ACS Catalysis
·
2020
·
IF 12.35
Qiang Deng,Rui Gao,Xiang Li,Jun Wang,Zheling Zeng,Ji-Jun Zou,Shuguang Deng
Upgrading furanic aldehydes (such as furfural or 5-hydroxymethyl furfural) to cyclopentanone compounds (such as cyclopentanone or 3-hydroxymethyl cyclopentanone) is of great significance for the synthesis of high-value chemicals and biomass utilization. Developing an efficient reduced metal/acidic support with Lewis acidity is the key to facilitating the carbonyl hydrogenation and hydrolysis steps in the hydrogenative ring-rearrangement reaction. Herein, three pure Lewis acidic pyrochlore supports of the form A2B2O7 (La2Sn2O7, Y2Sn2O7, and Y2(Sn0.7Ce0.3)2O7-δ) with the same crystal structures and different metals are synthesized. The Lewis acidity and the surface properties of the pyrochlore can be tuned by inserting different kinds of A and B site metals. After impregnation, Pd nanoparticles with appropriate particle sizes are uniformly loaded on the surface of pyrochlore. For the reaction of the furanic aldehydes, all of these pyrochlore-based catalysts exhibit hydrogenation and hydrolysis rates that are both faster than those of traditional support-based catalysts due to the oxygen vacancy and pure Lewis acidity of the support. Among these pyrochlore-based catalysts, Pd/Y2Sn2O7 exhibits activity and selectivity that are higher than those of Pd/La2Sn2O7. Moreover, the Y2Sn2O7-based catalyst partially substituted by Ce3+ ions at the B site is more efficient, with the highest cyclopentanone yield and 3-hydroxymethyl cyclopentanone yield of 95.0% and 92.5%, respectively. Furthermore, the catalyst can still maintain an effective activity and stability after 4 runs. This study not only presents an efficient biobased route for the production of cyclopentanone compounds but also focuses on the acid catalytic performance of pyrochlore based on its pure Lewis acidity.
研究领域:
催化化学
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生物质利用
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材料科学
✓ 已验证
DOI
高影响因子
MOLECULES
·
2023
·Vol. 28
·期 13
·5029
·
IF 4.6
Wei Wang,Ling An,Chi Qian,Yanqing Li,Meiping Li,Xianzhao Shao,Xiaohui Ji,Zhizhou Li
1,3-bis(cyclohexylmethyl)cyclopentane, a renewable high-density fuel, was first produced in a high overall carbon yield (79.5%) with vanillin and cyclopentanone, which can be derived from biomass. The synthetic route used in this work contains two steps. In the first step, 2,5-bis(4-hydroxy-3-methoxybenzylidene)cyclopentanone was synthesized by aldol condensation of vanillin and cyclopentanone under the catalysis of sulphuric acid. Over the optimized condensation, a high carbon yield (82.6%) of 2,5-bis(4-hydroxy-3-methoxybenzylidene) cyclopentanone was achieved at 80 ºC. In the second step, 2,5-bis(4-hydroxy-3-methoxybenzylidene) cyclopentanone was hydrodeoxygenated over the Pd/HY catalyst in cyclohexane as solvent. High carbon yields of 1,3-bis(cyclohexylmethyl)cyclopentane (96.2%) was obtained. The polycycloalkane mixture as obtained has a density of 0.943 g mL−1and a freezing point of −35 °C. It can be blended into conventional high-density fuels (e.g., JP-10) for rockets and missile propulsion as a potential application.Keywords:high-density fuel;vanillin;cyclopentanone;aldol condensation;hydrodeoxygenation
研究领域:
化学工程
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可再生能源
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Molecular Catalysis
·
2022
·
IF 5.089
Zhiquan Yu,Yan Li,Yunlong Yao,Yao Wang,Ying-Ya Liu,Zhichao Sun,Chuan Shi,Wei Wang,Anjie Wang
A bifunctional Ni 3 P/γ-Al 2 O 3 catalyst with both metal site and Lewis acid site was prepared by an electroless plating method, and applied in hydrogenative ring-rearrangement of furfural to cyclopentanone. The obtained catalyst was characterized by XRD, XPS, XAS, N 2 adsorption-desorption, ICP, TEM, CO chemisorption, NH 3 -TPD and Py-FTIR. The ultrafine Ni 3 P nanoparticles (∼3.8 nm) were highly dispersed in the catalyst. The exclusive Lewis acidity of Ni 3 P/γ-Al 2 O 3 was beneficial for the aqueous-phase hydrogenative ring-rearrangement. The effects of DP time, reaction parameters (temperature, H 2 pressure, solvent composition, and reaction time) on the catalytic performance were investigated. The yield of cyclopentanone was 74.6% at furfural conversion of 99.9% at 180 °C in 1 h over Ni 3 P/γ-Al 2 O 3 catalyst using pure water as the solvent. Moreover, the kinetics of hydrogenative ring-rearrangement of furfural catalyzed by Ni 3 P/γ-Al 2 O 3 was investigated.
