ACS Sustainable Chemistry & Engineering
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2017
·
IF 5.951
Huili Zhang,Qi Wu,Cong Guo,Ying Wu,Tinghua Wu
The photocatalytic selective oxidation of biomass derivate compound 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran is an environmentally friendly and energy-saving process. Nb2O5 was prepared and applied in the oxidation of HMF under visible light, although its bandgap energy is higher than 3.2 eV. The reaction process follows a special mechanism over a Nb2O5 catalyst different from the normal oxide semiconductor. The effect of calcination temperature, incident wavelength, and reaction time on photocatalytic performance was investigated. Nb2O5-800 exhibits the best performance in the presence of O2 with benzotrifluoride as a solvent under visible light irradiation.
研究领域:
化学工程
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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
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Zhenfei Yang,Xinnian Xia,Ming Fang,Longlu Wang,Yutang Liu
The selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-dicarbofuran (DFF), and 2,5-furanedicarboxylic acid (FDCA) is essential to its practical application. Herein, a novel Pt/ZIS/MnO 2 (PMZIS) photocatalysts with photothermal effect were well designed for selective and controlled oxidation of HMF toward DFF or FDCA. The product distribution of HMF photo-oxidation on PMZIS can be regulated by the photothermal effect. At a low temperature (10 °C) with PMZIS, DFF is the primary oxidation product with the yield of 54.6% and selectivity of 85.4%. At a high temperature (60–70 °C) induced by photothermal effect, the FDCA can be obtained with the yield of 61.5 % and selectivity of 82.9%. Moreover, the Z-scheme transfer pathway and Pt cocatalysts realize the spatial charge separation structure of PMZIS heterojunctions. This unique structure greatly inhibits charge recombination and maximizes the activation ability of molecular oxygen to efficiently generate of the reactive oxygen species (e.g., 1O 2 and O 2– ), thus significantly improving the photocatalytic performance. This work would provide valuable insight in the product regulation through photothermal effect for the photocatalytic specific selective oxidation of organic molecules.
研究领域:
化学
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材料科学
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DOI
高影响因子
ACS Omega
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2018
·
IF 0
Changhui Zhu,Qiying Liu,Dan Li,Haiyong Wang,Caihong Zhang,Chunhua Cui,Lungang Chen,Chiliu Cai,Longlong Ma
Crystal α-zirconium phosphate (α-ZrP) was prepared by a hydrothermal method and exfoliated into a layered structure by n-hexylamine (C6H13NH2). Ni-based catalyst (Ni/ZrP) was promoted by loading nickel on the layered α-ZrP via ion exchange. The catalyst was performed to catalyze hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF), and a 68.1% yield of DMF and 100% conversion of HMF were achieved at 240 °C, 5 MPa H2, and 20 h. The DMF yield can still retain 52.8% after five cycles. The characteristics of the catalyst were investigated via N2 adsorption–desorption, X-ray diffraction, field emission scanning electron microscopy, high-resolution transmission electron microscopy, pyridine-adsorbed Fourier transform infrared (FTIR) spectra, FTIR spectra, inductively coupled plasma mass spectrometry, and thermogravimetric analysis–mass spectrometry, as well as Raman spectroscopy. A pathway from HMF to DMF was found with MF as the intermediate product, and DMF production was preferable via the −CH2OH group hydrogenolysis of HMF over Lewis acidic sites of Ni/ZrP, which is caused by the zirconium vacant orbits.
