RENEWABLE ENERGY
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2024
·
IF 9
Cuicui Wu,Meng Wang,Yunming Fang
The productive motivation of high-energy-density fuels from sustainable feedstocks has been prompted by environmental concerns and resource scarcities. To address this demand, here, the energy-rich C10 cycloalkanes were first afforded with biomass-derived 2-cyclopentenone (2CPE). Initially, bio-based 2CPE can be converted to tricyclo-diketones by (2 + 2) cycloaddition under UV irradiation or zeolite catalysis. The UV-light photocatalysis for dimerization of 2CPE to diketol-cycloadducts disclosed outstanding advantages of cost-effectiveness and feasibility than traditional zeolite-catalyzed manner, with a yield of 53.61 % at ambient temperature for 2 h. Despite the potential for high dimer yield (77.28 %) under thermo-catalysis of H-ZSM-5 zeolite, the reaction conditions (120 °C, 18 h) were found to be suboptimal. Subsequently, diketol-cycloadducts were selectively and efficiently hydrodeoxygenated to provide cyclopentane-based hydrocarbons using a Huang-Minlon methodology with a yield of 97.04 %, where the target components were directly distilled during the reaction. Specifically, the as-synthesized C10 cycloalkane mixture originated from 2CPE possess high density of 0.96 g mL −1 , large volumetric heat net of combustion (NHOC) of 40.02 MJ L −1 , along with low freezing point of −49 °C. These properties suggest that the bio-liquid cycloalkanes can be used as a standalone high-energy fuel or as a blending agent to enhance the performance of conventional jet fuels.
研究领域:
生物化学
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能源科学
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DOI
高影响因子
Processes
·
2025
·Vol. 13
·期 5
·1435
·
IF 2.8
Zhongfeng Geng,Yunfei Bai,Ke Zhang,Feng Shi
2-Methyl-2-cyclopentenone (MCP) is the main by-product of the newly developed heterogeneous catalysis process for producing crotonaldehyde, which serves as an important intermediate for drug synthesis. However, how to recover and purify MCP from the product mixture is not known. To decipher this, a computer-aided process based on the measured phase-equilibrium data was developed. The improved Rose–Williams equilibrium kettle was used to measure the vapor–liquid equilibrium data for MCP–crotonaldehyde and MCP–water. Surprisingly, MCP and water formed a minimum azeotrope, which aided its own recovery from its dilute solution. The mole fraction of MCP in the azeotrope was 9.1%, the mole fraction of water was 90.9%, and the azeotropic temperature was 96.8 °C. Equilibrium data from the two binary systems were correlated using the Wilson and NRTL activity coefficient models. The NRTL-RK model was selected to simulate the process for recovering and purifying MCP. A two-column process was developed and optimized in this study, and the aim of effectively utilizing the by-product MCP was achieved with this process.
研究领域:
化学工程
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药物合成
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DOI
高影响因子
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
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2025
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IF 6.2
Zehao Li,Wanying Wang,Lulu Zhang,Jinchu Yang,Yongming Xu,Zhenzhen Huang,Wanzeng Li,Shiying Wang,Jingwen Yang,Zhifeng Zhang
Dihydrocarvone is extensively utilized in food, pharmaceutical, and cosmetic fields because of its pleasant odor, high economic value, and diverse pharmacological properties. In this study, an ene reductase KlebER3, which catalyzed the conversion of carvone to dihydrocarvone using NAD(P)H as a cofactor, was identified from Klebsiella sp. O852 through genome sequencing. This enzyme displayed optimal activity at 30 °C and pH 7 and maintained appreciable stability at 20–50 °C and pH 6–8. Besides, KlebER3 had good resistance to dimethyl sulfoxide and glycerine and exhibited wide-ranging substrate acceptance for α,β-unsaturated compounds. Furthermore, a Q26A mutant with enhanced activity, stability, and stereoselectivity was obtained by molecular docking, alanine scanning, and site-directed mutagenesis. Molecular dynamics simulations revealed that these improvements may be attributed to increased nonpolar interactions, elevated flexibility of the active pocket, reduced binding free energy, and strengthened rigidity of protein conformation. This study established a basis for further investigations of the function and modification of ene reductase as well as the efficient biosynthesis of dihydrocarvone.
