Molecular Catalysis
·
2019
·
IF 2.938
Wenke Li,Zhe Cai,Hang Li,Yu Shen,Yongqiang Zhu,Haichao Li,Xubin Zhang,Fumin Wang
One-pot conversion of furfural to the target product γ-valerolactone (GVL) is a challenging and meaningful part of biomass exploitation. Development of heterogeneous catalysts with both Brønsted and Lewis acid properties has proved to be promising and useful because they offer an efficient way to tandem cascade reactions from furfural to GVL. Herein, we successfully synthesized sulfated DUT-67(Hf), a novel bifunctional catalyst, via a post-synthetic modification method. The prepared sulfated DUT-67(Hf) was characterized by XRD, SEM, TEM, N 2 adsorption-desorption, Elemental (N, C, H, S) analyses, situ infrared spectra of pyridine adsorptions, XPS, FT-IR, TG, and NH 3 -TPD. The acidity of the catalysts could be adjusted by submersion in different concentrations of aqueous sulfuric acid, giving 0.01 mol/L sulfuric acid for 0.42 mmol/g acidity to 0.1 mol/L sulfuric acid for 2.16 mmol/g acidity. Sulfated DUT-67(Hf) possessed by 0.06 mol/L aqueous sulfuric acid exhibited optimal catalytic activity and showed an 87.1% yield of GVL under the conditions of 180 °C after 24 h of reaction. Moreover, the mechanism of introducing Brønsted acid sites into DUT-67(Hf) and the better hydrogen donors was also investigated through contrasting experiments.
研究领域:
化学工程
·
催化化学
✓ 已验证
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2024
·Vol. 18
·期 11
·1-14
·
IF 4.3
Mo Shuhua,Zheng Yao,Gong Jianyu,Lu Minsheng
The efficient fractionation and recovery of monosaccharides (xylose and glucose) from lignocellulosic biomass facilitates subsequent sugar-based derivative production. This study introduces a one-pot γ -valerolactone/ CuCl 2 biphasic pretreatment system (100-mmol·L -1 CuCl 2 , 180 °C, 60 min) capable of achieving removal rates of 92.25% and 90.64% for xylan and lignin, respectively, while retaining 83.88% of cellulose. Compared to other metal chlorides (NaCl, LiCl, FeCl 3 , and AlCl 3 ), the γ -valerolactone/CuCl 2 system recovered 121.2 mg·(g eucalyptus) -1 of xylose and 55.96 mg·(g eucalyptus) -1 of glucose during the pretreatment stage and 339.2 mg·(g eucalyptus) -1 of glucose during the enzymatic hydrolysis stage (90.78% of glucose yield), achieving a total monosaccharide recovery of 86.31%. In addition, the recovery of γ -valerolactone was 79.33%, exhibiting minimal changes relative to the pretreatment performance. The method proposed in this study allows a high total monosaccharides recovery and a circular economy-oriented pretreatment approach, offering a viable pathway for biorefinery.
研究领域:
生物工程
·
可再生资源技术
✓ 已验证
DOI
高影响因子
FUEL
·
2021
·
IF 6.609
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
✓ 已验证
DOI
高影响因子
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.
研究领域:
化学工程
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可再生能源
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2024
·Vol. 14
·期 2
·113
·
IF 3.8
Hongzhi Ding,Chenyu Yang,Congyan Jiang,Wei Luo,Qiuyue Wang,Xuefeng Guo
The use of eco-friendly biomass as a resource is an efficient way to address the problems of fossil fuel depletion and climate change. In biomass conversion, versatile γ-valerolactone (GVL) is generally obtained from levulinic acid (LA) hydrogenation via a multimetallic catalyst system. Despite conversion efficiency being enhanced in mild conditions due to metal interactions, maintaining high catalyst stability is still a challenge. In this study, we synthesized a surrounded Co0.52Ni0.48@Al2O3-IE catalyst that exhibited excellent alloying and synergistic interaction between the metal constituents. Under relatively mild reaction conditions, the GVL yield over the catalyst exceeded 99% in LA hydrogenation. The catalyst showed no deactivation in a test of five cycles, displaying superiority in stability, possibly due to reasons of the physical isolation of the shell and the alumina retention on the Co-Ni alloys surface caused by the reversibility of exchange equilibrium. The present work demonstrated that a surrounded structured catalyst fabricated by ion exchange (IE) with active metals physically enclosed can lead to high catalytic activity and superior stability.
研究领域:
催化化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2024
·
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.
研究领域:
生物质化学
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催化科学
·
可再生资源
✓ 已验证
DOI
高影响因子
Energy Sources Part A-Recovery Utilization and Environmental Effects
·
2021
·
IF 3.447
Xialing Lin,Mingrui Li,Yumei Jian,Jinshu Huang,Song Yang,Hu Li
γ-Valerolactone (GVL) is widely used as a green solvent and in the generation of liquid fuels. GVL can be obtained from biomass-derived furanic compounds through a cascade reaction process, which is extremely challenging due to the need for different active sites in a single pot. Here, we reported a domino conversion process of directly upgrading furfural (FF) to GVL in isopropanol over a commercially available and budget catalyst ZrCl4 that can in-situ release Brønsted acid (HCl) and Lewis acid/base species (ZrO(OH)n·xH2O). The in-situ formed bifunctional catalyst can significantly enable twice transfer hydrogenation, etherification, the ring-opening, and cyclization reactions, giving a high GVL yield of 56.5% from FF at 180°C for 6 h. In addition, the solid residues collected after reaction could be calcined to obtain t-ZrO2-(C) nanoparticles with a rough surface, in which the insoluble humin attached to the hydrolyzed solid was demonstrated to improve the layered aggregate structure of the resulting t-ZrO2-(C). Interestingly, t-ZrO2-(C) showed good performance in catalytic conversion of FF to furfuryl alcohol (FAOL) with ca. 80% yield. The developed bifunctional and recyclable catalytic system exhibits potential for one-pot multi-step biomass valorization.