研究领域:
化学工程
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催化
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材料科学
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产品关联
DOI
PubMed
Molecular Catalysis
·
2022
·
IF 5.089
Wenpeng Han,Shujuan Wang,Yajie Liu,Chaoqun Li,Ningning Yuan,Ligong Zhou,Mingxing Tang,Hui Ge
The transformation of biomass to liquid fuels and chemicals is of great interests. Herein, a series of reduced NiZn-CT (CT represents calcination temperature) catalysts with flower-like morphology and uniform particle sizes were prepared by co-precipitation method and used for hydrogenolysis of 5-hydroxymethylfural (HMF) to 2,5-dimethyfuran (DMF). The characterizations evidenced the formation of NiZn alloy phase in the catalysts through the strong metal-support interaction (SMSI), which had high C-O hydrogenolysis ability. The synergy of hydrogenation and C-O hydrogenolysis is essential for HMF to DMF, and we surprisingly found that this synergistic effect can be achieved just by controlling calcination temperature to regulated SMSI between Ni and ZnO. By this way, 99% DMF yield was gained at 180 °C for 4 h under 2 MPa H 2 over reduced NiZn-450 catalyst. More importantly, the active centers of this Ni/ZnO catalyst exhibited outstanding stability. There was no significant decrease in activity after reusing 9 times. The current research provided an easy-made catalytic system for HMF hydrogenolysis.
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
CHEMICAL ENGINEERING JOURNAL
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2021
·
IF 13.273
Xiaoqi Lyu,Hong Li,Huaizhong Xiang,Yibing Mu,Na Ji,Xuebin Lu,Xiaolei Fan,Xin Gao
Microwave (MW)-assisted process intensification of catalytic conversion of saccharides is a promising route for energy efficient production of value-added chemicals and fuels. This work presents the development of the MW-responsive catalysts (i.e., the acid functionalized spherical carbon superstructure, SCS) for converting fructose to 5-HMF effectively and efficiently under MW irradiation. Under a mild MW condition (at 70 °C, atmospheric pressure), the SCS catalyst (with surface sulfonic and carboxylic acid groups) achieved fructose conversion of ~ 97.8% and selectivity to 5-HMF of ~ 90.6% after 5 min reaction time with good recyclability, being significantly higher than that obtained by the system under the conventional heating. Importantly, the MW-assisted system showed very high energy efficiency coefficient of 1.01 mmol kJ −1 L −1 compared to that (0.09 mmol kJ −1 L −1 ) of the conventional thermal catalysis. The mechanism of process intensification of the system developed may be attributed to the combination of the dipole polarization of the MW-responsive sulfonic groups and the selective heating of the MW-absorbing SCS support under the MW condition.
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
APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
·
IF 19.503
Ming Zhang,Zhihao Yu,Jian Xiong,Rui Zhang,Xinzhong Liu,Xuebin Lu
The Cd x In y S ( x +1.5 y ) catalysts with gradient Cd:In ratios were controllably synthesized via an one-step hydrothermal approach. Particularly, the hydrothermal synthesis conferred those Cd x In y S ( x +1.5 y ) catalysts with Cd:In ratios over 1:2 with a one-dimensional–three-dimensional heterojunction structure composed of CdS nanorods and cubic-phase CdIn 2 S 4 . Our characterization evidences reflected that the CdS nanorods effectively promoted the separation of photoexcited electron–hole pairs in Cd x In y S ( x +1.5 y ) and enabled transboundary transfer of photogenerated carriers. Spectroscopic and experimental results were further employed to develop a detailed catalytic mechanism, in which the superoxide anion (•O 2 − ) plays an important role in the catalytic oxidation of HMF to DFF by Cd x In y S ( x +1.5 y ) . Unlike other photocatalysts with •O 2 − as the main active species, Cd 1.5 In 2 S 4.5 gives an excellent performance in HMF conversion. This shows the great potential of cadmium–indium sulfides as photocatalysts for biomass conversion under ambient conditions.
