EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
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2020
·Vol. 2020
·期 10
·833-840
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IF 2.529
Ruiping Wei,Jingdeng Fan,Xumin Qu,Lijing Gao,Yuanfeng Wu,Zongqi Zhang,Feng Hu,Guomin Xiao
Graphical Esterification of levulinic acid with ethanol was catalyzed by the cooperative effects between the Lewis acid sites offered by unsaturated Zr 6 nodes and Brønsted acid sites supplied by OH in defective UiO-66 MOFs with high defect density, which was tuned by precursor ratios and modulators. Due to their high stabilities and tunable defects, zirconium terephthalate UiO-66 type metal organic frameworks (MOFs) have been promising catalysts in many catalytic reactions. The catalytic activity of UiO-66 MOFs is significantly affected by the density of defects and hydroxyl groups bonded to Zr 6 nodes, which can be tuned by modulators. In this work, a series of defective UiO-66 were synthesized via tuning the ratio of H 2 BDC/Zr and adding monocarboxylic acids with different chain length as modulators. The synthesized UiO-66 MOFs were characterized by powder X-ray diffraction, N 2 physisorption, IR and 1 H NMR spectroscopy, scanning and transmission electron microscopy. Esterification of levulinic acid with ethanol was selected to reveal the influence of modulators, defects and hydroxyl groups. The results showed that UiO-66 with 0.5 of H 2 BDC/Zr ratio and lauric acid as the modulator owned excellent catalytic activity. The cooperative effects, between the Lewis acid sites offered by unsaturated Zr 6 nodes and Brønsted acid sites supplied by OH, has been revealed to have a significant influence on the catalytic activity.
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CATALYSIS LETTERS
·
2020
·Vol. 150
·期 9
·2709-2715
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IF 2.482
Mao Fei-Feng,Zhao Wenguang,Tao Duan-Jian,Liu Xianxiang
Abstract A new solid acid catalyst Fe 3 O 4 @TNTs-SO 3 H was successfully prepared, characterized, and applied for efficient conversion of renewable levulinic acid to n -butyl levulinate, serving as a promising liquid fuel additive. This catalyst was demonstrated to show high catalytic activity and afford n -butyl levulinate with a yield of 94.6% under optimum conditions. Graphic Abstract
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INDUSTRIAL CROPS AND PRODUCTS
·
2020
·
IF 4.244
Jing Gu,Jun Zhang,Yazhuo Wang,Denian Li,Hongyu Huang,Haoran Yuan,Yong Chen
A series of magnetic zirconium nanoparticles with varied Zr/Fe molar ratios were synthesized and developed as acid−base bifunctional catalysts in the catalytic transfer hydrogenation (CTH) of biomass-derived furfural (FFR) and levulinic acid (LA) using 2-propanol as both hydrogen donor and solvent. Zirconium constituents coated on nano-sized Fe 3 O 4 endowed the catalysts with abundant acid−base sites, moderate surface areas (94.0‒187.6 m 2 /g) and pore sizes (3.42–9.51 nm), thus giving nearly 100 % yields of furfuryl alcohol (FA) and γ-valerolactone (GVL) after 2 h of reaction. Particularly, competitive activation energy (E a ) for the CTH of FFR into FA over Zr 1 Fe 1 -300 was as low as 50.9 kJ/mol. Moreover, the easily separable nanocatalyst Zr 1 Fe 1 -150 was also applicable to CTH of various alkyl levulinates into GVL in high efficiency and could be reused for multiple cycles without obvious loss of its catalytic performance in the transfer hydrogenation of LA.
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ACS Omega
·
2021
·
IF 3.512
Lei Hu,Jiayi Zheng,Qing Li,Shunhui Tao,Xiaojie Zheng,Xiaodong Zhang,Yao Liu,Xiaoqing Lin
5-hydroxymethylfurfural (5-HMF) is a promising high value-added platform chemical, which can be produced from glucose, fructose, or lignocellulosic biomass via catalysis technology. However, the effective separation of 5-HMF from aqueous solution and actual biomass hydrolysate is still challenging because 5-HMF can be further rehydrated into levulinic acid (LA) and formic acid (FA) under acidic conditions. Herein, the adsorption behavior of glucose and 5-HMF and its follow-up products (LA and FA) from aqueous solutions onto polymeric adsorbents modified with various functional groups (XAD-4, XAD7HP, and XAD761 resins) was systematically investigated. The results showed that XAD761 resin exhibited the highest adsorption selectivity (α5-HMF/glucose = 42.42 ± 5.84, α5-HMF/FA = 18.41 ± 0.50, and α5-HMF/LA = 3.01 ± 0.10) and capacity for 5-HMF (106 mg g–1 wet resin). The adsorption equilibrium was better fitted by the Freundlich isotherm model at the studied range of 5-HMF concentrations. The thermodynamic study and activation energy also revealed that the adsorption process of XAD761 resin for 5-HMF was spontaneous, exothermic, and physical. The kinetic regression results revealed that the kinetic data of 5-HMF was accurately followed by the pseudo-second-order kinetic model. In conclusion, the present study revealed that the potential of phenol formaldehyde resin with hydroxyl groups could be used as an adsorbent for aldehyde organic compounds.
