Molecular Catalysis
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2020
·
IF 3.687
Yaowei Lu,Yongxing Wang,Yinghao Wang,Qiue Cao,Xiaoguang Xie,Wenhao Fang
A bifunctional Ru/(AlO)(ZrO) n catalyst was reported for efficient hydrogenation of levulinic acid to γ-valerolactone, an important and environmental-benign upgrading process of bio-platform compound. The optimal Ru/(AlO)(ZrO) 0.1 catalyst showed 100% yield to γ-valerolactone in water at 120 °C under 1 MPa H 2 , one of the best performances among Ru catalysts under mild conditions. And this catalyst also presented good stability and reusability. PXRD, TEM, XPS, CO chemisorption, CO adsorption DRIFT-IR, NH 3 -TPD and pyridine adsorption IR gave insights into the acidic property and surface synergy of the catalysts. Highly active electron-rich Ru 0 sites stabilized by strong metal-support interaction (SMSI) can effectively adsorb and activate molecular H 2 and C O bond in levulinic acid. Varying Zr/Al ratio and calcination temperature can rationally control the acid strength and acid sites distribution of support, and (AlO)(ZrO) 0.1 calcined at 400 °C exhibited the maximal proportion of Lewis acid sites. Ru 0 species and Lewis acid sites synergistically enhanced the conversion of levulinic acid and facilitated the intramolecular dehydration of 4-hydroxypentanoic acid as intermediate to γ-valerolactone ( i.e. , the rate-limiting step).
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高影响因子
NANOTECHNOLOGY
·
2018
·Vol. 29
·期 7
·075708
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IF 3.404
Hengcong Tao,Jingjing Ding,Chao Xie,Yunnan Gao,Jinliang Song,Zhenyu Sun
We demonstrate a facile and versatile method to grow Ru particles uniformly on pristine few-layer graphene (FLG) in supercritical diethylamine. In particular, a large number of Ru subnanometer clusters less than 1.0 nm were observed. The particle size can be tuned by manipulating the loading content of Ru and controlling the reaction temperature. The resulting Ru/FLG showed remarkably high activity, selectivity, and reusability towards the hydrogenation of levulinic acid to γ-valerolactone. This method is flexible, and can be extended to the synthesis of a variety of other ultrafine metal particles supported on FLG.
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PubMed
高影响因子
APPLIED CATALYSIS A-GENERAL
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2025
·
IF 4.8
Weimeng Cai,Haojie Du,Erju Wang,Yuting Qiang,Kunhong Hu,Jianhua Guo
The synthesis of value-added chemicals from renewable biomass is becoming increasingly important in the transition to a sustainable and low-carbon energy system. Herein, we demonstrate a solvent-polarity modulation strategy to engineer biomass-derived Cu-MOF using 2,5-furandicarboxylic acid (FDCA) as a renewable ligand, where tailored β/α ratios via Kamlet-Taft parameters balance nucleation-growth kinetics to optimize textural properties. Pyrolyzed Cu-MOF at 500 °C under a nitrogen atmosphere yield the Cu/C catalysts, which were subsequently employed in the selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). Among the various solvents used, the Cu-MOF precursor synthesized in a mixed solvent of methanol and N, N-dimethylformamide (DMF) demonstrated the highest catalytic performance, outperforming those synthesized in other solvents. This highlights the significant impact of solvent selection on the structure of Cu-MOF, which in turn affects their hydrogenation activity. Advanced characterization confirming that the uniform Cu dispersion (confirmed by HRTEM mapping) and Cu⁰/Cu⁺ electronic synergy (via Cu Auger analysis) enhanced hydrogenation performance. Additionally, the biomass-derived catalysts exhibited excellent durability. Overall, this research provides a promising approach to develop highly efficient catalysts using renewable ligands and demonstrates the potential of regulating catalyst properties through the strategic selection of solvents, as informed by Kamlet-Taft parameters.