研究领域:
酶学
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生物催化
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微生物生物技术
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分子生物学
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计算生物学
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产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2026
·
IF 21.1
Kaiyang Xu,Lingfeng Weng,Qing Han,Bo Liu,Lizhi Wu,Li Tan,Yihu Dai,Yuanjie Xu,Yu Tang
Cyclopentanone (CPO) as a key raw material has been widely applied in spices, pharmaceuticals, and sustainable fuels. The catalytic conversion of biomass-derived furfural (FAL) to CPO meets the requirements of sustainable development goal but still be challenging because of the relatively low selectivity of CPO in the complex tandem catalytic processes. Herein, a Ni/WO 3 -H 2 catalyst presents a cooperative interface that possesses hetero-valent interface of Ni 0 (metallic) and Ni 2+ (interfacial NiWO 4 ), oxygen vacancies (O v ), and acid sites simultaneously was prepared and applied in the tandem hydrogenative ring-rearrangement of FAL to CPO. Under 160 °C and 3 MPa of initial hydrogen pressure, the catalyst achieved 90.3 % furfural conversion and 96.9 % selectivity to CPO, with a turnover rate of 4.26 mmol·g cat ⁻¹ ·h⁻¹ . Moreover, the Ni/WO 3 -H 2 catalyst demonstrated excellent stability and recyclability. Further investigation on reaction mechanism shows that the synergy of each active site, Ni 0 , Ni 2+ (NiWO 4 ), oxygen vacancies (O v ), and acid sites, promotes the conversion of FAL to CPO and effectively avoids the undesired side reaction. Accordingly, a multi-site cooperative mechanism is proposed: FAL hydrogenates to FOL on Ni 0 sites; acid sites rearrange FOL to HCP, which dehydrates at O v sites to CPE; ultimately, CPE is hydrogenated to CPO on Ni hetero-valent interface.
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DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Quanxing Zhang,Caoying Kang,Zhaozhe Li,Kerui Hua,Dongpei Zhang,Wei Yu,Xin Jin,Chaohe Yang
Glutaric acid, a C 5 dicarboxylic acid, servers as an essential monomer in nylon industry. Currently, it is primarily obtained as a byproduct of adipic acid production. Green synthesis of glutaric acid from bio-resources remains a grand challenge. Here, we present a two-step synthesis of glutaric acid from furfural via cyclopentanone as the key intermediate. In the first step, a series of Ni modified CuO x catalysts derived from HKUST-1 (Cu) displays a record conversion rate (20.8 h −1 at 140 ℃) in converting furfural to cyclopentanone, with 99.8 % conversion of furfural and 87.4 % selectivity to cyclopentanone. The d-d orbital coupling between Ni and Cu through the oxygen bridge bond leads to an upshifted d band center of Cu sites, inducing the σ-bonding between the e g orbital of the electron-deficient Cu 2+ and C=O bond of furfural. In the second step, the C=O bond of cyclopentanone can be activated effectively over electron-rich Cu 2+ sites of HKUST-1 (Cu). The oxidation of cyclopentanone to glutaric acid was achieved on heterogeneous catalyst for the first time, with 40 % and 17.6 % yield of glutaric and succinic acids, respectively. The reaction mechanism has also been proposed. DFT calculation has revealed that 1,1,2-trihydroxy-cyclopentane is an important intermediate product, with proton removal to form C-O· radical as the rate-determining step. This work provides insights into the synthesis of bio-glutaric acid through a chemocatalytic route.
研究领域:
催化
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绿色化学
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有机合成
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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
FUEL
·
2024
·
IF 6.7
Yuan Liu,Fang Liu,Li Yang,Feiqiang Guo,Shiliang Wu,Rui Xiao
The work introduced an innovative pathway for converting biomass-derived carbonyls into long-chain ethers, examining their low-temperature oxidation in a modified Cooperative Fuel Research (CFR) engine. The conversion of 2-butanone achieved 100 % and the selectivity of sec -butyl isopropyl ether reached the maximum of 83.13 % under optimal reaction conditions. Conversion of biomass-derived carbonyls increased from 31.77 % at 1 h to 36.28 % at 12 h, with the mass yield of long-chain ethers rising from 53.94 % to 62.86 %. At the same compression ratio, the maximum in-cylinder pressure and temperature increased as the long-chain ethers blending ratio increased. At the critical compression ratio, the net heat release rates (NHR) for blended fuels with 10 vol%, 20 vol% and 30 vol% long-chain ethers at the low-temperature heat release peak were 9.6 J/deg, 10.1 J/deg, and 10.0 J/deg better than that of n -heptane (6.3 J/deg), respectively. CO emissions from blended fuels before compression ignition were higher than n -heptane, while the value for the blended fuel with 30 vol.% long-chain ethers was reduced by 44.97 % compared to n -heptane after autoignition.
