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Molecular Catalysis · 2021 · IF 5.062

Feasible synthesis of bifurfural from renewable furfural derived 5-bromofurfural for polymerization

Jinlian Zhu,Yu Lei,Zhuqi Chen,Yonggui Liao,Guochuan Yin

Deriving versatile monomers from bulky biomass for polymer production can greatly replace fossil resources as the carbon source of chemical industry. The present studies introduce the feasible synthesis of bifurfural, a bifunctionalized bifuran monomer, from the furfural platform. The reaction was carried out through reductive coupling of 5-bromofurfural with CO as the reductant source with commercial Pd/C as the catalyst under gentle conditions, and the catalyst is recyclable and reusable. So prepared bifurfural was preliminarily investigated as a monomer for poly(Schiff base) material synthesis, and it was found that the poly(Schiff base) derived from nonlinear bifurfural monomer polymerizing with linear p -phenylenediamine demonstrated larger surface area than that from petrochemical 4,4′-biphenyldicarboxaldehyde with excellent thermal stability, thus offering a new opportunity in bifurfural based furfural utilization in polymer industry.

CAS / MDL: 108-45-2
研究领域: 化学工程 · 材料科学
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ENERGY & FUELS · 2017 · IF 3.091

Conversion of C5 Carbohydrates into Furfural Catalyzed by SO3H-Functionalized Ionic Liquid in Renewable γ-Valerolactone

Haizhou Lin,Jingping Chen,Yuan Zhao,Shurong Wang

To obtain an efficient and green reaction system for the production of furfural (FF), this study investigated the use of a SO3H-functionalized ionic liquid as a catalyst for the conversion of xylose in a solvent of renewable γ-valerolactone (GVL). A high FF yield of 78.12% was obtained in this reaction system catalyzed by 1-propylsulfonic-3-methylimidazolium chloride at 140 °C. The GVL remarkably enhanced the reaction rate and increased the xylose conversion and FF yield because the solvent effect of GVL could improve the catalytic activity of the acidic protons and suppress the side reactions. In addition, the ionic liquids showed satisfactory catalytic performance in the conversion of xylose to FF due to functionalization by introducing a SO3H group. The conversion of other C5 carbohydrates (arabinose and xylan) was also tested in this system, and moderate FF yields were achieved.

CAS / MDL: 108-29-2 25990-60-7
研究领域: 生物化学 · 绿色化学
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS · 2022 · IF 6.437

Improving the production of furfural from cellulose catalytic pyrolysis using WO3/γ-Al2O3 composite oxides

Koïta Djakaria,Ziyue Tang,Jingai Shao,Xu Chen,Haoyu Xiao,Joseph Smith,Haiping Yang,Hanping Chen

Furfural is one of the top valuable building block chemicals, the selective production of furfural from biomass has attracted increasing concerns in recent years. In this work, a novel method for the selective production of furfural through cellulose catalytic pyrolysis with WO 3 /γ-Al 2 O 3 was reported, and the synergistic effect between γ-Al 2 O 3 and WO 3 was explored. Compared with cellulose pyrolysis alone, the addition of γ-Al 2 O 3 improved the selectivity of furans and greatly inhibited the formation of sugars; while, WO 3 addition promoted the formation of levoglucosenone . When (20–40%) WO 3 /γ-Al 2 O 3 were added, the amount of sugars was further reduced, and the yields of furans (furfural and 2-methylfuran, in particular) were further increased at the same time. Under the optimum conditions (temperature = 600 °C, residence time = 15 s, and catalyst to cellulose mass ratio of 4), 30%WO 3 /γ-Al 2 O 3 showed the best performance, and the selectivity and yield of furfural were improved by nearly 100% and 300%, respectively, as compared with cellulose pyrolysis alone. In addition, compared with γ-Al 2 O 3 , the addition of 30%WO 3 /γ-Al 2 O 3 further increased the yield of furfural and 2-methylfuran to about 50% and 200%, respectively. The high selectivity and yields of furans with WO 3 /γ-Al 2 O 3 addition might be due to that WO 3 crystals in the composite promote the formation of levoglucosenone, which is further converted to additional furans through the Lewis acid sites of γ-Al 2 O 3 . The study may provide some meaningful advices for improving the production of furfural from green catalytic pyrolysis of cellulose.

