ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Zizhao Qian,Yanglei Zheng,Qing Li,Lujie Wang,Feiya Fu,Xiangdong Liu
Diphenolic acid (DPA) is a renewable chemical attracting great interest in biobased polymer science. Despite their low toxicity and high recyclability, the undesirable decarboxylation of DPA-based polymers generally leads to poor thermal stability and material failure restricting their practical applications. Here, we demonstrate that the incorporation of amide groups into a benzoxazine molecule can effectively avoid this problem while improving the thermally mechanical performance of the polybenzoxazine resin. We first synthesized a tetra-phenolic compound via a condensation reaction of DPA with hexanediamine through an ammonium salt route and then prepared a tetrafunctional benzoxazine, denominating as DHDA-fa, by a further reaction with furfurylamine and formaldehyde in a polyethylene glycol 200 (PEG-200) medium. The glass transition temperature (Tg) and decomposition temperature (Td5) of the resulting poly(DHDA-fa) were found to be 326 and 384 °C by DMA and TGA, respectively, which outperformed many biobased benzoxazine resins previously reported. Experimental results revealed that the enhanced hydrogen bonding and doubled oxazine functionary are the important contributors for the improved thermal and mechanical performances. This work confirmed a novel way to perfect DPA-based benzoxazine resins resulting in an effective strategy for developing biobased materials with high performance for practical applications.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2021
·
IF 9.642
Wenran Gao,Gang Wu,Xun Zhu,Muhammad Asif Akhtar,Guiying Lin,Xun Hu,Yong Huang,Shu Zhang,Hong Zhang
The conversion of cellulose to platform chemicals has attracted much attention because of its renewability. This work proposed an earth-abundant cobalt disulfide as a heterogeneous catalyst for methyl levulinate production from cellulose. The highest yield of methyl levulinate reached 61 mol% under the tested conditions of 200 °C, 2 MPa initial pressure, 0.45 catalyst/cellulose mass ratio, and 3 h reaction time. The XRD and TEM analyses demonstrated the crystal facet (111) of cobalt disulfide as a robust active site, which was in good agreement with the highest acidity of the crystal facet (111) calculated by the work functions. The XPS characterization showed that the main chemical valence of cobalt disulfide responsible for the methyl levulinate production was the surface Co 2+ species. This study is valuable for the development of a recoverable catalyst for the cellulose to methyl levulinate process.
研究领域:
化学工程
·
催化
·
可再生能源
✓ 已验证
DOI
PubMed
高影响因子
Sustainable Energy & Fuels
·
2018
·Vol. 2
·期 5
·1035-1047
·
IF 0
Junfeng Feng,Jianchun Jiang,Chung-yun Hse,Zhongzhi Yang,Kui Wang,Jun Ye,Junming Xu
Selective catalytic conversion of biomass waste for producing methyl levulinate (MLA) via directional microwave-assisted liquefaction was investigated. The goal of the study was to develop a directional liquefaction process using dielectric heating with microwave energy. The methanolysis of biomass into methyl levulinate was studied in the presence of several acid catalysts. The C6 sugar substrates in biomass were successfully converted into methyl levulinate under the optimized conditions (180 °C, 40 min) with a yield of 29.39 wt%. 5-Hydroxymethyl furfural, glucose, fructose, cellobiose, corn starch, and microcrystalline cellulose were selected as models for directional microwave-assisted liquefaction. Therefore, the possible reaction pathway of biomass to methyl levulinate could be investigated. The selective catalytic conversion of biomass was found to be highly efficient for the generation of MLA (reaching a maximum yield of approximately 30 wt%), higher than the levulinic acid yield (14 wt%) in aqueous solution under the same reaction conditions. The results suggested that directional microwave-assisted liquefaction is an effective method that can produce a high value-added fuel additive (methyl levulinate) from lignocellulosic biomass under designated reaction processes.
