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
FUEL
·
2022
·
IF 8.035
Zhi Hu,Aidi Xie,Chun Chen,Zidan Zou,Yue Shen,Zhen Fu,Yunxia Zhang,Haimin Zhang,Huijun Zhao,Guozhong Wang
Aqueous-phase hydrogenation-rearrangement tandem (AP-HRT) reaction is a green and sustainable route to produce cyclopentanone from bio-based furan compounds. Herein, the ionic liquid was applied as the precursor to synthesize Ni@NP-C catalyst, which contains high dispersed nickel nanoparticles (Ni NPs) encapsulated in the N, P co-doped carbon layer , for the selectivity transformation of furfural towards cyclopentanone. The synthesized Ni@NP-C catalyst can afford 100% FAL conversion and 86.7% CPO yield at 130 °C and 1.5 MPa H 2 within 2 h AP-HRT reaction. The introduction of the electronegative heteroatom on the surface can not only improve the adsorption of reactant but also provide weak Lewis Acid sites for being beneficial to the high selectivity of cyclopentanone. The catalyst displays superior activity, selectivity, and stability in the tandem catalytic system in view of the tunable chemical states of the doped heteroatoms by handily adjusting the pyrolysis 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
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
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Honghui Gong,Fei Wang,Qi Li,Longxing Wei,Juan Zhang,Yuan Ma,Yifan Rui,Xian-Lei Shi
Selective synthesis of cyclopentanol (CPL) from biomass-derived furfural (FAL) is highly attractive, but it still faces serious challenges. In this work, an alloyed Cu–Co catalyst derived from Cu–Co–Al layered double hydroxide (LDH) was grafted onto sulfur-doped coffee biochar for the first time (Cu–Co–Al/SCB). Cu–Co–Al/SCB achieved a maximum CPL yield of 97.5% and a high turnover frequency (TOF) of 15.6 h–1 in the selective hydrogenative rearrangement of FAL at 140 °C. The characterization results demonstrated that grafting Cu–Co–Al onto SCB results in the formation of Cu–Co alloys and a strong interaction between them. Further characterization and activity tests demonstrated that the formation of a highly dispersed Cu–Co alloy and in situ generated Brønsted acid sites collaboratively catalyzes the selective hydrogenative rearrangement of FAL to CPL over Cu–Co–Al/SCB, and the strong interaction between the Cu–Co alloy and sulfur-doped coffee biochar endowed Cu–Co–Al/SCB with remarkable stability. As a result, Cu–Co–Al/SCB is a promising catalyst for the selective hydrogenative rearrangement of FAL.
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 Catalysis
·
2025
·
IF 13.1
Yuanjing Zhang,Guanyi Zhang,Quandong Hou,Shiquan Zhao,Si Wang,Enze Xu,Lei Wang,Xin Zhang,Feng Li,Yusen Yang,Min Wei
Aqueous-phase tandem reactions, as a fundamental aspect of green chemistry, hold a crucial position in the contemporary synthesis of fine chemicals, wherein the advancement of high-performance heterogeneous catalysts remains a formidable challenge. Herein, we report a Pt1Con single-atom alloy (SAA) catalyst in which Pt single atoms are immobilized onto the surface of Co nanoparticles through Pt–Co coordination. The Pt1Con SAA catalyst exhibits a high chemoselectivity for the aqueous-phase hydrogenation–rearrangement reaction of furfural (FAL) to cyclopentanol (CPL) (yield: >93%, considering the carbon loss), with a TOF value of 2257 h–1 (based on Pt). A joint investigation based on reaction dynamics, isotope-label tracing experiments, EPR, and in situ FT-IR verifies a five-step consecutive tandem reaction pathway for the formation of CPL. Notably, during the reaction, the rapid exchange of hydrogen atoms would occur between activated hydrogen species and the water solvent. Furthermore, the water molecule does not serve as a H-donor but is involved in the rearrangement reaction in the side chain of the furan ring. Kinetic studies combined with DFT calculations substantiate that the Pt–Co interface sites effectively lower the energy barrier of the cyclopentanone (CPO) hydrogenation step via facilitating activation adsorption of the carbonyl group, accounting for the largely enhanced catalytic behavior. This study sheds light on the advancement of a highly efficient and stable heterogeneous catalyst for a biomass upgrading reaction in the aqueous phase.
