ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Yu Zhang,Huai Liu,Rui Zhang,Wenlong Jia,Junhua Zhang,Lincai Peng
Simultaneous utilization of lignocellulose-related glucose and xylose to produce methyl levulinate (ML), a versatile industrial commodity, is important to fully expend biomass components. We herein report a promising catalytic protocol involving the Hβ zeolite in dimethoxymethane (DMM) and methanol (MeOH) cosolvent that enables the coconversion of glucose and xylose to ML under one-pot conditions. ML yield as high as 56% with a turnover frequency (TOF) of over 3.2 h–1 can be accomplished at 150 °C. Isomerization–dehydration of glucose/xylose represents the primary reaction path, whereas the production of glycosides through etherification constitutes the secondary reaction path. The suggested catalytic mechanism is the preferential adsorption of C–O–C and C–OH groups at different acid sites, which leads to the emergence of two distinct pathways for the conversion of glucose/xylose into ML. Hβ-25, featuring a high concentration of Lewis and Brønsted acid sites, facilitates two distinct pathways for the conversion of glucose/xylose into ML. DMM functions as a hydroxymethylation reagent in the conversion of xylose to ML and promotes the isomerization of glycosides via ether exchange reactions. This contribution devises an efficient strategy for producing ML from glucose and xylose while elucidating the reaction mechanism of a tailored monolithic catalytic system.
研究领域:
生物化学
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催化化学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2023
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IF 15.1
Yujia He,Rui Zhang,Weipeng Song,Huai Liu,Junhua Zhang,Wenlong Jia,Lincai Peng
The simultaneous valorization of biomass-based C5 and C6 sugars to furfural, a versatile intermediate, is of great significance to fully utilize biomass components. Inability to effectively transform C6 sugars remains a major barrier toward this challenging goal. We herein report the 1,4-dioxane-mediated solvent system with Hβ zeolite catalyst for the transformation of glucose giving high yield to furfural (57%). The maintenance of intrinsic balanced Lewis and Brønsted acid sites from Hβ zeolite that is credited to the positive solvent effect of 1,4-dioxane is highly conductive to the selective C-C bond cleavage of glucose. Also importantly, the introduction of proper amount of H 2 O into the reaction system results in a high formation rate and an improved selectivity toward furfural due to the induction of highly reactive acyclic glucose. Glucose-to-furfural through 3-deoxyglucose should be more favorable than that via fructose. Impressively, the developed protocol can also be adapted to C5 sugars dehydration, and the one-pot conversion of glucose and xylose mixtures gains a furfural yield as high as 63%. The activation energy barrier for furfural production is higher from glucose compared to xylose. This work not only develops a promising protocol for furfural production simultaneously from C5 and C6 sugars but also provides insights into the mechanistic role of the solvent 1,4-dioxane to availably manipulate the acid-catalyzed conversion of C6 sugars.
研究领域:
生物化学
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催化化学
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DOI
高影响因子
RARE METALS
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2025
·Vol. 44
·期 4
·2379-2392
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IF 11
Na Guo-Quan,Cui Wen-Gang,Shi Hang-Yan,Li Zheng-Long,Gao Fan,Wang Xing-Qiang,Wang Ke,Gao Yong,Yang Ya-Xiong,Shen Zi-Chao,Pan Hong-Ge
High-capacity LiBH 4 is a promising solid hydrogen storage material. However, the large electron cloud density between the B-H bonds in LiBH 4 induces high dehydrogenation temperatures and sluggish dehydrogenation kinetics. To solve the above problems, it is proposed to enhance the hydrogen storage properties of LiBH 4 through the synergistic effect of Brønsted and Lewis acid in Hβ zeolite. Composite hydrogen storage systems with different mass ratios were prepared by simple ball-milling. At a LiBH 4 -to-Hβ mass ratio of 6:4, the 6LiBH 4 -4Hβ system released hydrogen at 190 °C and achieved a hydrogen release capacity of 7.0 wt% H 2 upon heating to 400 °C. More importantly, the hydrogen release capacity of the system reached 6.02 wt% at 350 °C under isothermal conditions after 100 min and 7.2 wt% at 400 °C under isothermal conditions after 80 min, whereas the pristine LiBH 4 only achieved 2.2 wt%. The improvement in hydrogen storage performance of the system was mainly attributed to two factors: (i) Lewis acid sites with acceptable electrons in the Hβ weaken the electron density of B–H bonds in LiBH 4 , and (ii) the H + proton from the Brønsted acid sites and H − of LiBH 4 undergo a H + + H − = H 2 reaction. Theoretical calculations revealed that the Lewis and Brønsted acid sites in the Hβ zeolite are conducive to the weakening of B – H bonds and that storage charge transfer occurs near the Lewis acid sites. The present work provides new insights into improving the hydrogen storage performance of LiBH 4 by weakening the B–H bonds in the LiBH 4 .
