JOURNAL OF CATALYSIS
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2019
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IF 7.723
Wenxiu Cao,Lu Lin,Haifeng Qi,Qian He,Zhijie Wu,Aiqin Wang,Wenhao Luo,Tao Zhang
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is a key reaction for the production of renewable chemicals and fuels, wherein acid-resistant and robust catalysts are highly desired for practical usage. Herein, an ultra-stable 0.6 wt% Ir@ZrO 2 @C single-atom catalyst was prepared via an in-situ synthesis approach during the assembly of UiO-66, followed by confined pyrolysis . The Ir@ZrO 2 @C offered not only a quantitative LA conversion and an excellent GVL selectivity (>99%), but also an unprecedented stability during recycling runs under harsh conditions (at T = 453 K, P H2 = 40 bar in pH = 3 or pH = 1 aqueous solution). By thorough spectroscopy characterizations, a well-defined structure of atomically dispersed Ir δ+ atoms onto nano-tetragonal ZrO 2 confined in the amorphous carbon was identified for the Ir@ZrO 2 @C. The strong metal-support interaction and the confinement of the amorphous carbon account for the ultra-stability of the Ir@ZrO 2 @C.
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高影响因子
CATALYSIS LETTERS
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2020
·Vol. 151
·期 6
·1834-1841
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IF 2.482
Feng Xiaoqing,Zhang Lin,Zhu Xuan,Xia Yan,Ma Cuiluan,Liang Jianguang,He Yu-Cai
Furfurylamine is an important furfural-upgrading biobased chemical for the production of pharmaceuticals, biofuels, fibers, additives, polymers, etc. In one-pot reaction system, biomass was tandemly catalyzed to furfurylamine with aluminium-based alkaline-treated graphite (Al-AG) catalyst and recombinant ω-transaminase biocatalyst. Al-AG (3.6 wt%) catalyzed corncob (75.0 g/L) to 110.0 mM furfural at 56.8% yield (based on xylan in corncob) in γ-valerolactone–water (1:4, v:v; pH 1.0) for 40 min at 180 °C. The pH-adjusted corncob-slurry (pH 7.5) containing furfural were catalyzed to furfurylamine at high yield with γ-valerolactone-tolerant Aspergillus terreus ω-transaminase biocatalyst at 35 °C using isopropylamine (3 mol isopropylamine/mol furfural) as amine donor. Such an efficient and sustainable approach for catalytic conversion of biomass to high-value-added biobased furfurylamine was successfully established in tandem reaction with Al-AG and ω-transaminase biocatalyst. Graphic Abstract
研究领域:
生物化学
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催化化学
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可再生资源
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高影响因子
Journal of Environmental Chemical Engineering
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2026
·Vol. 14
·期 2
·121271
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IF 7.2
He Wan,Fanqi Yan,Yue Zhao,Yongwei Han,Zhong Sun,Xixin Duan
Biomass is a promising raw material to prepare green solvent of γ -valerolactone (GVL). A series of Ru-substituted vanadium-containing polyoxometalates (POMs) of Ru n /3 H 4- n PMo 11 VO 40 ( n = 1, 2, 3, 4) and Ru n /3 H 5- n PMo 10 V 2 O 40 ( n = 1, 2, 3, 4, 5) were prepared, which were loaded on metal organic frameworks (MOFs) to afford POMs@MOF with adjusting strong oxidizing abilities. This paper focused on the effects of POMs@MOF on improving the yield and selectivity of GVL in a green system of formic acid (FA) and water. When cellulose, glucose, and levulinic acid (LA) were used as substrates, the yields of GVL were 43.2 %, 69.7 %, and 98.3 % with the selectivity of 48.0 %, 71.9 %, and 99.3 %, respectively. The results indicate that the strong oxidizing ability of POMs favors the conversion of biomass to GVL. The proposed catalytic system greatly reduces the use of noble metal Ru while enhancing the catalytic transfer hydrogenation performances. The adjustment of the proportion of Ru in POMs can provide efficient and promising catalytic systems for one-pot production of GVL from biomass with different structures.