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高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2025
·
IF 6.2
Xiaoying Liu,Haimei Liao,Xingchen Zhu,Wentao Yue,Baojie Liu,Chengrong Qin,Chen Liang,Caoxing Huang,Shuangquan Yao
Lignin nanoparticles (LNPs) can significantly address the heterogeneity of lignin and enhance its application potential. However, the structure activity relationship between the structure of lignin and LNPs has been underexplored. In this study, lignin was extracted using a ternary deep eutectic solvents (DES) of choline chloride (ChCl)/5-sulfosalicylic acid (5Saa)/γ-valerolactone (GVL). The molecular structures of DES Ⅰ-L, DES Ⅱ-L, and DES Ⅲ-L were regulated by varying the temperature (85, 105, and 125 °C). Compared to softwood kraft lignin (SKL), lignin with small molecular weight was obtained. In particular, good homogeneity (PDI 1.55, 1.58, and 1.59) was found. The dispersion stability and pH response of DES Ⅰ-LNPs, DES Ⅱ-LNPs, and DES Ⅲ-LNPs were remarkable. In particular, DES Ⅱ-LNPs was the smallest (32 nm) and exhibited the highest stability (no flocculation within 90 d). DES-LNPs exhibited high shear viscosity, a gentle shear decay trend, low yield stress and shear sensitivity. The phenolic hydroxyl groups rich in lignin promoted the interaction, leading to an increase in the size of LNPs. Fortunately, its smaller molecular weight formed an effective complement. The structure activity relationship between the structure of lignin and LNPs was established, providing theoretical support for the efficient conversion and application of LNPs.
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高影响因子
APPLIED CATALYSIS A-GENERAL
·
2023
·
IF 5.5
Peng Zhang,Pan Hou,Mingwei Ma,Ke Bu,Qi Guo,Huijuan Yue,Ge Tian,Shouhua Feng
The transformation of lignocellulosic biomass to platform compounds (γ-valerolactone, GVL) was a significant component in biomass development. Herein, sulfonated Zr-based metal-organic frameworks (MOF-808), a bifunctional heterogeneous catalyst with Lewis and Bronsted acid sites, were prepared to catalyze the one-pot cascade reaction of furfural (FUR) to GVL. The successful modification of the sulfonic group on MOF-808 was substantiated by multiple characterization methods. By adjusting the sulfuric acid concentration to balance the Lewis acid and Bronsted acid sites of the catalyst, S-808–2.37 was confirmed as the preferred catalyst and a 60.4 % GVL yield was achieved with 99.1 % carbon balance under the optimal conditions. Moreover, the 72.8 % GVL yield reached in the 40x magnification experiment also boded well for the catalyst’s application potential. The work in this paper opened up new perspectives for the application of MOF-808 porous materials in the field of selective catalytic conversion of biomass involving multi-step reactions.
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高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2019
·Vol. 94
·期 7
·2355-2363
·
IF 2.659
Hui-Fang Ren,Dan Zhu,Ji-Fan Li,Chun-Ling Liu,Rong-Zhen Yang,Wen-Sheng Dong
BACKGROUND The chemical catalytic conversion of carbohydrates into γ-valerolactone (GVL) is a sustainable alternative to the petrochemical process starting from the depleting fossil resources. Direct conversion of carbohydrates (fructose, glucose, starch and cellulose) into GVL was achieved via the combined heteropoly acid based SO 3 H-functionalized ionic liquid (HAIL) and supported ruthenium (Ru) catalyst system in one pot and in water media. RESULTS A 63% GVL yield (based on fructose) was obtained under the catalysis of 1-methyl-3-(3-sulfopropylimidazolium)silicotungstate ([MIMPS] 4 SiW) and Ru/ZrO 2 at 180 °C, first in 0.1 MPa nitrogen (N 2 ) for 3 h (dehydration), and then in 4 MPa hydrogen (H 2 ) for 10 h (hydrogenation). Under the same reaction conditions, the GVL yields from glucose, starch and cellulose were 68%, 60% and 60%, respectively. The recyclability of the catalytic system consisting of [MIMPS] 4 SiW and Ru/ZrO 2 was investigated in four runs. The activity for [MIMPS] 4 SiW did not change after use. Partial deactivation of Ru/ZrO 2 was observed, which was ascribed to the severe carbon deposition. CONCLUSIONS In the present method, HAIL and Ru/ZrO 2 catalysts were loaded together. No separation and/or neutralization step reported in the literature was needed and only an atmosphere change (from N 2 to H 2 ) step was involved. Therefore, we provide a promising method for efficient conversion of carbohydrates into GVL. © 2019 Society of Chemical Industry