CAS / MDL: 9004-34-6 12036-22-5
研究领域: 化学工程 · 可再生能源
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ChemistrySelect · 2024 ·Vol. 9 ·期 40 ·e202402030 · IF 1.9

Efficiently Catalyzing Xylose to Furfural by Synthesizing Solid Acid Catalysts from Lignocellulosic Residues

Wei Tang,Haojie Qian,Xinyue Wang,Caoxing Huang

Graphical The solid acid catalysts were triumphantly prepared using the residues of poplar sawdust's enzymatic hydrolysis, which displayed the most acidic sites and high catalytic activity, and achieved the highest furfural yield and furfural selectivity during xylose conversion. The utilization of biomass as a carbon source for the synthesis of renewable solid acid catalysts (SA) has emerged as a prominent research direction in the field of heterogeneous catalysis. Based on the challenges associated with reusing residues from lignocellulosic biorefining, the biomass-based SA (BCSA) were prepared using poplar sawdust (PS), hydrothermally pretreated PS (PPS), and the residue of PPS's enzymatic hydrolysis (ER). The characterization revealed that all three types of BCSA were loaded with catalytic groups, and the BCSA synthesized using ER rich in lignin components exhibited a highly efficient catalytic structure. Furthermore, the catalysis of a 20 g/L xylose solution with BCSA-ER as SA also achieved the highest furfural yield (89.3%) and furfural selectivity (90.3%). The findings of this study suggested that lignin holds significant potential as a carbon carrier for SA, thereby offering a viable solution for utilizing by-products from lignocellulosic biorefining.

研究领域: 生物化学 · 催化材料科学
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Sustainable Energy & Fuels · 2018 ·Vol. 2 ·期 8 ·1863-1869 · IF 0

Synthesis of high-density and low-freezing-point jet fuel using lignocellulose-derived isophorone and furanic aldehydes

Jiawei Xie,Lei Zhang,Xiangwen Zhang,Peijuan Han,Junjian Xie,Lun Pan,De-Rong Zou,Song-Hua Liu,Ji-Jun Zou

Biofuels synthesized from lignocellulose-derived platform chemicals are very attractive for sustainable development. Here we reported a new and facile route to synthesize multi-substituted cycloalkanes with a high density and low freezing point using isophorone and furanic aldehydes (furfural and 5-hydroxymethylfurfural), by solvent-free aldol condensation, followed by hydrodeoxygenation. Catalysts were screened and NaOH showed good performance. The reaction conditions including catalyst dosage, isophorone/furanic aldehyde ratio, temperature and solvent were optimized, and finally the yields of 70.0% for isophorone/furfural and 72.8% for isophorone/5-hydroxymethylfurfural were obtained. Pt/HZSM-5 was prepared as the bifunctional catalyst for hydrodeoxygenation of the condensed product. The resultant multi-substituted cyclohexanes derived from isophorone/furfural and isophorone/5-hydroxymethylfurfural have a density of 0.813 g mL−1 and 0.846 g mL−1 respectively and both have a freezing point lower than −75 °C, and are very promising as stand-alone fuels or additives of other biofuels.

CAS / MDL: 98-01-1 78-59-1
研究领域: 生物化学 · 可再生能源
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INDUSTRIAL CROPS AND PRODUCTS · 2024 · IF 5.6

Microwave-enhanced pyrolysis of bamboo for furfural-rich bio-oil production over WS2 catalyst

Penghao Liu,Zhiwei Jiang,Yongjian Zeng,Yaolin Wang,Chen Zeng,Xin Tu,Kai Yan

The efficient utilization of bamboo waste has attracted increasing interest as a promising solution to address the challenges associated with climate change and promote a more environmentally friendly approach to resource utilization. Herein, we demonstrated the highly selective production of furfural from bamboo through a microwave-assisted pyrolysis (MAP) process using WS 2 catalysts. Firstly, the content of furfural can be precisely regulated by manipulating key process conditions such as microwave power, temperature and the mass ratio of WS 2 to bamboo. Notably, compared to non-catalyzed MAP, the presence of the WS 2 catalyst significantly enhanced the production of both furfural and furan components. The optimal content of furfural and furan components reached up to 66.9 area% and 75.6 area% in bio-oil under the conditions of 700 W, 400 °C and a 3:10 WS 2 to bamboo ratio for 15 min. Furthermore, the liquid oil mainly consisted of C5 and C6 products (86.5 area%), indicating that MAP enhances the selectivity of small molecular products and furan compounds when coupled with the WS 2 catalyst. Experimental results revealed that WS 2 played bifunctional roles as a microwave absorbent and catalyst, promoting the bio-oil content and limiting the secondary pyrolysis of furan components, leading to a high selectivity of furan and a high content of furan products. This work provides valuable insights into producing furan-rich bio-oil from bamboo through MAP over transition metal dichalcogenides materials.

