Tungsten Peroxopolyoxo Complexes as Advanced Catalysts for the Oxidation of Organic Compounds with Hydrogen Peroxide

Pai, Z. P.; Chesаlоv, Yuriy А.; Berdnikova, P. V.; Uslamin, Evgeny A.; Yushchenko, D. Yu.; Uchenova, Yulia V.; Khlebnikova, T. B.; Baltakhinov, V. P.; Kochubey, D.I.; Bukhtiyarov, Valerii I.

doi:10.1016/j.apcata.2020.117786

Cited by 20 publications

(17 citation statements)

References 46 publications

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“…In contrast, MNZ degradation closely relied on PMS loading, the increase of which would accelerate the generation of more oxidizing radicals for MNZ oxidation. Such results combined with the quenching experiments and EPR results in the Co−N 4 −C/PMS/MNZ system displayed two different reaction pathways: (i) free radicals played an exclusive role in the degradation of refractory MNZ; 49 the decomposition of BPA was mainly controlled by the nonradical oxidation pathway, which overlayed the effects of SO 4…”

Section: Resultsmentioning

confidence: 71%

“…In contrast, the MNZ and Co−N 4 −C-PMS* complex with a larger energy gap was not conducive to electron transfer. 49 The Co−N 4 −C sites could not only mediate the electron transfer from adsorbed electron-rich pollutants (e.g., BPA) to surface-confined PMS to realize BPA oxidation via ETP but also serve as critical active sites to enhance PMS adsorption and activation to generate radicals (SO 4…”

Section: Resultsmentioning

confidence: 99%

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Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N₄–C Intensified Radical and Nonradical Pathways

Yang

Hou

Zhang

et al. 2022

Environ. Sci. Technol.

255

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Single-atom catalysts (SACs)-based peroxymonosulfate (PMS) systems are highly selective to the type of organic pollutants while the mechanisms remain ambiguous. In this work, we carried out experimental and theoretical investigations to reveal the origins of selectivity of radical and nonradical pathways in a designated Co−N 4 −C/PMS system. Two typical pollutants [bisphenol A (BPA) and metronidazole (MNZ)] with different molecular structures were employed for comparison. We found that radical oxidation (SO 4•− and HO • ) and nonradical electrontransfer pathway (ETP) co-existed in the Co−N 4 −C/PMS system. Pollutants (e.g., MNZ) with a high redox potential were degraded primarily by free radicals rather than ETP, while the oxidization of low-redox pollutants (e.g., BPA) was dominated by ETP at the surface region of Co−N 4 −C which overwhelmed the contributions of radicals in the homogeneous phase. Intriguingly, the contributions of radical and nonradical pathways could be manipulated by the PMS loading, which simultaneously increased the radical population and elevated the oxidation potential of Co−N 4 −C-PMS* complexes in ETP. Findings from this work will unravel the mysterious selective behavior of the SACs/PMS systems in the oxidation of different micropollutants.

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Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N₄–C Intensified Radical and Nonradical Pathways

Yang

Hou

Zhang

et al. 2022

Environ. Sci. Technol.

255

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“…Also, the reaction is highly exothermic, which can cause thermal runaway. Because of the drawbacks of this method, the use of environmentally friendly green oxidants, solvents, and catalysts is becoming an alternative choice for the vegetable oil epoxidation reaction, e.g., heterogeneous metal-based materials, acidic ion exchange resins, − polyoxometalates, , and enzymes. − However, these processes have both advantages and bottlenecks. For example, the ion-exchange resin is highly selective and recyclable.…”

Section: Introductionmentioning

confidence: 99%

“…The stability and reusability of enzymes at high temperature limited the industrial application. Heterogeneous non-noble metal catalysts have been widely utilized in the epoxidation process, such as Ti, − W, ,, Al, ,, Zr, , Mo, , Nb, , V, − Co, , Cu, and Mn. − These catalysts epoxidized vegetable oil with only H 2 O 2 or tert -butyl hydroperoxide (TBHP) as the oxidant without adding extra acids, making the epoxidation process greener, safer, and easier. The performance of these catalysts can be improved by systematically studying the catalysts preparation, morphology, reusability, structure–function relationship, kinetics, and reaction mechanism.…”