研究领域:
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2017
·
IF 3.648
Gaoyin He,Liping Wang,Midong Shi,Qingsong Li,Yingmin Yu
The liquid–liquid equilibrium (LLE) data of the ternary systems (water + cyclopentanone + benzene or toluene) were determined at T = 303.2, 313.2, and 323.2 K, under 101 kPa. The reliability of the experimental tie-line data was sufficiently checked by the empirical Hand and Bachman equations. The distribution coefficient and separation factor were used to investigate the distribution of cyclopentanone between water and solvents. The results show that the separation factor decreases with increasing cyclopentanone amounts in organic phase and the influence of temperature is light in the study. The experimental tie-line data were correlated well with the NRTL and UNIQUAC activity coefficient models with a root mean square deviation (RMSD) as low as 0.81 and 0.50.
研究领域:
化学工程
·
物理化学
✓ 已验证
DOI
高影响因子
AICHE JOURNAL
·
2025
·
IF 4
Fuzeyu Zhong,Weixiao Sun,Xiaohu Ge,Keng Sang,Huihui Qian,Wenyao Chen,Gang Qian,Yueqiang Cao,Jianrong Zeng,Lina Li,Xuezhi Duan,Xinggui Zhou,Jing Zhang
Catalytic hydrogenative rearrangement of furanic aldehydes is crucial for producing biomass-derived cyclopentanone fine chemicals. However, designing highly selective catalysts remains challenging due to the interplay among tandem hydrogenation, ring-opening, aldol condensation, dehydration, and parallel ring-hydrogenation. Here, we employ a single self-assembly step by depositing phosphonic acids (PAs) on conventional Ni catalysts to introduce tunable interfacial Brønsted acid sites (BAS), resulting in an unprecedented 3-hydroxymethyl-cyclopentanone yield of 95.8% from hydroxymethylfurfural. Kinetic studies reveal a one-order-of-magnitude increase in ring-opening rates—the slow step in hydrogenative rearrangement—after PAs modification, accompanied by a drop in the apparent activation energy from 154.1 to 105.4 kJ mol −1 . In contrast, the activation energy for the ring-hydrogenation side reaction remains almost unchanged. Theoretical calculations suggest that BAS synergize with adjacent Ni to lower the C–O cleavage barrier by providing protons to attack the hydroxymethyl oxygen atom, which is the key step to initiate ring-opening.
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
RENEWABLE ENERGY
·
2022
·
IF 8.634
Yuewen Shao,Jie Wu,Zhiyuan Zheng,Mengjiao Fan,Kai Sun,Félix Mérimé Bkangmo Kontchouo,Lijun Zhang,Shu Zhang,Guangzhi Hu,Xun Hu
Production of cyclopentanone (CPO) from biomass-derived furfural is attractive but challenging, as deep hydrogenation or ring-opening of furan ring in furfural over Co-based catalysts hinders the formation of the targeting products. In this study, alloying Co with Fe species in Co–Fe–Al catalysts is proposed for selective conversion of furfural to CPO in water. The formation of CoFe alloy in Co–Fe–Al catalyst weakened the interaction between Co species and the alumina carrier, lowered the adsorption/activation of H 2 , suppressed the formation of especially Brønsted acidic sites, facilitated the electron transfer from Co 0 to Fe species, increased the activation energy for hydrogenation of furfural (from 17.2 kJ mol −1 over Co–Al to 33.4 kJ mol −1 over 1.5Co-1.5Fe-1.0Al), and weakened the adsorption of C C and C–O–C functionalities in furan ring of furfuryl alcohol (FA) on metallic sites. These factors together suppressed deep hydrogenation of furan ring in FA or ring-opening of FA to diols, producing CPO and CPL with total yield of 91.5%, which was attributed to the synergy between hydrogenation and Brønsted acidic sites. In addition, the presence of Fe in Co–Fe–Al catalysts also enhanced the structural stability of Co species, preventing the phase transformation and aggregation of Co species, and rendering the catalyst with superior reusability .
