INDUSTRIAL CROPS AND PRODUCTS
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2024
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IF 5.6
Almas Anwar,Tao Zhao,Sidra Ghaffar,Kai Nie,Wenying Xia,Lingyu Wang,Zhihao Cao,Xiaoli Yang,Chengfeng Zhou,Yuanming Zhang,Guangting Han,Wei Jiang,Haoxi Ben
Hemp, a sustainable crop, offers superior material properties suitable for diverse applications. This study aims to produce hemp fibre using a green and sustainable pretreatment method, thus exploring a novel microwave-assisted pretreatment method using a γ-valerolactone (GVL) and glycolic acid (GA) solution system, referred to as the GVL/GA pretreatment method. By optimising solid loading and reaction time, we significantly reduced water usage (50 %) and energy consumption (61.5 %) while maintaining fibre quality. The pretreatment method effectively removed lignin (88.7 %) and hemicellulose (39.3 %) without damaging the cellulose structure. The pretreated samples demonstrated a 45.7 % increase in glucose yield. Additionally, the characterisation of pretreated fibres revealed impressive fineness (4.4 dtex) and tenacity (4.0 cN/dtex), and the crystal structure remained intact with increased crystallinity (86 %). The HSQC NMR analysis unveiled that lignin undergoes structural modifications, enabling efficient lignin removal. GVL/GA pretreatment promotes green chemistry by minimising environmental impact and waste, using renewable resources. It provides a sustainable alternative to traditional methods, contributing to a greener industry.
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ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Wenjing An,Weiping Yang,Liqing Shi,Kejiang Qian,Huichao Suo,Peipei Ma,Tingzhao Xin,Jinhao Liu,Shuangxi Liu,Lan-Lan Lou,Kai Yu
Catalytic conversion of levulinic acid (LA) to γ-valerolactone (GVL) is one of the key reactions of biomass utilization, but the relatively high reaction temperature and H2 pressure always introduce safety and energy consumption issues. In this work, a photocatalytic transfer hydrogenation method was applied to achieve the hydroconversion reaction from LA to GVL under green and mild conditions using non-noble metal Bi2S3 materials as the catalyst. Up to 74.8% GVL yield and 76.3% selectivity can be achieved after 36 h of irradiation using the spherical Bi2S3 as the catalyst and isopropanol as the hydrogen source, which is significantly higher than any reported results on non-noble metal photocatalysts. The structural characterization and density functional theory calculation results indicated that the appropriate band position and lower adsorption energy toward LA rendered the spherical Bi2S3 catalyst highly reactive. Based on the results of electron paramagnetic resonance and density functional theory calculations, a reasonable photocatalytic transfer hydrogenation reaction pathway of LA to GVL was proposed. Bi2S3-photocatalyzed dehydrogenation of isopropanol generates H radicals, which react with LA adsorbed on the surface of Bi2S3 to form GVL through a hydrogenation-esterification process. The presence of Bi2S3 greatly promotes the adsorption of LA and reduces the energy barrier for LA hydrogenation.
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Molecular Catalysis
·
2024
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IF 3.9
Fukun Li,Ronghe Yang,Jinhang Dai,Hanyue Deng,Junjun Shi,Wucheng Xie,Juanhua Kong,Tingwang Guo
Biomass upgrading, which supplies important biomaterials, chemicals and fuels, is considered as an efficient way to realize the goal of carbon neutralization. Recently, γ-valerolactone (GVL) has gained increasing attention due to its wide applications. In this work, a novel protocol of microwave-assisted cascade catalytic upgrading of α-angelicalactone (α-AL) to GVL over metal triflate using alcohol as the hydrogen donor was proposed. The yield of GVL production from α-AL upgrading is strongly influenced by the Lewis acid strength of the metal triflate and the reduction potential of the employed alcohol. Among all tests, Sc (OTf) 3 showed the best catalytic performance in isopropanol media, giving 96.4 % GVL yield and 100 % α-AL conversion at 433 K within 3.0 h. Meanwhile, kinetic study indicated transfer hydrogenation of isopropyl levulinate to isopropyl 4-hydroxyvalerate was the rate-limited step with the apparent activation energy of 94.5 kJ/mol. This Sc (OTf) 3 catalyst was highly stable and could be reused for five cycles by simple vacuum distillation. In a word, this work provides an alternative for GVL production from biomass upgrading.
