GREEN CHEMISTRY
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2014
·Vol. 16
·期 5
·2762-2770
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IF 6.852
Zehui Zhang,Bing Liu,Kangle Lv,Jie Sun,Kejan Deng
In this study, we have successfully prepared a heterogeneous catalyst (K-10 clay-Mo) by the immobilization of bis(acetylacetonato) dioxo-molybdenum(VI) [MoO2(acac)2] on montmorillonite K-10 clay. The structure of the resultant catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electronic microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The catalytic activity of K-10 clay-Mo was tested in the aerobic oxidation of 5-hydroxymethylfurfural (HMF). Although a molecule of HMF contains one hydroxyl group and one aldehyde group, to our surprise, the catalyst showed high catalytic activity for the oxidation of the aldehyde group of HMF into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). A variety of important reaction parameters such as the reaction temperature, catalyst amount, and solvent were explored. HMFCA could be obtained in a high yield of 86.9% with a HMF conversion of 100% after a short reaction time of 3 h in toluene. More importantly, the catalyst K-10 clay-Mo could be reused several times without a significant loss of its catalytic activity.
研究领域:
化学工程
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催化材料
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2021
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IF 3.764
Jie Yang,Liyuan Huai,Jiang Gan,Hualei Hu,Shenghu Zhou,Jian Zhang
The 5,5′(oxy-bis(methylene))bis-2-furfural (OBMF) formation from the 5-hydroxymethylfurfural (HMF) self-etherification over zeolites is an important reaction for the synthesis of value-added chemicals from biomass resources. However, there is still a lack of knowledge about the reaction mechanism and the roles of different acid sites that impedes the exploitation of zeolite catalysts for efficient OBMF production. In the present study, the ZSM-5 (HPZ) catalysts of four hierarchically micromesopores were successfully synthesized in different Si/Al ratios by adjusting the amount of Al in the solvent evaporation with the assistance of a dry gel conversion method. The kinetics of OBMF formation from HMF self-etherification was investigated. The apparent activation energy and the conversion reaction order were calculated to be 104.6 kJ/mol and 0.65, respectively. The intrinsic activity comparison of four catalysts and density functional theory (DFT) calculations showed that HMF adsorption and etherification benefit from Brønsted-acid sites. Besides, the DFT results suggested that the etherification proceeds via a concerted step, instead of the sequential pathways, thus leading to the high selectivity of OBMF on hierarchically micromesoporous ZSM-5 (HPZ) catalysts.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
Catalysis Science & Technology
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2025
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IF 4.2
Yongle Zhang,Yingyi Tu,Yunying Huo,Guang Pan,Qiao Zhang,Zhiting Liu,Guangxing Yang,Feng Peng
The electrochemical catalytic oxidation of 5-hydroxymethylfurfural (HMF) to generate high-value products like 2,5-furandicarboxylic acid (FDCA) has become a prominent research interest. In this work, an economical and efficient transition metal ε-MnO2 catalyst was used to electrocatalyze the oxidation of HMF in acidic environments. The results revealed a highly efficient HMF conversion rate of 92.95% and a FDCA yield of 23.03% under the specific conditions of 60 °C, 0.5 M H2SO4 and 1.6 V (vs. RHE). Furthermore, the study outlined the oxidation pathway for HMF, which progresses through the following sequence: HMF → DFF → FFCA → FDCA. The apparent activation energies associated with each oxidation stage were found to be 25.52, 22.12 and 16.21 kJ mol−1, respectively. Moreover, the findings indicated a favorable relationship between the electrocatalytic oxidation activity of HMF and the average surface oxidation state of ε-MnO2.
