ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Shuang Wei,Kexin Li,Sheng Zhong,Ruirui Zhang,Guosheng Wang,Ruixia Liu
Selective conversion of inert C–H bonds in alkanes into high-value-added functional groups (alcohols, ketones, carboxylic acids, etc.) plays a vital role in establishing a green and sustainable chemical industry. Catalytic selective oxidation of cyclohexane to KA oil (cyclohexanol and cyclohexanone) is a typical representative of alkane functionalization. In this work, hollow cage-like Co3O4 (Co3O4-C) and particle Co3O4 (Co3O4-P) were synthesized by calcining two types of Prussian blue analogues (PBAs), which were used to catalyze the selective oxidation of cyclohexane. The Co3O4-C predominantly exposed (311) crystal plane is easier to adsorb cyclohexane than Co3O4-P, which is beneficial to shorten the induction period, accelerate the reaction rate, and improve the conversion. Consequently, Co3O4-C displayed a 10% conversion of cyclohexane within 1 h, and the KA oil selectivity reached 90%. The Co3O4-P exposed (220) crystal plane has a higher molar percentage of oxygen vacancies and more active oxygen species, as well as a strong cyclohexanone adsorption capacity, which is conducive to the deep oxidation of cyclohexanone to adipic acid and other diacid products. The mechanism analysis of cyclohexane oxidation catalyzed by PBA-based Co3O4 shows that it exemplifies the feasibility to tailor the surface of catalysts by modulating the PBAs, which ultimately influences their reaction performance for accelerating the reaction and maintaining high cyclohexane conversion and KA oil selectivity.
研究领域:
催化化学
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绿色化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 123
·101593-101598
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IF 3.84
Ze Feng,Yujia Xie,Fang Hao,Pingle Liu,He'an Luo
A series of meso-substituted metal tetraphenylporphyrins were synthesized and characterized by UV-vis, FT-IR and elemental analysis. The experimental results show that cobalt tetra(4-nitrophonyl)porphyrin (Co–TNPP) gives better catalytic performance in cyclohexane oxidation. The KA oil (cyclohexanol and cyclohexanone) selectivity is 79.54% at the cyclohexane conversion of 10.43%, and the turnover number reaches to 0.93 × 104. Cyclohexane oxidation catalyzed by meso-substituted metalloporphyrins was studied by molecular simulation and experiment. The results of molecular simulation performed by Materials Studio show that the substituted electron-withdrawing groups in the same central metal porphyrins reduce the HOMO and LUMO energies. The metalloporphyrins with lower energy gap have stronger ability to activate the oxygen, the metalloporphyrin intermediates with lower energy gap have stronger ability to activate the cyclohexane.
研究领域:
化学
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材料科学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
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IF 13.3
Shengxin Chen,Bin He,Yingwei Li,Ruirui Wang,Ping Chen,Xingang Li,Ruixia Liu
The selective oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oils) without additional initiator remains a challenge because of its inherent low activity and limited selectivity. To promote the selectivity of KA oils at high reaction conversion, a series of novel cobalt-based poly(ionic liquid)s (Co-PILs) catalysts were designed. The electronic structure and the microenvironment of Co sites in Co-PILs were regulated by tuning the contents of Co. By the regulation of the microenvironment, the cyclohexane conversion and KA oils selectivity are improved by 19% and 47% (Co-PIL-1–2.5) compared with traditional metal salt catalysts, respectively. Mechanistic studies demonstrated that the electronic structure and coordination environment of transition metals can be effectively tailored. Notably, Co-PILs with low metal loading exhibit a remarkable ability to improve the reaction by transitioning from a low-spin to a high-spin state. Moreover, by adjusting the ratio of cobalt ions to ionic liquid monomers derived from PILs, the acidity, oxygen activation, and desorption of reactive oxygen species were also regulated accordingly. These properties play a pivotal role in the oxidation process, ultimately allowing for precise control over the activity and selectivity.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF POROUS MATERIALS
·
2021
·Vol. 29
·期 2
