ACS Catalysis
·
2017
·
IF 10.614
Chengtao Wang,Zhiqiang Liu,Liang Wang,Xue Dong,Jian Zhang,Guoxiong Wang,Shichao Han,Xiangju Meng,Anmin Zheng,Feng-Shou Xiao
The metal-catalyzed selective hydrogenation of biomass-derived molecules is in great demand but is challenging due to the complex reaction pathways. Herein, we report a persuasive example for achieving selective hydrogenation of furfural over Pd catalysts by controllable sorption of molecules in zeolite micropores. The key to this success is fixation of Pd nanoparticles inside of silicalite-1 zeolite with controllable wettability (Pd@S-1-OH) by functionalizing silanol groups into the zeolite framework. In the hydrogenation of furfural as a model reaction, the Pd@S-1-OH catalyst with appropriate hydrophilicity exhibits extraordinary selectivity for the formation of furan, giving furan selectivity as high as >99.9% with a complete conversion of furfural, outperforming the conventional Pd nanoparticles supported on zeolite crystals (Pd/S-1) and S-1 zeolite fixed Pd catalysts without an artificially functionalized silanol group (Pd@S-1). The extraordinary performance of Pd@S-1-OH is reasonably attributed to the controllable diffusion of molecules within the hydrophilic zeolite micropores, which favors the adsorption of furfural and a series of byproducts but promotes the desorption of furan. Very importantly, Pd@S-1-OH is stable and gives the furan productivity of ∼583.3 g gPd–1 day–1 in a continuous test.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
CATALYSIS TODAY
·
2016
·
IF 4.312
Xiaodan Li,Xiaocheng Lan,Tiefeng Wang
The selective catalytic oxidation of furfural to 2(5H)-furanone, succinic acid (SA) and maleic acid (MA) was studied. Under optimized conditions, furfural was oxidized to 2(5H)-furanone with a yield of 60–62% in an aqueous/organic bi-phasic system using 1,2-dichloroethane or ethyl acetate as the solvent and formic acid as the catalyst, while the total yield of SA and MA was 15–20%. Compared with other homogeneous and heterogeneous acid catalysts, formic acid gave a much higher selectivity to 2(5H)-furanone because it reacted with hydrogen peroxide to generate performic acid that had a strong oxidizing nature and good solubility in both the aqueous and organic phases. The solvent had a significant influence on the product distribution. A simplified reaction network was established to quantitatively analyze the solvent effect based on the reaction rate constants. In the homogeneous system, the yield of 2(5H)-furanone decreased while the yield of SA increased with an increasing dielectric constant of the solvent. The formic acid/furfural molar ratio, reaction temperature and furfural concentration were optimized for the selective oxidation of furfural to 2(5H)-furanone in the bi-phasic reaction system.
研究领域:
化学工程
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催化化学
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DOI
高影响因子
Biomass Conversion and Biorefinery
·
2021
·Vol. 13
·期 9
·8115-8121
·
IF 4.987
Ren Dezhang,Jiang Xuelei,Zhang Nahui,Duo Jia,Norinaga Koyo,Huo Zhibao
Production of pyridine derivatives from bio-based feedstocks instead of fossil fuels is a promising strategy. The development of effective heterogeneous catalysts and mild reaction systems for pyridinization of renewable biomass derivatives remains a huge challenge. In this article, a direct and environment-friendly method was reported to produce 3-hydroxypyridine from bio-based furfural in water over a Raney Fe catalyst. Raney Fe exhibited an efficient catalytic performance for activation of the aldehyde group of furfural and afforded an 18.2% yield of 3-hydroxypyridine at 120 °C with ammonia as N source. The polymerization of furfural on the catalyst in hot water was the main cause of deactivation, which was verified by the scanning electron microscope (SEM), X-ray diffraction (XRD), and N 2 adsorption and desorption analysis. A possible mechanism for this reaction was also proposed. This study provides a new way for academia and industry to realize the synthesis of nitrogen-containing chemicals from biomass and its derivatives.
