ACS Omega
·
2019
·
IF 2.584
Xiaofang Liu,Hu Pan,Heng Zhang,Hu Li,Song Yang
Enlarging the dispersed micropores of metal-organic frameworks to the well-ordered mesostructure can enhance the accessibility of acidic sites for reactants resulting in the improvement of selectivity. With the regulation of cetyltrimethylammonium bromide/Cr3+ and ClSO3H sulfonation, a series of mesoporous MIL-101(Cr)-SO3H (MMSs) with multiple pore sizes and acidic properties were synthesized and explored to further facilitate the furfuryl alcohol (FA) ethanolization to ethyl levulinate (EL) for the first time. The optimal catalytic activity of 83.8% EL yield at full FA conversion demonstrated that the appropriate mesopore size, acidic density, and accessible −SO3H sites contributed to the superior performance of the MMS(0.3)-0.15. The turnover frequency value (14.8 h–1) obtained with MMS(0.3)-0.15 was comparable to the commercial Nafion NR50 (18.3 h–1) and much higher than the classical Amberlyst-15 (1.9 h–1), confirming the predominant catalytic performance. Furthermore, two coexistent reaction paths with 2-ethoxymethylfuran and 4,5,5-triethoxy-pentan-2-one as intermediates indicated the possibility of producing EL from FA.
研究领域:
化学工程
·
材料科学
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DOI
高影响因子
Molecular Catalysis
·
2020
·
IF 3.687
Na Ji,Zhenyu Liu,Xinyong Diao,Jinrong Bao,Zhihao Yu,Chunfeng Song,Qingling Liu,Degang Ma,Xuebin Lu
GVL (γ-valerolactone) is identified as an important biomass platform molecule due to its wide application. In this work, a series of novel supported Ni catalysts with different supports and Ni loading were synthesized via metal-organic chemical vapor deposition (MOCVD) method for the hydrogenation of EL (ethyl levulinate) to GVL. Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), nitrogen adsorption/desorption, inductively coupled plasma optical emission spectroscopy (ICP-OES) and transmission electron microscopy (TEM) were used to characterize the as-synthesized catalysts. The results showed that the 2 wt.% Ni/AC(MOCVD) presented superior catalytic activity when compared with the catalyst prepared by impregnation method. This behavior is explained in terms of the smaller Ni nanoparticles (4.28 nm) and higher dispersion on 2 wt.% Ni/AC(MOCVD). Among the catalysts, the 2 wt.% Ni/AC catalyst exhibited the best catalytic performance with 99.7 % EL conversion and 79.8 % GVL yield under 1 MPa initial H 2 pressure (measured at room temperature) at 250 °C for 2 h. In addition, the reaction conditions were optimized and the stability of the catalyst were also investigated. The insights gained from this study in the design of high dispersed Ni particles with smaller particle size via MOCVD method will facilitate the metal-catalyzed hydrogenation of EL to GVL.
研究领域:
化学工程
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生物质能源
·
催化科学
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DOI
高影响因子
Catalysts
·
2026
·Vol. 16
·期 2
·185
·
IF 4.5
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.
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DOI
高影响因子
Carbon Resources Conversion
·
2025
·
IF 7.5
Shuolin Zhou,Ying Liu,Yin Zhang,Zhijing Liu,You Wu,Xianxiang Liu
Alkyl levulinates (AL) are a class of important organic chemicals that play a significant role in organic synthesis, biofuel additives, and cleaning agents. In this work, low-dimensional titanium dioxide nanotubes were prepared under hydrothermal conditions as precursors, which were further modified to fabricate organic–inorganic hybrid solid acid catalyst (TNTs-PhSO 3 H). The catalyst was characterized using various techniques including Fourier transform infrared spectroscopy (FT-IR), thermogravimetric-differential thermal analysis (TG-DTA), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results indicated that the amount of bonded sulfonic acid in the catalyst was considerable, reaching up to 1.45 mmol/g. The esterification of levulinic acid (LA) with n -butanol was used as a probe reaction to systematically investigate the influence of reaction time, temperature, catalyst dosage, and molar ratio of reactants on the esterification reaction by the single-factor experiments. The catalytic reaction process was further optimized via the response surface methodology (RSM) using Box-Behnken design (BBD) method. Under the conditions of a catalyst dosage of 12 % (based on the mass of LA) at 120 °C for 3 h, the yield of the desired product, n- butyl levulinate, could reach 98.0 %. The catalyst maintained stable catalytic performance after being reused at least five times.