研究领域:
材料科学
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化学工程
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环境科学
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催化
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Ke Liu,Ling Jiang,Lun Wang,Qunfeng Zhang,Li-Rong Yang,Jianping Wu,Haoran Yu
2,5-furandicarboxylic acid (FDCA) is a potential platform chemical from renewable feedstocks to make various polymers and high-value compounds. Bioconversion of 5-hydroxymethylfurfural (HMF) to FDCA by biocatalysts has the advantages of high selectivity, cost-effectiveness, and eco-friendliness. However, the full oxidation of HMF often requires a combination of two or three enzymes, as the production of FDCA involves three consecutive oxidation steps. In this study, we identified a pyrroloquinoline quinone (PQQ) and lanthanide-dependent alcohol dehydrogenase, PedH, capable of directly converting HMF to FDCA, representing a rare and intriguing discovery. We then engineered the enzyme for improved thermostability and activity against HMF to improve FDCA yield. Using computational design method, the thermostability was first significantly improved, with the 4M variant obtained showing a Tm value increased by 9.6 oC, and a half-life improved by 10.3-fold compared to wild type. With the 4M as the template, potential mutation sites for engineering enzyme activity were identified based on calculation of binding free energy and a deep learning model MutCompute. An automatic high-throughput platform for site-saturation mutagenesis library construction and screening was developed and applied to the identified mutation targets. After five rounds evolution, a variant was obtained that produced FDCA at a yield 474-fold higher than that of 4M. Under optimized reaction conditions, the optimal variant achieved a FDCA yield of 96.4% with 40 mM HMF as the substrate. Molecular dynamics simulations revealed that the mutations expanded the substrate binding pocket and shortened the reaction distances between substrate and cofactors. This study provides a highly efficient evolution approach for PedH, and several variants that are potentially used for high yield production of FDCA in industrial fields.
研究领域:
生物化学
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酶工程
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合成生物学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
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2024
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IF 3.7
Xin Li,Yue Ma,Xuning Wang,Jianguo Wu,Dong Cao,Daojian Cheng
The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation, because it is a bridge between biomass resources and chemical industry. Here, we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method. By changing the reduction temperature, catalysts with different oxidation state could be precisely constructed. Moreover, the important correlation between the ratio of Pd 0 /Pd 2+ and catalytic activity is revealed during the selective hydrogenation of HMF. The Pd/g–C 3 N 4 –300 catalyst with a Pd 0 /Pd 2+ ratio of 3/2 showed the highest catalytic activity, which could get 96.9% 5-hydroxymethylfurfural conversion and 90.3% 2,5-dihydroxymethylfuran selectivity. Further density functional theory calculation revealed that the synergistic effect between Pd 0 and Pd 2+ in Pd/g–C 3 N 4 –300 system could boost the adsorption of the substrate and the dissociation of hydrogen. In this work, we highlight the important correlation between metal oxidation state and catalytic activity, which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.
研究领域:
化学工程
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催化科学
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生物质能
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产品关联
DOI
高影响因子
CATALYSIS TODAY
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2020
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IF 5.825
Linhao Yu,Hong Chen,Zhe Wen,Mengmeng Jin,Zewei Ma,Xueli Ma,Yushuai Sang,Mengmeng Chen,Yongdan Li
Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2, 5-diformylfuran (DFF) with molecular oxygen is realized with an α-MnO 2 catalyst under mild conditions. In this work, α-MnO 2 exhibited the best performance among the samples examined. Meanwhile, solvent shows a significant effect on the product selectivity and isopropanol is found good for improving the selectivity of DFF. 93.2 % conversion of HMF was achieved at 140 °C for 4 h with 84.3 % selectivity of DFF. Moreover, α-MnO 2 catalyst keeps good reusability in recycling for five times. The reaction pathway indicated that the lattice oxygen species on α-MnO 2 is involved in the selective oxidation of hydroxyl group in HMF molecule.