·371-380
·
IF 2.496
Zhang Wei,Xue Haonan,Wang Min,Wu Zeying,Ding Linlin,Deng Yaoyao,Wang Wei,Wei Xuejiao,Zhang Zhenwei,Xiang Mei
Cu-containing Beta zeolites (Cu-Beta) are straightforwardly synthesized in a one-pot method without template, where the crucial step is the co-hydrolysis/condensation of silica source and copper salt at the moderate acidic condition. In the solvent-free oxidation of cyclohexane with molecular oxygen (O 2 ), the best cyclohexane conversion result (9.7%) with a KA-oil (cyclohexanone and cyclohexanol) selectivity of 94.1% is obtained over Cu-Beta(100). Structure—activity relationship analysis indicates that the isolated tetrahedral framework Cu 2+ species and chemisorption oxygen species in high concentration on the catalyst surface enhannce the catalic performance. In addition, the catalyst can be easily separated and still remain stable after recycling five times, providing new insights into catalysts design for the catalytic oxidation of cyclohexane to KA-oil.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2026
·
IF 4.8
Jue Wang,Huitao Liu,Siyu Zeng,Jinyi Yang,Zaihui Fu,Youji Li,Senpei Tang,Anqun Su
Merely 1.2 wt% KCCN elevates cyclohexane conversion to 64.47%, 2.5-fold that of pure QA-DT. • QA-DT performs HAT cleavage, while KCCN activate O 2 , enabling an efficient catalytic cycle. • The system achieves high ketone/alcohol selectivity (K/A ratio ∼5) and total selectivity > 95%. • The nanosheet-cluster interface boosts visible light absorption and stabilizes the catalyst. The selective oxidation of cyclohexane to KA oil holds significant importance in both fundamental research and industrial applications, with the formation of cyclohexyl hydroperoxide serving as a crucial rate-determining step. In this study, a hybrid material designated as QA-DT@KCCN was constructed through the in-situ composition of potassium/cyano-comodified carbon nitride nanosheets (KCCN) and quaternary ammonium-decatungstate (QA-DT), aiming to enhance the mass transfer efficiency of O 2 and improve the utilization efficiency of hydrogen atom transfer products. The results demonstrate that a minimal KCCN doping of 1.2 wt% significantly enhanced the photocatalytic oxidation performance. Under light irradiation in acetonitrile for 2 h, a cyclohexane conversion rate of 64.47% was achieved (compared to 25.18% with pure QA-DT), with a ketone/alcohol ratio of 5.02 and overall selectivity exceeding 95%. Radical quenching and trapping experiments confirmed that superoxide anion radicals (•O 2 - ) and holes (h + ) are the key active species in this photocatalytic system. The unique nanosheet-cluster interfacial coupling effect in the hybrid material not only facilitates directional electron transfer but also enhances visible light absorption and stabilizes the ionic structure of decatungstate. This study provides a novel strategy for designing high-efficiency decatungstate catalysts, offering valuable insights to advance the technology of selective inert hydrocarbon oxidation. Download: Download high-res image (208KB) Download: Download full-size image
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DOI
高影响因子
Green Chemical Engineering
·
2023
·
IF 0
Ying Jin,Shengxin Chen,Ruirui Wang,Yumei Liu,Xinxin Li,Yingwei Li,Ruirui Zhang,Ruixia Liu
Poly(ionic liquids) (PILs) combined with the macromolecular structure and unique properties of ionic liquids show unlimited potential in catalysis. In this work, a series of metal-based PIL with different ionic ratios were prepared for the selective oxidation of cyclohexane. Characterization analysis reveals that different degrees of ionization could adjust the Co–N sites of the catalysts efficiently, leading to significant changes in their electronic structure, which strongly relate to catalytic performance in oxidation. 20.07% cyclohexane conversion and 13.06% cyclohexanone and cyclohexanol (KA oil) yield can be achieved by metal-based PILs that are better than other commercial catalysts. Compared with CoCl 2 , metal-based PILs perform well, with superior conversion and KA oil yield. More interestingly, the catalyst created in this study features a malleable Co–N site, which may potentially have an impact on how oxygen species adsorb and desorb from the catalyst. Therefore, the catalyst studied in this work is used as molecular oxygen for the selective oxidation of cyclohexane to produce KA oil, and its application prospect is promising.
