GREEN CHEMISTRY
·
2016
·Vol. 19
·期 3
·722-728
·
IF 8.506
Miaomiao Han,Xiao Liu,Xiaosa Zhang,Yuanyuan Pang,Peng Xu,Jianwei Guo,Yadong Liu,Shuangyan Zhang,Shengxiang Ji
5-Hydroxymethylfurfural (HMF) is an important platform chemical derived from biomass. Tremendous efforts have been made to transform HMF into valuable chemicals for applications in biofuels, materials science, and pharmaceuticals. Here we report the conversion of HMF into 5-hydroxymethyl-2-vinylfuran (HMVF), a versatile adhesive. HMVF can bond to a variety of substrates, e.g. metal, glass, plastics and rubber, under heating or acid treatment at room temperature. Mechanistic studies show that the vinyl group undergoes free radical polymerization and the hydroxyl group dehydrates to form an ether linkage to crosslink HMVF under either heating or acid treatment. The bonding strength (τ) of HMVF cured by heating (h-HMVF) is close to that of Krazy Glue (Loctite 401, cyanoacrylate) and higher than that of white glue (Pattex No. 710, PVA) and Pattex PKME15C epoxy glue. The outstanding adhesive performance of HMVF is attributed both to the interaction of hydroxyl groups with substrates and crosslinking by etherification between hydroxyl groups. Similar to Krazy Glue, HMVF is also used in its monomer form, which eliminates the use of solvents. Cells show good adhesion on crosslinked HMVF, which makes HMVF a potential bio-adhesive.
研究领域:
化学工程
·
材料科学
·
生物技术
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL PHYSICS
·
2021
·Vol. 34
·期 1
·102-111
·
IF 1.114
Qian Si-yu,Feng Bei-bei,Zhai Yi-tong,Zhao Wei,Wang Lei,Ao Cheng-cheng,Liu Yi,Liu Jing,Zhang Li-dong
To obtain insight into the catalytic reaction mechanism of biodiesels over ZSM-5 zeolites, the pyrolysis and catalytic pyrolysis of methyl butanoate, a biodiesel surrogate, with H-type ZSM-5 (HZSM-5) were performed in a flow re-actor under atmospheric pressure. The pyrolysis products were identified and quantified using gas chromatography-mass spectrometry (GC-MS). Kinetic modelling and experimental results revealed that H-atom abstraction in the gas phase was the primary pathway for methyl butanoate decomposition during pyrolysis, but dissociating to ketene and methanol over HZSM-5 was the primary pathway for methyl butanoate consumption during catalytic pyrolysis. The initial decomposition temperature of methyl butanoate was reduced by approximately 300 K over HZSM-5 compared to that for the uncatalyzed reaction. In addition, the apparent activation energies of methyl butanoate under catalytic pyrolysis and homogeneous pyrolysis conditions were obtained using the Arrhenius equation. The significantly reduced apparent activation energy confirmed the catalytic performance of HZSM-5 for methyl butanoate pyrolysis. The activation temperature may also affect some catalytic properties of HZSM-5. Overall, this study can be used to guide subsequent catalytic combustion for practical biodiesel fuels.
研究领域:
能源科学
·
催化化学
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2017
·Vol. 46
·期 36
·12209-12216
·
IF 4.029
Cong Lin,Jian Li,Fengjuan Pan,Yifang Zhao,Le Xu,Yanquan Yang,Xin Du,Xiaohuan Lin,Fuhui Liao,Jianhua Lin,Tao Yang,Junliang Sun
AlPO4-5 is the most extensively studied material in exploring the crystallization mechanism of aluminophosphate molecular sieves, and it can be synthesized using 4-dimethylaminopyridine (DMAP) as an organic structure-directing agent (OSDA). Achieving the AlPO4-5 intermediate in the crystalline form would be of great importance and significance for this purpose. In this study, we proposed a concept that by carefully regulating the synthesis conditions, crystalline alumimophosphate intermediates could be rationally prepared. A crystalline AlPO4-5 intermediate, (C7H11N2)2(H3O)(Al3P4O16)·(H2O)2.5 (1), was, therefore, synthesized by significantly increasing the amounts of orthophosphoric acid and DMAP. The intermediate 1 consists of alternating organic DMAP and inorganic [Al3P4O16]3− layers with abundant hydrogen bonds and can transform to the AlPO4-5 framework upon heating in air or through a steam-assisted conversion (SAC) method. To unravel the role of DMAP in the transformation, pure AlPO4-5 (2) was also synthesized by altering the synthesis conditions. The supramolecular assembly templating (SAT) effects of DMAP in 1 and 2 were verified via fluorescence spectra. Thus, the π–π stacking interactions between the DMAP molecules and the abundant hydrogen bonds between the adjacent layers are considered to be important for the phase transformation of 1. This crystalline intermediate would promote the understanding of the crystallization mechanism in the system of aluminophosphate molecular sieves.