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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DOI
高影响因子
CHINESE JOURNAL OF CHEMISTRY
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2017
·Vol. 35
·期 6
·984-990
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IF 1.852
Xiaofang Li,Xiuquan Jia,Jiping Ma,Yongming Xu,Yizheng Huang,Jie Xu
2,5-Furandicarboxamide was firstly synthesized in yield of 85% via catalytic oxidative amidation of 5-hydroxymethylfurfural with aqueous NH 3 over alkali manganese oxides of α -MnO 2 /Na x MnO 2 . The intermediates of 5-hydroxymethyl-furonitrile, 2,5-dicyanofuran, and 5-cyano-2-furancarboxamide were verified and their reactivities were further examined. The kinetic analysis results showed that the transformation of intermediate product of 5-cyano-2-furancarboxamide to 2,5-furan-dicarboxamide is a slower step, which is closely relative to the reaction temperature and basicity of catalyst.
研究领域:
化学工程
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催化化学
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产品关联
DOI
高影响因子
ChemCatChem
·
2024
·
IF 3.8
Jinlian Liu,Liang Jiang,Bo Xing,Fuping Zhang,Yi Wang,Qilong Zhao,Mingliang Wu,Xin Chen,Guo Yang
Graphical The Pd/ZrO 2 catalyst prepared by the impregnation reduction method showed excellent activity and selectivity in the synthesis of HMTHF via the selective hydrogenation of the furan ring in 5-HMF at ambient hydrogen pressure and room temperature. Furthermore, the influence of the type of active hydrogen species on the hydrogenation of furan rings was proved by hydrogen spillover experiments. 5-Hydroxymethylfurfural (5-HMF) derived from lignocellulose represents an important platform molecule that could be employed in the selective hydrogenation of the furan ring to prepare 5‑hydroxymethyltetrahydrofurfural (HMTHF). However, the reported catalytic systems for the synthesis of HMTHF using 5-HMF still require additional hydrogen pressure. In this study, the Pd/ZrO 2 catalyst with uniformly dispersed Pd nanoparticles was prepared via a simple impregnation reduction process. This catalyst exhibited excellent catalytic activity and selectivity for the hydrogenation of 5-HMF to HMTHF. High HMTHF yields up to 92.3% were produced under mild reaction conditions of ambient hydrogen pressure and room temperature in methanol solvent. This result was superior to the most catalytic systems that had been reported so far. The mechanism study revealed that the active hydrogen species on the surface of the Pd nanoparticles and the reaction solvent in this study were the pivotal factors influencing the hydrogenation of furan rings in 5-HMF.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
Journal of Energy Chemistry
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2024
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IF 14
Shilin Fan,Bin Zhu,Xiao Yu,Yang Gao,Weiping Xie,Yong Yang,Jian Zhang,Chunlin Chen
Biomass, derived from plant photosynthesis that captures carbon dioxide to form carbohydrates, offers vast renewable reserves. The electrooxidation of biomass, coupled with the hydrogen evolution reaction, enables the simultaneous production of biomass-based plastic monomers and green hydrogen, attracting significant scholarly interest. However, ambiguity remains regarding the adsorption mechanism at the catalyst surface (Langmuir-Hinshelwood or Eley-Rideal) and the adsorbed substrate groups. To address this, we prepared a Ni/Co electrode for the electrooxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) through a corrosion reaction and electro-reduction pathway. HMF conversion reached 100.00%, FDCA yield reached 96.82%, and Faradic efficiency (FE) reached 92.14%. Meaningfully, utilizing in-situ spectroscopy and electrochemical methods, this work provided valuable insights into active sites and catalyst surface adsorption.
