ChemSusChem
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2020
·Vol. 13
·期 12
·3127-3136
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IF 7.962
Peter Kisszekelyi,Rifan Hardian,Hakkim Vovusha,Binglin Chen,Xianhai Zeng,Udo Schwingenschlögl,Jozsef Kupai,Gyorgy Szekely
Graphical Up the tempo : An efficient TEMPO-based electrocatalytic transformation of biomass-based C 6 -platform chemical 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is reported. The molecular design and comparison of homogeneous (native, size-enlarged) and solid-supported (SiliaCAT, TurboBeads) TEMPOs is discussed for the oxidation in the ElectraSyn reactor with cost-effective electrodes and green solvents. Computational modeling reveals the synergistic effect of the catalyst/base system and facilitated the catalyst design. The catalytic transformation of bio-derived compounds, specifically 5-hydroxymethylfurfural (HMF), into value-added chemicals may provide sustainable alternatives to crude oil and natural gas-based products. HMF can be obtained from fructose and successfully converted to 2,5-diformylfuran (DFF) by an environmentally friendly organic electrosynthesis performed in an ElectraSyn reactor, using cost-effective and sustainable graphite (anode) and stainless-steel (cathode) electrodes in an undivided cell, eliminating the need for conventional precious metal electrodes. In this work, the electrocatalysis of HMF is performed by using green solvents such as acetonitrile, γ-valerolactone, as well as PolarClean, which is used in electrocatalysis for the first time. The reaction parameters and the synergistic effects of the TEMPO catalyst and 2,6-lutidine base are explored both experimentally and through computation modeling. The molecular design and synthesis of a size-enlarged C 3 -symmetric tris-TEMPO catalyst are also performed to facilitate a sustainable reaction work-up through nanofiltration. The obtained performance is then compared with those obtained by heterogeneous TEMPO alternatives recovered by using an external magnetic field and microfiltration. Results show that this new method of electrocatalytic oxidation of HMF to DFF can be achieved with excellent selectivity, good yield, and excellent catalyst recovery.
研究领域:
化学工程
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可再生资源化学
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计算化学
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产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
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2022
·
IF 9.224
Peng Zhu,Weizi Zhang,Qinfang Li,Haian Xia
Photocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is an environmental friendly way to convert platform molecules into high-value chemicals. Here, Au/ZnO catalysts with different oxygen vacancies were fabricated by the deposition precipitation method and were used for the photocatalytic oxidation of HMF to FDCA under visible light irradiation. All of the Au/ZnO catalysts showed excellent photocatalytic oxidation selectivity to FDCA greater than 90% under mild conditions. The Au/ZnODP-H catalyst treated by H2 afforded the highest HMF conversion and the selectivities of FDCA up to 96.9%. The localized surface plasmon resonance effect of Au nanoparticles, oxygen vacancy, and the existence of the Schottky barrier enhance the separation and transfer efficiency of photogenerated electron–hole pairs of the catalyst, so as to enhance its photocatalytic activity. The active species trapping experiment and electron spin resonance analysis showed that •O2– and h+ were the active species responsible for the oxidation reaction. The recycle experiment also proved that the catalyst has good stability. This work provides a new strategy for the design of photocatalysts for converting biomass into high-value chemicals.
研究领域:
化学工程
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材料科学
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环境科学
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DOI
高影响因子
GREEN CHEMISTRY
·
2015
·Vol. 18
·期 4
·1080-1088
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IF 8.02
Weiwei Hao,Weifeng Li,Xing Tang,Xianhai Zeng,Yong Sun,Shijie Liu,Lu Lin
An efficient process for the catalytic transfer hydrogenation of biomass-derived 5-hydroxymethyl furfural (HMF) to 2,5-bishydroxymethyl furan (BHMF) is presented using ethanol as a hydrogen donor and solvent over low-cost ZrO(OH)2. A HMF conversion of 94.1% and a DHMF selectivity of 88.9% were achieved at 423 K in 2.5 h. The fresh, spent, and regenerated catalysts were characterized comprehensively, and the OH group of ZrO(OH)2 as sites for ligand exchange with ethanol was considered to be important for the activity.
