na(2)SO(3) in alkali pretreatment can facilitate delignification and significantly improve the enzymatic saccharification.

Selective dehydration of fructose to 5-hydroxymethylfurfural catalyzed by mesoporous SBA-15-SO3H in ionic liquid BmimCl

Mesoporous SBA-15 materials functionalized with propylsulfonic acid groups (SBA-15-SO(3)H) were synthesized through a conventional one-pot route. It was used as a catalyst for the selective synthesis of 5-hydroxymethylfurfural (HMF) from the dehydration of fructose using BmimCl as solvent. Reaction time, temperature and fructose concentration were investigated during the HMF synthesis procedure. The catalyst SBA-15-SO(3)H exhibits high fructose conversion (near 100%) and HMF selectivity (about 81%) with good stability in the HMF synthesis. It was a suitable catalyst to produce HMF from renewable carbohydrates in potential industrial process.

Recent advances in the production of polyols from lignocellulosic biomass and biomass-derived compounds

The conversion of renewable, non-edible and resource-abundant lignocellulose to fuels, chemicals and materials has received significant attention as it holds the possibility of using carbon neutral technologies to combat global changes. Considering the relatively high oxygen content in cellulose, it is more desirable to be transformed into oxygenated chemicals rather than hydrocarbon fuels in view of atom efficiency. Among the oxygen-rich chemicals from biomass, polyols, such as ethylene glycol and propylene glycol, are widely used in polymer synthesis, food industry and manufacturing of pharmaceuticals. Hydrolysis, coupled with hydrogenation and hydrogenolysis serves as an effective approach to transform biomass to polyols. This review summarizes the recent advances in biomass upgrading reactions for the production of polyols with a special emphasis on the formation of glycols.

Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents

Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system.

Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water.

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g−1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.

Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods

In this work, nanocellulose was extracted from bleached corncob residue (CCR), an underutilized lignocellulose waste from furfural industry, using four different methods (i.e. sulfuric acid hydrolysis, formic acid (FA) hydrolysis, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and pulp refining, respectively). The self-assembled structure, morphology, dimension, crystallinity, chemical structure and thermal stability of prepared nanocellulose were investigated. FA hydrolysis produced longer cellulose nanocrystals (CNCs) than the one obtained by sulfuric acid hydrolysis, and resulted in high crystallinity and thermal stability due to its preferential degradation of amorphous cellulose and lignin. The cellulose nanofibrils (CNFs) with fine and individualized structure could be isolated by TEMPO-mediated oxidation. In comparison with other nanocellulose products, the intensive pulp refining led to the CNFs with the longest length and the thickest diameter. This comparative study can help to provide an insight into the utilization of CCR as a potential source for nanocellulose production.

Cellulose nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated oxidation

Cellulose nanocrystals (CNCs) as a renewable and biodegradable nanomaterial have wide application value. In this work, CNCs were extracted from bleached chemical pulp using two stages of isolation (i.e. formic acid (FA) hydrolysis and 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) mediated oxidation) under mild conditions. In the first stage, FA was used to remove hemicellulose, swell cellulose fibers, and release CNCs. The FA could be readily recovered and reused. In the second stage, the CNCs isolated by FA were further modified by TEMPO-mediated oxidation to increase the surface charge of CNCs. It was found that the modified CNCs with more ordered crystal structure and higher surface charge had better redispersibility and higher viscosity in aqueous phase. Therefore, the modified CNCs could be more effective when used as rheology modifier in the fields of water based coating, paint, food etc.

Effective low-temperature hydrolysis of cellulose catalyzed by concentrated H3PW12O40 under microwave irradiation

Concentrated H3PW12O40 (HPW) was first employed to decompose cellulose under microwave irradiation at low temperatures. 75.6% yield of glucose was obtained at 90 °C under microwave irradiation for 3 h, which was considerably high under such mild conditions using phosphotungstic acid as a catalyst. With the same effective acid concentration, HPW gave the highest cellulose conversion and glucose yield among the Bronsted acid catalysts, indicating that the strong Bronsted acid played an important role during cellulose hydrolysis. In the hydrolysis of cellulose with HPW as catalysts, microwave irradiation led to higher glucose yields than the conventional heating method. The recovery and reusability of HPW were investigated by extraction with diethyl ether from the reaction solution. At the same time, the performance of the concentrated HPW for real lignocellulosic biomass (corncob, corn stover and bagasse) hydrolysis was also investigated.