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高影响因子
GREEN CHEMISTRY
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2024
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IF 9.3
Mingzhu Yao,Baojie Liu,Lina Qin,Zicheng Du,Zenglin Wang,Chengrong Qin,Chen Liang,Caoxing Huang,Shuangquan Yao
Deep eutectic solvents (DESs) are widely used as recyclable green solvents for the separation of lignin from lignocellulosic biomass. However, the poor permeability of DES solution limits the green advancement of separation systems. In addition, lignin fragment molecules are susceptible to repolymerization reactions during separation, resulting in reduced lignin reactivity. In this study, a DES consisting of choline chloride (ChCl) as a hydrogen acceptor, 5-sulfosalicylic acid (5Saa) as a hydrogen donor, and a certain amount of γ-valerolactone (GVL) as an additive was designed. The system not only efficiently fractionated lignin from poplar (71.35%), but also selectively retained almost complete cellulose (retention 92.87%) under the optimal fractionation (ChCl/5Saa/GVL molar ratio 1/4/15, temperature 120 °C, time 3.0 h). Pre-crushing processing of raw materials was avoided as the new DES solution has stronger permeability compared to the previous DES solution. Selective deconstruction of lignocellulose was achieved due to a strong hydrogen network structure. The lignin fragments were effectively dissolved. The results showed that the stability of the carbo-positive active intermediates was enhanced by ChCl–5Saa/GVL. Lignin with a low molecular weight (2305 g mol−1), high purity (98.77%) and high total phenolic hydroxyl content (6.92 mmol g−1) was obtained. Homogeneous lignin nanoparticles (LNPs) were prepared with an average particle size of 23 nm. LNPs had high dispersion stability and excellent UV shielding properties. The green advancement of the new DES has been significantly improved and the efficient fractionation of high-value lignin was realized.
研究领域:
化学工程
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材料科学
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高影响因子
RENEWABLE ENERGY
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2024
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IF 9
Hongjin Qu,Tianliang Lu,Xiaomei Yang,Lipeng Zhou
Tin-containing β zeolite exhibits excellent catalytic performance in various biomass conversions to high-value chemicals due to its strong Lewis (L) acidity produced by framework Sn 4+ sites. However, it is difficult to incorporate Sn species into the framework of β zeolite due to that the ionic radius of Sn (0.69 Å) is larger than that of Si (0.40 Å). Herein, organic additives with carbonyl, hydroxyl , aldehyde or amine groups were used to stabilize Sn species in the gel and framework Sn 4+ in the zeolite. Among all additives, acetone (AC) has the best stabilizing effect on Sn species. The stabilization effect between AC and Sn 4+ sites was observed by FT-IR. The characterization results indicate that more tin species were incorporated into β framework and the L acid density increased due to the complexation between carbonyl group and Sn species. Compared to Sn-β-3d synthesized without additive, the L acid density of Sn-β-AC-3d increased by ∼50% (from 21 μmol g −1 to 34 μmol g −1 ). For the conversion of ethyl levulinate to γ-valerolactone, the reaction reached equilibrium faster over Sn-β-AC-3d than over Sn-β-3d at the investigated reaction temperatures. A yield of 98% was obtained over Sn-β-AC-3d at 110 °C. Besides, Sn-β-AC-3d exhibited good stability and reusability.
研究领域:
催化化学
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生物质转化
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高影响因子
RSC Advances
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2017
·Vol. 7
·期 24
·14330-14336
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IF 3.108
Minghao Li,Wenzhi Li,Yijuan Lu,Hasan Jameel,Hou-min Chang,Longlong Ma
Biomass derived 5-hydroxymethylfurfural (HMF) is regarded as an important platform molecule for the synthesis of value-added chemicals and fuels, but the high production cost has always been a bottleneck for the industrial scale use of HMF. Different mineral acids (HCl and H2SO4) being used as the catalyst and different salts being used as the reaction promoter were evaluated. It was found that HCl, in combination with NaCl, in a water/γ-valerolactone system showed high selectivity and impressive efficiency for the synthesis of HMF from glucose. The optimal conditions to obtain the best HMF yield (62.45%) were 0.2 M HCl and 0.1 M NaCl at 140 °C with a residence time of 60 minutes. An 18.22% molar yield of LA was obtained as a by-product. The effect of different anions was also investigated, and it was determined that not only the hydrogen ions, but also the nature of the acid and the type of salt played a joint role in improving the HMF yield. In addition, a possible synthesis pathway was proposed for large scale production of HMF.
