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γ-valerolactone
JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Using γ-Valerolactone as a Nontoxic Solvent for Fabricating Anion-Exchange Membrane via Nonsolvent-Induced Phase Separation

Yu-Xiang Jia,Lin Xie,Xiao-Guang Xu,Meng Wang

The nonsolvent induced phase separation (NIPS) method and its variants have garnered significant attention for the fabrication of ion-exchange membranes (IEMs) due to several potential advantages, including ease of scalability, reduced material requirements, and enhancements in operational performance. However, the hazards associated with traditional membrane fabrication solvents poses a considerable limitation to the advancement and application of NIPS. This study explores the use of a green solvent, specifically γ-valerolactone (GVL), for the first time in the preparation of IEMs via the NIPS technique. Initially, fundamental investigations, including thermodynamic and kinetic analyses of the casting solution composed of GVL and chloromethylated polysulfone (CMPS), as well as assessments of membrane morphology and electrochemical properties, are conducted to evaluate the feasibility of IEM production in comparison to the NMP/CMPS system. Additionally, some applied experiments, such as desalination by electrodialysis (ED) and acid recovery via diffusion dialysis (DD), are performed to examine the impacts of casting solution composition on the performances of the resulting membranes. The results from the ED experiments indicate that the membrane produced from a 19 w.% GVL/CMPS solution can achieve a 27% reduction in energy consumption while maintaining a comparable current efficiency to commercial membranes. Furthermore, the DD experiments reveal that this membrane exhibits a H + dialysis coefficient of 42 × 10 − 3 $$ 42\times {10}^{-3} $$ m/h and a separation factor of 256, significantly surpassing the performance metrics of commercial membranes. These findings clearly demonstrate that GVL is a viable green solvent for the preparation of polysulfone IEMs with highly competitive performance characteristics.

CAS / MDL: 108-29-2
研究领域: 材料科学 · 环境工程 · 化学工程
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BIORESOURCE TECHNOLOGY · 2024 · IF 9.7

Fully upgrade bamboo biomass into three multifunctional products through biphasic γ-valerolactone and aqueous phosphoric acid pretreatment

Leyu Zhu,Wenzhi Li,Xia Zhang,Liqun Wang,Jingting Jin,Zheng Zhou,Lulu Zhang

In this manuscript, three components of lignocellulosic biomass were obtained by deconstructing bamboo with γ-valerolactone-H 2 O biphasic system, and the delignification rate of 80.92 % was achieved at 120 °C for 90 min. Lignin nanospheres with diameters ranging from 75 nm to 2 um could be customized by varying the self-assembly rate. Furthermore, the lignin nanospheres-poly(vinyl alcohol) film was prepared by cross-linking lignin nanospheres and poly(vinyl alcohol), which can obtain 90 % ultraviolet absorption capacity, while the light transmittance in non-ultraviolet band was almost unchanged. At the same time, due to the strong hydrogen formation between lignin nanospheres and poly(vinyl alcohol) bond network, the tensile properties of the composite film were also improved by 30 %. Besides, the high specific surface area of biomass-derived porous biochar (2056 m 2 /g) can be obtained after carbonization of solid residues at 850 °C for 2 h, which was almost 8 times the specific surface area of the direct biomass carbonization due to the removal of lignin and hemicellulose. biomass-derived porous biochar can be used as an adsorbent, with a CO 2 capture capacity of 4.5 mmol g −1 at normal temperature (25 °C, 1 bar). The filtrate after the reaction contained a large amount of hemicellulose oligomers, which can be reacted with dichloromethane at 170 °C for 1 h to obtain the furfural yield of 74 %. In summary, the proposed biorefinery scheme achieves a full-component upgrade of lignocellulose and can be further applied in various downstream fields.

研究领域: 生物质能 · 材料科学 · 环境工程
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Catalysts · 2026 ·Vol. 16 ·期 2 ·185 · IF 4.5

Constructing Spatially Separated Ru Nanoparticles on Basic Support for the Hydrogenation of Ethyl Levulinate to γ-Valerolactone