研究领域:
能源存储
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催化
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材料科学
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无机化学
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DOI
高影响因子
BIOMASS & BIOENERGY
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2025
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IF 5.8
Jiapeng Zhang,Wuyu Wang,Linfei Zhou,Xinghua Zhang,Longlong Ma
The synthesis of high-performance jet fuel from biomass presents a solution to energy crises and environmental pollution. This paper introduces a novel strategy for producing jet fuel with a high heat sink and low freezing point using bio-derived phenol and ethanol. The production route comprises two successive steps: the alkylation of phenol with ethanol, followed by hydrodeoxygenation (HDO), catalyzed by Hβ zeolite and Pt/C, respectively. The alkylation conditions were optimized at 260 °C for 8 h, achieving phenol conversion rates exceeding 95 % and yielding 88.7 % alkylphenol at a phenol to ethanol molar ratio of 1:3. The final HDO products consisted of 20.25 % monoethylcyclohexane, 44.87 % diethylcyclohexane, and 28.32 % triethylcyclohexane. These products demonstrated a heat sink capacity of 3.3 MJ/kg, a freezing point below −65 °C, a heat value of 45.4 MJ/kg, and a density of 0.82 g/cm 3 at 20 °C, surpassing the performance metrics of conventional JP-8 fuel. Kinetic studies on the alkylation revealed activation energies of 58.36 kJ/mol for O-alkylation and 122.07 kJ/mol for C-alkylation. The findings contribute to understanding the mechanisms of alkylation reactions between phenolic compounds and short chain alcohols. This work offers a straightforward and energy-efficient way to synthesize high-performance jet fuel from lignocellulosic derivatives, reducing processing energy consumption and enhancing feedstock utilization rates.
研究领域:
能源化学
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催化
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燃料科学
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化学工程
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生物质转化
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DOI
高影响因子
Molecular Catalysis
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2025
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IF 4.9
Qian Li,Liang Gao,Hao Zou,Yibin Luo,Xingtian Shu,Hao Wang
The dehydration-Prins condensation of tert‑butanol (TBA) and paraformaldehyde to produce 4,4-dimethyl-1,3-dioxane (DMD) was investigated using Hβ zeolites with a controlled Si/Al ratio. The acidic properties, including type, strength, and density, were systematically characterized, revealing that both total acid density and weak Brønsted acid density critically govern DMD selectivity. Specifically, reducing the weak Brønsted acid density from 204.91 to 92.94 μmol/g resulted in an 18 % decrease in DMD selectivity. Reaction pathway analysis identified the dehydration of TBA to isobutene as the key initial step. Furthermore, the introduction of extra-framework aluminum species enhanced the Lewis acid density and the Brønsted-to-Lewis (B/L) acid ratio. TBA dehydration experiments confirmed that Lewis acids originating from extra-framework aluminum significantly promote this critical step. Under the optimized conditions of 125 °C, 3.0 MPa, 0.417 mol of paraformaldehyde, 0.208 mol of TBA, 20 wt % H 2 O, and 1.7 wt % Hβ22, the conversion of TBA reached 59.1 %, the selectivity for DMD was 57.3 %, and the main by-product was identified as an over-condensation product with a 1,3-dioxane structure.
研究领域:
催化化学
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有机化学
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物理化学
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材料科学
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化学反应工程
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Weipeng Song,Junhua Zhang,Yong Sun,Rui Zhang,Lincai Peng,Huai Liu
Functionalizing biomass-derived furanic chemicals is of great importance towards biorefinery processes but challenging, especially working at elevated substrate concentrations. We herein report the intervention of 1,4-dioxane co-solvent availably to catalyze hydroxymethylation of furfuryl alcohol (FA) in formalin over Hβ zeolite, giving high yield to 2,5-dihydroxymethylfuran (DHMF), a versatile building block. Impressively, the facilitating effect of 1,4-dioxane on DHMF production became more pronounced with increasing FA feeding concentration, and the yield raised from 19.5 % to 67.8 % from a high FA concentration of 10 wt%. The 1,4-dioxane served not only as a catcher of formaldehyde hydrate to access substrate FA, but also as a shield to restrain undesirable condensation side-reactions. The developed protocol demonstrated an excellent universality in boosting the hydroxymethylation of electrondrawing-group-free furanic molecules (e.g., furan, 2-methylfuran). The understanding of these solvation effects can be employed to effectively manipulate and improve the hydroxymethylation of furanic compounds.
研究领域:
化学工程
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催化
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绿色化学
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生物炼制
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）