研究领域:
生物化学
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可再生能源
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催化材料
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产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2018
·Vol. 93
·期 10
·3028-3034
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IF 2.587
Wei Chen,Yong Sun,Juan Du,Zhihao Si,Xing Tang,Xianhai Zeng,Lu Lin,Shijie Liu,Tingzhou Lei
BACKGROUND 5-(Aminomethyl)-2-furanmethanol (AMF), used widely in medicinal chemistry, is usually synthesized by the reductive amination of furfural or 5-hydroxymethylfurfural (HMF) with ammonia. However, a challenging task when synthesizing this furyl primary amine is to enhance the selectivity of the product due to its high nucleophilicity. Conventional measures have used excessive liquid ammonia and precious metal catalysts. Usually, the molar ratio of ammonia to substrate is up to 30:1. This study employed aqueous ammonia to synthesize AMF by the direct reductive amination of HMF using the non-noble metal Ni/SBA-15 catalyst. RESULTS The Ni/SBA-15 catalyst displayed higher catalytic selectivity in the reductive amination of HMF to AMF compared to other precious metal catalysts, such as Ru/C, Pd/C and Pt/C. The AMF yield of 89.8% was obtained at the relatively mild reaction temperature of 100 °C for 4 h. After the fifth cycle, an acceptable decrease in catalytic activity with 74.2% yield of AMF was observed. CONCLUSION An improved process was developed for preparing AMF by the reductive amination of HMF with aqueous ammonia using the non-noble Ni/SBA-15 catalyst. The high selectivity of nickel catalyst is attributed mainly to the moderate catalytic activity. Moreover, a small amount of water enhanced the yield of AMF by promoting the formation of ammonium ions to prevent the further side reaction of AMF with HMF. Results of recycling experiments and analyses showed that agglomeration, loss and oxidization of nickel species together with carbon deposition were responsible for the slight deactivation of the catalyst. © 2018 Society of Chemical Industry
研究领域:
有机化学
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催化
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药物化学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2020
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IF 10.652
Fengjiao Lai,Feng Yan,Pengju Wang,Shubin Wang,Shun Li,Zuotai Zhang
The design of stable heteropolyacid (HPA) catalysts with strong Brønsted acidity and mild Lewis acidity is crucial for the efficient conversion of renewable biomass to value-added chemicals. Firstly, a novel strategy was proposed to synthesize the Ce-based HPA of H 5 CeW 12 O 40 . Secondly, the H 5 CeW 12 O 40 was combined with ChCl to form a series of temperature-responsive HPA catalysts (Ch n H 5-n CeW 12 O 40 , n = 1–5), which allowed the catalysts to be applied as soluble catalysts at a temperature >80 °C and be easily separated as an insoluble catalyst at a temperature <80 °C. In the H 2 O/DMSO/MIBK biphasic system, one-pot production of 5-hydroxymethylfurfural (5-HMF) from cellulose was achieved with an excellent yield of 67.5% over ChH 4 CeW 12 O 40 catalysis at 140 °C for 6 h, and other carbohydrates were converted, including fructose (83.1%), glucose (74.2%), sucrose (75.8%), cellobiose (70.2%) and starch (68.7%). Such high efficiency was attributed to the homogeneous catalysis at high temperature, the strong Brønsted acidity of [H 5-n CeW 12 O 40 ] n− , and the appropriate Lewis acidity from Ce(III). Moreover, the temperature-responsive property and the high stability were beneficial for recycling without significant structural change and activity loss.
研究领域:
化学工程
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生物质能
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催化化学
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产品关联
DOI
高影响因子
Energy Technology
·
2017
·Vol. 5
·期 11
·2046-2054
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IF 2.789
Zhongwei Wang,Hu Li,Chengjiang Fang,Wenfeng Zhao,Tingting Yang,Song Yang
A series of organic–inorganic acidic hybrids in uniform nanospheres were prepared by self-assembly of phosphotungstic acid (HPW) and pyridine (PY) or triethylamine (TEA) without using a template and surfactant. The prepared samples were characterized by XRD, TEM, FTIR, and N 2 adsorption–desorption isotherms, and their surface acidity was determined by titration. Particularly, PY-PW-1 showed a predominant catalytic performance in the near complete etherification of 5-hydromethylfurfural (HMF) to 5-ethoxymethylfurfural (EMF) with a high yield of 90 % at 80 °C in 24 h, which might be ascribed to its relatively high acidity and smaller particle size. This kinetic study elucidated the superior activity of PY-PW-1 in the HMF-to-EMF conversion. Fructose could also be directly converted to EMF in a moderate yield of 55 % at an elevated temperature of 120 °C by a cascade reaction process. In addition, PY-PW-1 could be reused five times with no evident loss of its catalytic activity. Importantly, the downstream product of EMF (i.e., ethyl levulinate) in an excellent yield of 93 % could also be achieved from HMF by further increasing the reaction temperature to 140 °C.