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RENEWABLE ENERGY
·
2022
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IF 8.634
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.
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高影响因子
FUEL
·
2023
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IF 7.4
Zhongdi Liu,Rui Zhang,Huai Liu,Junhua Zhang,Yong Sun,Naya Li,Lincai Peng
Developing efficient and stable solid functional materials for the catalytic upgrading of biomass-based platform furanic molecules is of great significance to produce value-added chemicals and biofuels. We herein report β-zeolite (β)/biobased carbon hybrids supported Zr species towards the cascade conversion of furfural into γ-valerolactone (GVL) with high activity and favorable stability. The role and importance of carbon modifier were highlighted. The cellulose (CEL) modified Zr/β-CEL catalyst was found to be uniquely effective, leading to an increase of GVL yield from 49.3% to 81.1%. Catalyst characterizations revealed that the structural integrity of β was largely preserved using CEL as the carbon modifier, accompanied by the increased mesopore volume and pore size for better accessibility of active sites and diffusion of reactants. Simultaneously, the presence of CEL offered an appropriate ratio of Lewis and Brønsted acid sites due to the well incorporation and dispersion of Zr species, which ensured the successive transfer hydrogenation and ring-opening reactions. Kinetic studies demonstrated the positive effect of CEL modification on reducing the apparent activation energy and thereby facilitating the GVL formation. More importantly, Zr/β-CEL with enhanced structural stability also exhibited markedly higher recyclability compared with the pristine Zr/β. The understanding on the roles of carbon modifier can be employed to optimize the physicochemical properties of zeolite-based catalysts for roundly improving the catalytic reactivity of biomass-related compounds.
研究领域:
催化化学
·
材料科学
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Sustainable Chemistry and Pharmacy
·
2026
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IF 6.7
Deyang Zhao,Xinyu Zhao,Qikai Si,Kongde Li,Huawei Yang,Christophe Len
γ-valerolactone (GVL) is a renewable and sustainable platform chemical derived from biomass, with broad applications in chemical synthesis and energy-related fields. Consequently, the development of efficient strategies for GVL production has attracted significant attentions. In this study, the hydrogenation of ethyl levulinate (EL) to GVL was investigated using copper-cobalt basic carbonate, (CoCu) 2 (OH) 2 CO 3 , as a catalyst. The influence of different substrates—including esters and acids such as EL, GVL, ethyl acetate (EA), and levulinate acid (LA)-on catalyst recyclability and performance was systematically evaluated. Among the substrates tested, EL exhibited the most favorable behavior, delivering a GVL yield of up to 96% in the second recycling cycle under optimized conditions. This superior performance is attributed to the synergistic interaction between the basic sites of the catalyst and the ability of metallic Cu to activate hydrogen, as well as the formation of larger metal particle clusters when EL is used as the substrate. Notably, the catalytic activity remained largely preserved even after the third recycling cycle. In contrast, when GVL was sued as the substrate, moderate yields were obtained, accompanied by the formation of surface coatings on the catalyst particles. Furthermore, both EA and LA induced varying degrees of catalyst etching, resulting in a drastic loss of activity, with negligible catalytic performance observed in the second cycle. These findings indicate that catalyst deactivation due to etching has a more pronounced impact on catalytic performance than structural changes associated with bimetallic cluster formation. This observation indirectly highlights the critical role of basic sites in maintaining catalytic activity during the hydrogenation process.
