FUEL
·
2024
·
IF 6.7
Wenli Zhang,Yijie Zhou,Zhenzhen Wu,Cheng Pan,Qunpeng Cheng,Guozhi Fan
A porous sulfonic acid-functionalized zirconium-based metal–organic framework possessing both Lewis acid and Brønsted acid sites (UiO-66-SO 3 H) was synthesized and tested for the selective conversion of furfural (FUR) to isopropyl levulinate (IPL) through one-pot cascade reaction. UiO-66-SO 3 H exhibited excellent catalytic performance, and the conversion of FUR as well as the yield and selectivity of IPL reached 96.4 %, 86.0 %, and 89.2 %, respectively. UiO-66-SO 3 H could be simply recovered and reused, but the catalytic performance was significantly decreased. The FUR conversion and IPL yield dropped to 73.8 % and 65.1 %, respectively, after 1 cycle, and the reason for the decrease in the catalyst activity were also investigated. It was found that the decrease was mainly caused by the loss of some −SO 3 H groups, and the cyclic performance of UiO-66-SO 3 H could be restored by supplementing a small amount of BDC-SO 3 Na. A plausible mechanism for the selective synthesis of IPL from FUR was proposed, wherein both Lewis acid and Brønsted acid sites played important roles. This work provides guidance for the selective conversion of FUR into IPL, and the high-valued utilization of biomass and its derivatives.
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DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Xinyu Wang,Mingyang Hu,Yun Liu
This study investigates a one-step process for the simultaneous separation of cellulose, hemicellulose, and lignin from lignocellulosic biomass using γ-valerolactone (GVL)/H 2 O pretreatment, which also converts hemicellulose to furfural (FF). A response surface methodology (RSM) was applied to optimize the process parameters. Under optimal conditions (163 °C for 1.5 h), the maximum FF yield reached 85.36 %, and cellulose purity was 80.80 %. The extracted GVL-lignin was characterized as low-molecular-weight guaiacyl-syringyl (G-S) type nanospheres with significant antioxidant activity. The conversion of hemicellulose to FF was enhanced by the synergistic interaction of Lewis acid (MgCl 2 ) and Brønsted acid (H 2 SO 4 ), which promoted the isomerization of xylose and dehydration to FF. The high-purity cellulose yielded 18.87 g/L ethanol through separate hydrolysis and fermentation (SHF), 27 times higher than untreated solids. Additionally, GVL exhibited consistent performance in lignocellulose separation after six cycles. This method offers an efficient and sustainable approach to valorize lignocellulosic biomass, advancing the production of high-value products.
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DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Fei Wang,Yisong Zhang,Lupeng Shao,Chao Wang,Zhe Ling,Xianhai Zeng,Feng Xu,Yu Liu
The sustainability and profitability of biorefineries depend on the efficient utilization of all lignocellulosic components. Therefore, developing an integrated pretreatment process that facilitates efficient fractionation and targeted valorization is essential to ensure the viability of future biorefinery systems. Here, we present an integrated fractionation strategy that efficiently separates all major lignocellulosic components and converts them into a variety of valuable products. Specifically, an ultra-low concentration of p-toluenesulfonic acid (p-TsOH) selectively depolymerizes hemicellulose to xylose at a high yield (93.86%), while preserving cellulose and lignin. The resulting xylose hydrolysate is directly mixed with methyl isobutyl ketone (MIBK) to form a biphasic system, in which the Lewis acid AlCl3 cooperates with p-TsOH to dehydrate xylose into furfural with a yield of 93.14 mol%. The p-TsOH treated solids are subsequently subjected to mild hydrolysis in an acidified LiBr molten salt hydrate (MSH) system, yielding glucan oligomers at 76.34% and recovering lignin with a yield of 79.64%. Spectral analysis shows lignin enriched in less-condensed moieties (Hibbert's ketones, benzodioxane), favouring downstream valorization. Glucan oligomers are isolated by antisolvent precipitation. A screening environmental assessment based on the experimentally validated mass balance (100 kg bamboo feed) indicates a low fresh-material demand and manageable energy use: fresh PMI (process mass intensity, chemicals make-up only) ≈0.28 kg kg−1 combined products; E-factor ≈0.30 kg kg−1 (excluding water); and an energy intensity of ≈27.9 MJ kg−1 (≈1.39 kg CO2e per kg, assuming natural gas heating). This approach thus offers a practical and environmentally credible route to co-produce furfural, glucan oligomers, and structurally favourable lignin from lignocellulosic biomass.
