APPLIED CATALYSIS A-GENERAL
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2018
·
IF 4.521
Zhenzhen Lin,Mengting Luo,Yindi Zhang,Xiaoxue Wu,Yanghe Fu,Fumin Zhang,Weidong Zhu
Heterogeneous catalytic conversion of biomass-derived methyl levulinate (ML) to γ-valerolactone (GVL) is highly attractive as a sustainable route to mitigating the dependence on nonrenewable fossil resources. However, this route is limited by its low selectivity toward GVL and severe reaction conditions. Here, we present a synergistic catalytic process that offers exclusive GVL selectivity with complete ML conversion under mild conditions (80 °C, 0.5 MPa of H 2 pressure). This is achieved over a dual-functionalized catalyst of Ru nanoparticles (Ru-NPs) and Brønsted acid SO 3 H groups in a Cr-based metal-organic framework (MIL-101). The Ru-NPs served as metal sites for the hydrogenation of ML to methyl-3-hydroxyvalerate (MHV) and the acidic SO 3 H moieties promoted the cyclization of MHV to generate GVL via lactonization. In contrast, GVL production was significantly suppressed over the physically mixed congener (2.0 wt% Ru/MIL-101 + MIL-101-SO 3 H). This result demonstrates an unrivalled advantage of the dual integration of metal/acid sites in a single MOF crystal, and the relative amount of sulfonic acid groups in the catalyst can exert significant influence on the overall catalytic performances. The activation energies for the hydrogenation and lactonization steps with the developed catalyst were 29.5 and 42.1 kJ/mol, respectively, which are much lower than those observed with the traditional 5.0 wt% Ru/AC catalyst.
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高影响因子
FUEL PROCESSING TECHNOLOGY
·
2018
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IF 3.956
Feng Huang,Wenzhi Li,Qingchuan Liu,Tingwei Zhang,Shengxin An,Dawei Li,Xifeng Zhu
A carbon solid acid was made by grafting benzenesulfonic acid groups on the tobacco stem-derived porous carbon, which was prepared from waste tobacco stem by simple carbonization . The catalyst was characterized by scanning electron microscope (SEM), N 2 adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), pyridine FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS). The catalyst exhibited excellent catalytic activity for 5-hydroxymethylfurfural (HMF) production from fructose and glucose in γ-valerolactone/water solvent, and high yields of HMF reached 93.7 and 43.8%, respectively. In addition, the high yields of total furans derived from fructose and glucose reached 96.8 and 54.1%, respectively. The benzenesulfonic acid group grafted onto the surface of inner pores of carbon allowed reusing the catalyst for at least five runs without obvious activity reduction. The good performance of the tobacco stem-derived carbon solid acid was determined by the unique surface active sites, such as high density of Brønsted acid, Lewis acid sites, oxygen-containing weak acidic sites and protonated nitrogen-containing functional groups. This study offered a promising approach for efficient carbohydrate conversion.
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GREEN CHEMISTRY
·
2017
·Vol. 19
·期 9
·2201-2211
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IF 9.125
Wenxiu Cao,Wenhao Luo,Hongguang Ge,Yang Su,Aiqin Wang,Tao Zhang
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is a crucial reaction included in many biorefinery schemes for the production of renewable chemicals and fuels. The development of highly stable supported Ru-based catalysts in the polar protic liquid phase under hydrothermal conditions is still a major challenge. Here, we prepared a 0.85 wt% Ru/ZrO2@C catalyst using a new stabilization strategy based on the UiO-66 (Zr-MOF) material. The catalytic performance of this Ru/ZrO2@C in LA-to-GVL was tested and compared with commercial 5 wt% Ru/C at 10 bar H2, 413 K in water and also in high protic aqueous solution (pH = 1). The full conversion of LA and quantitative yield of GVL were achieved with both catalysts. However, the 5 wt% Ru/C showed poor resistance to deactivation already after the first run. ICP, XPS, HRTEM, AC-STEM, TPR and physisorption data showed that quick deactivation of Ru/C was mainly caused by the leaching of ruthenium in addition to the loss of surface area via carbonaceous deposition in micro-pores. In contrast, the self-prepared Ru/ZrO2@C catalyst showed no apparent drop in catalytic performance either in water or in high protic aqueous solution upon multiple recycling, and no leaching of ruthenium was found even under harsh conditions (pH = 1). Remarkably, in the Ru/ZrO2@C catalyst, Ru (probable single-atom) was highly dispersed on nanotetragonal ZrO2 (3.3 nm), embedded in the amorphous carbon, and no apparent Ru nanoclusters were observed even after reactions. TPR results indicated that this excellent stability might be attributed to strong metal–support interaction between Ru and nanotetragonal ZrO2.