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PubMed
高影响因子
Reaction Chemistry & Engineering
·
2021
·Vol. 6
·期 10
·1811-1818
·
IF 4.239
Hongxing Wang,Guoqiang Ding,Yubo Liu,Junbo Zhang,Yongwang Li,Yulei Zhu
A sustainable and cost-competitive catalytic process for high yield production of levulinic acid (LA) and γ-valerolactone (GVL) from biomass-derived furfuryl alcohol (FOL) fluid was proposed with GVL as a self-circulation solvent. The innovative process eliminated the separation of the final product GVL and intermediate product LA from the solvent, and the actual concentration of FOL was improved enormously. A higher yield (90.5%) of LA was realized in the fixed-bed reactors than that in the conventional autoclave since the short residence time of the FOL solution could alleviate the polymerization of FOL in the continuous process. UV-Raman spectroscopy demonstrated that fewer polymers deposited on the catalysts, so superior stability of the zeolite was observed in the fixed-bed reactors. Moreover, an 89.4% high yield of GVL can be achieved since the integration of the tandem reaction of hydration and hydrogenation could substantially avoid side reactions in the fixed-bed reactors.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Xiaoqing Gao,Shanhui Zhu,Mei Dong,Jianguo Wang,Weibin Fan
Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is still a challenge for Ru-based catalysts under mild condition. In this work, we have reported that ultrathin TiO 2 nanosheets supported Ru nanoparticles showed extraordinarily high catalytic activity, GVL yield (99.1%) and reusability owing to the formation of Ru O Ti interfacial structure. The turnover frequency (TOF) reached as high as 19,045 h −1 at 100 °C, much higher than those of Ru/SiO 2 , Ru/GO, Ru/MoS 2 , and commercial Ru/C. DFT calculation elucidates that the dominant reaction pathway of LA hydrogenation to GVL is preferentially hydrogenated to CH 3 CHOCH 2 CH 2 COOH*, followed by cyclization to CH 3 (OH)C 4 OH 4 OH* (GVL − OH) and final dehydroxylation, irrespective of surface structure. Compared to Ru (0 0 2) facet, Ru/TiO 2 interfacial structure changes the rate-determining step from initial hydrogenation to cyclization, which greatly declines the activation barrier from 0.81 eV to 0.48 eV.
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RSC Advances
·
2014
·Vol. 4
·期 29
·14985-14992
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IF 3.708
Jiang Li,Dao-jun Ding,Lu-jiang Xu,Qing-xiang Guo,Yao Fu
A biphasic system consisting of THF and water was studied to achieve the integrated conversion of cellulose and hemicellulose in lignocellulosic biomass to levulinic acid. As compared to previous studies using GVL as solvent, the utilization of a lower boiling point solvent, THF, also achieves the simultaneous hydrolysis of C6 and C5 carbohydrates in lignocellulosic biomass, and the results of simultaneous hydrolysis are comparable. Furthermore, it offers an alternative operation procedure after the hydrolysis. A distillation process is not only used to achieve the effective separation of the solid residue from the desired products, but it also helps in the complete isolation of furfural and formic acid from levulinic acid. Consequently, the utilization of by-product formic acid in the hydrogenation of furfural to furfuryl alcohol is explored, and the process is achieved with both model substrates and the feed from the lignocellulosic biomass feedstock. The hydrolysis of furfuryl alcohol gave C5 carbohydrate-derived levulinic acid. We finally explored the integrated conversion with five biomass raw materials, and the total yield of levulinic acid was quite obviously promoted by the additional conversion of pentose.
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JOURNAL OF CHEMICAL THERMODYNAMICS
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2016
·
IF 2.196
Dongshun Deng,Yaotai Jiang,Xiaobang Liu,Zhiliang Zhang,Ning Ai
Solubilities of CO 2 have been determined in five deep eutectic solvents (DESs) at temperatures (303.15–333.15) K with 10 K intervals under a pressure of (0–600.0) kPa using isochoric saturation method. These DESs were prepared from levulinic acid (LA) and quaternary ammonium salt (acetylcholine chloride, ACC; tetraethylammonium chloride, TEAC; tetraethylammonium bromide, TEAB; tetrabutylammonium chloride, TBAC; and tetrabutylammonium bromide, TBAB) with the mole ratio of 3:1. Henry’s constants and thermodynamic properties such as Gibbs energy, enthalpy and entropy of dissolution were deduced by correlating the solubility data. Results demonstrated that the solubility of CO 2 in DESs increased with the increasing pressure or the decreasing temperature. The enthalpies of dissolution were all exothermal in each condition. The Henry’s law constants based on mole fraction and molality of CO 2 in DESs vary from (12.30 to 28.66) MPa and (1.79 to 3.94) MPa, respectively.
