CELLULOSE
·
2017
·Vol. 24
·期 3
·1383-1394
·
IF 3.417
Wang Kui,Ye Jun,Zhou Minghao,Liu Peng,Liang Xinyu,Xu Junming,Jiang Jianchun
Direct conversion of cellulose into levulinic acid and furfural in sulfolane media with the aid of water and H 2 SO 4 was performed at 140–220 °C under the pressures of 0–1.5 MPa. This approach could obtain 72.5 mol% levulinic acid and 11.5 mol% furfural formation under an optimal condition in which the mass ratio of sulfolane, water and H 2 SO 4 was 90:10:1. It was found that the decrease of water content led to an increasing yield of furfural and that the maximum furfural yield (51.1 mol%) could be obtained in the absence of water. The synergism of sulfolane and water in the selective liquefied system was demonstrated to be responsible for not only reinforced effect of optimizing and isolating the target products but also for reducing re-polymerization and side reactions. Furthermore, sulfolane in our case could be recycled and re-used for the conversion of cellulose with the same yield, which shed light on the remarkable potential for future industrial application.
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高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Ying Yang,Shuo Wang,Yuhang Sun,Jihuan Song,Chenmeng Cui,Sungsik Lee
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is significant for producing chemicals and fuels from renewable resources, a promising direction in biomass refining. Currently, non-precious metal catalysts suffer from low activity due to a single electronic structure, which is incapable of effectively activating both C O in LA and H 2 . Herein we report in situ fabricated Co nanoclusters within positive and metallic Co sites on N-doped carbon, which can simultaneously activate LA's C O and H 2 , enhancing the activity and selectivity for GVL production. Urea-assisted Co dispersion coupled with variation of pyrolysis temperature, Co nanoclusters were formed via direct conversion of Co-containing zinc trimesic acid fibers. The resulting Co nanoclusters possess dual active sites of Co-N x and metallic Co, with adjustable electronic structures. Under the reaction conditions of 200 °C and 4.5 MPa H 2 for 4 h, LA was completely converted, achieving 95 % yield of GVL. The outstanding catalytic activity is attributed to the Co-N x and metallic Co active sites, which facilitate the activation of C O and H 2 , respectively. This research provides a new concept for converting N-free metal-organic frameworks into non-precious metal nanoclusters, offering valuable insights for designing high-performance non-precious metal catalysts for biomass-derived chemical and fuel production.
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高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Anon Bunrit,Teera Butburee,Meijiang Liu,Zhipeng Huang,Keerati Meeporn,Chaiyasit Phawa,Jian Zhang,Sanchai Kuboon,Huifang Liu,Kajornsak Faungnawakij,Feng Wang
Herein, we developed photo–thermo-dual catalytic strategies for the production of γ-valerolactone (GVL) from levulinic acid (LA) and its ester using platinum-loaded TiO2 as a dual-functional catalyst. Both catalytic systems were evaluated under mild reaction conditions. In the photocatalysis system, a base plays crucial roles in the conversion of LA and EL to GVL. The control experiments reveal that plausible mechanistic pathways of both systems proceed via the hydrogenation of the ketone group of LA to the corresponding alcohol as a major intermediate followed by a subsequent cyclization step to GVL. This dual-functional catalyst provides alternative strategies for the conversion of LA and its ester into GVL, which could pave the way for biomass utilization in a more effective and practical manner.
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·Vol. 65
·期 34
·18084-18092
·
IF 3.9
Xu Cuiwei,Jia Jinjie,Ouyang Sufang,Wu Jianguo,Li Xin,Liu Xiaolei,Qian Jun,Cao Dong,Cheng Daojian
Regulating
the size of the active metal is crucial to change the
electronic structure and catalytic activity. Here, five Ru/CN-ZrO 2 catalysts with different sizes are precisely constructed
via a two-step wet chemical synthesis method. Remarkably, a volcano
trend between the size of Ru and hydrogenation activity for levulinic
acid (LA) is disclosed. The Ru nanoclusters with an average size of
∼2.7 nm (Ru/CN-ZrO 2 -2) exhibit the highest catalytic
activity for LA hydrogenation, achieving an LA conversion of 99.4%
and a γ-valerolactone (GVL) selectivity of 99.3%. Besides, the
corresponding turnover frequency (TOF) is 4860.1 h –1 , which far surpasses that most reported for Ru-based catalysts.
Mechanism studies reveal Ru/CN-ZrO 2 -2 with moderate size
is beneficial to enhance the interaction between Ru and support, directly
promoting the adsorption of LA, and thereby exhibiting the lowest
activation energy. This work emphasizes the size effect to improve
the catalytic activity, which is an important guidance for the rational
design of hydrogenation catalysts.