研究领域:
化学工程
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可再生能源
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催化剂科学
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DOI
高影响因子
Journal of Energy Chemistry
·
2016
·
IF 2.322
Panpan Yang,Qineng Xia,Xiaohui Liu,Yanqin Wang
The catalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) has attracted extensive research interests because DMF can be used as potential and competitive renewable transportation fuel or additives. Here we report a non-noble bimetallic catalyst with improved activity for hydrogenation and hydrogenolysis by introducing active carbon as support into a nickel–cobalt catalyst. The characterizations of the catalyst indicate that the Ni and Co species are uniformly dispersed on the active carbon through the wetness impregnation method. The influences of reaction temperature and hydrogen pressure are systematically investigated and an excellent yield (up to 95%) of DMF can be obtained at relatively mild conditions, 130 °C and 1 MPa H 2 , over the carbon supported Ni–Co bimetallic catalyst. The high catalytic activity originates from the synergistic effect between Ni and CoO x species, the high BET surface area of the catalyst, and the uniform dispersion of Ni and Co species on the active carbon. The catalyst could be reused for 5 times without loss of activity in a batch reactor . Futhermore, the conversion of HMF to DMF on a fixed-bed reactor was also investigated and the 2%Ni–20%Co/C catalyst exhibited an excellent yield to DMF (>90%) for 71 h time on stream, indicating the high activity and stability of the catalyst.
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
SENSORS
·
2021
·Vol. 21
·期 24
·8292
·
IF 3.576
Kaixuan Li,Ding Li,Yan Zhang
Applications of terahertz time-domain spectroscopy (THz-TDS) in the fields of chemistry and biomedicine have recently received increased attention. Specifically, THz-TDS is particularly effective for the identification of alkaloid molecules, because it can distinguish the vibration types of base molecules in the THz band and provide a direct characteristic spectrum for the configuration and conformation of biomolecules. However, when THz-TDS technology is used to identify alkaloid molecules, most of them are concentrated in the 0.1–3.0 THz band, limiting the amount of information that can be obtained. In this work, a wide-spectrum THz-TDS system was independently built to explore the absorption spectra of uracil and its 5-substituents in the range of 1.3–6.0 THz. We found that, in the THz band, uracil and its 5-substituents have similar absorption peaks near 4.9 and 3.3 THz, while the 5-substituents have an additional absorption peak in the range of 1.5–2.5 THz. This absorption peak is red-shifted as the relative atomic mass of the 5-substituted atoms increases. Gaussian software was adopted to calculate the absorption spectra of the samples. The simulation conclusions were in good agreement with the experimental results, revealing that the vibration of the base molecule at low frequencies can be attributed to the inter-molecular vibration. This work demonstrates that THz-TDS technology can be used to accurately identify biomolecules with similar molecular structures, reflecting the importance of molecular structure in biological activity.Keywords:terahertz time domain spectroscopy;absorption peaks;5-substituents of uracil;vibration;broad spectrum;molecular structures
研究领域:
化学
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生物医学
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产品关联
DOI
PubMed
高影响因子
Biomass Conversion and Biorefinery
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2021
·Vol. 12
·期 8
·3503-3511
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IF 4.987
Huang Xin,Xu Anbang,Bu Xinyuan,Huang Yong,Ran Jingyu
Levoglucosenone (LGO), derived from catalytic pyrolysis of cellulose, has shown its potential as a bio-renewable platform for the production of fine and commodity chemical. In this study, we report a biphasic system for conversion of LGO to 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) with a substantial yield. The hydrolysis parameters, including single-biphasic phase, catalyst, temperature, and reaction time, were investigated on LGO conversion, respectively. The results showed that NaCl/H 2 O-MIBK biphasic system led to a profoundly increase of HMF selectivity by 37% compared to aqueous phase. An increase of acid site significantly enhanced LGO conversion and meanwhile promoted overreaction of HMF to LA and humins. Thus, HMF yield was observed firstly increased and then decreased with a maximum yield of 53.6% by using oxalic acid as a catalyst. The biphasic system effectively suppressed the humins formation and resulted in a maximum total HMF and LA yield of 86.7%.