Jie Yang,Yongsheng Liu,Xiaowen Guo,Qi Yang,Yejun Guan

Gamma-valerolactone (GVL) can be used as a renewable solvent, flavoring agent, and precursor to produce liquid fuels and fine chemicals. GVL is mainly produced by the efficient hydrogenation of levulinic acid and its esters over a wide range of bifunctional catalysts under harsh conditions because high temperature is generally required for GVL formation. So far, the hydrogenation of levulinic acids/esters under mild conditions remains a great challenge. In this study, 2 wt.% Ru was loaded onto ZSM-5 zeolite (MFI) via a deposition–precipitation method and further wrapped by crystallization, forming a core–shell structure. Moreover, the wrapped Ru catalyst was coated with a petal-like layer of Mg3Si4O9(OH)4(MgSiO3) via a hydrothermal reaction in a Mg(NO3)2solution, thereby introducing alkalinity and achieving spatial separation of Mg and Ru. This dual-functional catalyst reduces the inhibitory effect of Mg on the Ru active center and enables efficient preparation of GVL from ethyl levulinate (EL) under mild conditions, achieving 100% EL conversion and 98% GVL selectivity in the aqueous phase at 80 °C in 2 h under 0.5 MPa of H2.

CAS / MDL: 12125-02-9 1336-21-6
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JOURNAL OF THE CHINESE CHEMICAL SOCIETY · 2018 ·Vol. 65 ·期 11 ·1398-1406 · IF 0.862

Conversion of ethyl levulinate to γ-valerolactone catalyzed by the new Zr-containing organic–inorganic hybrid catalysts

Ruiying Wang,Jianjia Wang,Huimin Zi,Haijun Wang,Yongmei Xia,Xiang Liu

Three novel heterogeneous Zr-containing organic–inorganic hybrid catalysts were prepared for the transfer hydrogenation of biomass-derived ethyl levulinate (EL) to γ-valerolactone (GVL) with isopropyl alcohol (IPA) as the hydrogen donor and were characterized by Fourier transform infrared (FT-IR), Temperature-programmed desorption (TPD), Thermogravimetry (TG), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). On their basis, the effects of temperature, time, the amount of catalyst, and the solvent were investigated on the yield of GVL. A GVL yield of 96.5% with 99% EL conversion was obtained using Zr-Pg, which was prepared by the reaction of ZrCl 4 and phloroglucinol (Pg) in N , N -dimethylformamide (DMF) at room temperature. The high catalytic activity may be attributed to the strong basicity, which was increased by the sufficient quantity of phenate in the structure of Zr-Pg. Meanwhile, Zr-Pg could be efficiently and easily recycled at least five times without any notable loss of activity and selectivity. Through the results of comparative experiments and characterization, we propose a plausible reaction mechanism for the high activity of Zr-Pg.

CAS / MDL: 10026-11-6
研究领域: 催化化学 · 生物质转化 · 材料科学
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ACS Sustainable Chemistry & Engineering · 2015 · IF 4.642

Direct Conversion of Sugars and Ethyl Levulinate into γ-Valerolactone with Superparamagnetic Acid–Base Bifunctional ZrFeOx Nanocatalysts

Hu Li,Zhen Fang,Song Yang

Acid–base bifunctional superparamagnetic FeZrOx nanoparticles were synthesized via a two-step process of solvothermal treatment and hydrolysis–condensation, and were further employed to catalyze the conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) using ethanol as both H-donor and solvent. ZrFeO(1:3)-300 nanoparticles (12.7 nm) with Fe3O4 core covered by ZrO2 layer (0.65 nm thickness) having well-distributed acid–base sites (0.39 vs 0.28 mmol/g), moderate surface area (181 m2/g), pore size (9.8 nm), and strong magnetism (35.4 Am2 kg–1) exhibited superior catalytic performance, giving a high GVL yield of 87.2% at 230 °C in 3 h. The combination of the nanoparticles with solid acid HY2.6 promoted the direct transformation of sugars to produce GVL in moderate yield (around 45%). Moreover, the nanocatalyst was easily recovered by a magnet for six cycles with an average GVL yield of 83.9% from EL.

研究领域: 催化化学 · 材料科学 · 绿色化学
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BIORESOURCE TECHNOLOGY · 2016 · IF 4.917

Catalytic conversion of xylose and corn stalk into furfural over carbon solid acid catalyst in γ-valerolactone

Tingwei Zhang,Wenzhi Li,Zhiping Xu,Qiyu Liu,Qiaozhi Ma,Hasan Jameel,Hou-min Chang,Longlong Ma

A novel carbon solid acid catalyst was synthesized by the sulfonation of carbonaceous material which was prepared by carbonization of sucrose using 4-BDS as a sulfonating agent. TEM, N 2 adsorption–desorption, elemental analysis, XPS and FT-IR were used to characterize the catalyst. Then, the catalyst was applied for the conversion of xylose and corn stalk into furfural in GVL. The influence of the reaction time, temperature and dosage of catalyst on xylose dehydration were also investigated. The Brønsted acid catalyst exhibited high activity in the dehydration of xylose, with a high furfural yield of 78.5% at 170   °C in 30   min. What’s more, a 60.6% furfural yield from corn stalk was achieved in 100   min at 200   °C. The recyclability of the sulfonated carbon catalyst was perfect, and it could be reused for 5   times without the loss of furfural yields.