研究领域:
生物化学
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可再生资源与环境科学
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高影响因子
FUEL
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2024
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IF 6.7
Wei Xue,Mingwei Ma,Pan Hou,Peng Zhang,Wenzheng Liu,Yongchen Liu,Huijuan Yue,Xiaofeng Wang,Ge Tian,Shouhua Feng
The one-pot tandem conversion of furfural (FUR) to γ-valerolactone (GVL) is desirable due to the high value of GVL and the efficiency of the synthesis process. While MOF-808 presented a good catalytic potential among Zr-MOFs, it lacked the necessary Brønsted acidity for the tandem conversion. In this study, Zr-based metal–organic framework (MOF-808) was modified with acids of different strengths (triflic acid, sulfuric acid, sulfamic acid, and trifluoroacetic acid) using a two-step post-synthesis impregnation method. EPR results revealed the appearance of coordinatively unsaturated sites of Zr (Zr-CUS) in the first step of HCl-treated Zr-808-HCl and their disappearance in the subsequent acid-modified catalysts, clarifying the impregnation process. These modified frameworks (Zr-808-TF, Zr-808-S, Zr-808-SN, and Zr-808-CF) were employed as catalysts for the tandem conversion of FUR to GVL. Zr 3d XPS and solid-state 31 P MAS NMR spectra of TMPO adsorbed on the catalysts proved that Zr-808-TF outperformed other catalysts in terms of both Brønsted/Lewis acid strength and ratio. With such catalytic active sites, Zr-808-TF exhibited superior catalytic activity, achieving 83% GVL yield over an 8-hour reaction period. The four acid-modified catalysts not only differed in Lewis/Brønsted acid sites, but also exhibited different catalytic performances in the tandem conversion. The in-depth insight into the relationship between the modified functional groups and the acid-base sites provides a new avenue to optimize the acid-base sites and expands the application of MOFs in cascade catalysis.
研究领域:
化学工程
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催化科学
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高影响因子
INORGANIC CHEMISTRY
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2021
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IF 5.165
Jie Li,Shuaiheng Zhao,Zhen Li,Dan Liu,Yingnan Chi,Changwen Hu
Catalytic transformation of levulinic acid (LA) to γ-valerolactone (γ-GVL) is an important route for biomass upgradation. Because both Bro̷nsted and Lewis acidic sites are required in the cascade reaction, herein we fabricate a series of H3PW12O40@Zr-based metal–organic framework (HPW@MOF-808) by a facile impregnation method. The synthesized HPW@MOF-808 is active for the conversion of LA to γ-GVL using isopropanol as a hydrogen donor. Interestingly, with the increase in the HPW loading amount, the yield of γ-GVL increases first and then decreases, and 14%-HPW@MOF-808 gave the highest γ-GVL yield (86%). The excellent catalytic performance was ascribed to the synergistic effect between the accessible Lewis acidic Zr4+ sites in MOF-808 and Bro̷nsted acidic HPW sites. Based on the experimental results, a plausible reaction mechanism was proposed: the Zr4+ sites catalyze the transfer hydrogenation of carbonyl groups and the HPW clusters promote the esterification of LA with isopropanol and lactonization to afford γ-GVL. Moreover, HPW@MOF-808 is resistant to leaching and can be reused for five cycles without significant loss of its catalytic activity.
研究领域:
催化化学
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可再生能源
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PubMed
高影响因子
Molecular Catalysis
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2022
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IF 5.089
Peng Zhang,Mingwei Ma,Pan Hou,Jingjie Cao,Qi Guo,Huijuan Yue,Ge Tian,Shouhua Feng
A series of ultrathin metal intercalated montmorillonite (Mont) nanosheet materials were prepared and characterized for the one-pot cascade conversion of furfural (FAL) to obtain γ-valerolactone (γ-GVL). The coordination of the intercalated metal ions and the hydroxyl groups between the montmorillonite layers leads to an increase in the specific surface area and pore volume of the material, which coupled with the acidity of the metal ions themselves improves the catalytic performance of the material. Thus Zr-Mont-0.1 exhibited optimal catalytic performance with 100% conversion of FAL and 50.4% yield of GVL under mild conditions, and more importantly, the catalyst maintained its good catalytic performance after the fourth use. Meanwhile the number of Lewis and Brønsted acid sites in the Zr-Mont catalyst can be varied by adjusting the zirconium ion concentration. The proposed reaction mechanism provides initial insights into the role of metal-functionalized montmorillonite in catalyzing the reaction. In addition, the ten-fold magnification reaction confirmed the potential industrial application of the catalyst.
研究领域:
化学
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材料科学
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催化反应
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高影响因子
危险品化学品经营许可证（带存储）