研究领域:
催化化学
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绿色化学
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可再生资源转化
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DOI
高影响因子
Biomass Conversion and Biorefinery
·
2021
·Vol. 13
·期 9
·7895-7907
·
IF 4.987
Xia Qi,Peng Hong,Zhang Yu,Fu Guiming,Liu Yuhuan,Xiao Zhihong,Huang Lingling,Bi Haoran
Exploring environmental-friendly routine for efficient furfural production from lignocellulosic biomass is meaningful. Here, bamboo hemicellulose (BH) and xylose were used to produce furfural under microwave irradiation in a biphasic medium, in which 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO 4 ) served as the reaction phase and catalyst, whereas 1,4-dioxane served as the extraction phase. The effects of retention time, temperature, [Bmim]HSO 4 dosage, and water addition on the furfural yield were evaluated. Results showed the highest total furfural yields of xylose and BH could reach 55.65 mol% and 68.37 mol%, respectively, which were further enhanced to 63.87 mol% and 85.69 mol%, respectively, by adding a small amount of water. The kinetic analysis showed the dehydration rate constant of the formed xylose from BH to furfural was almost twice that of directly using xylose as substrate. Compared with the hydrolysis of BH to xylose, the dehydration of xylose to furfural required higher activation energy. The activation energy of consuming furfural to form by-products was higher than 73 kJ/mol. The recycled [Bmim]HSO 4 performed great reusability, and a small amount of ethanol residue could enhance the total furfural yields of xylose and BH, up to 73.48 mol% and 88.28 mol%, respectively.
研究领域:
生物化学
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可再生资源工程
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高影响因子
Biotechnology for Biofuels and Bioproducts
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2023
·Vol. 16
·期 1
·1-11
·
IF 0
Zhang Zhen,Tao Furong,Ji Hairui
Background As one of the most abundant bioresource in nature, the value-added utilization of lignocellulosic biomass is limited due to its inherent stubbornness. Pretreatment is a necessary step to break down the recalcitrance of cell walls and achieve an efficient separation of three main components (cellulose, hemicelluloses, and lignin).Results In this study, hemicelluloses and lignin in Boehmeria nivea stalks were selectively extracted with a recyclable acid hydrotrope, an aqueous solution of P-toluenesulfonic acid (p-TsOH). 79.86% of hemicelluloses and 90.24% of lignin were removed under a mild pretreatment condition, C80T80t20, (acid concentration of 80 wt%, pretreatment temperature and time of 80 °C and 20 min, respectively). After ultrasonic treatment for 10 s, the residual cellulose-rich solid was directly converted into pulp. Subsequently, the latter was utilized to produce paper via mixing with softwood pulp. The prepared handsheets with a pulp addition of 15 wt% displayed higher tear strength (8.31 mN m2/g) and tensile strength (8.03 Nm/g) than that of pure softwood pulp. What’s more, the hydrolysates of hemicelluloses and the extracted lignin were transformed to furfural and phenolic monomers with yields of 54.67% and 65.3%, respectively.Conclusion sThe lignocellulosic biomass, Boehmeria nivea stalks, were valorized to pulp, furfural, and phenolic monomers, successfully. And a potential solution of comprehensive utilization of Boehmeria nivea stalks was provided in this paper.Graphical Abstract
研究领域:
生物化学
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材料科学
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可再生资源利用
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DOI
PubMed
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2023
·Vol. 98
·期 5
·1166-1174
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IF 3.4
Min Yuan,Zhiqing Liu,Tiantian Lv,Jinxiang Dong,Qi Shi
BACKGROUND The separation of furfural from a low-concentration multicomponent and acid-containing aqueous solution is a highly demanding process; traditional distillation requires an excessive amount of energy. Herein, we demonstrated ZIF-8-derived microporous carbon (C) as a promising adsorbent for the separation of furfural using adsorption isotherms, dynamic column adsorption, adsorption kinetics and desorption studies. RESULTS In the competitive adsorption kinetics experiments with a furfural/acetic acid concentration of 50/20 g L −1 , the acetic acid adsorbed in the micropores of NC ZIF-8 1000C-800A gradually was replaced by furfural, whereas the amount of acetic acid in the mesopores of NC ZIF-8 800C-800A slowly increased. In addition, the micropores of NC ZIF-8 1000C-800A exhibited highly efficient and fast adsorption characteristics toward furfural over a wide furfural/acetic acid concentration range (0–50/0–20 g L −1 ) with the furfural adsorption capacity reaching an adsorption equilibrium within 10 min. The results show that the high Brunauer–Emmett–Teller surface area of NC ZIF-8 1000C-800A is responsible for the high furfural adsorption capacity (1205.3 mg g −1 ) and the confined microporous structure can strengthen the π–π interactions between porous C and furfural, thereby enhancing the selectivity of furfural/acetic acid (61.4) in the furfural/acetic acid (50/20 g L −1 ) dynamic column adsorption system. Meanwhile, the desorption ratio of furfural in the dynamic desorption system reached as high as 98.6%. CONCLUSION The unique micropore-confinement effect and excellent adsorption behavior make NC ZIF-8 1000C-800A an efficient adsorbent for furfural in the furfural–acetic acid system. © 2023 Society of Chemical Industry (SCI).