研究领域:
催化化学
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材料科学
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DOI
JOURNAL OF CATALYSIS
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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
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催化反应
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产品关联
DOI
高影响因子
Molecular Catalysis
·
2026
·
IF 4.3
Bingjie Li,Jincheng Liu,Xiaoyan Xiang,Wenxin Yang,Yang Liang,Lei Li,Yanxiong Fang
The selective oxidation of inert C-H bonds in cycloalkanes to high-value KA oil (the mixture of cyclohexanone and cyclohexanol) is a major industrial challenge, primarily due to the inherent trade-off between conversion and selectivity. To address this, we developed a novel photoelectrocatalyst for the oxidation of cyclohexane under ambient conditions. The catalyst was constructed by first synthesizing blue, oxygen-vacancy-rich MoO 3-x nanowires via a hydrothermal method, followed by the in-situ deposition of AuAg alloy nanoparticles with tunable compositions. Comprehensive characterization confirmed the uniform distribution of the alloy nanoparticles and the formation of a Schottky heterojunction with the MoO 3-x support. This design promotes efficient separation of photogenerated charge carriers and enhances visible-light absorption through the localized surface plasmon resonance (LSPR) effect. During photoelectrocatalytic oxidation, the optimized catalyst (MoO 3-x -Au 20 Ag 20 ) exhibited exceptional performance, achieving a cyclohexane conversion of 30.24% with 93.7% selectivity to KA oil under 2.6 V applied bias and 2 h of irradiation. This represents a 1.9-fold increase in conversion compared to pristine MoO 3-x nanowires. This work provides an efficient and selective pathway for alkane oxidation and advances the strategy for designing synergistic photoelectrocatalytic systems.
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产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Zhaoqiang Jian,Haipeng Zhao,Zhengyan Qu,Jiuxuan Zhang,Zhenchen Tang,Hong Jiang,Rizhi Chen
Electrocatalytic hydrogenation (ECH) of phenol to cyclohexanone and cyclohexanol (collectively termed KA oil) offers a green alternative to traditional thermal catalytic hydrogenation (TCH). ECH enables efficient synthesis under mild conditions with enhanced safety and sustainability. This study investigates the influence of different carbon-based supports (carbon paper, carbon cloth, and carbon felt) and noble metal catalysts (Ru, Rh, Pd, Ir, and Pt) on the ECH performance for the conversion of phenol to KA oil. Carbon paper-supported Rh/C (Rh/C/CP) exhibited superior activity, achieving a phenol conversion of 97.4%, a KA oil selectivity of 100% at −500 mV in a 0.5 M H2SO4 solution. This high performance is attributed to the support’s high graphitization, low defect density, and uniform catalyst dispersion, which collectively enhance charge transfer and active site accessibility. In situ Raman spectroscopy elucidated the adsorption and transformation mechanisms of phenol and its intermediates and revealed Rh/C/CP’s optimized balance of hydrogen and phenol adsorption. Systematic optimization of catalyst loading and applied potential further improved the ECH efficiency. This work provides theoretical and experimental insights into designing selective and efficient ECH catalysts and highlights their potential for sustainable conversion of biomass-derived compounds.
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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
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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
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产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Yu-Dong Shan,Yu-Le Wang,Qing He,Yi-Fang Lu,Song-Hai Wu,Yong Liu,Xu Han
Selective oxidation of cyclohexane (CHA) to KA-oil (cyclohexanol/cyclohexanone) is an important reaction in the chemical industry, which is constrained by high energy consumption and low selectivity. In this study, Mo-doped mesoporous TiO2 (Mo-MT) has been successfully synthesized via calcinating MIL-125(Ti) doped with molybdenum acetylacetonate. A series of characterizations and density functional theory (DFT) calculations reveal that the doped Mo not only decreases the band gap from 3.02 eV (MT) to 2.71 eV (Mo-MT-2) and enhances efficiencies in charge separation and photogenerated carrier transfer but also directly reduces O2 to Mo-η2-O2 peroxo on Mo-MT-2, achieving a 3.2 times higher yield of KA-oil (62.7 μmol) than that by P25 and a high selectivity toward KA-oil of 99.9% under visible-light irradiation. Meanwhile, electron shuttling of benzoquinone facilitates electron transfer from CHA to O2, thus significantly enhancing the KA-oil yield from 62.7 to 431.0 μmol. Diffuse reflectance infrared Fourier transform spectroscopy and electron paramagnetic resonance analyses confirm the electron-shuttling roles of benzoquinone in H-abstraction and H-transfer during selective photooxidation of CHA by Mo-MT-2. DFT calculations further reveal that the benzoquinone-hydroquinone/semiquinone-benzoquinone cycle shuttles electrons from CHA to Mo-η2-O2 peroxo on the surface of Mo-MT-2, thus facilitating H-abstraction from CHA to form C6H11·, coupled with the formation of H2O2. The produced C6H11· then eventually reacts with O2 to form KA-oil. This study enriches our understanding of the importance of peroxo species and electron shuttles in selective photooxidation of C(sp3)–H.
研究领域:
催化
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材料科学
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物理化学
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化学反应工程
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环境化学
✓ 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）