研究领域:
化学工程
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能源与燃料
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催化
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环境科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Weichen Wang,Hongke Zhang,Fangyuan Zhou,Yidan Wang,Zhiyu Xiang,Wanbin Zhu,Hongliang Wang
Developing cost-effective and highly active catalysts for the selective hydrogenation of furfural to target products is significant yet remains a substantial conundrum in the chemical industry. Herein, we present a phytic acid-assisting pyrolysis strategy to phase-controlled synthesis of a series of nickel phosphides catalysts (Ni 3 P/mSiO 2 , Ni 12 P 5 /mSiO 2 and Ni 2 P/mSiO 2 ), which exhibited phase-dependent catalytic performance in furfural hydrogenation. Ni 12 P 5 /mSiO 2 achieved the highest yield (97.3 %) of cyclopentanone under 1 MPa H 2 at 150 °C, and Ni 3 P/mSiO 2 could further hydrogenate cyclopentanone to a 60.8 % yield of cyclopentanol when the H 2 pressure increased to 2 MPa. Meanwhile, Ni 2 P/mSiO 2 demonstrated temperature-controlled selectivity for switching between furfuryl alcohol and cyclopentanone. Detailed characterizations and density functional theory calculations elucidated that the differences in catalytic performance were primarily attributed to the hydrogenation ability and acidity of catalysts as well as furfural adsorption configuration, which were determined by the tunable crystal phases of nickel phosphides. This work paves the promising avenue for the rational design of metal phosphide catalysts and harnessing their considerable potential for biomass conversion.
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
·
2021
·
IF 19.503
Jyoti Gupta,Konstantinos Papadikis,Elena Yu. Konysheva,Yi Lin,Ivan V. Kozhevnikov,Jingjing Li
The impact of CaO on oakwood pyrolysis was explored by the Py-GC/MS at 500 °C. Ca(OH) 2 presents on the CaO surface, indicating its partial hydration (noted as CaO OH ). CaO OH promoted the ketonisation of carboxylic acids to aliphatic ketones, furfural to cyclopentanone/2-cyclopentenone, facilitated the elimination of the methoxy-phenolic compounds. The catalyst loading did not show any significant effect on the formation of acetone, while a noticeable reduction in the phenolics was revealed. Increasing catalyst loading almost eliminated CO 2 , acids, furans, aldehydes, ether groups, whilst the fractions of alcohols, esters, sugars, and alkoxybenzene decreased noticeably. The use of partially hydrated CaO OH in the CFP can create conditions where by-products generated during the ketonisation and phenolics upgrading reactions (CO 2 , H 2 O, CO) interact through the adsorption enhance water-gas-shift reaction and through coking reactions with formation of H 2 used for hydrogenation during multistep conversion of furfural to cyclopentanone in a vapour phase.
研究领域:
能源化学
·
催化化学
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产品关联
DOI
高影响因子
Nano Research
·
2021
·Vol. 14
·期 8
·2846-2852
·
IF 8.897
Wang Dongdong,Al-Mamun Mohammad,Gong Wanbing,Lv Yang,Chen Chun,Lin Yue,Wang Guozhong,Zhang Haimin,Zhao Huijun
The cyclopentanone and derivatives are a class of crucial fine chemicals for various industries and currently produced by conventional petrochemical synthetic routes. Here, we demonstrated a new synthetic approach to directly fabricate N-doped carbon nanotube (N-CNTs) networks with confined Co nanoparticles from Co 2+ -impregnated bulk g-C 3 N 4 as high performance hydrogenation rearrangement (HR) catalyst to efficiently convert a wide spectrum of biomass-derived furanic aldehydes to the corresponding cyclopentanones in water under a record-low H 2 pressure of 0.5 MPa and mild temperature. We unveiled a Co-catalysed bulk g-C 3 N 4 decomposition/carbonisation CNTs formation mechanism. A new HR pathway was also unveiled.