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RSC Advances
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2017
·Vol. 7
·期 48
·29916-29924
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IF 3.108
Yuanshuai Zhu,Wenzhi Li,Yijuan Lu,Tingwei Zhang,Hasan Jameel,Hou-min Chang,Longlong Ma
A resorcinol-formaldehyde resin carbon (RFC) catalyst with a well-developed, ordered, mesoporous framework was prepared using a soft template method at room temperature. The carbon was sulfonated in water using sulfanilic acid under mild atmospheric conditions. The sulfonated RFC (S-RFC) was characterized by N2 adsorption–desorption, elemental analysis, TEM, XPS, and FT-IR. It was determined that S-RFC is an efficient solid acid catalyst for furfural production from xylose and corn stover in γ-valerolactone (GVL). The effects of reaction time, reaction temperature, catalyst loading, substrate dosage and water concentration were investigated. 80% furfural yield and 100% xylose conversion were obtained from xylose at 170 °C in 15 min with 0.5 g catalyst. Comparatively, 68.6% furfural yield was achieved from corn stover at 200 °C in 100 min when using 0.6 g catalyst. Since there was no discernable decrease in furfural yield after multiple conversions utilizing the same catalyst, the recyclability of the catalyst is considered good.
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INDUSTRIAL CROPS AND PRODUCTS
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2024
·
IF 5.6
Xiaoxue Zhao,Xin Xu,Zhe Ling,Caoxing Huang,Chenhuan Lai,Qiang Yong
Developing green pretreatment technologies that prioritize the selective separation of lignin is of significant importance for the industrialization of biorefining. This work employed H 2 SO 4 -catalyzed γ-valerolactone (GVL) pretreatment on masson pine sawdust (GAM) to investigate process conditions and the enzymatic hydrolysis performance of masson pine. The results indicated that the lignin removal rate was 87.2% under the optimal pretreatment conditions (150ºC, 75 mM H 2 SO 4 ). The synergistic effect of the H 2 SO 4 catalyst and GVL pretreatment resulted in an enzymatic hydrolysis yield for GAM (76.8%) nearly six times higher than that of other non-synergistic systems (5.7%∼13.0%). Furthermore, the enzymatic hydrolysis yield increased to 97.3% upon the addition of bovine serum albumin . Microscopic visualization was used to analyze the morphological changes of cells and the micro-distribution of lignin within GAM cell walls after pretreatment. Additionally, structural changes in the molecular weight , functional groups, and linkage contents of GAM lignin were analyzed. This research provides valuable insights for masson pine in producing fermentable monosaccharides and acquiring lignin with enhanced processing properties.
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INDUSTRIAL CROPS AND PRODUCTS
·
2024
·
IF 5.6
Jiarong Qiu,Yi Liu,Jingwen Zhang,Ben Zhou,Qiyue Yang,Liangqing Zhang,Jianfeng Chen,Bingshu Wang,Lu Lin,Xianhai Zeng
A series of zirconium phosphate (ZrP) loaded H-beta-25 zeolite (i.e., ZrP@HB) multifunctional composite catalysts were synthesized by a simple co-precipitation method, and the one-pot upgrading for the transfer hydrogenation of furfural to γ-valerolactone (GVL) was systematically investigated through various characterizations and catalytic evaluation experiments. Comparative characterization analysis of the ZrP@HB-X(Y) catalysts showed that the ZrP@HB-4(4) catalyst has uniform distribution of elements, exhibiting a large specific surface area and hierarchical mesoporous/microporous structure. Fourier transform infrared spectroscopy of pyridine (Py-FTIR) and NH 3 temperature-programmed desorption characterizations indicated the presence of Lewis and Brønsted acid sites, as well as weak, moderate, and strong acid sites in the ZrP@HB-4(4) catalyst. It was confirmed by X-ray photoelectron spectroscopy and FTIR that the main reason for Lewis and Brønsted acid sites formation is the presence of P-O-Zr, P-O-H, and HB zeolite on the ZrP@HB-4(4) catalyst. The HB zeolite as well as Zr and P ratio, can be easily adjusted to efficiently regulate the acidity strength and Lewis and Brønsted acid sites of the ZrP@HB-X(Y) catalysts. The catalytic experiments demonstrated that the physicochemical properties of the ZrP@HB-4(4) catalyst mentioned above significantly enhance the GVL production. Notably, Lewis and Brønsted acid sites as well as transition metal sites of Zr in the ZrP@HB-4(4) catalyst were identified as the main factors that enhance the yield of the target product. By optimizing the reaction conditions, the yield of GVL could be as high as 88.16%. Reusability experiments demonstrate that the ZrP@HB-4(4) catalyst possesses excellent stability. Using levulinic acid as the substrate, the yield of GVL reached 93.92%, suggesting its potential versatility.