CAS / MDL: 75-09-2 12138-09-9
研究领域: 能源与环境科学 · 催化化学
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CATALYSIS TODAY · 2017 · IF 4.636

Efficient and selective transformation of biomass-derived furfural with aliphatic alcohols catalyzed by a binary Cu-Ce oxide

Xinli Tong,Linhao Yu,Xuan Luo,Xuli Zhuang,Shengyun Liao,Song Xue

The efficient transformation of furfural (FUR) with aliphatic alcohols to achieve the carbon-chain growth has been developed using a binary Cu-Ce oxide as the catalyst. In the presence of molecular oxygen, the tandem oxidative condensation of FUR with n -propanol is successfully performed, in which an 85.4% conversion of FUR in 95.3% selectivity of 3-(furan-2-yl-)-2-methylacryaldehyde was obtained. The effects of different Cu/Ce ratios and base additives were investigated in detail. As a result, it is found that the CuO-CeO 2 (1: 9) catalyst is optimal and potassium carbonate is a suitable additive. Next, the recycling of CuO-CeO 2 catalyst was tested and there is no obvious activity loss after being reused five times. Moreover, the oxidative condensation of FUR with various aliphatic alcohols including ethanol, isopropanol, n -butanol and n -hexanol was studied where the long chain alcoholic molecule hinders the proceeding of reaction. Finally, based on the experimental results and reaction phenomena, a possible mechanism for the oxidative condensation of FUR with n -propanol-O 2 is proposed.

研究领域: 化学工程 · 催化化学
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BIORESOURCE TECHNOLOGY · 2022 · IF 11.889

Exploration of deep eutectic solvent-based biphasic system for furfural production and enhancing enzymatic hydrolysis: Chemical, topochemical, and morphological changes

Li-Li Sun,Zhuang Yue,Shao-Chao Sun,Shao-Ni Sun,Xue-Fei Cao,Tong-Qi Yuan,Jia-Long Wen

Developing a biorefinery process for a highly integrated valorization and fractionation of lignocellulose is crucial for its utilization. Herein, a biphasic system comprising choline chloride/lactic acid and 2-methyltetrahydrofuran with Al 2 (SO 4 ) 3 and H 2 SO 4 as catalysts was applied to pretreat Eucalyptus . Results showed that under the optimized conditions (150 °C, 30 min, 0.2 M Al 2 (SO 4 ) 3 , 0.075 M H 2 SO 4 ), the furfural yield and enzymatic hydrolysis efficiency could reach 54.7% and 97.0%, respectively. The efficient cellulose conversion was attributed to remarkable removal of lignin (91.0%) and hemicelluloses (100.0%), thereby causing the disruption of cell wall structure and enhancement of cellulose accessibility. Meanwhile, confocal Raman microscope and atomic force microscope displayed that the pretreatment resulted in the decreasing intensities of carbohydrates and lignin different regions of cell walls, and exposing of the embedded microfibers from noncellulosic polymers. Overall, the deep eutectic solvent-based biphasic system displayed high performance for effective utilization of carbohydrate components in lignocellulose.

研究领域: 生物化学 · 生物质能 · 林学
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ACS Catalysis · 2020 · IF 12.35

Hydrogenative Ring-Rearrangement of Biobased Furanic Aldehydes to Cyclopentanone Compounds over Pd/Pyrochlore by Introducing Oxygen Vacancies

Qiang Deng,Rui Gao,Xiang Li,Jun Wang,Zheling Zeng,Ji-Jun Zou,Shuguang Deng

Upgrading furanic aldehydes (such as furfural or 5-hydroxymethyl furfural) to cyclopentanone compounds (such as cyclopentanone or 3-hydroxymethyl cyclopentanone) is of great significance for the synthesis of high-value chemicals and biomass utilization. Developing an efficient reduced metal/acidic support with Lewis acidity is the key to facilitating the carbonyl hydrogenation and hydrolysis steps in the hydrogenative ring-rearrangement reaction. Herein, three pure Lewis acidic pyrochlore supports of the form A2B2O7 (La2Sn2O7, Y2Sn2O7, and Y2(Sn0.7Ce0.3)2O7-δ) with the same crystal structures and different metals are synthesized. The Lewis acidity and the surface properties of the pyrochlore can be tuned by inserting different kinds of A and B site metals. After impregnation, Pd nanoparticles with appropriate particle sizes are uniformly loaded on the surface of pyrochlore. For the reaction of the furanic aldehydes, all of these pyrochlore-based catalysts exhibit hydrogenation and hydrolysis rates that are both faster than those of traditional support-based catalysts due to the oxygen vacancy and pure Lewis acidity of the support. Among these pyrochlore-based catalysts, Pd/Y2Sn2O7 exhibits activity and selectivity that are higher than those of Pd/La2Sn2O7. Moreover, the Y2Sn2O7-based catalyst partially substituted by Ce3+ ions at the B site is more efficient, with the highest cyclopentanone yield and 3-hydroxymethyl cyclopentanone yield of 95.0% and 92.5%, respectively. Furthermore, the catalyst can still maintain an effective activity and stability after 4 runs. This study not only presents an efficient biobased route for the production of cyclopentanone compounds but also focuses on the acid catalytic performance of pyrochlore based on its pure Lewis acidity.