研究领域:
能源与环境科学
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化学工程
·
生物质能
✓ 已验证
产品关联
DOI
Nature Communications
·
2025
·Vol. 16
·期 1
·1-12
·
IF 15.7
Chen Guangyu,Fu Cenfeng,Zhang Wenhua,Gong Wanbing,Ma Jun,Ji Xiaomin,Qian Lisheng,Feng Xuefei,Hu Chuansheng,Long Ran,Xiong Yujie
Solar-driven, selective biomass hydrogenation is recognized as a promising route to renewable chemicals production, but remains challenging. Here, we report a TiO 2 supported Cu single-atom catalyst with a four-coordinated Cu 1 −O 4 structure, which can be universally applied for solar-driven production of various renewable chemicals from lignocellulosic biomass-derived platform molecules with good yields using green methanol as a hydrogen donor, to address this challenge. It is significant that the biomass upgrading driven by natural sunlight on a gram scale demonstrates the great practical potential. By combining in situ soft X-ray absorption spectroscopy with theoretical calculations, we successfully identify the dynamic evolution of Cu sites along with the biomass hydrogenation and methanol oxidation, where the tandem process is enabled by the photogenerated electrons and holes to complete a chemical cycle. The concept of solar-driven biomass hydrogenation proposed here provides an efficient and sustainable methodology for the sustainable production of renewable chemicals.
研究领域:
化学工程
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催化科学
·
可再生能源
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Sustainable Chemistry and Pharmacy
·
2024
·
IF 5.5
Zhi-Gang Zhang,Yan Yi,Jia-Chun Lin,Dong Chen,Xiao-Jun Ji
2, 5-furandicarboxylic acid (FDCA) is a versatile bio-based building block that can be used for the synthesis of degradable polymers. Recently, developing green and sustainable catalytic processes for producing FDCA from renewable platform chemical molecules has attracted continuing attention. In this study, we proposed a green and sustainable one-pot, two-step biocatalytic process for the sequential oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to form FDCA with good yield and excellent selectivity. The initial step involves the oxidation of HMF to 2, 5-diformylfuran (DFF) and 5-formyl-2-furancarboxylic acid (FFCA) catalyzed by recombinant E. coli cells expressing a 5-hydroxymethylfurfural oxidase . The second step is to convert DFF and FFCA into FDCA final product via aldehyde oxidation reaction catalyzed by Deinococcus wulumuqiensis R12 whole cells . Combining the two different whole-cell biocatalysts , 180 mM of HMF could be easily converted into FDCA with a yield of 99% under optimized reaction conditions. This study offers an efficient and sustainable approach for the valorization of biomass-based HMF to form value-added FDCA.
研究领域:
生物技术
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化学工程
·
可持续化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2025
·
IF 6.2
Tong Zhang,Haiyong Wang,Chenguang Wang,Qiying Liu
Acetol is the important platform molecule, which showed diversified applications in organic synthesis, pharmaceutic, food and polymer industrials. The production of acetol from selective fructose hydrogenolysis is of scientific and practical interests. However, by catalysis, precisely controlling the target C-C and C-O bonds splitting is an open challenge, resulting in the low target product yields. Herein, by regulating the metal-support-interactions, which enhanced electron transfer capacity and improved acetol production from fructose hydrogenolysis through controlling the important intermediate species, obtaining the highest 53.6 % yield and an average conversion rate of 1.24 × 10 −5 mol/(g cat .s) within short time of 10 min. The interfacial charge transfer in the surface structure of the catalyst along with the Ni metal content was revealed by various characterizations. This research provides a preliminary method for electron transfer regulation of Ni/CeO 2 catalysts in acetol production from fructose hydrogenolysis, showing practical application potentials due to the simple preparation of the catalyst that possibly contribute to the reactions on a large scale.
研究领域:
催化化学
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可再生化学
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生物质转化
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多相催化
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Biobased Materials and Bioenergy
·
2019
·Vol. 13
·期 5
·677-682
·
IF 0
Zhu Qiao-Qiao,Zhuang Jun-Ping,Wang Lan-Ying,Liu Ying,Wu Shu-Bin
Three kinds of silicotungstate, Zn2SiW12O40, Ag4SiW12O40 and Al4/3SiW12O40 were performed for the dehydration reaction to produce valuable platform chemicals levulinic acid
(LA) and 5-hydroxymethylfurfural (HMF) from glucose. The results showed that Al4/3SiW12O40 seemed beneficial for LA and HMF production from glucose. The highest LA yield of 50.4% was obtained when the glucose conversion was almost 100% at 180 °C
for 120 min with glucose was 0.5 g and the catalyst dosage was 0.45 g. The recycling of Al4/3SiW12O40 catalyst can be reused at least for four times with the activity loss less than 18.4% and the SEM images showed that the activity loss less may
due to the formation of the clustered fine particles on catalyst surface. This work provided a promising strategy for the production of LA from carbohydrates using inexpensive silicotungstate catalysts in aqueous medium.
