Molecular Catalysis
·
2018
·
IF 0
Zhongzhe Wei,Xuefeng Li,Jiang Deng,Jing Wang,Haoran Li,Yong Wang
The catalytic transformation from levulinic acid (LA) into γ-valerolactone (GVL) is of great interest as it is an impressive strategy to convert lignocellulosic platform chemical into high value-added compounds. Herein, a novel heterogeneous catalyst made of Ru nanoparticles (NPs) supported on N-doped hierarchically porous carbon from biomass, Ru/NHPC, was shown to be highly active, selective and stable in this transformation. The reaction can proceed smoothly under mild conditions in aqueous media even at room temperature. The catalyst Ru/NHPC could be recycled for 13 consecutive runs exhibiting no obvious activity decay, much better than that of Ru NPs supported on activated carbon. The process offers an efficient, environmentally responsible, and safe approach to high production of GVL.
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DOI
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Chanjuan Yang,Shoukang Xiao,Liyu Chen,Yingwei Li,Kui Shen
γ-Valerolactone (GVL) as an important high-value chemical can be readily produced through the catalytic hydrogenation of renewable levulinic acid (LA). However, high reaction temperatures (70–240 ℃) and H 2 pressures (0.5–6 MPa) are usually required to achieve full LA conversion and desired GVL yield in previous studies. Herein, we report, for the first time, the ambient-condition upgrading of LA to GVL by rationally constructing a series of metallic–acidic Ru x Pt y /MIL-101 catalysts comprising RuPt-alloyed nanoparticles (NPs) and Lewis-acid sites within a chromium-based MOF (namely MIL-101). Benefiting from the favorable synergy between Ru and Pt in their alloyed NPs and abundant Lewis-acid sites in MIL-101, the best Ru 4 Pt 1 /MIL-101 featuring an optimized Ru/Pt molar ratio of 4:1 shows a complete LA conversion with > 99.9 % yield of GVL under unprecedented ambient temperature and pressure, affording a high turnover frequency (TOF) of 1480.5h −1 , which is 15.1 and 10.1 times that of its monometallic Pt/MIL-101 (98.3 h −1 ) and Ru/MIL-101 (146.7 h −1 ) counterparts, respectively. Detailed experiments and density functional theory (DFT) calculations suggest the RuPt-alloyed effect and Lewis-acid sites in Ru 4 Pt 1 /MIL-101 can optimize the adsorption energy of 4-hydroxyvaleric acid (HPA) to remarkably boosting its catalytic performance for this reaction.
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高影响因子
GREEN CHEMISTRY
·
2013
·Vol. 15
·期 10
·2967-2974
·
IF 6.828
Tao Pan,Jin Deng,Qing Xu,Yang Xu,Qing-Xiang Guo,Yao Fu
The development of the catalytic conversion of biomass-based platform molecules into oxygenated fuel molecules is of great significance in order to reduce the dependence on fossil resources and to solve environmental problems. Alkyl valerate esters were proven to have the potential to be renewable additives of gasoline and diesel. In this work, we studied the hydrogenation of levulinic acid (LA) to valerate esters over supported Ru catalysts, and found that the acidity was an important factor for the catalyst performance. A bifunctional catalyst Ru/SBA-SO3H was developed as an active catalyst, and a highest yield of 94% to ethyl valerate (EV) was achieved. The catalyst was characterized by nitrogen adsorption/desorption methods, X-ray power diffraction (XRD), transmission electron spectroscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The effects of reaction conditions were comprehensively investigated and probable reaction pathways were proposed and verified. The conversion of LA to various alkyl valerate esters can also be catalyzed by the bifunctional catalyst. In addition, supported Cu and Ni catalysts were also screened under similar reaction conditions as Ru-based catalysts, and the combination of Ni/SBA-15 and SBA-SO3H exhibited activity for the conversion of LA to EV.