研究领域: 化学工程 · 可再生能源
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FUEL · 2022 · IF 8.035

Organic acid-assisted design of zirconium-lignocellulose hybrid for highly efficient upgrading levulinic acid to γ-valerolactone

Yao Liu,Feiyi Chen,Junhua Zhang,Liang He,Lincai Peng

Acid treatment is the key to improve the physicochemical properties of metal-lignocellulosic hybrid, thus contributing to the catalytic performance for catalytic transfer hydrogenation (CTH) of carbonyl compounds to their corresponding alcohols. Herein, a series of organic acids were introduced to assist the design of Zr- Pennisetum sinese hybrid. Comprehensive studies demonstrated the dramatic changes of specific surface and acid/base sites of the prepared hybrid. Remarkably, formic acid-assisted Zr@ PS -FA possessed the largest surface area and enhanced interaction effects between acids (Lewis acid and Brønsted acid) and Lewis base sites, which exhibited excellent catalytic activity for CTH of levulinic acid to γ-valerolactone with a high yield of 95.6% in isopropanol under moderate reaction conditions (180 °C and 1.5 h). Zr@ PS -FA also showed remarkable cycle stability, and it could be consecutively used at least six runs without a significant loss in catalytic activity. More gratifyingly, Zr@ PS -FA displayed a superior universality for CTH of various carbonyl compounds to their corresponding alcohols, demonstrating great potential for upgrading biomass-derived aldehydes/ketones.

CAS / MDL: 84596-08-7 108-29-2
研究领域: 化学工程 · 生物质能 · 催化科学
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Molecular Catalysis · 2022 · IF 5.089

Fast synthesis of K-4Al catalyst with acid sites for catalyzing biomass-derived γ-valerolactone to butene

Ying Xiong,Xinwei Du,Peng Wang,Xiaogeng Feng,Junshuo Cui,Zhenning Lou,Weijun Shan,Haibiao Yu

This work aimed at elucidating the beneficial effect of the solid-phase grinding method on the catalytic performance of K- x Al for catalyzing γ-valerolactone to butene. Research indicated that a part of Al species was successfully introduced into the framework of KIT-6 support without destroying its original ordered mesoporous structure by the solid-phase grinding treatment method. Hence, Lewis and Brønsted acid sites were formed on the surface of the catalyst. By adjusting the amount of Al species, the content of weak acid sites (100-300 °C) on the catalyst surface can reach as much as 0.31 mmol·g −1 . Through the catalytic activity tested, the K-4Al catalyst exhibited optimum catalytic performance. The GVL conversion rate and butene yield can reach 96.2% and 90.1% at 300 °C, respectively. In addition, the K-4Al catalyst also showed satisfactory renewable performance in cycle tests. These findings will provide useful guidelines for further catalyst design for the preparation of butene from γ-valerolactone.

CAS / MDL: 108-29-2
研究领域: 催化化学 · 生物质转化 · 材料科学
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CATALYSIS TODAY · 2022 · IF 6.562

Conversion of biomass to γ-valerolactone by efficient transfer hydrogenation of ethyl levulinate over Al-SPAN nanosheets

Ying Ji,Huifang Liu,Feng Wang,Xinwen Guo

It is a green and environment-friendly strategy to use biomass to assist the synthesis of catalysts and use the prepared catalysts for biomass utilization. In this study, aluminum-rich silicon-phosphorus-aluminum nanosheet (Al-SPAN) was synthesized with biomass amino acids as additives for catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone. Compared with commercial Al 2 O 3 , Al-SPAN showed greatly improved catalytic performance for the reaction. The conversion of ethyl levulinate was increased by 47 % and the yield of γ-valerolactone was increased by 52 %. The effects of different alcohol on the reaction properties were investigated, with isopropanol used as a safe and efficient hydrogen source. The catalyst has good stability with little change in reaction performance after five cycles.