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高影响因子
JOURNAL OF CATALYSIS
·
2026
·
IF 6
Jiaxing Zhang,Qi Jiang,Yongwang Li,Zheng Wang,Wanli Wang,Bingxin Zhu,Xingtao Wang,Kaiwei Wang,Yihao Wang,Yan Chen,Tianlei Wang,Xubin Zhang,Fumin Wang
SnO x clusters anchor and disperse Ni nanoparticles on Y zeolite. • Electronic transfer creates Ni δ+ sites, switching FOL adsorption flat to vertical. • Rearrangement Ea drops 52.9 to 38.8kJ·mol −1 ; over-hydrogenation Ea rises 59.9 to 88.3 kJ· mol −1 . • 10Ni/Sn-Y-30 affords 95.3% cyclopentanone yield at full conversion. The highly efficient and directionally selective hydrogenation-rearrangement of the biomass platform molecule furfural (FF) to high-value-added cyclopentanone (CPO) represents a core pathway for biomass upgrading and utilization. However, constructing highly active and selective non-noble metal catalysts that precisely suppress over-hydrogenation remains elusive. In this work, we report a SnO x cluster-modified Ni-based catalyst (10Ni/Sn-Y-30) supported on Y-type zeolite. According to the characterization and density functional theory (DFT) calculations, surface SnO x clusters act as robust anchoring sites for metallic Ni, thereby significantly boosting the dispersion of Ni nanoclusters. Furthermore, the directional electron transfer from Ni to SnO x creates electron-deficient Ni δ+ centers, which lowers the reduction energy barrier and optimizes the substrate adsorption configuration. The superiority of this regulation strategy is further corroborated by kinetic tests, attesting to its effective modulation of the rates of the primary and competing reactions. In an aqueous reaction system at 150 °C, the optimized 10Ni/Sn-Y-30 catalyst delivers exceptional catalytic activity, yielding a peak CPO yield of 95.3%. This study provides a novel design strategy for the precise structural modulation of low-cost, non-noble metal catalysts and the directional upgrading of biomass resources. Download: Download high-res image (125KB) Download: Download full-size image
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DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 86
·70139-70146
·
IF 3.84
Xing-Long Li,Tao Pan,Jin Deng,Yao Fu,Hua-Jian Xu
Furfural is a biomass-based bulk chemical and its derivatives have potential applications as renewable fuels and chemicals. A water-tolerant and stable solid acid catalyst modified hydrated tantalum oxide (TA-p) was developed for catalytic conversion of D-xylose to furfural in water–organic solvent biphasic system. This process was performed both in a batch reactor and a continuous fixed-bed reactor. In the batch process, D-xylose conversion and furfural yield were significantly affected by the organic solvent, reaction temperature and reaction time. 1-Butanol, which could be obtained through the fermentation of biomass-based carbohydrates, was selected as organic phase and the highest furfural yield of 59% was achieved with D-xylose conversion of 96% at 180 °C in the continuous process. Moreover, the long-time stability test for 80 h under the optimal conditions showed the excellent stability of TA-p catalyst.
