Catalyst-free and solvent-free oxidation of cycloalkanes (C5-C8) with molecular oxygen: Determination of autoxidation temperature and product distribution

Shen, Hai‐Min; Wang, Yan; Deng, Juan; Zhang, Long; She, Yuanbin

doi:10.1016/j.cjche.2018.02.019

Cited by 17 publications

(1 citation statement)

References 96 publications

(115 reference statements)

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“…For this reason, in this work, two-dimensional MOFs with double metal cores (Co and Ni, Co and Fe, Co and Mn) were constructed using metalloporphyrins (tetrakis(4-carboxylphenyl)porphyrin metal(II), abbreviated as TCPPM or T(4-COOH)PPM) as organic linkers, as shown in Scheme 1 [ 56 , 57 , 58 , 59 , 60 ] to suppress deep oxygenation during C–H bond oxygenation. As a continuation and extension of our prior work, the pores in two-dimensional MOFs were exploited to govern chaotic radical transport under mild conditions (120 °C) because they can confine free radicals in fixed realms [ 40 , 41 , 42 , 61 , 62 , 63 , 64 , 65 ]. In the obtained catalytic systems, cobalt was used as a catalytically active center to oxygenate C–H bonds to R–OOH with oxygen.…”

Section: Introductionmentioning

confidence: 99%

Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins

Zhou

Jin

et al. 2023

Biomimetics

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Confined catalytic realms and synergistic catalysis sites were constructed using bimetallic active centers in two-dimensional metal-organic frameworks (MOFs) to achieve highly selective oxygenation of cycloalkanes and alkyl aromatics with oxygen towards partly oxygenated products. Every necessary characterization was carried out for all the two-dimensional MOFs. The selective oxygenation of cycloalkanes and alkyl aromatics with oxygen was accomplished with exceptional catalytic performance using two-dimensional MOF Co-TCPPNi as a catalyst. Employing Co-TCPPNi as a catalyst, both the conversion and selectivity were improved for all the hydrocarbons investigated. Less disordered autoxidation at mild conditions, inhibited free-radical diffusion by confined catalytic realms, and synergistic C–H bond oxygenation catalyzed by second metal center Ni employing oxygenation intermediate R–OOH as oxidant were the factors for the satisfying result of Co-TCPPNi as a catalyst. When homogeneous metalloporphyrin T(4-COOCH3)PPCo was replaced by Co-TCPPNi, the conversion in cyclohexane oxygenation was enhanced from 4.4% to 5.6%, and the selectivity of partly oxygenated products increased from 85.4% to 92.9%. The synergistic catalytic mechanisms were studied using EPR research, and a catalysis model was obtained for the oxygenation of C–H bonds with O2. This research offered a novel and essential reference for both the efficient and selective oxygenation of C–H bonds and other key chemical reactions involving free radicals.

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Section: Introductionmentioning

confidence: 99%

Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins

Zhou

Jin

et al. 2023

Biomimetics

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Selective Solvent-Free and Additive-Free Oxidation of Primary Benzylic C–H Bonds with O2 Catalyzed by the Combination of Metalloporphyrin with N-Hydroxyphthalimide

Shen

et al. 2020

Catal Lett

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SBA-15 Supported Silver Catalyst for the Efficient Aerobic Oxidation of Toluene Under Solvent-Free Conditions

Chen

Xuan

et al. 2021

Catal Lett

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The efficient SBA-15 supported silver catalysts(Ag/SBA-15) were prepared and characterized by ICP-OES, XRD, TEM, SEM, XPS and N 2 adsorption-desorption techniques. The catalysts exhibited an excellent catalytic activity for the aerobic oxidation of toluene to benzaldehyde under solvent-free conditions. Conversion of toluene and selectivity of benzaldehyde were 50% and 89% respectively over catalyst with 9.1 wt% Ag loading (10Ag/SBA-15). A wide range of substrates were tolerated under the selected reaction conditions. The kinetic study shows that the oxidation of toluene over 10Ag/SBA-15 is pseudo-first-order reaction and the activation energy E a is 45.1 kJ/mol. A plausible mechanism involving oxygen free radicals was proposed for the aerobic oxidation reaction. Compared with the traditional method, the newly designed heterogeneous catalytic system shows better economic applicability, environmental friendliness and broader application prospects.

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Catalyst-free and solvent-free oxidation of cycloalkanes (C5-C8) with molecular oxygen: Determination of autoxidation temperature and product distribution

Cited by 17 publications

References 96 publications

Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins

Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins

Selective Solvent-Free and Additive-Free Oxidation of Primary Benzylic C–H Bonds with O2 Catalyzed by the Combination of Metalloporphyrin with N-Hydroxyphthalimide

SBA-15 Supported Silver Catalyst for the Efficient Aerobic Oxidation of Toluene Under Solvent-Free Conditions

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