研究领域:
化学工程
·
可再生化学
✓ 已验证
DOI
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Yun Wang,Haimei Wu,Jiale Wang,Kaiyue Zhang,Yingxin Liu,Zuojun Wei
A highly effective transformation from renewable biomass and its derivatives into high-value-added chemicals and biofuels is important and challenging. Herein, a N-doped mesoporous carbon (NMC)-supported Ru catalyst developed by an incipient wetness impregnation method was reported for the reductive amination of levulinic acid (LA)/esters with amines to N-substituted 5-methyl-2-pyrrolidinones. A complete conversion of LA with a 99.8% yield of N-hexyl-5-methyl-2-pyrrolidinone (HMP) was achieved over 0.05 mol % Ru/NMC under mild conditions of 120 °C and 1.5 MPa H2 for 4 h, giving a high turnover frequency (3667 h–1). Furthermore, Ru/NMC exhibited superior stability and recyclability (reusable 21 cycles without loss of activity). The excellent performance of the Ru/NMC catalyst was mainly attributed to the introduction of N species to the mesoporous carbon, which not only improved the anchoring and the dispersion of Ru nanoparticles on the catalyst surface but also provided moderate basic sites and transferred electrons from NMC to Ru nanoparticles, as revealed by detailed characterizations. Additionally, the developed Ru/NMC catalytic system was applicable to LA/esters and various amines to afford the corresponding N-substituted 5-methyl-2-pyrrolidinones with excellent yields (80–99%).
研究领域:
催化化学
·
可再生化学
·
材料科学
✓ 已验证
DOI
高影响因子
FUEL
·
2021
·
IF 6.609
Xueying Gao,Xin Yu,Lincai Peng,Liang He,Junhua Zhang
A magnetically-recoverable multifunctional catalyst (Fe 3 O 4 /ZrO 2 @MCM-41) was tailored by the impregnation of ZrO 2 supported on mesoporous MCM-41 coated Fe 3 O 4 nanoparticles, which successfully served as a monolithic catalyst for the cascade conversion of furfural (FAL) giving high yield to γ-valerolactone (GVL), a versatile platform molecule. The ordered hexagonal framework of the parent MCM-41 well reserved after the embedding of Fe 3 O 4 and ZrO 2 . The incorporation of Fe 3 O 4 could not only impart the catalyst with a strong magnetism, but also tune its acidity to promote GVL production. An impressive yield of 85% was accomplished straight from FAL processing with iso -propanol as a hydrogen donor and solvent. The kinetic study demonstrated higher activation energy for levulinate-to-GVL step (86.9 kJ/mol) than FAL transfer hydrogenation (35.0 kJ/mol) and subsequent alcoholysis process (51.0 kJ/mol). The catalyst could be fully recovered by an external magnetic field and showed good reusability. The sustainability of this conversion represents greatly improved by the process intensification based on one-pot reaction, magnetically-recoverable multifunctional catalyst, and mild operating conditions without using gaseous hydrogen.
研究领域:
催化化学
·
纳米材料科学
·
可再生化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2015
·
IF 3.942
Jian He,Hu Li,Ye-Min Lu,Yan-Xiu Liu,Zhi-Bing Wu,De-Yu Hu,Song Yang
A series of Al–Zr mixed oxides with different molar ratios were prepared by co-precipitation method and utilized to catalyze conversion of ethyl levulinate (EL) to γ -valerolactone (GVL). Those as-prepared catalysts were characterized by XRD, SEM, N 2 adsorption–desorption, XPS, TG, NH 3 -TPD, CO 2 -TPD and pyridine-IR. The introduction of Al into ZrO 2 was demonstrated to enlarge surface areas, as well as increase the number of acid and base sites that were catalytically active for transfer hydrogenation. Effects of Al–Zr molar ratio, calcination temperature, reaction temperature and time, catalyst dosage, and alcohols used as hydrogen donors on the catalytic performance were investigated. A high GVL yield of 83.2% at EL conversion of 95.5% could be achieved at 220 °C in 4 h over Al 7 Zr 3 -300 using 2-propanol as hydrogen donor and solvent. Poisoning experiments verified that acid–base sites played a synergic role in producing GVL from EL. Moreover, the Al–Zr mixed oxide catalyst was able to be reused for several times with a slight loss in its catalytic activity.