研究领域:
催化化学
·
生物质能
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Liting Ti,Xueru Sheng,Haiyuan Jia,Qingwei Ping,Ning Li
Self-condensation of biomass-derived cyclopentanone is an attractive reaction for sustainable aviation fuel production. Ball-milling is an effective method for this reaction. However, the effect of process parameters on product yield has not been explored and is still unclear. In this work, the process parameters in the ball-milling process are optimized by orthogonal experiment and subsequently investigated by the response surface methodology. Rotate speed is a critical index for dimer yield, and catalyst dosage is an essential index for trimer yield and selectivity. In addition, a life cycle assessment of both ball-milling and magnetic stirring methods is conducted to reveal the difference between the two methods. The ball-milling method shows relatively excellent economic and environmental potential impact, especially for the toxic consumption of marine aquatic organisms, which is a 38.2% reduction compared to the magnetic stirring method. The ball-milling method introduced in cyclopentanone self-condensation is more sustainable and economical than the magnetic stirring method.
研究领域:
化学工程
·
环境科学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2024
·
IF 3.8
Libin Liu,Yuxi Si,Wenjie Zhao,Qingqin Zhu,Zhaoran Yang,Jing He,Yangqiang Huang,Youwei Cheng
Cyclopentanone (CPO) and cyclopentanol (CPL), derived from renewable biomass resource hemicellulose, are considered sustainable chemicals that can substitute fossil-based products, which could be obtained through the hydrogenation-rearrangement reaction of furfural (FFA). However, the inevitable condensation reactions of FFA and furfuryl alcohol (FA) in aqueous solutions generate humins and result in carbon loss, limiting the industrial application of this process. Herein, a series of Cu-based catalysts were synthesized using the reverse co-precipitation method with various metal promoters and applied in the FFA hydrogenation-rearrangement reaction. The highest yield of 97.1% CPO/CPL achieved in a typical reaction condition at 200 °C, 4 MPa, in 20 wt% isopropanol-water mixed solvent over CuZnZr catalyst and the recyclability test confirmed that the catalyst had excellent stability. Experimental studies and characterizations showed that the enhanced performance could be attributed to the adequate Lewis acid sites, regulated through the synergistic interaction between Cu, Zn, and Zr compounds. The simultaneous introduction of Zn and Zr promotes the Cu reduction, and results in more dispersed Cu0 and Cu+, providing an ample and reliable active site. This study outlines a viable method for the catalyst designing and valorizing biomass into high-value-added products.
研究领域:
催化化学
·
可再生资源化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2018
·
IF 3.886
Hao Tang,Fang Chen,Guangyi Li,Xiaofeng Yang,Yancheng Hu,Aiqin Wang,Yu Cong,Xiaodong Wang,Tao Zhang,Ning Li
A new route was developed for the synthesis of renewable decalin with cyclopentanone which can be derived from lignocellulose. It was found that 1,2,3,4,5,6,7,8-octahydronaphthalene could be selectively produced by the hydrogenation/dehydration/rearrangement of [1,1′-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclopentanone) over a dual-bed catalyst system. Among the investigated catalysts, the Ru/C and Amberlyst-15 resin exhibited the highest activities for the hydrogenation of [1,1′-bi(cyclopentylidene)]-2-one to [1,1′-bi(cyclopentan)]-2-ol and the dehydration/rearrangement of [1,1′-bi(cyclopentan)]-2-ol to 1,2,3,4,5,6,7,8-octahydronaphthalene, respectively. Using Ru/C and Amberlyst-15 resin as the first bed and the second bed catalysts, 1,2,3,4,5,6,7,8-octahydronaphthalene was directly produced in high carbon yield (83.7%) under mild conditions (393 K, 1 MPa). After being hydrogenated, the 1,2,3,4,5,6,7,8-octahydronaphthalene was converted to decalin which can be used as additive to improve the thermal stability and volumetric heat value of jet fuel.