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高影响因子
MOLECULES
·
2024
·Vol. 29
·期 16
·3779
·
IF 4.2
Pan Hou,Haopeng Su,Keyan Jin,Qiang Li,Wenfu Yan
γ-valerolactone (GVL), derived from biomass, is a crucial platform compound for biofuel synthesis and various industrial applications. Current methods for synthesizing GVL involve expensive catalysts and high-pressure hydrogen, prompting the search for greener alternatives. This study focuses on a novel zirconium phosphate (ZrP)-pillared zeolite MCM-36 derivative catalyst for converting levulinic acid (LA) to GVL using alcohol as a hydrogen source. The incorporation of ZrP significantly contributes to mesoporosity and greatly enhances the acidity of the catalysts. Additionally, we employed31P MAS NMR to comprehensively investigate the influence of phosphorus species on both the acidity and the catalytic conversion of LA to GVL. By adjusting the Zr-to-P ratios, we synthesized catalysts with enhanced acidity, achieving high conversion of LA and selectivity for GVL. The catalyst exhibited high recyclability, showing only minor deactivation over the course of five cycles. Furthermore, the catalyst was successfully applied to the one-pot conversion of furfural to GVL, showcasing its versatility in biomass conversion. This study highlights the potential of the MCM-ZrP1 catalyst for sustainable biomass conversion and offers insights for future research in renewable energy technologies.
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PubMed
高影响因子
JOURNAL OF CATALYSIS
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2024
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IF 6.5
Xiaoqing Gao,Shanhui Zhu,Mei Dong,Hongyan Zheng,Yanfeng Xue,Xiaojing Cui,Yulan Niu,Weibin Fan
Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is of interest for biomass refinery, but it suffers from great challenge to design highly active Ru-based catalyst at low temperature. ZIF-8 derived ZnO@NC nanocomposite can firmly anchor Ru nanoparticles to create strong Ru-ZnO interfacial structure, as revealed by characterization techniques and DFT calculations. By optimizing Ru content and ZnO particle size, Ru/ZnO@NC achieved excellent reaction activity with a turnover frequency (TOF) of 6032 h −1 at low temperature of 40 °C, which is never reported before. After etching the accessible ZnO, the TOF value was significantly declined to 125 h −1 on Ru/ZnO@NC-HF owing to the lack of effective Ru-ZnO interface. DFT calculation results demonstrate that the Ru-ZnO interfacial structure can facilitate the activation of intermediate CH 3 CHOCH 2 CH 2 COOH* and remarkably decline the activation energy barrier of rate-determining step (CH 3 CHOCH 2 CH 2 COOH + H = HPA) from 1.28 eV to 0.82 eV, thus leading to excellent activity of LA hydrogenation at low temperature.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2025
·
IF 8.5
Tianyuan Xiao,Jiahui Song,Wenchao Jia,Yanning Sun,Yanzhu Guo,Pedram Fatehi,Haiqiang Shi
The chemical bond cleavage of lignin is a research focus for achieving depolymerized lignin for such applications as adhesives, fuels, fertilizers, etc. The depolymerization of an industrially available sustainable material, i.e., industrial alkali lignin, in LiBr·3H 2 O/HBr-γ-valerolactone (GVL) was systematically investigated in this study. It was observed that using 3/1 mL/g of HBr/lignin and 8/1 mL/g of GVL/lignin at 110 °C for 90 min, i.e., optimized conditions, resulted in lignin derivatives with an M w of 1889 g/mol and M n of 895 g/mol. The characteristics of the products were studied using FTIR, NMR, SEM, and DLS techniques. The results confirmed that the Hibbert-ketone end group was formed, while the structure of the aromatic ring was not changed on the depolymerized lignin. After the depolymerization process, the hydroxyl content in lignin increased from 1.91 mmol/g to 2.96 mmol/g. The product derived from the LiBr·3H 2 O/HBr-GVL depolymerization system displayed a spherical particle morphology. The addition of GVL to lignin depolymerization processes improved the bonding between lignin and inorganic molten salts, thereby promoting the acid-catalyzed cleavage of aryl ether bonds in lignin. Current research supports the conclusion that LiBr·3H 2 O/HBr-GVL lignin depolymerization is a sustainable and effective chemical pathway for generating depolymerized lignin.