研究领域:
催化化学
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绿色化学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2014
·Vol. 17
·期 3
·1610-1617
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IF 6.852
Bing Liu,Yongshen Ren,Zehui Zhang
In this study, Pd nanoparticles were immobilized on the core–shell structure C@Fe3O4 (carbon is the shell and Fe3O4 is the core) magnetic microspheres via in situ adsorption and reduction to generate the magnetically separable Pd/C@Fe3O4 catalyst. In this method, no excess reductant and capping reagents were required, and it is a clean, simple and green process for the preparation of the magnetic Pd nanocatalyst. The Pd/C@Fe3O4 catalyst showed high activity and extraordinary stability during the oxidation of biomass derived 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) under mild conditions. A study aimed at optimizing the reaction conditions such as reaction temperature, reaction solvent and base amount has been performed. Under optimal reaction conditions, HMF conversion of 98.4% and FDCA yield of 86.7% were achieved after 6 h at 80 °C. After reaction, the Pd/C@Fe3O4 catalyst could be easily recovered by an external magnet and reused without the loss of its activity.
研究领域:
化学工程
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催化化学
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绿色化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Aiyong He,Liangliang Dong,Ning Xu,Soliman I. El-Hout,Jun Xia,Zhongyang Qiu,Jianlong He,Yuanfang Deng,Xiaoyan Liu,Lei Hu,Jiaxing Xu
2,5-Furandicarboxylic acid (FDCA) is a well-known biobased platform chemical to produce sustainable polyethylene furanoate (PEF) and other valuable furanic chemicals. The eco-friendly enzyme cascade reactions have been adopted to synthesize FDCA using the multistep oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) based on different oxidoreductases. However, the coordination of natural oxidoreductases in cascade reactions presents challenges because of their different adaptabilities and catalytic environments. A robust and efficient catalyst herein was developed by the hybridization of a designed hemin–peptide (HP-7) complex and natural aryl-alcohol oxidase (AAO) in iron phosphate solution to achieve the cascade oxidation of HMF to FDCA. HMF is first transformed in 5-formylfurancarboxylic acid (FFCA) based on the oxidizability of AAO toward benzylic alcohol, and then the latent activity of AAO on FFCA was activated by the catalase activity of the HP-7@Fe 3 (PO 4 ) 2 nanozyme with the in situ consumption of H 2 O 2 initially produced by AAO. Moreover, closer inspection demonstrated the oxidizability of the HP-7@Fe 3 (PO 4 ) 2 nanozyme on FFCA in both the presence and absence of H 2 O 2 for the first time. Consequently, the hybrid catalyst AAO/HP-7@Fe 3 (PO 4 ) 2 enabled the self-activated and efficient oxidation of HMF by integrating multiple reaction processes. A complete conversion of HMF with excellent selectivity (100%) toward FDCA was finally observed.
研究领域:
生物化学
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环境科学
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材料科学
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2014
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IF 2.235
Lei Hu,Xing Tang,Jiaxing Xu,Zhen Wu,Lu Lin,Shijie Liu
A simple and efficient process was presented for the selective hydrogenation of 5-hydroxymethylfurfural (HMF) into the high-quality liquid fuel 2,5-dimethylfuran (DMF) in the presence of tetrahydrofuran (THF). Among the employed metal catalysts, the relatively inexpensive carbon-supported ruthenium (Ru/C) displayed the highest catalytic performance, which led to 94.7% DMF yield with 100% HMF conversion at a relatively mild reaction temperature of 200 °C for only 2 h. Although Ru/C had a little loss in the catalytic activity when it was used for five successive reaction runs, the partially deactivated Ru/C could be easily regenerated by heating at a mixed flow of H2 and N2. Moreover, the plausible mechanism involving an aldehyde group, a hydroxyl group, and a furan ring for the selective hydrogenation of HMF into DMF was also proposed. Subsequently, DMF was separated from the crude hydrogenation mixture according to their various boiling points by the combination of atmospheric distillation and vacuum distillation, and then, the chemical structures and physical properties of the separated DMF were confirmed to be consistent with the authentic DMF. More gratifyingly, Ru/C and THF were also found to be a good combination for the direct hydrogenation of carbohydrate-derived HMF into DMF, which is very important for the practical production of DMF from a variety of biomass-derived carbohydrates such as fructose, glucose, sucrose, maltose, cellobiose, starch, and cellulose.
研究领域:
化学工程
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能源科学
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催化科学
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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）