研究领域:
催化化学
·
可再生化学
✓ 已验证
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2024
·
IF 5.6
Jiarong Qiu,Yi Liu,Jingwen Zhang,Ben Zhou,Qiyue Yang,Liangqing Zhang,Jianfeng Chen,Bingshu Wang,Lu Lin,Xianhai Zeng
A series of zirconium phosphate (ZrP) loaded H-beta-25 zeolite (i.e., ZrP@HB) multifunctional composite catalysts were synthesized by a simple co-precipitation method, and the one-pot upgrading for the transfer hydrogenation of furfural to γ-valerolactone (GVL) was systematically investigated through various characterizations and catalytic evaluation experiments. Comparative characterization analysis of the ZrP@HB-X(Y) catalysts showed that the ZrP@HB-4(4) catalyst has uniform distribution of elements, exhibiting a large specific surface area and hierarchical mesoporous/microporous structure. Fourier transform infrared spectroscopy of pyridine (Py-FTIR) and NH 3 temperature-programmed desorption characterizations indicated the presence of Lewis and Brønsted acid sites, as well as weak, moderate, and strong acid sites in the ZrP@HB-4(4) catalyst. It was confirmed by X-ray photoelectron spectroscopy and FTIR that the main reason for Lewis and Brønsted acid sites formation is the presence of P-O-Zr, P-O-H, and HB zeolite on the ZrP@HB-4(4) catalyst. The HB zeolite as well as Zr and P ratio, can be easily adjusted to efficiently regulate the acidity strength and Lewis and Brønsted acid sites of the ZrP@HB-X(Y) catalysts. The catalytic experiments demonstrated that the physicochemical properties of the ZrP@HB-4(4) catalyst mentioned above significantly enhance the GVL production. Notably, Lewis and Brønsted acid sites as well as transition metal sites of Zr in the ZrP@HB-4(4) catalyst were identified as the main factors that enhance the yield of the target product. By optimizing the reaction conditions, the yield of GVL could be as high as 88.16%. Reusability experiments demonstrate that the ZrP@HB-4(4) catalyst possesses excellent stability. Using levulinic acid as the substrate, the yield of GVL reached 93.92%, suggesting its potential versatility.
研究领域:
催化化学
·
可再生化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2019
·
IF 4.978
Huai Liu,Xuejuan Cao,Ting Wang,Junnan Wei,Xing Tang,Xianhai Zeng,Yong Sun,Tingzhou Lei,Shijie Liu,Lu Lin
The conversion of concentrated 5-hydroxymethylfurfural (HMF) or fructose to 2,5-furandicarboxylic acid (FDCA), a renewable alternative to petroleum-derived terephthalate acid, is highly desirable but challenging for FDCA production in an industrial scale. In this contribution, DMSO/H 2 O mixture was demonstrated as an effective medium for the production of FDCA from high concentration of HMF or fructose. For example, FDCA yield up to 93% was achieved at 10 wt% HMF concentration in DMSO/H 2 O over commercially available Ru/C (2 equiv. NaHCO 3 , 130 °C, 4 MPa O 2 and 12 h). Furthermore, an overall FDCA yield of 65% was achieved from concentrated fructose (19 wt%) through a facile two-step process. Notably, it is so far the highest HMF or fructose concentration employed for FDCA formation. As compared to pure water or DMSO , DMSO/H 2 O mixed system is able to stabilize HMF in an alkaline environment, which allows the efficient oxidation of HMF at high concentrations.
研究领域:
生物化学
·
可再生化学
·
绿色化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）