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高影响因子
ChemCatChem
·
2022
·Vol. 14
·期 13
·e202200311
·
IF 5.497
Yuyao Zeng,Bowei Wang,Fanyong Yan,Wensheng Xu,Guoyi Bai,Yang Li,Xilong Yan,Ligong Chen
Graphical Through a convenient impregnation method, highly-distributed and stable Cu nanoparticles were dispersed on the boron doped γ-Al 2 O 3 support, which catalyzed continuous reductive amination of levulinic acid to corresponding N-substituted pyrrolidinones. The reductive amination of biomass-derived levulinic acid (LA) to value-added N-substituted pyrrolidinones with amine and molecular hydrogen over heterogeneous catalyst represents an atom-economical and scalable route. In this paper, a series of boron doped Cu/Al 2 O 3 catalysts via kneading and impregnation method are developed for the continuous reductive amination of LA. Compared with Cu/Al 2 O 3 , Cu 10 /AlB 3 O catalyst exhibits greatly improved catalytic performance for this reaction at low operation temperature. Structure-property correlation investigations were performed with diverse characterization methods, and the results revealed that the excellent catalytic performance of boron doped Cu/Al 2 O 3 catalysts was mainly attributed to the synergistic effect of its well-dispersed Cu nanoparticles, appropriate surface Cu electronic state and surface acidic sites nearby. Besides, Cu 10 /AlB 3 O shows great stability during the reaction over 200 h. This work provides a low-cost, efficient and environmentally friendly heterogeneous catalytic system for the continuous production of N-substituted pyrrolidinones.
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高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Shengbin Shi,Yuanfeng Wu,Mengting Zhang,Ruiping Wei,Lijing Gao,Guomin Xiao
A series of new SO 3 H-functionalized ionic liquids (ILs) were synthesized and characterized, which were successfully applied to catalyze cellulose to produce levulinic acid (LA) via one-pot reaction. The structure, thermal property, and acidity of ILs were characterized by NMR, TGA, and Hammett acidity measurement. The Hammett acidity (H 0 ) of ILs increase in the following order: [BSim]H 2 PO 4 <[BSim]TsO < [BSim]CF 3 SO 3 < [BSim]HSO 4 , which is consistent with their yield of LA order using these ILs as catalysts. Under the optimum conditions, the yield reached up to 65% when [BSim]HSO 4 was used as catalyst and solvent, which is one of the best results compared to those reported in literature. Moreover, the ILs were easily recycled without structural change even after four cycles, and the yield of LA was up to 44% at the fifth cycle. Furthermore, TGA indicated that these SO 3 H-functionalized ILs exhibited excellent thermal stability. These efficient ILs will provide new options for converting biomass resources to LA and other chemicals.
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DOI
高影响因子
RENEWABLE ENERGY
·
2019
·
IF 5.439
Xueyan Zhang,Xiaoyu Zhang,Ningyue Sun,Shengtian Wang,Xiaohong Wang,Zijang Jiang
Heteropolyacids (HPAs), super strong Brønsted acid solids, were recently reported to achieve cellulose conversion with high efficiency. To achieve higher levulinic acid (LA) yield, a series of Lewis metal-substituent phosphotungstic acids H n PW 11 LO 39 (HPWL, L = Cu II , Sn IV , Cr III , Zn II , Fe III ; L = Ti IV , Zr IV , oxygen is 40) were used as catalysts in polysaccharides conversion. Identification of the reaction intermediates and products provided some information for cellulose conversion pathway. H 5 PW 11 TiO 40 (Brønsted/Lewis acid = 2.84:1) was found to be most active with highest cellulose conversion giving highest glucose yield in water and highest LA yield in methyl isobutyl ketone (MIBK)/water. In addition, for overcome the drawbacks in mass transferring and separation, the temperature-responsive catalyst of HOCH 2 CH 2 N(CH 3 ) 3 H 4 PW 11 TiO 40 (ChH 4 PWTi) was prepared giving as high as 76.1% LA yield at 93.8% cellulose conversion more than those by HPWTi (65.6%, 90.5%). Also, ChH 4 PWTi was obtained 93.7% conversion and 70.9% yield at microwave. ChH 4 PWTi also presented higher feedstocks - tolerance to mono-, di- or polysaccharides and even lignocellulose (corn straw, pinewood, husk of xanthoceras, coconut shell) to LA. As highest as 33.0% LA yield at 68.0% conversion was obtained by ChH 4 PWTi from husk of xanthoceras under mild conditions. ChH 4 PWTi could be recycled 12 times without significant loss of activity, which showed longer duration.