研究领域:
催化
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材料科学
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化学工程
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绿色化学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 21
·5886-5895
·
IF 9.405
Junjian Xie,Lun Pan,Genkuo Nie,Jiawei Xie,Yakun Liu,Chi Ma,Xiangwen Zhang,Ji-Jun Zou
The photoinduced conversion of biomass-derived chemicals to high value chemicals and advanced fuels is of great significance but still challenging. Herein, a green and efficient self-sensitized [2 + 2] cycloaddition process is developed to convert biomass-derived β-pinene and isophorone to spirocyclic molecules, which cannot be achieved by thermal catalytic conversion. The photoreaction can take place with isophorone as the self-sensitizer, with high selectivity and a yield of up to 91.1%. A triplet sensitization mechanism is disclosed by a combination of triplet quenching, phosphorescence quenching, Stern–Volmer kinetic analysis, DFT calculations and photochemical kinetic studies. When combined with hydrodeoxygenation, spiro-fuel is obtained with an overall yield of 85.0% showing a high density of 0.911 g mL−1 which is 16.8% higher than that of conventional aviation kerosene (ca. 0.78 g mL−1), along with excellent cryogenic properties. Notably the self-sensitized cycloaddition strategy can be extended to a wide range of biomass derived α,β-unsaturated ketones and alkenes. Thus, this work provides a promising ring-increasing route to upgrade low-density bio-derived feedstocks to high-density hydrocarbons.
研究领域:
化学工程
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能源科学
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绿色化学
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产品关联
DOI
高影响因子
Asia-Pacific Journal of Chemical Engineering
·
2017
·Vol. 12
·期 3
·422-431
·
IF 0.836
Yuan Wang,Wei Zhu,Shengya Sang,Lijing Gao,Guomin Xiao
Aqueous-phase processing of biomass-derived furfural is one of the promising ways to convert biomass into useful chemicals. Supported metal catalysts are crucial in the aqueous-phase hydrogenation of furfural. Understanding the effect of acid and basic properties of supports on the performance of the catalysts will help understand the reaction pathways and develop more efficient catalysts. Here, a series of Cu-based catalysts with different supports (Al 2 O 3 , ZnO, SiO 2 , MgO, and ZSM-5) have been investigated in hydrogenation of furfural in aqueous phase. The properties of the supports have been characterized by X-ray diffraction, N 2 adsorption–desorption, transmission electron microscope, H 2 temperature-programmed reduction, and CO 2 and NH 3 temperature-programmed desorption. The results show that pure acid support leads to the formation of oligomers and pure basic support results in furfuryl alcohol as the main product. And the mass balance in reaction system catalyzed by Cu-based catalysts with higher acidity amount is lower. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
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
Materials Advances
·
2022
·Vol. 3
·期 9
·3885-3896
·
IF 0
Xing-Long Li,Rui Zhu
Developing an economic catalyst to upgrade furfural to cyclopentanol is highly significant for fine chemical synthesis and biomass utilization. In this manuscript, an efficient and economical multi-functional porous Co-400 catalyst was developed. This catalyst obtained porosity, magnetism, Lewis acidity and hydrogenation activity via simple reduction of purchased Co3O4. Various factors were investigated in detail, and 87% yield of CPL could be obtained when Co-400 was used as the catalyst. The active sites of the catalyst were identified according to XRD, IR, XPS, SEM and Raman analysis. Moreover, the keys to the high activity and chemoselectivity of the Co-400 catalyst were mainly attributed to highly dispersed Co0 species and amorphous porous Co3O4 species, which were precisely controlled by the reduction temperature. The catalyst can be easily separated by magnetism. Furthermore, a possible reaction mechanism was proposed based on a series of controlled experiments and catalyst characterizations.
研究领域:
化学工程
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生物质利用
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催化科学
✓ 已验证
产品关联
DOI
危险品化学品经营许可证（带存储）