Section: Introductionmentioning

confidence: 99%

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Opportunities and Emerging Challenges of the Heterogeneous Metal-Based Catalysts for Vegetable Oil Epoxidation

Yan

Wang

Luo

et al. 2022

ACS Sustainable Chem. Eng.

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Epoxidized vegetable oils obtained from either edible or nonedible vegetable oil have drawn extensive attention ascribing to the inherent nature of good biodegradability, renewableness, nontoxicity, and environmental friendliness. It has a broad application in the chemical industry, e.g., biolubricants, polyurethane, cross-linked polymers, coatings, and biodiesel. Currently, it is produced industrially by a homogeneous epoxidation process using in situ formed peracarboxylic acid. However, this method gives poor selectivity toward epoxides and causes severe corrosion to reactors. Efficient and recyclable heterogeneous metal-based materials have become promising alternatives for vegetable oil epoxidation due to the good activity and selectivity in the absence of any corrosive acids. Hence, the development of highly active, selective, and stable heterogeneous catalysts for the epoxidation of vegetable oils and their derivatives has becoming a major task for both academic and industrial communities. In this work, we have reviewed and summarized the most recent progress of catalysts development in the aspects of catalysts preparation, morphology, reusability, structure−function relationship, and reaction mechanism in the past five years. The effects of solvent, oxidant, type of reactor, and operating conditions as well as the reaction kinetics will also be reviewed and discussed to provide guidance for the future study of vegetable oil epoxidation.

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Selective oxidation of benzyl alcohols by silica‐supported heterogeneous catalyst containing dioxidotungsten(VI) core

Heydari

Bikas

Shaterian

et al. 2022

Applied Organom Chemis

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A dioxidotungsten(VI) complex, [WO 2 L(CH 3 OH)]Á0.5(CH 3 OH) (1), was prepared by the reaction of WCl 6 and tridentate ONO-donor Schiff base ligand (H 2 L) that was obtained from the reaction of 2-hydroxy-1-naphthaldehyde with 4-aminobenzoic hydrazide. Both H 2 L and 1 were characterized by various analyses including nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and UV-Vis spectroscopy, and elemental analysis. Single crystal X-ray analysis was used to determine the crystal structure of the complex, which revealed that there is a free -NH 2 group in its structure.

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Tungsten Peroxopolyoxo Complexes as Advanced Catalysts for the Oxidation of Organic Compounds with Hydrogen Peroxide

Cited by 20 publications

References 46 publications

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N₄–C Intensified Radical and Nonradical Pathways

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N₄–C Intensified Radical and Nonradical Pathways

Opportunities and Emerging Challenges of the Heterogeneous Metal-Based Catalysts for Vegetable Oil Epoxidation

Selective oxidation of benzyl alcohols by silica‐supported heterogeneous catalyst containing dioxidotungsten(VI) core

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Tungsten Peroxopolyoxo Complexes as Advanced Catalysts for the Oxidation of Organic Compounds with Hydrogen Peroxide

Cited by 20 publications

References 46 publications

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N4–C Intensified Radical and Nonradical Pathways

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N4–C Intensified Radical and Nonradical Pathways

Opportunities and Emerging Challenges of the Heterogeneous Metal-Based Catalysts for Vegetable Oil Epoxidation

Selective oxidation of benzyl alcohols by silica‐supported heterogeneous catalyst containing dioxidotungsten(VI) core

Contact Info

Product

Resources

About

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N₄–C Intensified Radical and Nonradical Pathways

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N₄–C Intensified Radical and Nonradical Pathways