研究领域:
生物化学
·
催化化学
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DOI
高影响因子
GREEN CHEMISTRY
·
2017
·Vol. 19
·期 16
·3869-3879
·
IF 9.125
Shurong Wang,Yuan Zhao,Haizhou Lin,Jingping Chen,Lingjun Zhu,Zhongyang Luo
For the purpose of building a green reaction system to produce furfural (FF), the conversion of two important pentoses from hemicellulose, namely xylose and arabinose, was investigated in an aqueous reaction system including a Lewis acidic ionic liquid as a catalyst and renewable γ-valerolactone (GVL) as a co-solvent. The results showed that the introduction of GVL greatly improved the reactivity of pentose and inhibited the secondary decomposition reaction of FF compared to a pure-water reaction system. NMR analysis suggested that the composition of pentose conformers was greatly altered towards a reactive distribution. The highest FF yields were 79.76% (from xylose) and 58.70% (from arabinose), which were obtained at 140 °C. The influence of reaction parameters on pentose conversion was also studied. A comparison between different reaction conditions suggested that arabinose had less reactivity than xylose, leading to its lower conversion rate and FF yield. Furthermore, xylan and real biomass materials were tested in the proposed reaction system, and decent FF yields of up to 69.66% (from xylan) and 47.96% (from corn stalk) were obtained.
研究领域:
生物化学
·
绿色化学
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DOI
高影响因子
CELLULOSE
·
2018
·Vol. 25
·期 7
·3843-3851
·
IF 3.809
Hu Hui-Chao,Zhang Yu,Zeng Tong,Zhou Weining,Chen Lihui,Huang Liulian,Ni Yonghao
This paper reports a robust method for rapid determination of cellulose derived 5-hydroxymethyl-2-furfural (5-HMF) in biomass hydrolysate suspension based on headspace gas chromatography (HS-GC). The headspace equilibration at 150 °C for longer than 4 min with a pH range of 2.0–3.5 and a 50% (v/v) of ethanol content can obtain the full evaporation of 5-HMF, and eliminate the formation of additional 5-HMF generation from hexose. The linear GC response of 5-HMF was achieved by controlling the sample size within 20 μL. The results showed that this method has a good precision (relative standard deviation < 6.97%) and accuracy (recoveries ranged from 94.0 to 104.8%). The limit of quantification of the method was 51 mg/L. It was also found that a considerable amount of furfural (13.8%) and 5-HMF (18.7%) was adsorbed on condensed lignin and humins in residual biomass, and the washing procedure with ethanol can completely extract the adsorbed furfural and 5-HMF. The present method is accurate, simple, and robust, it will be a powerful tool for determining the content of 5-HMF in the liquid samples from biorefinery related processes.
研究领域:
分析化学
·
生物能源
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DOI
高影响因子
Journal of Chemistry
·
2020
·
IF 1.79
Zhaozhuo Yu,Weibo Wu,Hu Li,Song Yang
Hydrogenation of bio-based furfural (FUR) to furfuryl alcohol (FFA) is tremendously expanding the application of biomass in many industries such as resins, biofuels, and pharmaceuticals. However, mass manufacture of FFA from FUR is restrained by strict requirements of reaction conditions and expensive catalysts. In this work, an economical and benign catalytic system, containing an easily prepared and reusable catalyst 5 wt.% KF/ZrO2 and a low-cost hydrogen source polymethylhydrosiloxane (PMHS), was developed to be efficient for the hydrogenation of FUR to high-value FFA under mild conditions. The catalyst reactivity was found to be remarkably influenced by the support acid-base properties and KF loading doge. In the presence of 5 wt.% KF/ZrO2, a high FFA yield of 97% and FUR conversion of 99% could be obtained at 25°C in just 0.5 h, which was superior to those attained with other tested catalysts. The KF/ZrO2 catalyst could be recycled at least five times, with the FFA yield slightly decreasing from 97% to 71%. The spare decrease in FFA yield is possibly attributed to the catalyst pore blocking, as clarified by SEM, BET, XPS, and ICP-MS measurements of the fresh and reused catalysts.
