CATALYSIS LETTERS
·
2019
·Vol. 150
·期 2
·322-331
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IF 2.372
Wang Kaifeng,Liu Ya,Wu Wufeng,Chen Yu,Fang Lina,Li Wanbin,Ji Hongbing
Abstract In this study, Zr-MOF material (UiO-66) was modified with different metal oxides (CeO 2 , Ga 2 O 3 , and CoO) and employed in the conversion of cellulose to levulinic acid (LA) in aqueous medium. The research results showed that the introduction of the metal oxides increased the acid content of the catalysts, especially in medium-strong acid. The selectivity of LA was related to the type of metal oxide and the content of medium-strong acid. Due to the activity of Ga 2 O 3 and more medium-strong acid, the yield of LA reaches a maximum yield of 32.0 mol% at 513 K for 360 min when Ga 2 O 3 -UiO-66 was employed as the catalysts. The combination of metal oxide and UiO-66 enables the reaction to proceed, providing a new direction for the conversion of cellulose to LA in the aqueous phase. Graphic Abstract In this study, Zr-MOFs material (UiO-66) was modified with different metal oxides (CeO 2 , Ga 2 O 3 , and CoO) and employed in the conversion of cellulose to levulinic acid in aqueous medium. The results indicated that the addition of metal oxides changes the acidity of UiO-66, which improves the catalytic activity. The selectivity of LA was related to the type of metal oxide and the content of medium-strong acid.
研究领域:
化学工程
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材料科学
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DOI
高影响因子
CATALYSIS TODAY
·
2017
·
IF 4.636
Zhijie Wu,Min Zhang,Yirong Yao,Jingtuo Wang,Danhong Wang,Minghui Zhang,Yongfeng Li
1,3-propanediol (1,3-PDO) and γ-valerolactone (GVL) were simultaneously obtained via the hydrogenolysis of glycerol in levulinic acid (LA) using Ru/C catalysts. Ru/C catalyst exhibited a high LA conversion (∼99%) and a high GVL selectivity (∼99%) for the hydrogenation of LA; while a low conversion (∼11%) and little selectivity of 1,3-PDO for the hydrogenolysis of glycerol. LA promoted the hydrogenolysis of glycerol over Ru/C catalyst, in which LA catalyzed dehydration of glycerol into acetol (precursor of 1,2-propanediol (1,2-PDO)), and glycerol acetalization with the hydrogenated GVL into cyclic acetals, resulting in the formation of 1,3-PDO. A reaction scheme involves the formation of cyclic acetal ethers between GVL and glycerol was proposed to explain the product distributions in the one-pot synthesis of 1,3-PDO and GVL. 64.5% conversion of glycerol and 35.8% selectivity of 1,3-PDO together with 99.1% conversion of LA and 85.8% selectivity of GVL were obtained during one-pot converting glycerol and LA with 3.0 MPa H 2 at 200 °C for 6 h. We reported an effective strategy for the preparation of 1,3-PDO by selective hydrogenolysis of dioxan originated from glycerol with aldehydes or ketones.
研究领域:
生物化学
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催化化学
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产品关联
DOI
高影响因子
ChemSusChem
·
2017
·Vol. 10
·期 8
·1720-1732
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IF 7.226
Zuojun Wei,Jiongtao Lou,Chuanmin Su,Dechao Guo,Yingxin Liu,Shuguang Deng
Graphical Stability through doping : The embedding of Ru nanoparticles in N-doped mesoporous carbon effectively improve the dispersion and decrease the average size of the Ru nanoparticles, improve the adsorption of levulinic acid, and increase the interaction between Ru and the support. The strategy prevents the Ru nanoparticles from migration, aggregation, and leaching, and consequently increases the reusability of the catalyst. To achieve a higher activity and reusability of a Ru-based catalyst, Ru nanoparticles were embedded in N-doped mesoporous carbon through a hard-template method. The catalyst showed excellent catalytic performance (314 h −1 turnover frequency) and recyclability (reusable five times with 3 % activity loss) for the hydrogenolysis of levulinic acid to γ-valerolactone. Compared with the mesoporous carbon without N-doping and conventional activated carbon, the introduction of N-dopant effectively improved the dispersion of Ru nanoparticles, decreased the average size of Ru nanoparticles to as small as 1.32 nm, and improved the adsorption of levulinic acid, which contributed to the increase in the activity of the catalyst. Additionally, the embedding method increased the interaction between Ru nanoparticles and carbon support in contrast with the conventional impregnation method, thus preventing the Ru nanoparticles from migration, aggregation, and leaching from the carbon surface and therefore increasing the reusability of the catalyst.