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Catalysts
·
2024
·Vol. 14
·期 2
·113
·
IF 3.8
Hongzhi Ding,Chenyu Yang,Congyan Jiang,Wei Luo,Qiuyue Wang,Xuefeng Guo
The use of eco-friendly biomass as a resource is an efficient way to address the problems of fossil fuel depletion and climate change. In biomass conversion, versatile γ-valerolactone (GVL) is generally obtained from levulinic acid (LA) hydrogenation via a multimetallic catalyst system. Despite conversion efficiency being enhanced in mild conditions due to metal interactions, maintaining high catalyst stability is still a challenge. In this study, we synthesized a surrounded Co0.52Ni0.48@Al2O3-IE catalyst that exhibited excellent alloying and synergistic interaction between the metal constituents. Under relatively mild reaction conditions, the GVL yield over the catalyst exceeded 99% in LA hydrogenation. The catalyst showed no deactivation in a test of five cycles, displaying superiority in stability, possibly due to reasons of the physical isolation of the shell and the alumina retention on the Co-Ni alloys surface caused by the reversibility of exchange equilibrium. The present work demonstrated that a surrounded structured catalyst fabricated by ion exchange (IE) with active metals physically enclosed can lead to high catalytic activity and superior stability.
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CARBON
·
2024
·
IF 10.5
Hao Wen,Fubin Ma,Haoyang Li,Yi Yue,Jiacheng Luo,Ruiyang Qu,Hepeng Zhang,Yueling Cao
Fabrication of metal/porous carbon catalysts with high catalytic activity and stability is highly desirable but challenging because the metal nanoparticles in these catalysts cannot have both high exposure and strong interaction with carbon support. Here, for the first time, a facile CO 2 -assisted one-pot pyrolysis (CAOP) strategy was developed to in situ liberate the inaccessible Ru sites without obviously affecting the size of Ru nanoparticles . The Ru@CN-700-80 prepared with the assistance of CO 2 exhibits a remarkable improvement in catalytic activity for levulinic acid hydrogenation compared with that without CO 2 during pyrolysis, giving a TOF of 28449 h −1 under mild conditions, which is superior to the reported Ru-based catalysts. Additionally, the Ru@CN-700-80 also demonstrates an excellent stability without activity loss after 10 cycles. We anticipate that this CAOP strategy addresses a crucial issue that currently plagues the design of metal/porous carbon catalyst with high catalytic performance applied in energy and environmental fields.
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ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Wenjing An,Weiping Yang,Liqing Shi,Kejiang Qian,Huichao Suo,Peipei Ma,Tingzhao Xin,Jinhao Liu,Shuangxi Liu,Lan-Lan Lou,Kai Yu
Catalytic conversion of levulinic acid (LA) to γ-valerolactone (GVL) is one of the key reactions of biomass utilization, but the relatively high reaction temperature and H2 pressure always introduce safety and energy consumption issues. In this work, a photocatalytic transfer hydrogenation method was applied to achieve the hydroconversion reaction from LA to GVL under green and mild conditions using non-noble metal Bi2S3 materials as the catalyst. Up to 74.8% GVL yield and 76.3% selectivity can be achieved after 36 h of irradiation using the spherical Bi2S3 as the catalyst and isopropanol as the hydrogen source, which is significantly higher than any reported results on non-noble metal photocatalysts. The structural characterization and density functional theory calculation results indicated that the appropriate band position and lower adsorption energy toward LA rendered the spherical Bi2S3 catalyst highly reactive. Based on the results of electron paramagnetic resonance and density functional theory calculations, a reasonable photocatalytic transfer hydrogenation reaction pathway of LA to GVL was proposed. Bi2S3-photocatalyzed dehydrogenation of isopropanol generates H radicals, which react with LA adsorbed on the surface of Bi2S3 to form GVL through a hydrogenation-esterification process. The presence of Bi2S3 greatly promotes the adsorption of LA and reduces the energy barrier for LA hydrogenation.
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RENEWABLE ENERGY
·
2022
·
IF 8.634
Rulu Huang,Huai Liu,Junhua Zhang,Yuan Cheng,Liang He,Lincai Peng
Design catalytic materials with high Lewis acid/base sites for catalytic transfer hydrogenation (CTH) of levulinic acid (LvA) to γ-valerolactone (GVL) is highly demanded but challenging. Herein, we report a concept of metal ion-polymer hybridization to design a tea polyphenol (TP) and HfCl 4 co-doped polyacrylonitrile (PAN) nanofiber (Hf@PAN-TP) via electrospinning technique . Comprehensive characterization revealed the well coordination between hafnium ions and phenolic hydroxyl groups of TP on PAN fiber, which promoted the formation of Lewis acid and Lewis base sites. As expected, a satisfactory GVL yield of 99.1% with 100% of LvA conversion was obtained using isopropanol as a hydrogen donor at 170 °C in 5 h, and the catalytic activity remained unchanged for five cycles. The kinetic study revealed the lower activation energy for CTH of LvA to GVL (33.5 kJ/mol), demonstrating the outstanding GVL formation rate of 3383.9 μmol/g . h. Based on the systematical combine of catalyst characterization and catalytic behavior, the structure-function relationship and reaction mechanism were proposed. More gratifyingly, Hf@PAN-TP was applicable for catalytic reduction of various carbonyl compounds, demonstrating a great potential for upgrading biomass-derived aldehydes/ketones.
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