研究领域:
化学工程
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材料科学
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催化化学
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产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Yanbin Sun,Jianfeng Zheng,Jiajia Xu,Kaixuan Yang,Zhiguo Zhu,Ting Su,Hui Ge,Wanzhong Ren,Hongying Lü
Aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is an environmentally sustainable, economically feasible, but substantially challenging conversion owing to the high energy barrier of O 2 activation. Herein, we report a catalyst with Mo 5+ connected to the oxygen vacancies (Mo 5+ -□) in Anderson-type polyoxometalate (POM) [(C 18 H 37 ) 2 N(CH 3 ) 2 ] 6 Mo 7 O 24 for oxidizing HMF to DFF. The resultant catalyst with high Mo 5+ content presents superior HMF oxidation performance, delivering a > 99% DFF selectivity with complete HMF conversion. Mechanistic studies and density functional theory (DFT) calculations reveal that the Mo 5+ -□ species in the catalyst facilitate O 2 activation and HMF oxidation. Moreover, the catalyst exhibits outstanding catalytic stability during the aerobic oxidation of HMF to DFF.
研究领域:
催化化学
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环境科学
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材料科学
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产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
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2024
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IF 4.8
Tianyu Bai,Jinquan Tao,Yijing Jia,Wenbin Huang,Rongpeng Yao,Xinan Xue,Yasong Zhou,Qiang Wei
In the research of directly synthesizing H-form ZSM-5, ammonium hydroxide is commonly used as an alkali source instead of NaOH to avoid multiple ion exchange steps. However, the volatile nature and the lack of structure-directing effect of ammonium hydroxide limit its application in practical. In this study, n -butylamine (NBA) was used as the main alkali source to directly prepare HZSM-5 zeolites with SiO 2 /Al 2 O 3 ratios ranging from 40 to 300 under traditional hydrothermal conditions. The influence of the amount of NBA, ethanol, seed, and pre-crystallization on the synthesis products was investigated under the condition of SiO 2 /Al 2 O 3 = 80. Theoretical simulation suggested that n -butylamine cations (NBA + ) play the most potent directing role in the formation of the MFI structure but could lead to difficulties in removal during calcination. The addition of ethanol as the zeolite growth modifier (ZGM) could decrease the usage of NBA and reduce the difficulties in calcination, and the addition of seed provided the conditions for initiating crystallization in the system that could not spontaneously nucleate. HZSM-5 with different SiO 2 /Al 2 O 3 ratios were prepared under the optimal crystallization conditions, and the as-synthesized samples exhibited superior textural and acid properties compared to commercial zeolite. Finally, the 1 L scale-up synthesis and MTP reaction were conducted to demonstrate the practicality of this economically and environmentally-friendly synthesis strategy.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2023
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IF 16.5
Hongfang Wang,Leitao Xu,Jingcheng Wu,Peng Zhou,Shasha Tao,Yuxuan Lu,Xianwen Wu,Shuangyin Wang,Yuqin Zou
5-Hydroxymethylfurfural (HMF) electrooxidation in neutral conditions is a promising strategy to suppress the formation of humins and corrosive effects on electrochemical devices. However, scarce studies have been reported in neutral media due to the deficiency in electrophilic oxygen (eg OH – ) required for the activation of HMF. Herein, 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO)/Co 3 O 4 was utilized to co-catalyze HMF in neutral media, successfully achieving 2,5-furandicarboxylic acid (FDCA) with yield > 99%. It was found that TEMPO could promote HMF dehydrogenation to 2,5-diformylfuran (DFF) and simultaneously activated water via hydrogen-bonding interactions. As a result, the formation of OH* in neutral electrolytes was favored, which was absorbed by electrogenerated active Co species to facilitate subsequent conversion of formyl-group-involved intermediates to FDCA. This work provides a current understanding of the catalytic mechanism for HMFOR in neutral media and guides the design of highly efficient electrocatalysts for biomass upgrading.
研究领域:
化学工程
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催化科学
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生物质转化
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）