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高影响因子
RESEARCH ON CHEMICAL INTERMEDIATES
·
2018
·Vol. 44
·期 9
·5439-5453
·
IF 1.674
Huang Feng,Li Wenzhi,Zhang Tingwei,Li Dawei,Liu Qiyu,Zhu Xifeng,Ma Longlong
A carbonaceous solid acid catalyst with high strong-acid density was synthesized by facile functionalization of a biomass-derived mesoporous carbon with benzenesulfonic acid. The catalyst was characterized by using Fourier transform infrared spectroscopy, elemental analysis, X-ray photoelectron spectroscopy, transmission electron microscopy, and N 2 adsorption–desorption. The carbonaceous solid catalyst containing Brønsted acid sites was used for the production of 5-hydroxymethylfurfural (HMF) from hexoses such as fructose, glucose, and cellulose in γ-valerolactone (GVL)-H 2 O mixture. By reaction at 130 °C for 20 min using fructose as a feedstock, an HMF yield 78.1% was achieved. The catalytic performance of the catalyst in conversion of fructose into HMF hardly changed over seven cycles, demonstrating that the catalyst had excellent recyclability. The yields of HMF derived from glucose and cellulose reached 33.2 and 22.5%, respectively, whereas those of total furans were 42.1 and 33.7%, respectively. The proposed reaction system was promising in transforming biomass-based carbohydrates into fine chemicals, given the use of green functionalization methods, the utilization of sustainable biomass-derived carbon precursor and solvents, catalyst with high acid density, and the availability of high HMF yield.
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高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 16
·4499-4511
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IF 9.405
Yuewen Shao,Kai Sun,Qingyin Li,Qianhe Liu,Shu Zhang,Qing Liu,Guangzhi Hu,Xun Hu
γ-Valerolactone (GVL) and 1,4-pentanediol (1,4-PDO) are value-added chemicals that can be produced from levulinic acid/ester via hydrogenation coupled with acid/base-catalyzed reactions. In this study, we demonstrate that the Cu-based catalysts produced via the hydrotalcite precursors with tunable distribution of acidic and basic sites could, according to the requirement of the target products, effectively tune the production of GVL or to 1,4-PDO from levulinic acid/ester. The abundant Brønsted acid sites over the CuAl catalyst suppressed the opening of the ring of GVL, achieving a higher GVL selectivity while inhibiting 1,4-PDO formation. The introduction of Mg species to the catalyst significantly increased the abundance of the basic sites on the surface of the catalyst, which was essential for the selective conversion of GVL to 1,4-PDO via the opening of the ring structure of GVL, the rate-determining step in the conversion from levulinic acid/ester to 1,4-PDO. In addition, the CuMgAl catalyst showed a much superior catalytic stability to the CuMg or CuAl catalyst due to the more stable crystal structure, the more developed porous structure, the higher dispersion of the Cu species and the higher capability to suppress the growth of metallic Cu species under hydrothermal conditions.
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高影响因子
Molecular Catalysis
·
2017
·
IF 0
Ruiying Wang,Jianjia Wang,Huimin Zi,Yongmei Xia,Haijun Wang,Xiang Liu
Zr(IV)-salphen-MCM-41 was prepared by immobilizing a zirconium(IV) Schiff base complex onto the surface of MCM-41. The structural properties of the heterogeneous catalysts were characterized by FT-IR, UV, TG, XRD, SEM, TEM, BET, EDX, CO 2 -TPD, NH 3 -TPD and ICP-OES. Studies on the catalytic properties of the immobilized Zr(IV)-Schiff base complexes were performed using the reduction and cyclization of ethyl levulinate (EL) to γ-valerolactone (GVL) with isopropanol as the hydrogen source. Various reaction parameters, such as temperature, reaction time, solvent and catalyst loading were carefully investigated. The optimal conditions (GVL yield up to 90%) involved the utilization of Zr(Salphen)-MCM-41 as the catalyst in isopropanol. The key to heightened reaction performance was the incorporation of the phenolate and aniline groups in the ligands of bound to Zr. This increased the basicity of the catalyst, which subsequently enhances the efficiency of the transfer hydrogenation reported herein. Meanwhile, the immobilized catalyst can be easily separated and efficiently recycled at least five times without significant loss of activity. Finally, we proposed a plausible reaction mechanism based on experimental and characterization data.