研究领域:
化学工程
·
可再生能源
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2021
·
IF 8.271
Shujing Zhang,Hong Ma,Yuxia Sun,Xin Liu,Meiyun Zhang,Yang Luo,Jin Gao,Jie Xu
Tandem catalysis for the hydrogenation rearrangement of furfural (FA) provides an attractive solution for manufacturing cyclopentanone (CPO) from renewable biomass resources. The CuNi/Al-MCM-41 catalyst was synthesized and afforded excellent catalytic performance with 99.0% conversion and 97.7% selectivity to CPO in a near-neutral solution under 2.0 MPa H 2 at 160 °C for 5 h, much higher than those on other molecular sieve supports including MCM-41, SBA-15, HY, and ZSM-5. A small amount of Al highly dispersed in MCM-41 plays an anchoring role and ensures the formation of highly dispersed CuNi bimetallic nanoparticles (NPs). The remarkably improved catalytic performance may be attributed to the bimetallic synergistic and charge transfer effects. In addition, the initial FA concentration and the aqueous system pH required precise control to minimize polymerization and achieve high selectivity of CPO. Fourier transform infrared spectroscopy and mass spectra results indicated that polymerization was sensitive to pH values. Under acidic conditions, FA and intermediate furfuryl alcohol polymerize, while the intermediate 4-hydroxy-2-cyclopentenone mainly polymerizes under alkaline conditions, blocking the cascade of multiple reactions. Therefore, near-neutral conditions are most suitable for minimizing the impact of polymerization. This study provides a useful solution for the current universal problems of polymerization side reactions and low carbon balance for biomass conversion .
研究领域:
催化化学
·
生物质转化
·
材料科学
✓ 已验证
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Xing Gao,Yingying Ding,Lilin Peng,Dan Yang,Xiaoyue Wan,Chunmei Zhou,Wen Liu,Yihu Dai,Yanhui Yang
Aqueous phase hydrogenative rearrangement of furfural (FAL) to cyclopentanone (CPO) via furfuryl alcohol (FOL) has been studied over Pd catalysts supported on H–ZSM–5 zeolites. Pd states, zeolite properties and reaction condition parameters were optimized, affording 98% selectivity and 120 h −1 specific reaction rate over 2% Pd/H–ZSM–5(25) catalyst at 160 °C and 3 MPa H 2 . For hydrogenation of FAL–to–FOL, the activity was related to the Si/Al ratio and acid property of zeolite supports. For hydrogenative rearrangement of FOL–to–CPO, pure H–ZSM–5 zeolite could catalyze single–step conversion with relatively low reaction rate, whereas the presence of Pd sites could achieve multi–step transformation with remarkably increased rate, highlighting Pd–zeolite acid sites synergy. Proton and furanylmethoxy–relevant intermediates were captured with spin trapping electron paramagnetic resonance experiments, and 4–hydroxy–2–cyclopentenone and 2–cyclopentenone were also identified as key intermediates in tandem reaction pathway to produce CPO.
研究领域:
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2017
·
IF 5.951
Wei Wang,Ning Li,Guangyi Li,Shanshan Li,Wentao Wang,Aiqin Wang,Yu Cong,Xiaodong Wang,Tao Zhang
1-(3-Cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane, a renewable high-density fuel, was first produced in a high overall carbon yield (∼70%) with cyclopenanone that can be derived from hemicellulose. The synthetic route used in this work contains three steps. In the first step, 2-cyclopentyl cyclopentanone was synthesized for the first time by a one-pot reaction of cyclopentanone and hydrogen under the catalysis of Raney metal and alkali hydroxides. Over the optimized catalyst (Raney cobalt + KOH), a high carbon yield (83.3%) of 2-cyclopentyl cyclopentanone was achieved at 353 K. In the second step, 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone was produced in a high carbon yield (95.4%) by the solvent-free self-aldol condensation of 2-cyclopentyl cyclopentanone under the vacuum conditions. In the third step, the 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone was hydrodeoxygenated over the Ni-SiO2 catalyst under solvent-free conditions. High carbon yields of 1-(3-cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane (88.5%) and polycycloalkanes (99.0%) were obtained. The Ni-SiO2 catalyst was stable under investigated conditions. No evident deactivation was noticed during the 50 h time on stream. The as-obtained polycycloalkane mixture has a density of 0.943 g mL–1 and a freezing point of 233.7 K. As a potential application, it can be blended into conventional high density fuels (e.g., JP-10) for rockets and missile propulsion.
研究领域:
化学工程
·
能源科学
✓ 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）