研究领域:
催化
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化学工程
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材料科学
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产品关联
DOI
PubMed
高影响因子
GREEN CHEMISTRY
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2019
·Vol. 21
·期 3
·606-613
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IF 9.405
Zhenbing Xie,Bingfeng Chen,Haoran Wu,Mingyang Liu,Huizhen Liu,Jianling Zhang,Guanying Yang,Buxing Han
Transformation of biomass or biomass-based feedstocks into fuels or valuable chemicals is of great importance for the sustainable development of our society. Mesoporous Al2O3–ZrO2 with different Al : Zr molar ratios was prepared by the sol–gel method, and Cu–Ni/Al2O3–ZrO2 catalysts were fabricated by the impregnation method. The catalytic performances of the bifunctional catalysts were studied in the selective hydrogenation of levulinic acid (LA) into 2-methyltetrahydrofuran (MTHF). It was demonstrated that both Cu : Ni and Al : Zr ratios affected the selectivity to MTHF significantly. The bimetallic catalysts Cu–Ni/Al2O3–ZrO2 containing 10 wt% Ni and 10 wt% Cu gave 99.8% MTHF selectivity at full conversion of LA when the Al : Zr ratio was 9 : 1. The outstanding catalytic performance of the catalyst is related to the mesoporous structure, the acidic properties of the support and the synergistic effect between Cu and Ni. The catalyst could be reused five times without a considerable loss of catalytic activity and selectivity.
研究领域:
化学工程
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催化科学
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可再生能源
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产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
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2022
·
IF 8.129
Yiwei Tang,Junyan Fu,Yicong Wang,Haixin Guo,Xinhua Qi
Hydrogenation of levulinic acid to γ-valerolactone is one of the important reactions for conversion of biomass into renewable fuels and chemicals. Ni-Zn non-noble bimetallic catalysts supported on ordered mesoporous carbon (Ni-Zn@OMC) were prepared by one-pot solvent evaporation induced self-assembly (EISA) method and used for hydrogenation of levulinic acid to γ-valerolactone (GVL) in water. A GVL yield of 93% was obtained over bimetallic Ni 1 -Zn 1 @OMC catalyst at 180 °C in 90 min reaction time, with a turnover frequency (TOF) of 686.4 h −1 . Compared with Ni@OMC, the incorporation of Zn metal leads to the formation of Ni-Zn alloy and high dispersion of Ni particle on the catalyst surface . NiO sites on the catalysts lowered competitive adsorption between H 2 and levulinic acid on Ni 0 sites, as well as the Ni-Zn alloy is beneficial to the activation of carbonyl group in levulinic acid, and they synergistically promote the hydrogenation of levulinic acid to 4-hydroxyvaleric acid (4-HVA). Zn content in the catalyst influences both the activity of Lewis acid sites and the ratio of Lewis acid to Brønsted acid sites, and the active sites of Ni δ– Zn δ+ can facilitates the weakening and cleavage of C-O in 4-HVA, both of them are beneficial to the dehydration of 4-HVA to GVL.
研究领域:
催化
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可再生能源
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化学工程
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材料科学
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产品关联
DOI
高影响因子
AICHE JOURNAL
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2022
·Vol. 69
·期 2
·e17973
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IF 4.167
Hong Xu,Di Hu,Lu Lin,Man Zhang,Xin Li,Yongjian Zeng,Mahmoud Amer,Wenhao Luo,Kai Yan
The selective hydrogenation of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) is one of pivotal reactions in many of the biorefinery schemes for the production of value-added chemicals and biofuels. Herein, we have fabricated carbon-supported bimetallic NiCo catalysts based on the metal–organic framework (MOF) material via a pyrolysis method. The as-obtained Ni 1 Co 1 bimetallic catalyst outperforms monometallic counterparts in the catalytic performance of LA-to-GVL, with a nearly full conversion of LA and a GVL yield of 95.2%, in particular with an excellent catalyst stability up to seven consecutive runs at 160°C and 4 MPa H 2 . Based on a combined characterization study by employing advanced techniques, for example, extended x-ray absorption fine structure (EXAFS), high-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM), and electron paramagnetic resonance (EPR), we reveal that the enhanced catalytic performance, in particular the excellent stability, could be attributed to the formation of the bimetallic alloys, which efficiently alleviates the metal leaching and sintering during catalysis.
