JOURNAL OF CATALYSIS
·
2022
·
IF 8.047
Yujun Zhang,Hao Tian,Zhaowei Cui,Zhen Yin,Hongsen Hui,Hong Wang,Lei Zhang,Hongchang Pei,Zhenhuan Li,Bhekie B. Mamba,Jianxin Li
To further improve the capability of flow electrochemistry, the multistage plug-flow electrochemical membrane reactor (PF-ECMR) with membrane electrode was developed for enhancing the oxidation of cyclohexane (CHA) to produce KA oil (mixture of cyclohexanol and cyclohexanone). The catalytic results demonstrated that the CHA conversion and the selectivity to KA oil were up to 95.6% and > 99%, which was the highest in comparison with most of the state-of-the-art catalytic processes reported in the previous works. The mechanism was explored by density functional theory (DFT) calculations, indicating the auxo-action effect of cyclohexanone was beneficial for the formation of cyclohexyl hydroperoxide so as to enhance the CHA conversion. The excellent performance of PF-ECMR was also attributed to the staggered electric field and the accumulative effect of the multi-electrodes. This study provided a successful case of a combination of theoretical prediction and experimental verification together for organic synthesis.
研究领域:
有机合成
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电化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2018
·Vol. 10
·期 24
·5689-5697
·
IF 4.674
Wei Hong,Zhi-Qiang Wang,Shihui Zou,Yuheng Zhou,Linfang Lu,Qiuyue Zhou,Xue-Qing Gong,Jie Fan
Graphical Pt does it again ! The morphology of Pt nanoparticles was successfully regulated by calcinating Pt/SiO 2 catalysts in different atmospheres and achieved a 78.1 % cyclohexanone yield at 170 °C in oxidative dehydrogenation of KA-oil. It is industrially attractive to produce cyclohexanone directly from gas-phase oxidative dehydrogenation (ODH) of KA-oil (a mixture of cyclohexanone and cyclohexanol) since extra alcohol-ketone separation process can be potentially omitted. Herein, by simply tuning the calcination atmosphere of Pt/SiO 2 , we successfully regulated the morphology of Pt nanoparticles and optimized their catalytic performance in ODH of KA-oil. Pt/SiO 2 calcined in O 2 atmosphere showed a cube-like morphology and achieved a 78.1 % cyclohexanone yield at 170 °C, which surpassed its counterpart calcined in H 2 and most of the reported catalysts. Further experimental and theoretical calculation results indicated that cubic Pt nanoparticles possessed stronger adsorption ability to cyclohexanol and therefore performed better in ODH of KA-oil.
研究领域:
催化
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化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2015
·
IF 2.587
Yujia Xie,Fengyong Zhang,Pingle Liu,Fang Hao,Hean Luo
Direct functionalization of saturated C–H bonds by metalloporphyrin catalysts is among the topical and challenging areas within the chemical industry and synthetic chemistry. In this work, supported CoD(p-Cl)PPCl metalloporphyrin catalysts were prepared and characterized. It has been found that the CoD(p-Cl)PPCl/ZnO catalyst shows better catalytic activity than the supported catalyst (ZrO2, MCM-41, kaolin, Zr(OH)2, and boehmite (BM)) in cyclohexane oxidation with dioxygen. The effects of the reaction pressure, reaction temperature, and reaction time on the catalytic activity were considered by the supported CoD(p-Cl)PPCl/ZnO catalyst. The CoD(p-Cl)PPCl/ZnO catalyst can be facilely recovered and was recycled up to seven times without a significant decrease in catalytic performance. The average cyclohexane conversion and selectivity to KA oil are 10.98% and 84.34%, respectively, and the turnover number is 2.10 × 107.