研究领域:
催化化学
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材料科学
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绿色化学
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化学工程
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可再生能源
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产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2018
·
IF 3.849
Chun Chang,Lin Deng,Guizhuan Xu
Wheat straw can be converted into biofuel candidate-methyl levulinate with copper sulfate as the cheap catalyst. To take advantage of the whole components of wheat straw, a two-stage pretreatment process was developed in this study. In the first-stage process, the hemicellulose component in wheat straw can be converted into biosurfactant at the mild conditions, and the lignin component can be extracted as another value added by-product in the second stage. On the basis, the pretreated wheat straw was used as raw material for methyl levulinate production, and a yield of 20.2 wt% can be obtained under the optimum reaction conditions. Meanwhile, the catalyst recycling experiments showed that copper sulfate was stable and can be reused more than five times. The results of mass balances and preliminary economic analysis further indicated that the production of integrated biorefinery processes producing diversified products offers potential for the sustainable valorization of wheat straw.
研究领域:
生物化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2016
·
IF 2.322
Jun Zhang,Jinzhu Chen
A series of metal salt-modified carbon catalysts had been prepared to study the selective transformation of various carbohydrates into ethyl levulinate in an ethanol medium. The specific textural and chemical characteristics of prepared carbon samples were identified by Raman, XRD , XPS , NH 3 -TPD, FT-IR and nitrogen physisorption . Various parameters such as ethanol/water volume ratio, NaCl addition, reaction temperature, and catalyst dosage played a great role in ethyl levulinate production. A desirable ethyl levulinate yield of 58.0 mol% with a highest ROF (rate of ethyl levulinate formation per gram of catalyst per hour) value of 2148.3 µmol/(g cat ·h) was achieved at 468 K over FeCl 3 modified carbon catalyst with respect to fructose conversion. The recycling experiments revealed that the sulfonated carbon catalysts exhibited relatively satisfied activity and stability.
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
高影响因子
RSC Advances
·
2013
·Vol. 4
·期 8
·4194-4202
·
IF 2.562
Jinzhu Chen,Guoying Zhao,Limin Chen
Direct conversion of fructose into 5-hydroxymethylfurfural (HMF) and alkyl levulinate is achieved by making use of ionic liquid-based polyoxometalate salts (IL-POMs) as solid acid catalysts. Among these solid acids, phosphotungstic acid-derived IL-POM shows the highest catalytic performance in both the HMF and ethyl levulinate (EL) formation. A study for optimizing the reaction conditions such as the reaction time and the temperature has been performed. High HMF and EL yields of up to 99% and 82%, respectively, are obtained from fructose under the investigated conditions. Moreover, the generality of the catalyst is further demonstrated by processing representative di- and polysaccharides such as sucrose and inulin with good yields to HMF (76% from inulin and 48% from sucrose) and EL (67% from inulin and 45% from sucrose), again under mild conditions, thereby eliminating the separate hydrolysis step before the dehydration reaction. The catalyst recycling experiment indicates that the adsorption and accumulation of oligomeric products on the catalyst surface results in a partial deactivation of catalyst. The mechanism research reveals that a major pathway for EL formation involves a fructose-to-HMF transformation followed by HMF etherification and rehydration of HMF-ether to give EL. The research highlights an efficient, environment-friendly and recyclable solid acid for biomass valorization.