研究领域: 催化化学 · 生物质利用 · 材料科学
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FOOD CONTROL · 2025 · IF 6.3

Quantification of three furfurals in food using a triazine-based hydrazine derivatization reagent by MALDI mass spectrometry

Zhang-Na Qin,Zhen-Peng Zhen,Yu-Feng Gao

In this study, a high-throughput matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) method was developed for detecting three furfurals (furfural, 5-methylfurfural, and 5-hydroxymethylfurfural) in food. The derivatization of furfurals with 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH) resulted in a substantial increase in the m/z values of furfurals and an improvement in detection sensitivity. The compound 5-methoxymethylfurfural, a structural analogue of furfurals, was utilized as an internal standard to correct for fluctuations in mass spectrometry signals and matrix effects present in the real samples. The calibration curves exhibited good linearity in the furfural concentration range of 0.5–50 μg/mL, with correlation coefficients (R) exceeding 0.9996. The limits of quantification were in the range of 0.20–0.39 μg/mL. The furfural recoveries ranged from 89.2% to 116.2%, and the intra- and inter-day precisions were less than 10.8%, indicating high detection accuracy and precision. The developed method was successfully applied to the detection of furfurals in a variety of real samples, including roasted coffee beans, honey, and vinegar. The results demonstrated that the developed method was rapid and high-throughput, meeting the requirements for accurately detecting furfurals in various foods.

研究领域: 分析化学 · 食品科学 · 质谱技术
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CATALYSIS TODAY · 2018 · IF 4.667

A catalytic oxidative valorization of biomass-derived furfural with ethanol by copper/azodicarboxylate system

Hongge Cui,Xinli Tong,Linhao Yu,Ming Zhang,Yongtao Yan,Xuli Zhuang

An efficient tandem process for the oxidative condensation of furfural (FUR) with ethanol catalyzed by the copper/azodicarboxylate system has been developed. Firstly, the hydrogen transferring between FUR and ethanol is investigated under the nitrogen atmosphere by combining the azodicarboxylate and alkali carbonates, in which the main products are furfuryl alcohol and furan-2-acrolein. In the following, the cuprous halides and molecular oxygen are supplemented into the reaction system in order to improve the yield of furan-2-acrolein; therein, it is found that furfuryl alcohol is further oxidized and the selectivity of furan-2-acrolein is obviously elevated when CuI and o-phenanthroline (Phen) are used as the co-catalysts. Under optimal reaction conditions, 82.5% conversion of FUR with 87.7% selectivity of furan-2-acrolein is obtained with the assistance of diethyl azodicarboxylate (DEAD) and potassium carbonate. At last, a possible catalytic mechanism is proposed for the oxidative condensation reaction between FUR and ethanol in the presence of O 2 .

研究领域: 化学 · 生物质转化
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

Catalyst-Free Acetalization of Biobased Furfural into Cyclic Acetal Fuel Additives with Biogenic Ethylene Glycol

Li Bai,Mei Wu,Huazhong Yu,Shima Liu,Ke Song,Xianwu Zhou,Jie Guo,Jian He

Acetalization is a promising method for upgrading biomass-derived molecules into valuable chemicals, and acetal products are considered excellent oxygenated fuel additives. Herein, a catalyst-free, facile, and effective protocol for the acetalization of furfural and ethylene glycol is established, affording a 78.6% yield of 2-(furan-2-yl)-1,3-dioxolane with a furfural/ethylene glycol molar ratio of 1:15 in cyclohexane at 160 °C after 2 h. Moreover, the lower activation energy (15.8 kJ/mol) corroborates that the established system is efficient, and the thermodynamic studies demonstrate that catalyst-free acetalization is an endothermic, nonspontaneous, and endergonic reaction. A plausible mechanism including two pathways for catalyst-free acetalization of furfural and ethylene glycol is proposed, wherein the formed water from the acetalization process can render the ethylene glycol to be hydrolyzed, which plays a positive role in facilitating the acetalization of furfural and ethylene glycol. In addition, the excess ethylene glycol in the reaction mixture can be easily recovered and almost shows the same activity as fresh ethylene glycol in catalyst-free acetalization. Furthermore, the established catalyst-free protocol is viable for various biobased furanic compounds and alcohols, enabling broad access to various acetals. Finally, catalyst-free acetalization of furfural and ethylene glycol can be magnified to 10 times, showing the promising potential of large-scale production.

CAS / MDL: 620-02-0
研究领域: 生物化学 · 可再生资源 · 绿色化学
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