研究领域:
绿色化学
·
催化剂开发
·
生物质转化
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Zhi Hu,Miaomiao Han,Chun Chen,Zidan Zou,Yue Shen,Zhen Fu,Xiaoguang Zhu,Yunxia Zhang,Haimin Zhang,Huijun Zhao,Guozhong Wang
As green chemistry, aqueous-phase reactions play a vital role in modern fine chemical synthesis. Herein, an encapsulated nickel in a hollow carbon sphere (Ni@HCS) catalyst was constructed to effectively catalyze an aqueous-phase hydrogenation-rearrangement tandem (AP-HRT) reaction, in which water was employed as the solvent and reactant simultaneously. The activity is relevant to the HCS and Ni loading. The optimal Ni@HCS catalyst can release 100% furfural conversion and 99.1% cyclopentanone selectivity at 150 °C and can maintain its activity after 10 cycles of experiments. The superior catalytic performance comes from the fact that each independent Ni@HCS can be treated as an individual nanoreactor with a void-confinement effect, which not only reduces the side reactions due to the size-selective effect but also prevents active metal from leaching under harsh conditions. The reaction mechanism of FAL AP-HRT was further investigated via kinetic experiments combined with DFT calculations.
研究领域:
化学工程
·
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2018
·
IF 6.14
Wanbing Gong,Chun Chen,Haimin Zhang,Guozhong Wang,Huijun Zhao
Herein, we report that highly dispersed copper–cobalt mixed metal/metal oxide nanoparticles embedded into three-dimensional porous carbon were highly catalytic active nanocomposites for transforming bioderived furfural (FAL) to cyclopentanone (CPO) via aqueous-phase hydrogenation/rearrangement. This simple and efficient catalyst was prepared by controlled pyrolysis procedure using glucose as the carbon source at 500 °C under N2 atmosphere. Characterization of the as-prepared CuCo0.8@C-500 catalyst by XRD, STEM, SEM, TEM, and XPS suggested that there was a synergism between copper and cobalt. Under an extremely low H2 pressure (0.5 MPa), 90.2% yield of CPO could be attained at 150 °C. In addition, the sample could be recycled for several times without decrease in catalytic activity. Two critical reaction intermediates of furfuryl alcohol (FOL) and 2-cyclopentenone (2-CPE) were detected in the tandem catalytic process. These results demonstrated that this synthetic strategy represented a simple and effective way for utilization of inexpensive biomass resources to obtain some valuable chemicals.
研究领域:
催化化学
·
能源化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2021
·
IF 3.764
Hongyu Niu,Yuan Cheng,Chuang Li,Shaojie Li,Jingjie Luo,Changhai Liang
Rational design of promising Cu catalyst requires better understanding of the Cu–support perimeter for reactions such as hydrogenation rearrangement of furfural─a pivotal and alternative transformation to produce cyclopentanol. Herein, a series of Cu catalysts with constructed Cu-M-Ox interfaces (M = Zn or Al) have been synthesized. In freshly reduced Cu/ZnO-Alx samples, aluminum species was enriched surrounding Cu. The Cu-Al-Ox contacting interface was formed, and the CuAl2O4 spinal structure was detected as a combining consequence only if Zn and Al species coexisted. The specific metal–support synergistic interaction and Cu-Al-Ox contacting interface simultaneously aroused the enhanced redox property and large number of surface acid sites, facilitating the adsorption/activation of hydrogen and reactants. During the reaction, Al2O3 retreating from the Cu-Al-Ox interface caused the replacement of Cu-Al-Ox by new Cu-Zn-Ox interface, which was directly correlated with the irreversibly changed chemical structure and decreased cyclopentanol yield, although the furfural conversion was well sustained. In this work, we confirmed that supported copper catalysts were competent for the activation and conversion of furfural, with the turnover frequency reaching 28.1 h–1 by the Cu/ZnO-Al3 sample at temperatures as low as 90 °C. The further transformation of cyclopentanone to cyclopentanol was largely depending on the maintenance of a steady Cu-Al-Ox contacting interface.
研究领域:
催化
·
化学工程
·
材料科学
·
有机化学
✓ 已验证
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
·
材料科学
·
化学工程
·
绿色化学
✓ 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）