研究领域:
催化
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材料科学
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化学工程
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生物化学
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产品关联
DOI
高影响因子
FUEL
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2023
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IF 7.4
Xiaoqi Wang,Xinhua Qi,Mo Qiu,Feng Shen,Jirui Yang,Boxiong Shen
Herein, a Ni/Ru bimetallic ordered mesoporous carbon (Ni/Ru@WOMC) was prepared through solvent evaporation induced self-assembly (EISA) method with walnut shell organosolv lignin as carbon precursor and Ni 2+ as crosslinking agent followed by impregnating small amount of Ru, where the mass ratio of Ni/Ru was about 10:1. The resulting material showed superior catalytic activity on hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). A nearly 100 % GVL yield could be obtained in 2-propanol solvent under mild conditions at a low reaction temperature of 80 °C in 4 h reaction time. The Ni/Ru@WOMC catalyst could be used at least 5 times without obvious loss of its catalytic performance, which can be ascribed to the confinement effect provided by their ordered mesoporous structure. This successful development of Ni/Ru@WOMC in the hydrogenation of LA to GVL opens up new opportunities for the catalytic application of lignin derived functionalized ordered mesoporous carbon in biomass transformation reactions.
研究领域:
化学工程
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生物质转化
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催化材料
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Yufei Li,Kai Cui,Junwen Chen,Qingsong Xue,Peng Wu,Xiaohong Li
Levulinic acid (LA), as a pivotal biomass platform compound, has attracted significant interest in the field of biorefining, particularly owing to its importance in the synthesis of the high value-added 1,4-pentanediol (1,4-PeD) via a two-step conversion, the hydrogenation of LA and dehydrative lactonization to the intermediate γ-valerolactone (GVL), and the subsequent ring-opening hydrogenolysis of GVL to 1,4-PeD. However, the ring-opening hydrogenolysis of GVL is kinetically restricted by a high reaction energy barrier. Therefore, the development of outstanding non-noble metal catalysts remains a significant challenge for the efficient conversion of GVL to 1,4-PeD. Herein, ternary CuMgAl catalysts were prepared via a coprecipitation method and applied to the one-pot cascade hydrogenation of LA to 1,4-PeD in water. Notably, a Cu 1 Mg 0.5 Al 1 catalyst achieved an impressive 1,4-PeD yield of 94.2% under mild conditions. The structure-performance relationship investigation on the Cu 1 Mg 0.5 Al 1 catalyst revealed a remarkable synergistic effect among Cu 0 sites, Cu + sites, oxygen vacancies and a well-balanced acid-base microenvironment. In particular, the medium-to-strong acidity derived from Cu + species and oxygen vacancies promotes GVL adsorption and subsequent ring-opening hydrogenolysis, while the basic sites effectively buffered the acidity to suppress the dehydrative side reaction of 1,4-PeD. Concurrently, adjacent highly dispersed Cu 0 sites supplied dissociated hydrogen atoms, a synergy that was crucial for achieving high 1,4-PeD yields. This work presents a feasible and sustainable route for producing 1,4-PeD from bio-based LA and offers valuable insights into the mechanism of GVL ring-opening hydrogenolysis.
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DOI
高影响因子
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.
研究领域:
催化
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绿色化学
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可再生能源
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材料科学
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化学工程
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产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
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2015
·
IF 2.679
Meizhen Lu,Guoqiang Han,Yaotai Jiang,Xudong Zhang,Dongshun Deng,Ning Ai
The solubilities of carbon dioxide (CO 2 ) in the renewable deep eutectic solvents (DESs) containing levulinic acid (or furfuryl alcohol) and choline chloride were determined at temperatures (303.15, 313.15, 323.15, and 333.15) K and pressures up to 600.0 kPa using an isochoric saturation method. The mole ratios of levulinic acid (or furfuryl alcohol) to choline chloride were fixed at 3:1, 4:1 and 5:1. Standard Gibbs free energy , dissolution enthalpy and dissolution entropy were calculated from Henry’s law constant of CO 2 in the DESs. Results indicated that levulinic acid based DESs are more effective to capture CO 2 than furfuryl alcohol based ones. The solubility of CO 2 in the DESs increased with increasing mole ratio of levulinic acid (or furfuryl alcohol) to choline chloride as well as pressure and decreased with increasing temperature.
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DOI
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.
研究领域:
催化化学
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能源化学
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绿色化学
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生物质能源
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有机合成
✓ 已验证
DOI
高影响因子
Molecular Catalysis
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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.
研究领域:
生物化学
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催化化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）