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高影响因子
FUEL
·
2023
·
IF 7.4
Honghui Gong,Juan Zhang,Qi Li,Longxing Wei,Ya Hu,Yifan Rui,Xian-Lei Shi
A series of sulfonic acid functionalized coffee biochar (SFCB-x) with high acid density and strength were prepared by using sulfuric acid as the sulfating agent. The obtained catalysts could be directly used for esterification of levulinic acid (LA) and alcoholysis of furfural alcohol (FA) affording ethyl levulinate (EL). Further activity tests and characterization confirmed the linear correlation between the catalytic activity and -SO 3 H density of the catalyst, SFCB-4 holds the highest -SO 3 H density and thus exhibits the highest catalytic activity towards the production of EL. Under mild conditions, about 97.6% and 81.7% yield of EL could be obtained for LA esterification and alcoholysis of FA, respectively. The catalyst also shows high stability during consecutive catalytic recycles. Furthermore, hot filtration testing suggested that the leaching of the active species was not observed during catalytic recycles, which could be attributed to the covalently linked -SO 3 H groups on SFCB-4 skeleton. The rational design and construction of SFCB-4 will drive the development of solid acid catalyst derived from natural biomass for the production of bio-based chemicals.
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高影响因子
FUEL
·
2022
·
IF 8.035
Lungang Chen,Yong Liu,Xinghua Zhang,Jianguo Liu,Qi Zhang,Longlong Ma
Catalytic conversion of biomass to liquid fuel is one of critical part to ease dependence on fossil fuel. Herein, a route of transformation of biomass-derived furfural and levulinic acid into long-chain hydrocarbon fuels was developed. A C20 oxygenate with 95 % mol yield was firstly synthesized through condensation-polymerization reactions catalyzed by NaOH. Various techniques were employed to verify the chemical structure of the C20 oxygenate. The condensation mixture was then directly subjected to hydrodeoxygenation reaction to prepare long-chain hydrocarbons with a catalytic system of Pd/C and H 3 PO 4 in aqueous phase. A 57.1 % weight yield of liquid fuel was obtained with main products of C12, C14, and C18 hydrocarbons. The mass percent of carbon and hydrogen in fuel was significant improved to 95.91 %, as well as the high heat value was increased to 47.04 MJ/kg.
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Lungang Chen,Yong Liu,Canshuo Gu,Gang Feng,Xinghua Zhang,Jianguo Liu,Qi Zhang,Chenguang Wang,Longlong Ma
Selective production of 2-butanol from levulinic acid (LA) hydrogenolysis over a non-precious catalyst is long desirable. However, the process requires the precious metal Ru, and the yield of 2-butanol was less than 65%. Herein, we prepared Ni-based bimetallic catalysts, among which the NiMn catalyst exhibited the highest efficiency and reached an 84.5% yield of 2-butanol at 100% LA conversion under optimal conditions. The electronic states and surface properties were characterized by various techniques such as X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed desorption, temperature-programmed reduction, and scanning electron microscopy/transmission electron microscopy. The high efficiency of the NiMn catalyst was due to the synergy between Ni0 and Mn2+ species, and the modified surface showed a high basicity and a high affinity to adsorb LA and LA-derived molecules with C═O or COOH. The high affinity of the NiMn catalyst was further confirmed by density functional theory calculations.
