Aerobic Baeyer–Villiger oxidation of cyclic ketones over periodic mesoporous silica Cu/Fe/Ni/Co-HMS-X

Rahman, Sumbul; Enjamuri, Nagasuresh; Gomes, Ruth; Bhaumik, Asim; Sen, Debasis; Pandey, Jai Krishna; Mazumdar, Shyamalava; Chowdhury, Biswajit

doi:10.1016/j.apcata.2015.03.014

Cited by 22 publications

(7 citation statements)

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“…7,8 So far, many metal-based (such as metal porphyrin, supported titanium silicate molecular sieve, Co, Fe, etc. ), 9,10 enzyme-based (such as monooxygenase) 11−15 catalysts have been proposed for this aerobic oxidation. Cao et al used ironbased metalloporphyrin (FPOP-3) to catalyze the Baeyer− Villiger oxidation and obtained a 98% yield of ε-CL.…”

Section: Introductionmentioning

confidence: 99%

Solvent-Free Production of ε-Caprolactone from Oxidation of Cyclohexanone Catalyzed by Nitrogen-Doped Carbon Nanotubes

Cai

Liu

Huang

et al. 2022

Ind. Eng. Chem. Res.

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As an important raw material for the synthesis of polycaprolactone, a significant alternative for the nondegradable plastic, ε-caprolactone (ε-CL) monomer is typically produced through the Baeyer–Villiger oxidation of cyclohexanone (CyO). In this work, a solvent-free, highly efficient, and nonmetallic catalytic system was developed to produce the ε-CL monomer with dioxygen as the oxidant and benzaldehyde (BEA) as the co-oxidant. Nitrogen-doped carbon nanotubes (NCNTs) as the catalyst boost the catalytic activity (10.09% conversion, 10.06% yield of ε-CL), much higher than other carbon catalysts. The normalized specific activity of NCNTs reached 2964.80 mmol/g/h and 20.02 mmol/m2/h, which are 2–4 orders of magnitude higher than the state-of-the-art catalysts. The structure-dependent activity result shows that the ratio between pyridine nitrogen (NP) and graphite nitrogen (NG) on the surface of NCNTs positively affects the catalytic performance. Oxygen functionalities on the NCNT surface inhibit the activity by suppressing the auto-oxidation of BEA, which unexpectedly increases aldehyde efficiency. Finally, this process could be scaled up to a molar-scale reaction with a similar activity, which lays down the foundation of the industrial application of the solvent-free Baeyer–Villiger oxidation catalyzed by nanocarbons.

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Section: Introductionmentioning

confidence: 99%

Solvent-Free Production of ε-Caprolactone from Oxidation of Cyclohexanone Catalyzed by Nitrogen-Doped Carbon Nanotubes

Cai

Liu

Huang

et al. 2022

Ind. Eng. Chem. Res.

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“…There are seldom other metal oxides except for stannide . While in the aldehydes/O 2 system, it usually employs different metallic catalysts, including metal complexes, hydrotalcite, metallic oxides, and supported metal and metal oxides, − because metal active sites could speed up the initiation of the radical chain reaction. However, these catalysts need a large amount of consumption of metal and are harmful to the environment due to metal pollution.…”

Section: Introductionmentioning

confidence: 99%

Metal-Free Mesoporous SiO₂ Nanorods as a Highly Efficient Catalyst for the Baeyer–Villiger Oxidation under Mild Conditions

Zhang

Yang

et al. 2018

ACS Sustainable Chem. Eng.

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The development of efficient and environmentally friendly catalysts for oxidative reaction is of great importance in applied catalysis. In this work, a simple and environmentally benign approach for highly selective preparation of ε-caprolactone by oxidation of cyclohexanone has been carried out, which employed metal-free mesoporous silica (mSiO2) nanorods as catalyst under atmospheric pressure. The metal-free silica catalyst was applied for the first time in the Baeyer–Villiger (B–V) oxidation reaction. It showed efficient catalytic performance for the B–V oxidation of various cyclic ketones and aliphatic ketones with O2/benzaldehyde as oxidant. The catalyst could be easily separated from the reaction system by filtration and reused several times without significance loss of activity. Moreover, electron paramagnetic resonance (EPR) spectra of the reaction were obtained, indicating the existence of benzoyloxyl radical. The mechanism study of the reaction demonstrated that the super large surface area diluted the concentration of radicals and the adsorption of radicals could protect the radical species from inhibition.

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“…In‐TUD‐1 shows sponge like morphology because of no long range order of pores. In‐HMS‐X shows wormlike morphology and In‐KIT‐6 showing chain like morphology because the bimodal pores of the KIT‐6 are continuous and la3d symmetry . EDX profiles of the catalysts show the presence of indium on silica surface.…”

Section: Resultsmentioning

confidence: 97%

Aerobic Oxidation of Styrene over Indium‐Impregnated Mesoporous Silica: Distinctive Effect of Supports on Epoxidation Activity

Das

Chowdhury

2020

ChemistrySelect

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Liquid phase oxidation of styrene was performed over a series of indium impregnated mesoporous silica materials In-KIT-6, In-HMS-X and In-TUD-1of different morphologies with a constant indium loading of 1 wt % using molecular oxygen as an oxidant. Among these catalysts, In-HMS-X showed superior catalytic activity in terms of styrene conversion of 57 % and In-TUD-1 in terms of styrene oxide selectivity of 90 %. Larger surface area, larger pore diameter, more surface hydrophobicity, more surface acidity were found to be the deciding factors for better conversion. More oxygen uptake, higher reducibility of In species and well dispersion of metal over support were found to be the key enablers for better selectivity. All the catalysts were recyclable up to 5 th cycle.

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Aerobic Baeyer–Villiger oxidation of cyclic ketones over periodic mesoporous silica Cu/Fe/Ni/Co-HMS-X

Cited by 22 publications

References 50 publications

Solvent-Free Production of ε-Caprolactone from Oxidation of Cyclohexanone Catalyzed by Nitrogen-Doped Carbon Nanotubes

Solvent-Free Production of ε-Caprolactone from Oxidation of Cyclohexanone Catalyzed by Nitrogen-Doped Carbon Nanotubes

Metal-Free Mesoporous SiO₂ Nanorods as a Highly Efficient Catalyst for the Baeyer–Villiger Oxidation under Mild Conditions

Aerobic Oxidation of Styrene over Indium‐Impregnated Mesoporous Silica: Distinctive Effect of Supports on Epoxidation Activity

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Aerobic Baeyer–Villiger oxidation of cyclic ketones over periodic mesoporous silica Cu/Fe/Ni/Co-HMS-X

Cited by 22 publications

References 50 publications

Solvent-Free Production of ε-Caprolactone from Oxidation of Cyclohexanone Catalyzed by Nitrogen-Doped Carbon Nanotubes

Solvent-Free Production of ε-Caprolactone from Oxidation of Cyclohexanone Catalyzed by Nitrogen-Doped Carbon Nanotubes

Metal-Free Mesoporous SiO2 Nanorods as a Highly Efficient Catalyst for the Baeyer–Villiger Oxidation under Mild Conditions

Aerobic Oxidation of Styrene over Indium‐Impregnated Mesoporous Silica: Distinctive Effect of Supports on Epoxidation Activity

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Metal-Free Mesoporous SiO₂ Nanorods as a Highly Efficient Catalyst for the Baeyer–Villiger Oxidation under Mild Conditions