研究领域:
材料科学
·
晶体化学
✓ 已验证
DOI
PubMed
高影响因子
CRYSTENGCOMM
·
2020
·Vol. 22
·期 21
·3670-3682
·
IF 3.117
Xia-Lin Dai,Chao Wu,Jin-Hui Li,Lian-Chao Liu,Xin He,Tong-Bu Lu,Jia-Mei Chen
5-Fluorouracil (5FU) is a classical anti-metabolic drug with broad-spectrum antitumor effects. However, the oral absorption of 5FU is incomplete with a short biological half-life and an obvious peak-valley phenomenon, leading to the frequent administration requirement and severe side effects. Herein, a pharmaceutical cocrystallization approach based on crystal engineering was employed to modulate the pharmacokinetic properties of 5FU by changing its aqueous solubility. Four cocrystals of 5FU with a group of dihydroxybenzoic acids were synthesized and characterized. The powder dissolution experiments showed that all the cocrystals exhibited different aqueous solubilities and dissolution rates in comparison with pure 5FU. As compared to pure 5FU, the apparent solubility values of two cocrystals were increased by 34% and 11% while those of the other two cocrystals were reduced by 27% and 51%, respectively. The pharmacokinetic parameters of all the cocrystals, including Cmax, tmax, MRT0–t, t1/2 and AUC0–t, as well as the shape of the pharmacokinetic curves, were accordingly altered in the in vivo pharmacokinetic study. This study has important implications for using cocrystallization techniques to modulate the pharmacokinetic properties of drugs with undesirable oral absorption, especially to avoid the in vivo peak-valley effect and reduce side effects in clinical practice.
研究领域:
药物化学
·
药理学
·
晶体工程
✓ 已验证
DOI
高影响因子
ENZYME AND MICROBIAL TECHNOLOGY
·
2019
·
IF 3.553
Zhi-Hao Xia,Min-Hua Zong,Ning Li
2,5-Bis(hydroxymethyl)furan (BHMF) is a versatile building block in the synthesis of polymers, fuels, and macrocycle polyethers. In this work, alcohol dehydrogenases (ADHs) were identified from Meyerozyma guilliermondii SC1103 and were heterologously expressed in Saccharomyces cerevisiae for the synthesis of BHMF from 5-hydroxymethylfurfural (HMF). Of recombinant strains constructed, S. cerevisiae expressing an aryl ADH ( Mg AAD1669) was observed to be the best catalyst. Upon process optimization, BHMF was afforded with a 99% selectivity and a 94% yield within 24 h at the substrate concentration of 250 mM. The space-time yield up to 3.4 g/L h was achieved in the fed-batch synthesis of BHMF. Inexpensive corncob hydrolysate proved to be a promising alternative to glucose as co-substrate for biocatalytic synthesis of BHMF, thus resulting in the significantly reduced production cost.
