INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Yunfei Zhang,Yi Shen
Converting levulinic acid (LA) to fuel precursors such as gama-valerolactone (GVL) and valeric acid (VA) via an efficient and low-cost method is of great significance. Herein, a series of free-standing electrodes consisting of metallic metals supported by carbon felts (CFs) were fabricated via a facile electro-deposition process. The resulting M/CFs (M = Pb, Cd, Co, Ni, Cu and Bi) electrodes were evaluated for electrocatalytic hydrogenation (ECH) of LA. The electrocatalytic activity of the electrodes was extensively studied by various electrochemical methods including cyclic voltammetry , linear sweep voltammetry and chronoamperometry measurements. The products of the ECH processes were analyzed by gas chromatography-mass spectrometry. Of all the prepared samples, the Pb/CFs and Cd/CFs electrodes showed superior performance for ECH of LA. The selectivity of VA reached up to 91.7% when the Pb/CFs was used and the conversion of LA reached to 57.2% using the Cd/CFs electrode, rendering them as one of the best electrodes for ECH reported in the literature. The effects of applied potentials on the ECH process were investigated. To further optimize the ECH performance of the Pb/CFs electrodes, several key parameters including deposition time , pH value of the electrolyte and reaction time were studied. When the electrodeposition time was 600 s and the concentration of sulfuric acid in the electrolyte was 0.5 M, the complete transformation of 0.2 M of LA was achieved after 6 h. This study may afford an alternative way to the conversion of LA to GVL or VA.
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DOI
高影响因子
Journal of Energy Chemistry
·
2021
·
IF 9.676
Ziyi Li,Haigang Hao,Jingjing Lu,Chengming Wu,Rui Gao,Jifan Li,Chun-Ling Liu,Wen-Sheng Dong
Here we exquisitely fabricated Cu/ZrO 2 -dp catalysts with plentiful Cu-ZrO 2 interfaces by depositing amorphous ZrO 2 onto Cu nanoparticles for the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). With the created plentiful Cu-ZrO 2 interfaces, the optimal catalyst 3Cu/ZrO 2 -dp exhibited exceptional catalytic performance under mild reaction conditions, and achieved the highest GVL mass productivity of 266.0 mmol GVL·h −1 ·g −1 Cu, which was 12.5 and 2.3 times of Cu/ZrO 2 catalysts with equivalent Cu loadings prepared by traditional impregnation (3Cu/ZrO 2 -im) or co-precipitation (3Cu/ZrO 2 -cp). As far as we know, this GVL mass productivity stood at the highest level compared with those obtained using non-noble metal catalysts under similar reaction conditions. By systematic investigation with multiple characterizations, density functional theory (DFT) calculations, and kinetic studies, it was found that interfacial active centers were created at Cu-ZrO 2 interfaces, which contained oxygen vacancies (O v ), negatively charged Cu δ− and partially reduced Zr 3+ . The O v favored the adsorption and activation of LA via its ketone group, while negatively charged Cu δ− was able to enhance heterolysis of H 2 , which resulted in the formation of H + -Cu δ− and Zr 3+ -H − active species via hydrogen spillover. Also, plentiful acid sites, which derived from coordinatively unsaturated and defective Zr species, generated at Cu-ZrO 2 interfaces. With the cooperation of interfacial active centers (Cu δ− -O v -Zr 3+ ) and acid sites, the fabricated 3Cu/ZrO 2 -dp with plentiful Cu-ZrO 2 interfaces achieved excellent catalytic performance for the hydrogenation of LA to GVL. Hence, the synergistic catalysis of Cu-ZrO 2 interfaces provided an effective strategy for designing catalysts with a satisfactory performance for the hydrogenation of LA, which also can be expanded to other hydrodeoxygenation reactions.
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高影响因子
BIOCHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 4.446
Xi Cheng,Qingge Feng,Dachao Ma,Feifan Xing,Xu Zeng,Xiaoxiao Huang,Jiayang Teng,Lin Feng
A CH 3 -SBA-15-SO 3 H catalyst was synthesized for the conversion of glucose to levulinic acid. The performance of the catalyst was demonstrated by comparative experiments using γ-valerolactone solution system versus pure water system. Significantly, the conversion efficiency was almost five times higher for γ-valerolactone solution than that of the pure water. The side reactions of the γ-valerolactone solution system were probably less than that of water system. In order to provide a better understanding of the catalytic reaction and guide the engineering design, the kinetics of levulinic acid production from glucose over CH 3 -SBA-15-SO 3 H catalyst in γ-valerolactone solution were investigated. The kinetic model was established based on four differential equations, and the model results were fitted well to the experimental results. Notably, the activation energies of the production of 5-HMF and levulinic acid were 76.55 kJ/mol and 62.66 kJ/mol, respectively, which were obviously smaller than those previously reported, this may be attributed to the synergistic effect of the solid acid and the high concentration of γ-valerolactone solution.