✓ 已验证
DOI
高影响因子
Energy Sources Part A-Recovery Utilization and Environmental Effects
·
2021
·
IF 3.447
Yan Li,Weibo Wu,Hu Li,Wenfeng Zhao,Song Yang
γ-Valerolactone (GVL) is a versatile biomass-derived molecule for both value-added chemicals and biofuels, which is typically prepared from levulinates over metal particles or oxides in the presence of hydrogen, formic acid or alcohol. Herein, we reported a rapid and mild approach for cascade hydrogenation-cyclization of ethyl levulinate (EL) to GVL in the presence of readily available ionic liquid tetrabutylammonium fluoride ([TBA]F) and polymethylhydrosiloxane (PMHS) as catalyst and hydrogen source, respectively. After reacting at room temperature for 30 min, a high GVL yield of 85% with TOF value of 52 h−1 could be obtained over 3 mol% [TBA]F. In addition to optimizing reaction parameters, the catalytic mechanism was also elucidated for the one-pot sequential transformation of EL to GVL.
✓ 已验证
DOI
高影响因子
RENEWABLE ENERGY
·
2022
·
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.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Xiaoqing Gao,Shanhui Zhu,Mei Dong,Jianguo Wang,Weibin Fan
Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is still a challenge for Ru-based catalysts under mild condition. In this work, we have reported that ultrathin TiO 2 nanosheets supported Ru nanoparticles showed extraordinarily high catalytic activity, GVL yield (99.1%) and reusability owing to the formation of Ru O Ti interfacial structure. The turnover frequency (TOF) reached as high as 19,045 h −1 at 100 °C, much higher than those of Ru/SiO 2 , Ru/GO, Ru/MoS 2 , and commercial Ru/C. DFT calculation elucidates that the dominant reaction pathway of LA hydrogenation to GVL is preferentially hydrogenated to CH 3 CHOCH 2 CH 2 COOH*, followed by cyclization to CH 3 (OH)C 4 OH 4 OH* (GVL − OH) and final dehydroxylation, irrespective of surface structure. Compared to Ru (0 0 2) facet, Ru/TiO 2 interfacial structure changes the rate-determining step from initial hydrogenation to cyclization, which greatly declines the activation barrier from 0.81 eV to 0.48 eV.
研究领域:
化学工程
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2019
·
IF 5.439
Jian He,Hu Li,Yufei Xu,Song Yang
γ-Valerolactone (GVL) is an interesting bio-based platform molecule that is utilized as green solvent and a versatile building block for the synthesis of bio-fuels and chemicals. Herein, an investigation on the efficient production of GVL from biomass-based carbonyl compounds such as furfural, levulinic acid, and its esters using 2-propanol as H-donor and solvent over stable Zr-incorporated mesoporous silica (KIT-5) catalysts was presented. Both Lewis and Brønsted acid sites were generated by the introduction of Zr into KIT-5, and the acid density of the resulting Zr-KIT-5(Si/Zr) could be controlled by simply adjusting Si/Zr molar ratio . Among these bifunctional catalysts , Zr-KIT-5(10) showed superior catalytic performance in the production of GVL (>91% selectivity) from biomass-derived carboxides (ca. 94% conversion), which was demonstrated to positively correlate with its large amount of acidic sites and facile access of active sites to interconnected pores. Moreover, the spent catalyst held about 90% of its original activity in the sixth run. Due to the presence of Brønsted and Lewis dual acidic sites in Zr-KIT-5, the direct conversion of furfural to GVL was also permitted in a single pot via tandem reactions involving hydrogenation, ring-opening, secondary hydrogenation, and subsequent cyclization.
研究领域:
催化化学
·
生物质能
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2017
·
IF 4.601
Chuang Li,Guangyue Xu,Yongxiang Zhai,Xiaohao Liu,Yanfu Ma,Ying Zhang
Gamma-valerolactone (GVL) has been identified as a sustainable high-value platform molecular for the production of fuels and carbon-based chemicals. In this work, a series of activated carbon supported low-cost bimetallic Ni-Fe catalysts (Ni-Fe/AC) with different molar content of Fe species were prepared by using co-precipitation method for the liquid phase hydrogenation of ethyl levulinate (EL) to produce γ-valerolactone. The Ni-Fe 0.5 /AC exhibited the highest activity among the bimetallic or monometallic catalysts under mild reaction conditions (100 °C, 4 MPa H 2 , 6 h) and achieved 99.3% conversion of EL and 99.0% yield of GVL. Under more mild conditions (60 °C, 2 MPa H 2 ) and prolonging the reaction time to 24 h, EL could be converted completely and the obtained GVL yield was more than 98%. The catalysts were characterized by various techniques including XRD, TEM, HRTEM, EDX, XPS, H 2 -TPR and NH 3 -TPD. Based on the structure and activity relationship study, the formation of highly dispersed Ni-Fe alloy structure and the co-presented FeO x nanoparticles could be responsible for the high catalytic hydrogenation activity.
研究领域:
催化化学
·
可再生资源化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）