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高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 1
·163-175
·
IF 10.182
Shanta Dutta,Iris K. M. Yu,Jiajun Fan,James H. Clark,Daniel C. W. Tsang
A considerable amount of food waste generated globally could be upcycled to synthesise platform chemicals to enhance environmental sustainability and realise a circular economy. This study investigates the catalytic production of the vital platform molecule levulinic acid (LA) from bread waste, a typical stream of starch-rich food waste generated worldwide. Gamma-valerolactone (GVL), isopropanol (IPA), and propylene carbonate (PC) were evaluated as bio-derived and CO2-derived green co-solvents for LA synthesis. In-vessel pressure generated in PC/H2O (1 : 1) solvent was conducive to rapid LA production from bread waste compared to GVL/H2O and IPA/H2O. In PC/H2O, 72 mol% total soluble product yield was observed quickly within 1 min in moderate reaction conditions (130 °C, 0.5 M H2SO4), whereas ∼15–20 mol% of LA could be obtained when the reaction was prolonged for 10–20 min at 130 °C. The yield of LA could be significantly enhanced in GVL/H2O through phase separation using NaCl (30 wt%(aq)). LA yield increased up to a maximum of ∼2.5 times in the biphasic system (28 mol%, 150 °C, 15 min) (representing a theoretical yield of 66%) in GVL/H2O (1 : 1) compared to the monophasic system (∼11 mol%) under the same reaction conditions. The partition coefficient for LA achieved was 4.2 in the GVL/H2O (1 : 1) biphasic medium, indicating that the system was efficient for simultaneous production and extraction of LA. Biphasic GVL/H2O facilitated selective LA production, which could be optimised by tuning the reaction conditions. These new insights can foster the development of high-performance LA production and sustainable biorefinery.
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高影响因子
ENERGY & FUELS
·
2020
·
IF 3.421
Yang Qu,Yuan Zhao,Shanshan Xiong,Chenguang Wang,Shurong Wang,Lingjun Zhu,Longlong Ma
5-Hydroxymethylfurfural (HMF) and levulinic acid (LA) are two important platform compounds that can be produced by the dehydration of hexoses from hydrolysis of cellulose. In this study, glucose dehydration was catalyzed by the SO42–/ZrO2 catalyst in the NaCl–THF/H2O biphasic solvent system. Complete conversion of glucose was achieved at 160 °C. The highest HMF yield and LA yield were 61.84% and 29.68%, respectively. The results showed that the conversion and product distribution were influenced by catalyst acidity, solvent composition, temperature, and time. The SO42– load greatly changed the acidity of the catalyst, thus affecting the product distribution. By changing the composition of the catalyst and the biphasic solvent system, different yields of HMF and LA could be obtained, so as to realize directional synthesis of the target products.
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Wenlin Li,Feng Li,Junwen Chen,Luis E. Betancourt,Chunyan Tu,Mingjie Liao,Xing Ning,Jiajun Zheng,Ruifeng Li
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is an essential reaction step to produce value-added renewable chemicals and fuels. In this study, it is demonstrated that the dispersed state of metal and the acid properties of the support can be tuned directly in the synthesized stage for the Ru/MCM-49 catalysts. The average metal particle size of Ru was found at ∼2.0 nm, and strong metal–support interaction was observed for the Ru/MCM-49(DP) catalyst. Mesopores presented can enhance the conversion rate for LA to GVL. The presence of a higher amount of Lewis acid sites can promote the ring closure esterification of the intermediate 4-HPA. High catalytic activity with a TOF value of >3000 h–1, as well as excellent reusability, were achieved by Ru/MCM-49(DP). The agglomeration of Ru particles and the coke formation were thought to be responsible for the deactivation of the catalyst.
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高影响因子
危险品化学品经营许可证（带存储）