研究领域:
化学工程
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材料科学
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环境科学
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高影响因子
ACS Catalysis
·
2022
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IF 13.7
Weipeng Song,Huai Liu,Junhua Zhang,Yong Sun,Lincai Peng
Furfural represents one of the most valuable biomass-derived platform molecules. Its selective production with a smart and tractable catalytic system is highly attractive for technical implementation, yet remains challenging. We herein report a promising protocol involving the mature Hβ zeolites in pure 1,4-dioxane to convert hemicellulose-related sugars into furfural with high rate and impressive selectivity under mild operating conditions. Furfural yields as high as 93.6% (from xylose) and 85.9% (from xylan) were accomplished at 140 °C in 40 min. The solvent 1,4-dioxane served as a shield to maintain the crystal structure and acidic center of Hβ as well as to inhibit the polymerization of furfural. The synergistic action of Hβ with 1,4-dioxane largely promoted the selective conversion of xylose to furfural, as the multiple immobilized acid sites of Hβ in 1,4-dioxane medium accelerated xylose-to-xylulose isomerization. The dehydration process was favorable based on its apparent activation energy of 39.1 kJ mol–1, leading to a high turnover frequency of 53.8 h–1. Density functional theory calculations revealed that the superior catalytic behavior could be ascribed to the higher adsorption of xylose than 1,4-dioxane, allowing xylose molecules to fully access the open Al sites of Hβ and the low Gibbs free energy barrier of xylose isomerization to xylulose in 1,4-dioxane over the Hβ catalyst. Moreover, the heterogeneous zeolite catalyst and the single low-boiling-point solvent 1,4-dioxane (101 °C) were readily recovered from the product with outstanding reusability. This contribution not only opens a high potential avenue for the selective production of furfural but also sheds light on the coordination mechanism of Hβ zeolite and 1,4-dioxane toward developing tailored processes.
研究领域:
化学工程
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催化
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生物质转化
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绿色化学
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DOI
高影响因子
Catalysts
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2023
·Vol. 13
·期 4
·663
·
IF 3.9
Xu Wu,Heqin Guo,Litao Jia,Yong Xiao,Bo Hou,Debao Li
The base-free oxidation of furfural by non-noble metal systems has been challenging. Although MnO2emerges as a potential catalyst application in base-free conditions, its catalytic efficiency still needs to be improved. The crystalline form of MnO2is an important factor affecting the oxidation ability of furfural. For this reason, four crystalline forms of MnO2(α, β, γ, and δ-MnO2) were selected. Their oxidation performance and surface functional groups were analyzed and compared in detail. Only δ-MnO2exhibited excellent activity, achieving 99.04% furfural conversion and 100% Propo.FA(Only furoic acid was detected by HPLC in the product) under base-free conditions, while the furfural conversion of α, β, and γ-MnO2was below 10%. Characterization by XPS, IR, O2-TPD and other means revealed that δ-MnO2has the most abundant active oxygen species and surface hydroxyl groups, which are responsible for the best performance of δ-MnO2. This work achieves the green and efficient oxidation of furfural to furoic acid over non-noble metal catalysts.Keywords:base-free;MnO2;crystal type;furfural oxidation to furoic acid
研究领域:
催化化学
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绿色化学
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DOI
高影响因子
ENVIRONMENTAL TECHNOLOGY
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2023
·
IF 2.8
Haihong Xia,Jing Li,Jun Zhao,Minghao Zhou,Jianchun Jiang
Cyclopentanol (CPL) was an eco-friendly solvent as well as important platform chemical which could be generated from biomass-derived furfural (FFA). In this paper, a series of Ni, Cu, Mo, Co bimetallic catalysts with different metals loadings supported on carbon nanotubes (CNT) were synthesized by an impregnation method for aqueous-phase hydrogenation of FFA to obtain CPL. Various effects of reaction parameters such as reaction solvent, reaction temperature, reaction time and different loading amounts of Ni over bimetallic Ni-based CNT catalysts were fully investigated. Among the catalysts studied, (15 + 5) wt% NiCu/CNT catalysts showed a high conversion of FFA and 88% selectivity towards CPL in water and 96% selectivity towards acetal in methanol at the mild condition of 160℃, 2 MPa hydrogen and 4 h reaction time. NiCu bimetallic synergistic effect was interpreted through H2-TPR and NH3-TPD measurement and a possible pathway was proposed. The features of the CNT-supported catalysts were investigated via XRD, XPS, TEM, H2-TPR and NH3-TPD. The Ni and bimetallic NiCu catalysts synthesized in this work were inexpensive and simple, which made them a promising candidate for the conversion of biomass-derived FFA to CPL.