研究领域:
生物技术
·
生物化学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ChemCatChem
·
2019
·Vol. 11
·期 11
·2649-2656
·
IF 4.495
Kuo Zhou,Haiyan Liu,Huimin Shu,Shuwen Xiao,Dechao Guo,Yingxin Liu,Zuojun Wei,Xiaonian Li
Graphical Raney to the rescue ! High value-added 2,5-bisaminomethylfuran was one-pot synthesized from 5-HMF over Raney Ni with a yield of 60.7 %. DFT calculations were conducted to support our speculation that Ni can harmonize NH 3 and H 2 on its surface most suitably for the reductive amination reactions. Reductive amination of furfuryl alcohol, furfural and 5-hydroxymethylfurfural (5-HMF) were carried out on various metal catalysts. Over Raney Ni catalyst, we obtained the highest furfurylamine yields of 81.8 % and 94.0 % from furfuryl alcohol in absence and presence of H 2 , respectively. While furfural was used as the substrate, 100 % yield of furfurylamine could be achieved over Raney Ni under rather moderate conditions. Although 5-HMF was completely converted over all catalysts used, the highest yield of 2,5-bisaminomethylfuran (60.7 %) was obtained over Raney Ni at 160 °C in 12 h. The DFT calculations on the adsorption behavior of NH 3 and H 2 on different metal surfaces showed that the difference of the adsorption energy between NH 3 and H 2 on Ni is lower than those of other metals, indicating that less metal active sites on Ni surface is occupied by NH 3 , which leaves more active sites for dehydrogenation/hydrogenation reactions and in the end promotes the reductive amination reactions.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2018
·
IF 4.667
Mei Cui,Renliang Huang,Wei Qi,Rongxin Su,Zhimin He
2,5-Diformylfuran (2,5-DFF) is an important furan-based chemical with broad application potential. To address the difficulties in isolating/purifying the product and recycling the 2,2,6,6- tetramethylpiperidine-1-oxy (TEMPO)-based catalysts, we employed a solvent with a low boiling point in which TEMPO has a low solubility to investigate the effects of TEMPO and its analogs on catalyzing the oxidation of 5-hydroxymethylfurfural (5-HMF). The results indicated that in ethyl acetate with the substitution of one H of TEMPO at the C4 position with either an acetamido ( NH-Ac), methoxy ( OCH 3 ), hydroxy ( OH) or isothiocyanato ( N C S) group, the resulting compound had a product selectivity similar to that of TEMPO (>86%), except for the 4-isothiocyanato-TEMPO-catalyzed reaction. However, after two Hs were substituted with an oxo group ( O), the catalytic efficiency significantly decreased (product yield 16%, selectivity 52%). Based on both the catalytic efficiency and catalyst solubility, a highly efficient method for preparing 2,5-DFF was established using ethyl acetate as the solvent, 4-acetamido-TEMPO as the catalyst and Fe(NO 3 ) 3 and NaCl as cocatalysts. At 40 °C with a substrate concentration of 0.125 mol/L, 5-HMF was completely converted in 2 h, and the yield of 2,5-DFF was 89%. Moreover, when the substrate concentration increased to 0.25 mol/L, the yield of 2,5-DFF was 87%. When 4-acetamido-TEMPO was recovered by centrifugation, the product yield remained as high as 86% after three cycles, demonstrating good recyclability.
研究领域:
化学工程
·
催化化学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2019
·
IF 3.372
Jun Zhang,Kaijun Dong,Weimin Luo
A facile and mild method for the catalytic production of 2,5-dimethylfuran (DMF) from 5-hydroxymethylfurfural (HMF) was developed, which utilized commercial PdCl 2 as the catalyst together with the green, non-toxic and low-cost hydride source, polymethylhydrosiloxane (PMHS). A synergistic effect among hydrogen donor, in situ generated metallic Pd 0 species and acid site HCl in the reaction played a key role in DMF formation. Gratifyingly, the desirable yield of hydrodeoxygenation product DMF as high as 89.7% from HMF was attained at room temperature (298 K) in 0.5 h. Meanwhile, biomass derived sugars also could be converted into DMF in relative high efficiency via a one-pot reaction in the present system. A plausible pathway for the hydrodeoxygenation of HMF into DMF in the present system was also proposed. The study thus highlights a new perspective for a simple, green, and efficient hydrodeoxygenation of biomass derivatives under milder conditions, employing a readily available, inexpensive and practical catalytic system of PdCl 2 -PMHS-ethanol, but without any external hydrogen supplies and pre-reduction treatments.
研究领域:
化学工程
·
可再生能源
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 26
·19823-19829
·
IF 3.84
Zhenzhen Miao,Tianxiao Wu,Jingwei Li,Ting Yi,Yibo Zhang,Xiangguang Yang
The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) was efficiently catalyzed when Pt nanoparticles (NPs) were supported onto a Ce0.8Bi0.2O2−δ solid solution. 98% yield of FDCA was achieved within 30 min at room temperature and the catalyst was reused five times without much loss of FDCA selectivity. It is the first report on the oxidation of HMF, an alcohol and an aldehyde, effectively catalyzed by a ceria-based material supported Pt catalyst. The individual properties of the Pt NPs and the ceria-based support were retained and not affected after their combination. The superior oxygen activation ability of the Bi-doped ceria thoroughly changed the performance of the ceria supported Pt catalyst. Pt NPs were responsible for the formation of the Pt–alkoxide intermediate, followed by β-H elimination with the help of hydroxide ions. Bi-containing ceria accelerated the oxygen reduction process because of the presence of a large amount of oxygen vacancies and the cleavage of the peroxide intermediate promoted by bismuth. These specific functions were well incorporated during the catalytic oxidation cycle, leading to the generation of the highly efficient Pt/Ce0.8Bi0.2O2−δ catalyst for HMF oxidation at room temperature.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ChemistrySelect