研究领域: 化学工程 · 环境科学
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FUEL · 2023 · IF 7.4

Mechanistic role of γ-valerolactone co-solvent to promote ethyl levulinate production from cellulose transformation in ethanol

Qiang Lu,Yuefang Chen,Weipeng Song,Chaonan Tao,Junhua Zhang,Yong Sun,Lincai Peng,Huai Liu

Direct utilization of cellulosic material to produce specialty chemicals such as levulinate ester could greatly increase biorefinery profitability, but low-level efficiency due to its structural nature limits the strategy for industrial deployment. We report herein that adding γ-valerolactone (GVL) co-solvent during the acid-catalyzed conversion of cellulose in ethanol leads to a high reaction rate and improved catalytic activity towards ethyl levulinate (EL) production. With GVL as the co-solvent (the volume ratio of GVL to ethanol in 1:4), the yield of EL highly enhanced from 31% to 56% under mild operating conditions (170 °C for 2 h) over a low loading Al(OTf) 3 of 0.005 mol/L. The mechanistic role of GVL co-solvent to accelerate EL formation from cellulose has been fully elucidated via the combination of experimental and theoretical approaches. It demonstrates that GVL intervention not only favored the dissolution and depolymerization of cellulose, but also enabled the formation of Al species with higher acidity and catalytic activity by modulating the solvation environment, both of which are in charge of promoting cellulose conversion to EL. The activation energy barriers for cellulose depolymerization and glucoside alcoholysis have decreased by 30.8 kJ/mol and 24.8 kJ/mol, respectively. The understanding of this solvation effect can be employed to optimize the rate and yield for production of the versatile bio-based ester compound straight from cellulose valorization.

研究领域: 化学工程 · 可再生资源与环境科学
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FUEL · 2021 · IF 6.609

Cooperation between hydrogenation and acidic sites in Cu-based catalyst for selective conversion of furfural to γ-valerolactone

Yuewen Shao,Qingyin Li,Xinyi Dong,Junzhe Wang,Kai Sun,Lijun Zhang,Shu Zhang,Leilei Xu,Xiangzhou Yuan,Xun Hu

The production of γ-valerolactone (GVL) receives increasing attention due to its extensive applications as a promising fuel and fuel additive. In this study, the direct conversion of biomass-derived furfural to GVL with a unprecedent yield of 90.5% was achieved via consecutive hydrogenation and acid-catalyzed reactions over CuAl for hydrogenation and a co-catalyst (i.e. H-ZSM-5) for acid-catalysis in ethanol. The relative abundance of the hydrogenation sites and acidic sites determines the reaction network and the transfer of the main products from furfuryl alcohol (FA) to ethyl levulinate (EL) or GVL, as the acidic sites, especially the Brønsted acidic sites, not only catalyze the formation of EL from FA, but also affect the hydrogenation activity of CuAl. However, the Lewis acidic sites facilitate the opening ring of FA to 1,4-pentanediol, preventing the GVL formation. The acid catalyst and hydrogenation catalyst deactivate via varied mechanisms in the conversion of furfural to GVL, which is required to be considered in the further development of the robust catalysts.

研究领域: 化学工程 · 催化科学
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RENEWABLE ENERGY · 2022 · IF 8.634

Tea polyphenol and HfCl4 Co-doped polyacrylonitrile nanofiber for highly efficient transformation of levulinic acid to γ-valerolactone

Rulu Huang,Huai Liu,Junhua Zhang,Yuan Cheng,Liang He,Lincai Peng

Design catalytic materials with high Lewis acid/base sites for catalytic transfer hydrogenation (CTH) of levulinic acid (LvA) to γ-valerolactone (GVL) is highly demanded but challenging. Herein, we report a concept of metal ion-polymer hybridization to design a tea polyphenol (TP) and HfCl 4 co-doped polyacrylonitrile (PAN) nanofiber (Hf@PAN-TP) via electrospinning technique . Comprehensive characterization revealed the well coordination between hafnium ions and phenolic hydroxyl groups of TP on PAN fiber, which promoted the formation of Lewis acid and Lewis base sites. As expected, a satisfactory GVL yield of 99.1% with 100% of LvA conversion was obtained using isopropanol as a hydrogen donor at 170 °C in 5 h, and the catalytic activity remained unchanged for five cycles. The kinetic study revealed the lower activation energy for CTH of LvA to GVL (33.5 kJ/mol), demonstrating the outstanding GVL formation rate of 3383.9 μmol/g . h. Based on the systematical combine of catalyst characterization and catalytic behavior, the structure-function relationship and reaction mechanism were proposed. More gratifyingly, Hf@PAN-TP was applicable for catalytic reduction of various carbonyl compounds, demonstrating a great potential for upgrading biomass-derived aldehydes/ketones.

研究领域: 材料科学 · 催化化学
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