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高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2026
·
IF 4.5
Yongtai Li,Yuanting Du,Yushan Jia,Ruixi Yang,Weijun Shan,Zhenning Lou,Haibiao Yu,Ying Xiong
Hollow coral-like MCM-41-C was successfully prepared by adjust ethanol dosage. • Hollow coral-like 7wt%Al-MCM-41-C with rich weak acid site was prepared by impregnation. • Butene yield was 92.26% for 7wt%Al-MCM-41-C catalyst (300 °C, 90 min). • Due to hollow coral-like structure, 7wt%Al-MCM-41-C exhibits high catalytic stability. In this paper, the hollow coral-like ordered mesoporous MCM-41-C zeolites were synthesized by hydrothermal method, and their synthesis conditions were thoroughly investigated. Then, x wt%Al-MCM-41-C catalysts feature with hollow coral-like morphology were prepared by impregnation method, and used for the catalytic conversion of γ-valerolactone (GVL) to butene. The results showed that the introduction of Al species not only did not destroy the original special microscopic morphological structure of the MCM-41-C, but also co-existed on the surface and skeleton of the catalyst, resulting in a large number of weak acid sites. The optimal 7wt%Al-MCM-41-C catalyst has a specific surface area of 708.56 m 2 g −1 . The content of weak acid was 0.7262 mmol g −1 . At 300 °C, the GVL conversion and butene yield over the catalyst can reach 99.10% and 92.26%, respectively, within just 90 min of reaction. Meanwhile, the 7 wt%Al-MCM-41-C catalysts also demonstrated excellent catalytic cycle stability, and the butene yield remained above 90% after the 4th cycle. Download: Download high-res image (330KB) Download: Download full-size image
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CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Xiaoyan Yin,Tingting Cai,Chao Liu,Chen Huang,Jia Wang,Jun Hu,Neng Li,Jianchun Jiang,Kui Wang
Efficient depolymerization of lignocellulosic biomass into platform chemicals is of great importance to bring the comprehensive bio-refinery concept into industrial reality. Herein, we reported an environmentally benign pretreatment process for full components utilization of moso bamboo in co-solvent of γ-valerolactone (GVL) and aqueous solution of p -toluenesulfonic acid (TsOH aq). Notably, over 98 wt% of lignin and hemicelluloses could be simultaneously degraded into oligomeric phenols and pentose under the mild condition of 130 °C for 60 min with GVL/TsOH aq volume ratio of 4/1, following with 91.5 wt% of cellulose retained which was then enzymatic hydrolyzed into 773.2 mg/g glucose. All of the obtained platform chemicals could be easily separated and purified, which significantly facilitate the excellent retrieve of the co– solvent. Moreover, the synergistic effect between GVL and TsOH on efficiency and specificity was proposed by control group experiment and verified by molecular dynamics simulation and quantum chemical calculation. This study provides a facile pretreatment and direct conversion strategy for biorefinery process of lignocellulosic biomass in novel GVL/TsOH aq co-solvent.
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2021
·
IF 6.064
Yafei Li,Xiaocheng Lan,Boyang Liu,Tiefeng Wang
A stable and highly efficient supported Cu-Ni catalysts for the conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) was developed. The catalysts were characterized by XRD, TEM, TPD, TPR, and XPS. The support effect of metal oxides (Al 2 O 3 , SiO 2 , ZrO 2 , and TiO 2 ) revealed that Cu-Ni supported on Al 2 O 3 showed the highest activity for EL hydrogenation to ethyl 4-hydroxypentanoate (EHP) and the subsequent intramolecular esterification of EHP to GVL. EHP intramolecular esterification to GVL in the ethanol solution was a reversible reaction with an equilibrium constant of 24 at 453 K. A simplified reaction kinetic network was established. The solvent had a significant influence on the reaction equilibrium and the catalyst stability. Cu-Ni/Al 2 O 3 in n-hexane solvent gave a higher GVL yield than that in ethanol solvent, and showed better recyclability than that in toluene solvent. With optimizing the conditions, Cu-Ni/Al 2 O 3 gave 99.9% conversion and 98% selectivity to GVL with a space–time yield of 1.13 g GVL g cat -1 h −1 in n-hexane solvent with good recyclability.
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危险品化学品经营许可证（带存储）