研究领域:
催化化学
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有机合成
·
工业化学
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材料化学
·
绿色化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2025
·
IF 4.8
Kuan Wang,Tong-Le Dang,Sheng-Li Lv,Xin-Peng Li,Kai-Xiong Dai,Zhen-Hong He,Weitao Wang,Huan Wang,Zhao-Tie Liu
The photo-thermo synergy catalytic cyclohexane oxidation has been identified as an efficient and environmentally friendly approach for the preparation of cyclohexanone and cyclohexanol (KA oil). However, this strategy encountered several challenges that impeded its implementation for the one-step production of adipic acid (AA), highlighting the need for further advancements. Herein, a robust strategy for tailoring multi-channel charge transfer pathways in LaVO 4 /WO 3 @H x V 2 O 5 nanospherical composites was developed by constructing double Z-scheme heterojunctions. The LaVO 4 /WO 3 @H x V 2 O 5 exhibited exceptional photothermal catalytic performance for the cyclohexane oxidation, achieving the cyclohexane conversion of 11.01 % with the total selectivity of 96.38 % (solid product AA of 58.51 % and liquid product KA oil of 37.87 %). The exceptional performance of LaVO 4 /WO 3 @H x V 2 O 5 can be ascribed to the double Z-scheme heterojunctions with multi-channel charge transfer and high redox potentials, which facilitates the efficient separation and transfer of photo-generated electron-hole pairs. This deliberate design of double Z-scheme heterojunctions provides valuable insights into the meticulous construction of efficient pathways with multi-channel charge transfer for the field of photothermal catalysis applications.
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2020
·
IF 3.687
Yepeng Xiao,Jincheng Liu,Hui Wang,Chong Yang,Huicheng Cheng,Yiqiang Deng,Lihua Cheng,Yanxiong Fang
Designing high-performance catalyst for the oxidation of cyclohexane (CyH) into value-added products like cyclohexanol and cyclohexanone (the mixture called KA oil) is of paramount significance in chemical industry. Herein, the catalytic activity of graphene oxide coupled with Ag and Fe 3 O 4 nanopaticles composites (GO-Ag&Fe 3 O 4 NPs) was investigated to understand the synergistic effect between Ag and Fe 3 O 4 NPs in photothermal oxidation of CyH. The comparative experiments between thermal and photothermal catalysis indicated that: (a) Conversion efficiency was facilitated by temperature rise, but less than 50 % of selectivity to KA oil was obtained at high temperature (140 °C); (b) Higher selectivity and milder condition were achieved by photothermal catalysis comparing to that of the thermal catalysis; (c) Ag NPs played more important role in photocatalysis, while thermocatalysis was intensified by Fe 3 O 4 NPs. Using 1.5 MPa of dry air as oxidant, 6.6 % of CyH conversion with over 98 % of selectivity was gained by GO-Ag&Fe 3 O 4 NPs. Additionally, no obvious decline in catalytic efficiency was observed after 5 cycles. The concept of photothermal cooperation for CyH oxidation over GO-Ag&Fe 3 O 4 NPs may provide a new approach for the partial oxidation of saturated C H and the design of high-performance catalysts.
研究领域:
化学工程
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材料科学
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2019
·
IF 2.938
Jijin Mai,Yanxiong Fang,Jincheng Liu,Jinhong Zhang,Xiaolan Cai,Yuying Zheng
Partial oxidation of cyclohexane (CHA) to KA oil (cyclohexanone (-one) and cyclohexanol (-ol)) with dry air is one of the most important industrial process. Despite great efforts have made in developing new catalysts, industrial processes are still limited by low conversion and selectivity with harsh condition. Here we report a significantly improved cyclohexane conversion and KA oil selectivity under solar light irradiation by anew photothermal synergistic catalyst, which was prepared by loading Au nanoparticles (Au NPs) onto WO 3 nanosheets (WO 3 NSs) with simple ultrasonic method. A high conversion of 9.0% and a high selectivity of 99.0% are acquired by WO 3 nanosheets-Au nanoparticles (WO 3 -Au) composite under dry air, which are much higher than the simple sum of photocatalysis and thermal catalysis. The significantly improved catalytic properties of cyclohexane oxidation by the WO 3 -Au composite are mainly attributed to the improved light absorption, the effective charge separation and the synergistic effect of photocatalysis and thermal catalysis. The photothermal synergy to improve catalytic activity may be widely used in green industrial catalytic processes.
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
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2015
·
IF 3.615
Ze Feng,Yujia Xie,Fang Hao,Pingle Liu,He'an Luo
A series of manganese metalloporphyrins were prepared and tested in cyclohexane oxidation. It has been found that the manganese 5,10,15,20-tetrakis(4-nitrophonyl) porphyrin (Mn-TNPP) presents better catalytic performance. The Mn-TNPP was then immobilized on different supports, and characterized by UV–vis, FT-IR, XRD, TG/DTG and ICP. Among these supported Mn-TNPP catalysts, Mn-TNPP/ZnO exhibits the best selectivity to KA oil and higher turnover number in cyclohexane oxidation. The influence of the reaction conditions and the recycle of the catalysts are discussed. Mn-TNPP/ZnO catalyst presents the average cyclohexane conversion of 7.17%, KA oil selectivity of 91.18%, and the average catalytic turnover number of 6.53 × 10 4 after six times of recycle under 150 °C and 1.0 MPa.