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INDUSTRIAL CROPS AND PRODUCTS
·
2024
·
IF 5.6
Ni Wei,Xin Xu,Jiushun Qin,Wei Lai,Ruoyan Li,Chenhuan Lai,Qiang Yong
Development of green pretreatment strategies with excellent lignin removal ability is particularly important for masson pine biorefinery. γ-Valerolactone (GVL), as a green and recyclable solvent, has unique solvent characteristics to extract lignin. In this study, three acid catalysts, including sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl) and p -toluenesulfonic acid (TsOH), were used to catalyze γ-valerolactone (GVL) pretreatment of masson pine. Among them, the TsOH-catalyzed GVL pretreatment achieved the highest lignin removal ratio and the best cellulose enzymatic hydrolysis yield. Under the optimized pretreatment conditions (150 ℃, 150 mM TsOH, GVL/H 2 O (4:1, w/w), 1 h), the lignin removal ratio reached 89.0 %, achieving a 72 h glucose yield of 87.1 % from the pretreated residues. The solvent lignins from pretreatment liquid was separated and characterized by NMR analysis. Meanwhile, the hexoses in pretreatment liquid were further converted into levulinic acid (LA) using the TsOH-catalyzed bi-phase reaction systems. This study gives insights into developing a biorefining process for the effective utilization of masson pine.
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高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Yue Wang,Huai Liu,Junhua Zhang,Yuan Cheng,Wansi Lin,Rulu Huang,Lincai Peng
The development of efficient and reusable catalysts to improve the catalytic transfer hydrogenation (CTH) of biomass-derived platform molecules into high value-added chemicals is always desired. For this purpose, the magnetic Fe 3 O 4 @Zr-FDCA hybrid with Lewis acid and Lewis base sites was first designed by simple assembly of biomass derived 2,5-furandicarboxylic acid (FDCA) with zirconium and grown directly on the surface of carboxylated Fe 3 O 4 . The resulting Fe 3 O 4 @Zr-FDCA exhibited a unique core-shell structure with high specific surface area and proper acid/basic strength, it performed well in CTH reaction of diverse carbonyl compounds, especially for the conversion of ethyl levulinate to γ-valerolactone with the yield of 94.5% at 180 °C for 5 h. Furthermore, the good magnetic responsibility of Fe 3 O 4 @Zr-FDCA made it could be easily separated from the reaction mixture by an external magnet, and displayed a good reusability with no significant loss in the activity after reuse for five runs.
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高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Wenxiu Cao,Lu Lin,Haifeng Qi,Qian He,Zhijie Wu,Aiqin Wang,Wenhao Luo,Tao Zhang
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is a key reaction for the production of renewable chemicals and fuels, wherein acid-resistant and robust catalysts are highly desired for practical usage. Herein, an ultra-stable 0.6 wt% Ir@ZrO 2 @C single-atom catalyst was prepared via an in-situ synthesis approach during the assembly of UiO-66, followed by confined pyrolysis . The Ir@ZrO 2 @C offered not only a quantitative LA conversion and an excellent GVL selectivity (>99%), but also an unprecedented stability during recycling runs under harsh conditions (at T = 453 K, P H2 = 40 bar in pH = 3 or pH = 1 aqueous solution). By thorough spectroscopy characterizations, a well-defined structure of atomically dispersed Ir δ+ atoms onto nano-tetragonal ZrO 2 confined in the amorphous carbon was identified for the Ir@ZrO 2 @C. The strong metal-support interaction and the confinement of the amorphous carbon account for the ultra-stability of the Ir@ZrO 2 @C.
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高影响因子
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