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RSC Advances
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2013
·Vol. 3
·期 26
·10277-10284
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IF 2.562
Xing Tang,Lei Hu,Yong Sun,Geng Zhao,Weiwei Hao,Lu Lin
A green and efficient process was developed for the conversion of biomass-derived ethyl levulinate (EL) into γ-valerolactone (GVL) using supercritical ethanol as the hydrogen donor and the reaction medium over low-cost and eco-friendly ZrO2 catalysts, which were prepared by the precipitation method and characterized by BET, SEM, XRD, FT-IR, TGA-DTA, TPD-NH3 and TPD-CO2. The results indicated that amorphous ZrO2 with a high specific surface area and a large number of acid–base sites exhibited the highest catalytic activity, an excellent GVL yield of 81.5% with 95.5% EL conversion was achieved at 523 K over 3 h. In addition, combined with the results of poisoning experiments, a plausible mechanism of catalytic transfer hydrogenation (CTH) via a six-membered ring transition state was also presented.
研究领域:
生物质化学
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催化反应工程
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EUROPEAN POLYMER JOURNAL
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2026
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IF 6.8
Mingtao Ding,Song Feng,Tongjun Yang,Yuanlong Guo,Lihua Zhang,Haibo Xie
Chitin dissolution is prerequisite to allow its homogeneous processing and develop value-added regenerated/derivative chitin-based materials. In this work, in combination of [EMIM][OAc] ionic liquids, biomass-derived γ -valerolactone (GVL) was delicately screened as a co-solvent to construct benign organic electrolyte solutions (OESs) for chitin dissolution and homogeneous processing. Kamlet-Taft parameters ( α , β , and π*) of [EMIM][OAc]/GVL OESs with varying molar ratios are examined. Introduction of [EMIM][OAc] into GVL can notably increase the polarity, supported by the increased E T (30) values. The NMR studies of N -acetylglucosamine (GlcNAc, the repeating unit of chitin) solvation further indicate that the hydrogen bonding between GlcNAc and both the anions and cations of the ILs. Rheological properties of chitin/[EMIM][OAc]/GVL solutions are studied, and lower viscous activation energy ( E η ) accompanies the increase of GVL content in the OESs, as the addition of GVL reduces the energy barrier for viscous flow and facilitates the mobility of chitin molecular chains. Furthermore, the potential of the chitin solutions for homogeneous processing into films is primarily demonstrated via a conventional solution casting approach using water as the coagulation bath. Regenerated chitin films are systematically characterized by FTIR, NMR, XRD, TGA, UV–vis, SEM and tensile tests. Thus, it seems that the [EMIM][OAc]/GVL OESs present a green platform for fabricating chitin-based materials.
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RENEWABLE ENERGY
·
2020
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IF 6.274
Han Chen,Qiong Xu,Du Zhang,Wenzhu Liu,Xianxiang Liu,Dulin Yin
A series of mesoporous nickel catalysts with different molar ratios of citric acid and nickel nitrate were synthesized via a simple two-step method by solid-state grinding and in-situ reduction; these catalysts were further employed for the catalytic transfer hydrogenation of levulinate esters to γ-valerolactone (GVL) with 2-propanol as the hydrogen donor. The effects of C 6 H 8 O 7 /Ni molar ratios , catalyst dosage, reaction temperature and time on the catalytic performance were investigated. An excellent GVL selectivity of 99.1% and an ethyl levulinate (EL) conversion of 100% could be achieved at 180 °C in 6 h over Ni-1.0 catalyst with a 1.0:1 M ratio of C 6 H 8 O 7 /Ni. The characterization results showed that the Ni-1.0 catalyst was composed of mesoporous metallic Ni bulk and a surface Ni–NiO composite, and the acid sites of NiO played a synergistic catalytic role in producing GVL from EL. The superior mesoporous structure and large surface area of Ni-1.0 increased the atomic utilization rate of nickel metallic active centers. Moreover, Ni-1.0 catalyst could be easily separated and reused ten times, with an EL conversion above 95% remaining in each recycle. This work provids a highly efficient and environmentally friendly catalytic procedure for the conversion of biomass into GVL, a fuel additive compound.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
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IF 22.1
Xinlei Ji,Jia Kou,Gökalp Gözaydın,Xi Chen
Chitin biorefinery offers a unique opportunity to sustainably produce highly-valued organonitrogen compounds such as the versatile pharmaceutical precursor 3-acetamido-5-acetylfuran (3A5AF), bypassing the Haber process and mitigating the consumption of fossil feedstocks. However, the reported protocols engaged large quantities of toxic organic solvents and required harsh conditions. In this work, a highly efficient catalytic system has been developed in the nontoxic, biobased γ-valerolactone (GVL) solvent under relatively mild conditions. 3A5AF was selectively obtained with an unprecedent yield of 75.3% at 140 °C for 2 h by adding NH 4 SCN and HCl. The high yielding was exclusively promoted by a dissolution-dehydration effect. Based on the UPLC-TOF-MS and NMR analyses, the presence of NH 4 SCN has induced a very rapid NAG conversion possibly by coordinating with the acetamido group and the hydroxyl groups, and the 3A5AF product was obtained in a subsequent dehydration pathway from NAG with the Chromogen I and Chromogen III as the intermediates.