研究领域:
化学工程
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催化材料
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
·
IF 22.1
Wanying Liang,Guangyue Xu,Yao Fu
A series of metal-TS-1 zeolite catalysts were designed to selectively catalyze the photo oxidation of furfural to C 4 carboxylic acid derivatives at ambient temperature and pressure. The photocatalytic preparation of malic acid from furfural was realized for the first time. The selective distribution of products could be controlled by adjusting the physical and chemical characteristics of the catalyst. Smaller pore size prevented the further conversion of maleic acid to malic acid; moderate acidity was beneficial for the preparation of malic acid; lower valence band was in favor of maleic acid production while higher valence band tended to form malic acid. The synergistic effect of pore structure, acidity and energy band structure of catalysts affected the product distribution. The yield of maleic acid reached as high as 40% over Fe-TS-1, meanwhile, the yield of malic acid reached as high as 63% over Ni-TS-1. The doping of metal was believed to be an effective procedure to adjust the structure and physicochemical properties of zeolite. Matel-TS-1 zeolite was also expected to be widely used in photocatalytic system to achieve more selective reactions.
研究领域:
化学工程
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材料科学
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DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Yang Peng,Haikuan Yang,Ting Zhang,Songsong Zhou,Haiwei Jiang,Yongjie Zheng,Weiran Yang
Synthesis of γ -butyrolactone (GBL) from renewable biomass resources under mild reaction condition with catalysis is attractive but challenging. Herein, we report the photocatalytic oxidation of the biomass-based furfural derivative tetrahydrofurfuryl alcohol (THFAL) to prepare GBL under light irradiation (365 nm) in air at room temperature. Utilising Ru/TiO 2 as the photocatalyst and air as the oxidant, a GBL yield as high as 73 % was achieved. The reaction mechanism was studied rigorously by performing photocatalyst performance evaluation, material characterisation, free-radical quenching reactions and electron spin resonance (ESR). In situ diffuse reflectance infrared Fourier transform spectroscopy was employed to detect intermediate products and elucidate the mechanism at the molecular level. Based on the in-situ monitoring results, we propose a pathway for the oxidation decarbonylation of THFAL to produce CO 2 and GBL.
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高影响因子
Journal of Biobased Materials and Bioenergy
·
2014
·Vol. 8
·期 4
·437-443
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IF 0.586
Wang Wenju,Ren Junli,Li Huiling,Peng Feng,Sun Runcang,Liu Shijie
A feasible and environmental-friendly approach was developed for the dehydration of xylose into furfural using AlCl3-dominant catalysts in a homogeneous DMSO/H2O system. Results showed that the paired chlorides (AlCl3/KCl) in the molar fraction (χAlCl3
)
of 0.6 displayed the better catalytic performance than the single AlCl3 and the other paired chlorides. The influences of catalyst amount, reaction temperatures as well as xylose concentration on the dehydration of xylose into furfural were studied. The effects of co-solvents (DMF,
DMI, DMAC and NMP) on the production of furfural were also investigated. DMSO exhibited the better enhancement effect and the desirable DMSO/water volume ratio was 5:5, indicating DMSO could efficiently suppress the side reaction and enhance the selectivity. The maximum furfural yield of 43.6%
with xylose conversion of 97.9% and the selectivity of 44.6% was achieved at 170°C for 2 h with a total catalyst/xylose molar ratio of 0.5 at the solid to liquid ratio of 1:10.
研究领域:
化学工程
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生物质转化
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DOI
高影响因子
危险品化学品经营许可证（带存储）