研究领域:
催化化学
·
有机合成
·
工业化学
·
材料化学
·
绿色化学
✓ 已验证
DOI
高影响因子
CARBON
·
2020
·
IF 8.821
Cai Xu,Leilei Jin,Xiaozhong Wang,Yingqi Chen,Liyan Dai
In heterogeneous catalysis , developing robust catalysts and preventing the metal leaching during the reactions still remain challenging. Herein, a porous honeycomb-like nanostructure with bimetallic Ce–Cr oxide supported on N-doped carbon was prepared via a facile in-situ pyrolysis method. The prepared catalyst was highly active, selective, and stable in the transformation of cyclohexane to KA oil with H 2 O 2 as the oxidant. The N-doped carbon served as an excellent support for the metal nanoparticles and greatly promoted their dispersion, and displayed a comparable or superior catalytic activity compared to the other traditional supports. It was found that the pyridinic N and pyrrolic N species of N-doped carbon were the main active sites for the metal immobilization , and the strong electronic interaction between N-doped carbon and Ce–Cr oxide was formed. The results revealed that the increased low-valence metal species might be responsible for the improved catalytic activity, and EPR analysis indicated that the hydroxyl radicals played a crucial role during the oxidation process . Besides, the catalyst can be easily separated and still remained stable after recycling seven times, making it a promising candidate for the catalytic oxidation of cyclohexane to KA oil under mild conditions.
研究领域:
催化化学
·
材料科学
·
环境化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2023
·
IF 7.3
Jin Yuan,Zhiwei He,Hongbo Zhang
Selective C–H bond oxidation of cyclohexane into KA oil (ketone-alcohol) is of vital importance in both fundamental research and industrial applications while limited by complex reaction network and suffering from low efficiency. In this study, Ce(OH)SO 4 · x H 2 O was chosen as a probe to systematically investigate the C–H bond activation and C–C bond rupture as a function of various reaction parameters, including the reactant/product concentrations, catalyst applied, reaction temperatures, acidic concentrations etc, and found that bi-molecule of C 6 H 12 was probably involved in both C–H bond rupture and C–C bond cleavage and both were controlled by one deprotonation elementary step with ·O 2 – and h + as the key active components, which were supported by parity fittings and primary KIEs determined. In addition, the C–C bond rupture was found to be mainly following C 6 H 10 O to ε-caprolactone and further to linear acids reaction path. Hopefully, this study could help people find/optimize reaction systems in selective hydrocarbon upgradings.
研究领域:
化学工程
·
有机化学
·
催化
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-16
·
IF 14.7
Liu Xiang,Zhu Yu-Quan,Li Jing,Wang Ye,Shi Qiujin,Li An-Zhen,Ji Kaiyue,Wang Xi,Zhao Xikang,Zheng Jinyu,Duan Haohong
Electrosynthesis of adipic acid (a precursor for nylon-66) from KA oil (a mixture of cyclohexanone and cyclohexanol) represents a sustainable strategy to replace conventional method that requires harsh conditions. However, its industrial possibility is greatly restricted by the low current density and competitive oxygen evolution reaction. Herein, we modify nickel layered double hydroxide with vanadium to promote current density and maintain high faradaic efficiency (>80%) within a wide potential window (1.5 ~ 1.9 V vs. reversible hydrogen electrode). Experimental and theoretical studies reveal two key roles of V modification, including accelerating catalyst reconstruction and strengthening cyclohexanone adsorption. As a proof-of-the-concept, we construct a membrane electrode assembly, producing adipic acid with high faradaic efficiency (82%) and productivity (1536 μmol cm −2 h −1 ) at industrially relevant current density (300 mA cm −2 ), while achieving >50 hours stability. This work demonstrates an efficient catalyst for adipic acid electrosynthesis with high productivity that shows industrial potential.
研究领域:
化学工程
·
电化学
·
材料科学
·
可持续化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）