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APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Junbo Liu,Shengyang Tao
Electrocatalysis of biomass-derived platform molecules is an effective way to utilize biomass. Electrodes for the electrocatalytic hydrogenation of levulinic acid (LA) to selectively produce valeric acid (VA) have been extensively studied. Improving the electrocatalytic activity of electrodes for LA conversion is a meaningful and challenging task. This paper prepared β-PbO/Pb electrodes by laser processing. The higher adsorption of LA on the β-PbO surface was confirmed by in situ infrared and Raman spectra and density functional theory (DFT) calculations. The β-PbO/Pb electrode exhibited higher electrocatalytic activity than the α-PbO/Pb and Pb electrodes. Complete conversion of LA was achieved at a much lower electrode potential of −1.4 V (vs RHE) with an 85 % yield of VA and greater than 90 % selectivity. In addition, laser processing technology provides a strategy for the rapid processing of electrodes to enable large-scale continuous production in industry.
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Biomass Conversion and Biorefinery
·
2022
·
IF 4.05
Yu Nanxi,Lu Houfang,Yang Wei,Zheng Yuxin,Hu Qiang,Liu Yingying,Wu Kejing,Liang Bin
In the process of converting biomass into high value-added chemicals, transfer hydrogenation as a mild hydrogenation method has attracted more and more attention. The catalysts with hydrogenation sites (nano CuNi alloy) and acid sites (Al oxide) highly dispersed on the surface of a stable support (active carbon) were prepared and the importance of acid sites for the activity of CuNi catalysts in transfer hydrogenation was demonstrated. The catalysts showed promising catalytic activity on the transfer hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). The CuNi-1Al/AC with 5 wt.% CuNi alloy and 5 wt.% Al got 97.2% GVL yield and 100% LA conversion at 220 ℃ in isopropanol for 2 h. The high activity of the catalyst is attributed to the promoted esterification by the supported acid sites. The Al-modified catalyst also showed activity for esterification reaction in different alcohol hydrogen donors. The catalyst occurs inactive during the cycle due to the shedding of the active components, and the stability of catalyst is effectively improved by a stepwise impregnation. Graphical abstract
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高影响因子
Biomass Conversion and Biorefinery
·
2022
·
IF 4.05
Xi Xi,Sun Daolai,An Hualiang,Zhao Xinqiang,Wang Yanji
The self-condensation of levulinic acid was studied using cesium silicotungstate (Cs x H 4-x SiW 12 O 40 ) catalyst without solvent. The Cs x H 4-x SiW 12 O 40 catalyst was characterized by FT-IR, Raman, XRD, NH 3 -TPD, N 2 adsorption–desorption, SEM, and ICP. The results showed that the structure of Keggin was well retained in all samples of Cs x H 4-x SiW 12 O 40 catalyst. With a decrease of Cs content, the acid strength of Cs x H 4-x SiW 12 O 40 catalyst decreased, and thus the yield of cyclic C 10 products decreased accordingly, while that of linear C 10 products increased. The effect of reaction conditions on levulinic acid self-condensation was studied using Cs 2.5 H 1.5 SiW 12 O 40 (H 2 SO 4 ) catalyst. Under the conditions of catalyst amount of 15 wt.%, reaction temperature of 130 °C, and reaction time of 6 h, the conversion of levulinic acid was 53.8%, and the total selectivity of C 10 products were 83.1%. Through spectroscopic characterization and DFT calculation, the possible structures of C 10 products of levulinic acid aldol self-condensation were deduced. The results showed that levulinic acid condensed in two different paths to form two intermediates, 4-hydroxy-4-methyl-6-oxononanedioic acid and 3-acetyl-4-hydroxy-4-methylheptanedioic acid. The two intermediates were then subjected, respectively, to lactonization and intramolecular dehydration to three cyclic C 10 products: 5-(2-methyl-5-oxotetrahydrofuran-2-yl)-4-oxopentanoic acid, 3-(2-methyl-5-oxotetrahydrofuran-2-yl)-4-oxopentanoic acid, and 3-(3-acetyl-2-methyl-5-oxotetrahydrofuran-2-yl) propanoic acid, and to obtain the linear C 10 product, (E)-4-methyl-6-oxonon-4-enedioic acid.
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Zuojun Wei,Qing Li,Yuran Cheng,Mei Dong,Zuyi Zhang,Xinmiao Zhu,Yingxin Liu,Yong Sun
CoRe bimetallic catalysts with low loading were designed for hydrodeoxygenation of levulinic acid to γ-valerolactone. Results show that the 1 wt % Co0.5Re0.5/TiO2 catalyst achieved the highest yield of γ-valerolactone (>99%) at 220 °C, 3 h, a 1,4-dioxane solvent and Co/levulinic acid molar ratio of 1:1760, with a turnover frequency (TOF) of 1328 h–1. The catalyst can be reused four times with only slight activity loss. The catalyst was characterized with various physicochemical measurements, and its adsorption styles with H2 and levulinic acid were calculated by density functional theory. The results reveal that four main factors are related to its excellent catalytic performance. First, the Re oxides synergize with Co by spillover of the dissociated H atoms, which increases the apparent dispersion of Co and promotes the reaction. Second, the low loading of 1 wt % allowed the metal nanoparticles to be well dispersed with a very fine size of ca. 1.24 nm, which may expose more active sites to the substrate and result in a higher catalytic efficiency. Third, CoRe formed an amorphous alloy with the formula Co-ReO1.6, which showed a synergistic effect during the reaction. Finally, the TiO2 support was nonporous and hydrophilic, which would be beneficial for the mass diffusion of the reaction components to be adsorbed/desorbed onto the vicinity of the metallic active sites and lead to a high TOF in the hydrodeoxygenation process.