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高影响因子
RSC Advances
·
2018
·Vol. 8
·期 71
·40989-40995
·
IF 2.936
Ruifeng Wang,Lungang Chen,Xinghua Zhang,Qi Zhang,Yuping Li,Chenguang Wang,Longlong Ma
Novel catalytic material with high catalytic activity and hydrothermal stability plays a key role in the efficient conversion of levulinic acid (LA) to γ-valerolactone (GVL) in water. In this study, mixed oxides Al2O3–TiO2, Al2O3–MoO3 and Al2O3–Co3O4 were synthesized by co-precipitation using aqueous solution of NaOH as precipitant. Ru catalysts supported on mixed oxides were prepared by impregnation method and their catalytic performances were tested in the hydrogenation of LA to GVL on a fixed bed reactor. The physicochemical properties of the catalysts were characterized by XRD, H2-TPR, NH3-TPD, and BET techniques. The TiO2 component significantly affected the acidity of the catalyst, and thus its catalytic activity for the GVL yield was affected. The desired product GVL with a yield of about 97% was obtained over the Ru/Al2O3–TiO2 catalyst under mild conditions (WHSV = 1.8 h−1, T = 80 °C). Moreover, the catalyst Ru/Al2O3–TiO2 exhibited excellent thermal stability in the test period of time.
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PubMed
高影响因子
CHEMICAL ENGINEERING RESEARCH & DESIGN
·
2022
·
IF 4.119
Bin Wang,Haifeng Cong,Xingang Li,Hong Li,Xin Gao
The recovery of levulinic acid (LA) and formic acid (FA) from aqueous solutions and actual biomass hydrolysates by using the stepwise adsorption method was investigated for the first time. The carbon molecular sieve was used as the adsorbent for FA and microporous activated carbon was used as the adsorbent for LA according to the steric hindrance effect of the pore channels and the difference in molecular diameter of FA and LA. The adsorption data of LA and FA onto their respective adsorbents were measured and numerically analyzed by adopting batch adsorption experiment and fixed-bed column methods. In the study of static adsorption equilibrium experiment, the Langmuir equation fitted the data of LA adsorption on activated carbon, while the Freundlich equation fitted well the adsorption data of FA adsorption on carbon molecular sieve. In the kinetic study, the LA adsorption on activated carbon and FA adsorption on carbon molecular sieve confirmed the PSO model. Moreover, the effect of various conditions on fixed-bed column adsorption progress was investigated, which indicated that the adsorption property improved with feed flow rate, column length, temperature decreasing and initial concentration increasing. The Yoon-Nelson model was adopted to predict and analyze the whole process of adsorption breakthrough and consistent well with the experimental data. The separation of LA and FA was realized by continuous fractional adsorption.
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DOI
高影响因子
ENERGY & FUELS
·
2013
·
IF 2.853
Fan Yang,Jie Fu,Jing Mo,Xiuyang Lu
The mixed-acid systems of four Lewis acids (FeCl3, CrCl3, ZnCl2, and CuCl2) combining three Brønsted acids (H2SO4, HCl, and H3PO4) were evaluated for the decomposition of glucose to produce levulinic acid (LA). The CrCl3–H3PO4 system had a strong synergic catalytic activity for the decomposition of glucose to LA. The effects of the ratio of CrCl3 and H3PO4 on glucose, fructose, and 5-hydroxymethylfurfural (5-HMF) decompositions were investigated. The mixed-acid system showed the strongest synergic catalytic activity for glucose, fructose, and 5-HMF decompositions when the ratio of CrCl3 in the CrCl3–H3PO4 system was 0.4–0.5. To probe the synergic catalysis mechanism of the CrCl3–H3PO4 system, the synergic catalytic activities of CrCl3–phosphates (KH2PO4, K2HPO4, and K3PO4) systems on glucose decomposition were also evaluated. The possible synergic catalysis mechanisms were proposed. This study provides insights for the synergic catalysis mechanism of hexose conversion to yield LA.