研究领域:
化学工程
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催化
·
绿色化学
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可再生能源
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DOI
高影响因子
RESEARCH ON CHEMICAL INTERMEDIATES
·
2019
·Vol. 46
·期 2
·1469-1485
·
IF 2.064
Yu Xin,Peng Lincai,Pu Qiuyu,Tao Ruili,Gao Xueying,He Liang,Zhang Junhua
The preparation and application of biorenewable carbon-based catalyst are attracting increasingly attention in the field of green and sustainable chemistry. Here, a facile and low-cost lignosulfonate-based carbonaceous solid acid (LSS) was availably prepared via directly sulfonating lignosulfonate that was from sulfite pulping industry, and used to catalyze biomass-derived furfuryl alcohol to yield versatile butyl levulinate. The fabrication and properties of LSS were highly sensitive to the sulfonation conditions (i.e., lignosulfonate-to-H 2 SO 4 ratio and temperature). The physicochemical properties of the as-prepared LSS were well characterized using BET surface area, acid–base titration, SEM, XRD, FT-IR, XPS, and TGA techniques. The LSS contained –SO 3 H, –COOH and phenolic –OH groups and was ideal to perform the reaction of furfuryl alcohol with n-butanol to obtain butyl levulinate in yield higher than 95% at 110 °C for 8 h with catalyst dosage of 15 g/L. Meanwhile, the catalyst deactivated increasingly with a recycle number that was attributed to the adsorption of formed polymeric by-products on the active catalyst sites, and the slightly deactivated catalyst after plain sulfonation treatment was found to remain active with an almost unchanged product yield in consecutive cycles. This work highlights an economic, eco-friendly, sustainable and promising protocol for catalytic upgrading of bio-based compounds.
研究领域:
绿色化学
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可再生资源利用
·
催化化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2016
·
IF 8.328
Hu Li,Zhen Fang,Jia Luo,Song Yang
A series of metal-zeolite hybrids was prepared by impregnation and deposition-precipitation methods and charaterized with different techniques. Catalytic performance of these catalysts on microwave-assisted conversion of selected carbohydrates to the fuel component methyl levulinate (ML) in methanol was studied. It was demonstrated that metal oxide content/type and acid-base bifunctionality were closely correlated with substrate conversion and ML yield, respectively. Among various as-prepared catalysts, zirconia-zeolite hybrid ZrY6(0.5) with moderate acid-base site content (0.97 & 0.08 mmol g −1 ), high stability and porosity (average mesopore diameter: 6.2 nm) exhibited superior catalytic activity. At 180 °C, around 67–73%, 78%, 53% and 27% yields of ML could be achieved from monosaccharides (e.g., glucose, mannose and galactose), sucrose, starch and cellulose, respectively. The Zr-Y6(0.5) hybrid exhibited good stability, and could be reused for five times with ML yields of ≥63% from glucose.
研究领域:
能源化学
·
催化科学
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产品关联
DOI
高影响因子
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
·
2018
·Vol. 65
·期 11
·1398-1406
·
IF 0.862
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.
研究领域:
催化化学
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生物质转化
·
材料科学
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2015
·
IF 4.642
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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产品关联
DOI
高影响因子
Sustainable Energy & Fuels
·
2019
·Vol. 4
·期 3
·1383-1395
·
IF 4.912
Mengmeng Wang,Lincai Peng,Xueying Gao,Liang He,Junhua Zhang
An integrated catalytic protocol involving dehydration, transfer-hydrogenation and alcoholysis towards one-pot conversion of xylose to alkyl levulinate was invented using a combination of Zr(20)-MCM-41 and H3O40PW12 catalysts. Secondary alcohols like 2-propanol and 2-butanol as the reaction medium exhibit equally superior hydrogen donating capability, but the dehydration step of xylose in 2-butanol is preferred probably due to its stronger hydrophobicity. A good alkyl levulinate yield of 53% can be achieved under optimized conditions. The spent dual catalysts can be effectively recovered and they exhibit good reusability after thermal regeneration of Zr(20)-MCM-41. Research on the catalytic mechanism shows that well-dispersed ZrO2 supported on MCM-41 is responsible for the catalytic transfer hydrogenation step of furfural to furfuryl alcohol. Proper tuning of the Lewis and Brønsted acidities can efficiently promote the acid-driven reaction steps of xylose conversion and simultaneously inhibit the alkyl levulinate-to-γ-valerolactone side reaction. The sustainability of this conversion is greatly improved by process intensification based on the new catalytic strategy and mild reaction conditions.
研究领域:
生物化学
·
催化化学
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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）