研究领域:
化学工程
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可再生资源利用
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DOI
高影响因子
APPLIED THERMAL ENGINEERING
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2020
·
IF 4.725
Xiaoxiao Xia,Zhilu Liu,Song Li
Adsorption-driven heat pumps (AHPs) powered by low-grade waste heat and solar energy are promising to reduce the energy consumption for cooling and heating. Seeking novel high-performing adsorbents of AHPs is the key to improve their cooling/heating performance. Very recently, the potential use of covalent-organic frameworks (COFs) adsorbents of AHPs has won increasing research interests. However, the adsorption cooling/heating performance of COFs under varying working conditions is still unexplored. In this study, COF-5 was synthesized and tested to obtain the adsorption isotherms of ethanol working fluid. For comparison, three commonly used metal-organic frameworks (MOFs), including Cu-BTC, MIL-101(Cr), and ZIF-8, were also investigated. The cooling/heating performance of COF-5/ethanol and MOF/ethanol working pairs was evaluated by mathematical modelling based on the basic thermodynamic cycle of AHPs. The results demonstrated that COF-5 with the high coefficient of performance for cooling/heating (COP C /COP H ) under wide temperature lift (ΔT lift ) outperformed MOFs, especially for cooling.
研究领域:
材料科学
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能源工程
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
·
IF 13.2
Changcheng Sun,Lyumeng Ye,Peng Lu,Xianhui Yan,Jianhang Huang,Zhixiong Tang,Dongyao Chen,Chaoping Cen
The key point to broaden the operating temperature window for synergistic control of NO x and oxygenated volatile organic compounds (OVOCs) with high NO x /VOCs conversion and N 2 /CO 2 selectivity relies on development of appropriate catalysts. Herein, a silver-modified Mn/HZSM-5 catalyst was designed, which achieved an effective NO x and acetone co-removal activity and maintained over 90 % N 2 /CO 2 selectivity at a broad temperature range from 293 to 400 °C. The excellent performance of MnAg/HZSM-5 was due to large surface area, plenty of oxygen vacancies and Lewis acid sites, as well as outstanding oxygen mobility and reducibility that derived from the interactions between Mn 4+ /Mn 3+ and Ag + /Ag 0 . NO x reduction followed both Eley-Rideal and Langmuir-Hinshelwood mechanisms, while acetone hardly replaced NH 3 as a reduction agent. Acetone oxidation underwent acetone → acetate → formate → carbonate → CO 2 and H 2 O following a Mars-van Krevelen mechanism. NH 3 participated in acetone oxidation, forming amide and nitrile species, which caused catalyst deactivation and secondary pollution.
研究领域:
环境科学
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催化化学
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2021
·
IF 8.128
Weiqi Wei,Gaojing Lyu,Weikun Jiang,Zhengyu Chen,Shubin Wu
In this work, a sulfonic acid-functionalized magnetic separable solid acid (Fe 3 O 4 @SiO 2 -SO 3 H) was synthesized, characterized, and tested for fructose conversion to 5-hydroxymethylfurfural (HMF). Results indicated that the prepared catalyst had a good efficacy for fructose dehydration to HMF due to its larger specific surface area, appropriate acid amount and homogeneous acid distribution. The maximum HMF yield of this work was 96.1 mol%. It was obtained at 120 °C for 1.5 h with 100 mol% fructose conversion. More importantly, the produced HMF could be further in-situ oxidized into 2,5-diformylfuran (DFF) after the replacing of the Fe 3 O 4 @SiO 2 -SO 3 H with a ZnFeRuO 4 catalyst, and the highest DFF yield of 90.2 mol% (based on initial fructose) was obtained after reaction another 8.5 h. The production of DFF from fructose through the above two consecutive steps avoids the intermediate HMF separation, which saves time and energy. In addition, both Fe 3 O 4 @SiO 2 -SO 3 H and ZnFeRuO 4 catalysts exhibited satisfied stability in the recycling experiments, which can be reused at least for five times with the HMF and DFF yield loss<5.3% and 3.3%, respectively. Finally, the plausible reaction mechanisms for fructose conversion to HMF or DFF over Fe 3 O 4 @SiO 2 -SO 3 H or/and ZnFeRuO 4 catalysts were also proposed in this work.