·
2025
·Vol. 10
·期 4
·e202404857
·
IF 2
Wei Jiang,Chenkang Zhao,Yanfeng Liu,Yu Zu,Hongyu Guo,Guanghui Zhao,Weizhong Wang,Yong Sun
Graphical In this study, a straightforward coprecipitation method was employed to synthesize the bimetallic catalyst MnO@Co-CN, which demonstrates high efficiency in catalyzing the direct oxidative esterification of HMF to produce FDMC with a yield reaching 90.3%. The synergistic interactions between the dual metals during the reaction significantly enhance the catalytic performance for optimal oxidative esterification. As a versatile platform molecule derived from biomass, 5-hydroxymethylfurfural (HMF) has the potential to be transformed into a variety of chemicals. Of these, furan-2,5-dimethylcarboxylate (FDMC) stands out as an excellent precursor for the synthesis of poly(ethylene furandicarboxylate) (PEF), a polymer with broad applications in the production of various polymeric materials. However, a majority of studies have focused on the use of noble metal catalysts to achieve the direct oxidative esterification of HMF for the production of FDMC. Given the scarcity and high cost of noble metal catalysts, there is a pressing need to develop non-noble metal catalysts to efficiently facilitate the direct oxidative esterification of HMF. Accordingly, a bimetallic catalyst, MnO@Co-CN, was prepared in this paper by a simple coprecipitation method, and a 90.3% FDMC yield was obtained under optimal conditions. The findings revealed that in the oxidative esterification of HMF, MnO x predominantly adsorbs the reactants onto the catalyst surface, whereas CoO x is primarily responsible for the oxidation. The synergistic interaction between Mn and Co enhances the catalytic performance, leading to the superior oxidative esterification outcomes. This work offers a cost-effective, scalable method for FDMC synthesis, highlighting potential for industrial applications.
研究领域:
化学工程
·
催化材料
·
可再生资源转化
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Yuan Bao,Weijia Pu,Yiwei Zhang,Yahui Xiao,Yong Liu
Ni-Co nano-alloys confined by in-situ formed N-doped porous carbon overlayer have been prepared through chelation of metal cations with citric acid and urea followed by carbonization for hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) into 2, 5-dimethylfuran (DMF). The results indicated that the Ni-Co nano-alloys were formed and homogeneously distributed within the N-doped porous carbon overlayer. The electronic effect of the Ni-Co nano-alloys significantly boosted hydrodeoxygenation activity of the Co 2 Ni 1 @NC catalyst and simultaneously inhibited further hydrogenation and opening of furan ring. The N-doped porous carbon overlayer around Ni-Co nano-alloys not only facilitated to disperse and stable Ni-Co nano-alloys through strong metal-support interaction, but also protected the Ni-Co nano-alloys from aggregation. Therefore, the Co 2 Ni 1 @NC catalyst offered superior catalytic performance with the HMF conversion of 100 % and DMF selectivity of 93.0 %. Moreover, the Co 2 Ni 1 @NC catalyst displayed excellent stability without significant activity loss after five recycles due to the spatial confinement of N-doped carbon overlayer.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Jiashi Wang,Qinhong Wei,Qingxiang Ma,Zhongya Guo,Fangfang Qin,Zinfer R. Ismagilov,Wenzhong Shen
At present, the increasing consumption of fossil fuels as well as the expanding of more effective avenues to prepare carbon materials have inspired scholars' confidence to seek for alternative carbon sources. To address this issue, a N-doped graphene shell encapsulated metallic Co (Co@NGs) catalyst was fabricated using glucose and melamine as carbon source and nitrogen source via carbonization and employed for 5-hydroxylmethylfurfural (HMF) hydrogenation to produce 2,5-dimethylfuran (DMF) biofuel. Here, the prepared Co@NGs catalyst which possessed striking Mott-Schottky effect presented strong electronic interaction at the interface of surface metallic Co and doped N, leading to the electron transfer from metallic Co to doped N on carbon substrate. Experimental results indicated that the decreased electron density of metallic Co was more conductive to selective catalytic hydrogenation of HMF to form DMF. More importantly, the catalytic activity of the Mott-Schottky-type Co@NGs catalyst could be regulated by adjusting the nitrogen content. That is, the high nitrogen content increased the work function of Co@NGs and thus the enhanced rectifying response at the interface by which to enhance the catalytic performance. The best Co@NGs catalyst exhibited both high HMF conversion (close to 100 %) and DMF selectivity (94.7 %), much better than those of conventional N-doped carbon supported Co catalysts.
研究领域:
材料科学
·
催化化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）