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Siwei Liu,Xiangqian Wei,Weitao Sun,Chenguang Wang,Wenzhi Li,Longlong Ma,Qiying Liu
Considering process efficiency, flow and coking are important aspects in biomass and its derivatives for catalytic conversion to value-added products. However, these investigations are scarcely involved due to the very complex reaction environment and coupling mass transfer and coking process. To better understanding the coking process in glucose catalytic conversion to levulinic acid (LA), a particle-scale model based on the lattice Boltzmann model (LBM) was proposed. In this model, a coking model based on te volume of pixels scheme was developed to simulate the coking deactivation process, and a zeolite permeability model based on the gray LBM scheme was developed for fluid permeation inside shaped zeolite. The model was validated by both analytical and experimental data. The effects of temperature, particle porosity, and coking on catalyst deactivation, product yield, and selectivity were investigated. The numerical results indicated that the deactivation time of shaped zeolite peaked at the particle porosity of 0.20 and increased as the operating temperature decreased. Glucose conversion, LA yield, and humins yield increased with the increase of particle porosity and operating temperature. The opposite trend of the intermediate 5-hydroxymethylfurfural (HMF) was found when the temperature and porosity were increased. The results also showed that the LA selectivity and the yield ratio of LA to humins peaked at a porosity of 0.45 and a reaction temperature of 180 °C.
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CATALYSIS COMMUNICATIONS
·
2020
·
IF 3.612
Jingru Wang,Yingyong Wang,Xili Tong,Yunwei Wang,Guoqiang Jin,Xiangyun Guo
A 3 wt% Ir/SiC catalyst prepared by the wet impregnation method showed excellent catalytic activity and stability for the aqueous hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) in a batch reactor system. LA was completely converted to GVL at 50 °C and 0.2 MPa of H 2 pressure with 100% selectivity and a high turnover frequency (TOF) of 333 h −1 . The high activity of Ir/SiC catalyst could be related to the Schottky-type contact between Ir and SiC solid phases, which promotes electron transfer between support and metal. Due to the excellent acid resistance of SiC support, the Ir/SiC catalyst showed high catalytic stability and nearly no loss of activity after 5 consecutive catalytic operation cycles.
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高影响因子
CARBOHYDRATE POLYMERS
·
2014
·
IF 3.916
Huifang Ren,Buana Girisuta,Yonggui Zhou,Li Liu
Cellulose depolymerization to levulinic acid (LA) was catalyzed by acidic ionic liquids (ILs) selectively and recyclably under hydrothermal conditions. The effects of reaction temperature, time, water amount and cellulose intake were investigated. Dilution effect becomes more pronounced at lower cellulose intake, dramatically improving the yield of LA to 86.1%. A kinetic model has been developed based on experimental data, whereby a good fit was obtained and kinetic parameters were derived. The relationships between IL structure, polymeric structure and depolymerization efficiency were established, shedding light on the in-depth catalytic mechanism of IL, inclusive of acidity and hydrogen bonding ability. The LA product can be readily separated through extraction by methyl isobutyl ketone (MIBK) and IL can be reused over five cycles without loss of activity. This environmentally friendly methodology can be applied to selective production of LA from versatile biomass feedstocks, including cellulose and derivatives, glucose, fructose and HMF.
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PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2017
·
IF 5.951
Mei Xiang,Jingna Liu,Wenqian Fu,Tiandi Tang,Dongfang Wu
A hierarchically porous ETS-10-supported highly dispersed Ni catalyst was designed to selectively catalyze the conversion of cellulose to levulinic acid under mild reaction conditions. Full conversion of cellulose and remarkably high yield (91.0%) of levulinic acid are achieved due to the synergistic effect of the unique porous structures and Lewis acid sites in the presence of a hydrogen atmosphere. Moderate Lewis acidic centers of the heterogeneous catalyst are revealed to play a positive role in activating the reaction substrates and intermediates, resulting in prominently catalytic activity. Meanwhile, hierarchical pores centered at 16 nm in ETS-10 benefit the mass transfer and therefore further enhance its catalytic performance. Also, during the process of levulinic acid formation, introduction of hydrogen is responsible for converting cellulose thoroughly and keeping the metal Ni from oxidization by the oxy-compounds, which is distinctive from the widely reported pathway dominated only by cellulose hydrolysis.
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高影响因子
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