研究领域:
化学工程
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催化
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可再生能源
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产品关联
DOI
PubMed
高影响因子
BIOMASS & BIOENERGY
·
2022
·
IF 5.774
Gang Liu,Yujiao Xie,Chunjie Wei,Chang Liu,Feng Song,Xiuyu Sun,Yuan Zhang,Hongyou Cui
The one-pot approach was developed by using molten salt hydrate consisting of ZnCl 2 ·4H 2 O and LiCl·3H 2 O to produce 5-hydroxymethylfurfural (5-HMF) from cellulose . Cellulose was dissolved and regenerated to study the interaction of cellulose and molten salt hydrate. The effects of ZnCl 2 ·4H 2 O concentration, reaction time, and temperature on the conversion of cellulose to 5-HMF were investigated. 5-HMF yield increased when ZnCl 2 ·4H 2 O was mixed with LiCl·3H 2 O, and the maximum value (44.1%) was reached at 160 °C and 90 min when ZnCl 2 ·4H 2 O concentration was 64.9 mol%. The species of ZnCl 2 ·4H 2 O–LiCl·3H 2 O were analyzed, and the function of species concentration was correlated with the 5-HMF yield from the conversion of glucose and fructose. It was found that the synergistic catalysis of ZnCl 3 − , Zn 2+ , Zn(OH) + , H + as well as Li + promoted the efficiently cellulose conversion to 5-HMF.
研究领域:
化学工程
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催化
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生物化工
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可再生能源
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产品关联
DOI
高影响因子
CELLULOSE
·
2025
·
IF 4.8
Xuan Xiang-Tao,Zhang Hui,Yao Jia-Le,Miao Ya-Ping,Fan Wei,Dong Xiang-Zhi,Dai Chen-Min,Miao Jiao-Jiao
Photoreforming cellulose to simultaneously produce 5-hydroxymethylfurfural (5-HMF) and hydrogen represents a promising strategy for harnessing solar energy. However, the development of highly efficient photocatalysts for this reaction remains a challenge, and the influence of cellulose’s crystalline structure on conversion efficiency is not well understood. In this study, a Pt-modified g-C 3 N 4 –Bi 3 TiNbO 9 heterojunction photocatalyst was synthesized to explore the photocatalytic reforming of four crystalline forms of cellulose. The results demonstrate that the crystalline structure of cellulose significantly affects hydrogen and 5-HMF production, with the order of activity being cellulose III > IV > II > I. Among the cellulose types tested, cellulose III exhibited the highest performance, achieving 51.8 μmol g⁻ 1 h⁻ 1 of hydrogen and 113.4 μmol g⁻ 1 h⁻ 1 of 5-HMF, surpassing the yields from cellulose I, II, and IV when using the Pt 1.0 –g-C 3 N 4 –Bi 3 TiNbO 9 (2:1) heterojunction. Additionally, a lower degree of polymerization of cellulose was found to favor the coproduction of hydrogen and 5-HMF, as it enhances the breakdown of cellulose via reactive species. Factors such as cellulose powder size, solution pH, and catalyst-cellulose interactions were also shown to influence the yields. Density functional theory (DFT) calculations revealed an electron migration of 0.019684e between the O 2 p and Bi 6 p orbitals of Bi 3 TiNbO 9 (220) and the C 2 p and N 2 p orbitals of g-C 3 N 4 , confirming interfacial electron transfer. The calculated adsorption energies followed the trend: cellulose IV (− 1.72 eV) > I (− 1.73 eV) > II (− 1.94 eV) > III (− 2.07 eV), consistent with experimental results, except for cellulose IV. Graphical abstract
研究领域:
能源科学
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材料科学
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化学工程
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产品关联
DOI
高影响因子
Molecular Catalysis
·
2019
·
IF 2.938
Chenglong Dong,Hongtao Wang,Haochen Du,Jiebang Peng,Yang Cai,Shuai Guo,Jianli Zhang,Chanatip Samart,Mingyue Ding
Furfurylamine converted from biomass-based platform molecules furfural was proven a significant intermediate in the synthesis of different valuable compounds. The combination of Ruthenium with HZSM-5 was acted as an excellent selective and reusable catalyst for the reduction amination of furfural with environmentally friendly ammonia and hydrogen. Incorporation of Ru species into HZSM-5 had a significant enhancement to the acid sites of Ru/HZSM-5. The Ru/HZSM-5(46) catalyst with optimized acid sites and interaction of the Ru-O-Al bond displayed an excellent catalytic performance, producing 76 % yield of furfurylamine at only 15 min, and could be recycled five times without loss of performance. Synergistic effect between RuO 2 and metallic Ru in the Ru/HZSM-5 catalyst facilitated the reduction amination of furfural.
研究领域:
催化
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化学工程
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可持续化学
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绿色化学
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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）