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高影响因子
Catalysts
·
2015
·Vol. 6
·期 1
·6
·
IF 2
Jie Fu,Dong Sheng,Xiuyang Lu
Four types of nickel catalysts supported on aluminum oxide (Ni/Al2O3) with different nickel loadings were synthesized using the co-precipitation method and were used for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL). The synthesized Ni/Al2O3catalysts exhibited excellent catalytic activity in dioxane, and the activity of the catalysts was excellent even after being used four times in dioxane. The catalytic activity in dioxane as a solvent was found to be superior to the activity in water. Nitrogen physisorption, X-ray diffraction, and transmission electron microscopy were employed to characterize the fresh and used catalysts. The effects of the nickel loading, temperature, hydrogen pressure, and substrate/catalyst ratio on the catalytic activity were investigated.Keywords:nickel supported on aluminum oxide;γ-valerolactone;levulinic acid;hydrogenation;dioxane
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高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2021
·
IF 6.165
Shengbin Shi,Yuanfeng Wu,Mengting Zhang,Zongqi Zhang,Olayinka Oderinde,Lijing Gao,Guomin Xiao
The conversion of cellulose to levulinic acid (LA) and other platform chemicals is a promising route to solve the energy crisis. For this purpose, a series of new SO 3 H-functionalized ionic liquids (ILs), containing different halogen-anions were synthesized and applied for catalytic conversion of cellulose to LA. The structure, thermal stability, and acidity of SO 3 H-functionalized ILs were characterized by Nuclear magnetic resonance (NMR) spectra, Fourier-transform infrared (FT-IR), High resolution mass spectrometry (HRMS), thermogravimetric analysis (TGA), and Hammet acidity method. The results revealed that as the size of halogen anions increased, the Hammett acidity gradually increased from SO 3 H-functionalized ILs containing fluorine- to chlorine- and then to bromine-anions. When SO 3 H-functionalized ILs were used as a catalyst for the production of LA from cellulose, the yield of LA gradually increased as the size of halogen-anions increased from fluorine- to chlorine- and then to bromine-anions. Among the SO 3 H-functionalized ILs, 1,1-bis(3-(4-sulfobutyl)imidazolium-1-yl)butylene bromine ([BSim]Br) exhibited the best catalytic activity with 76.5% yield of LA in cellulose/[BSim]Br/H 2 O ( m / m / m = 1:9:8) reaction system at 180 °C for 20 min, which was the highest yield compared to previous literature reports using ILs as catalyst. Besides, the [BSim]Br was easily recovered and showed high catalytic activity after five cycles. The efficient catalyst, [BSim]Br is then proposed to have a great potential for mass production of LA from biomass.
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高影响因子
FUEL PROCESSING TECHNOLOGY
·
2019
·
IF 4.507
Haonan Qu,Bingyi Liu,Guohua Gao,Yiming Ma,Yanmei Zhou,Hua Zhou,Li Li,Yonghong Li,Shengjian Liu
Levulinic acid (LA) is a versatile key building block in the conversion of carbohydrates and it is an important basic chemical with various potential uses. MIL-100(Fe) loading with insoluble lysine functionalized phosphotungstic acid (Lys-PM 2 ) as heterogeneous catalysts have been synthesized for the conversion of glucose to LA in water. The optimized yield of LA is obtained by using Lys-PM 2 to catalyze glucose conversion is comparable to the majority of effective catalysts. The highest yield of LA (57.9%) is obtained at 150 °C for 9 h with 100 mg glucose and 25 mg Lys-PM 2 , since the Brønsted acidity and Lewis acidity of Lys-PM 2 . And the catalyst is able to recycle at least four times. It demonstrates the potential of Lys-PM 2 for the conversion of biomass.
研究领域:
催化化学
·
绿色化学
·
生物质能源
·
有机转化
·
材料化学
·
可持续化学
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高影响因子
FUEL
·
2023
·
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.
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产品关联
DOI
高影响因子
AICHE JOURNAL
·
2022
·Vol. 69
·期 2
·e17973
·
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.
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产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
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.
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DOI
高影响因子
危险品化学品经营许可证（带存储）