研究领域:
化学工程
·
可再生资源利用
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 13.2
Yinze Yang,Pengxiao Wei,Yan Du,Shiyu Huang,Dongyang Li,Haiyang Cheng,Fengyu Zhao
The sustainable synthesis of primary amines from renewable biomass is a key goal of green chemistry. Reductive amination of furfural (FAL), a representative biomass platform molecule, provides a direct route to furfurylamine (FAM), yet noble-metal catalysts remain dominant in this field, limiting large-scale application due to high cost and scarcity. Herein, we report non-noble Ni/HZSM-5 catalysts with tunable SiO 2 /Al 2 O 3 ratios that achieve up to 99% yield of FAM with a high generation rate (10.8 mmol FAM mmol Ni −1 h −1 ) under mild conditions (90 °C, 1 MPa H 2 , 0.8 MPa NH 3 ). Mechanistic studies reveal that the synergistic interface between metallic Ni and Brønsted acid sites facilitates hydrogen activation and spillover, enhances imine adsorption, and stabilizes gem- diamine and is beneficial for its ammonolysis. The catalyst also demonstrates excellent recyclability and broad substrate scope, affording >90% yields of primary amines for the reductive amination of the various aldehydes and ketones. This work provides mechanistic insights into Brønsted acid–metal synergy and establishes a sustainable, cost-effective strategy for the green synthesis of primary amines.
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DOI
高影响因子
CATALYSIS LETTERS
·
2022
·Vol. 153
·期 4
·956-964
·
IF 2.936
Han Song,Chen Wen-Ting,Gao Zi-Teng,Guan Hua,Li Zhang-Min,Tao Duan-Jian
A mechanochemical treatment and subsequent high temperature annealing strategy was developed for the synthesis of nitrogen-doped carbon supported cobalt catalysts. The as-prepared Co/NC 800 catalyst was demonstrated for efficient and selective hydrogenation of furfural into furfuryl-based alcohols and amines with good to excellent yields under optimum conditions. Graphical
研究领域:
催化
·
材料科学
·
有机化学
·
化学合成
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DOI
高影响因子
ACS Catalysis
·
2016
·
IF 9.307
Shanhui Zhu,Yanfeng Xue,Jing Guo,Youliang Cen,Jianguo Wang,Weibin Fan
The high-yield synthesis of the biofuel γ-valerolactone (GVL) is a challenging task, which currently stems from the depolymerization of cellulose to levulinic acid, followed by its hydrogenation. We have developed a novel integrated process for the production of GVL from hemicellulose without using liquid acids and external hydrogen. The hemicellulose feed underwent hydrolysis and consecutive dehydration to produce furfural over ZSM-5 catalyst. Subsequently, the formed furfural with 2-propanol performed tandem conversion to GVL over Au/ZrO2 catalyst combined with ZSM-5. This process gave a high yield of GVL under mild conditions: up to 61.5% based on hemicellulose. The outstanding performance was mainly ascribed to the strong interface interaction of Au with ZrO2 species, large amounts of medium-strength acid sites over ZSM-5, and efficient synergy between active metal and acid sites.
研究领域:
生物化学
·
催化化学
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DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2026
·Vol. 14
·期 2
·121185
·
IF 7.2
Peng Gao,Li Liu,Guirong Bao,Dequan Chen,Jia Luo,Xuewu Ji,Wenyao Deng
The conversion of furfural (FF) to cyclopentanone (CPO) via selective hydrogenation-rearrangement represents a crucial route for sustainable, high-value valorization of renewable biomass feedstocks. In this study, carbon dots (CDs) were utilized as both a reducing and a dispersing agent for the one-pot green photoreduction synthesis of PdAg bimetallic catalysts supported on CDs (Pd x Ag y /CDs) in aqueous phase. Among the catalysts with varying Pd-to-Ag molar ratios, the Pd 0.5 Ag 1 /CDs catalyst demonstrated exceptional performance, achieving 100 % FF conversion and 93.3 % CPO selectivity within 4 h at 200 °C. The superior activity is attributed to a synergistic effect between the acid sites on the CDs and the PdAg alloy, which facilitates the rearrangement of the intermediate furfuryl alcohol (FA). Mechanistic studies, including calculations of the free energy barriers for elementary steps from FA to 4-hydroxy-2-cyclopentenone, revealed a ring-opening pathway for the furan methyl carbocation, which dramatically reduces the reaction energy barrier to 47.1 kJ/mol from 195.8 kJ/mol of the Piancatelli pathway. This work not only presents an efficient and green catalyst for FF upgrading but also highlights the promising application of CDs in advanced catalytic systems for circular economy-driven chemical production.
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高影响因子
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