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CATALYSIS LETTERS
·
2023
·
IF 2.8
Xiang Yuchen,Zhang Huiming,Zhang Jingyi,Xu Qiong,Liu Xianxiang,Yin Dulin
Comprehensive use of available biomass, especially low-cost forestry waste to produce bioenergy, materials have great meaning for realization of green and sustainable chemical processes. In this work, forestry sawdusty waste (SD) was used to produce biochar (SDBC-P) via a H 3 PO 4 assisted hydrothermal carbonization method. And a novel zirconium-coordinated biochar catalyst Zr-SDBC-P has been prepared by self-assembly method. Characterization results revealed that hydrothermal carbonization in the presence of H 3 PO 4 promoted the formation of oxygen-containing functional groups (–COOH, Ar–OH) which were used as ligand to obtain high contents of Lewis acid − base sites (Zr 4+ –O 2− ). Zr-SDBC-P-4 showed satisfactory catalytic activity in synthesis of bioderived γ-valerolactone (GVL) from ethyl levulinate (EL). EL conversion of 98.2% and GVL selectivity of 85.4% were obtained within 5 h at 170 °C. In addition, Zr-SDBC-P-4 displayed outstanding chemical stability. There was no obvious decrease of GVL yield after being used for six cycles. Overall, this work offered a viewpoint to design catalyst from value-added utilization of biomass waste. Graphical Abstract
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Molecular Catalysis
·
2023
·
IF 4.6
Bo Li,Haijun Guo,Zhen Xiong,Lian Xiong,Shimiao Yao,Mengkun Wang,Hairong Zhang,Xinde Chen
γ-valerolactone (GVL) is a sustainable chemical, which can be obtained by hydrogenation of levulinic acid (LA) and levulinate. Herein, we reported a solvent-free hydrogenation of butyl levulinate (BL) to GVL and 1,4-pentanediol (1,4-PDO) over a skeletal Cu-Al-Zn catalyst. The skeletal Cu-Al-Zn catalyst was prepared from Devarda's alloy by alkali leaching and the catalyst was characterized by different analysis methods. The aluminum in the Devarda's alloy was dissolved by sodium hydroxide in the leaching process and many active Cu atoms were generated on the catalyst surface and the skeletal Cu-Al-Zn exhibited many micrometer-scale irregular particles with rough surface. The skeletal Cu-Al-Zn catalyst showed the excellent performance in the solvent-free hydrogenation of BL to GVL under constant hydrogen pressure (5 wt% catalyst loading, 180°C, 6 MPa of H 2 , 6 h): the LA conversion was 100%, the GVL yield was 74.75% and the 1,4-PDO yield was 25.63%. Moreover, the catalyst showed stable performance and it was reusable up to 5 times without apparent loss of activity. A stable hydrogen pressure with Zn would suppressed the dehydration of 1,4-PDO.
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