Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts

The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via <i>ipso</i> nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy,...

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Main Authors:	Lucas D. Dias, Fábio M. S. Rodrigues, Mário J. F. Calvete, Sónia A. C. Carabineiro, Marisa D. Scherer, Anderson R. L. Caires, Josephus G. Buijnsters, José L. Figueiredo, Vanderlei S. Bagnato, Mariette M. Pereira
Format:	Article
Language:	English
Published:	MDPI AG 2020-12-01
Series:	Catalysts
Subjects:	nanodiamonds copper (II) porphyrin allylic oxidation
Online Access:	https://www.mdpi.com/2073-4344/10/12/1402

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spelling	doaj-afa9295df3ea421ea00a4698e12d8fd92020-12-02T22:38:55ZengMDPI AGCatalysts2073-43442020-12-01101402140210.3390/catal10121402Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation CatalystsLucas D. Dias0Fábio M. S. Rodrigues1Mário J. F. Calvete2Sónia A. C. Carabineiro3Marisa D. Scherer4Anderson R. L. Caires5Josephus G. Buijnsters6José L. Figueiredo7Vanderlei S. Bagnato8Mariette M. Pereira9Departamento de Química, CQC, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra, PortugalDepartamento de Química, CQC, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra, PortugalDepartamento de Química, CQC, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra, PortugalLaboratory of Catalysis and Materials, Associate Laboratory LSRE-LCM, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, PortugalGrupo de Óptica e Fotônica, Universidade Federal de Mato Grosso do Sul, CP 549, Campo Grande 790070-900, BrazilGrupo de Óptica e Fotônica, Universidade Federal de Mato Grosso do Sul, CP 549, Campo Grande 790070-900, BrazilDepartment of Precision and Microsystems Engineering, Micro and Nano Engineering, Delft University of Technology, 2628 CD Delft, The NetherlandsLaboratory of Catalysis and Materials, Associate Laboratory LSRE-LCM, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, PortugalSão Carlos Institute of Physics, University of São Paulo, São Carlos 13566-590, BrazilDepartamento de Química, CQC, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra, PortugalThe quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via <i>ipso</i> nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, infrared spectroscopy (IR) and thermogravimetry-differential scanning calorimetry (TG-DSC). The amine-functionalized nanodiamonds (ND@NH<sub>2</sub>) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPP<i>p</i>CF<sub>3</sub>) were tested using <i>Allium cepa</i> as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPP<i>p</i>CF<sub>3</sub>-Cu(II) was also evaluated as a reusable catalyst in cyclohexene allylic oxidation, and displayed a remarkable turnover number (TON) value of ≈265,000, using O<sub>2</sub> as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPP<i>p</i>CF<sub>3</sub>-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.https://www.mdpi.com/2073-4344/10/12/1402nanodiamondscopper (II) porphyrinallylic oxidation
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Lucas D. Dias Fábio M. S. Rodrigues Mário J. F. Calvete Sónia A. C. Carabineiro Marisa D. Scherer Anderson R. L. Caires Josephus G. Buijnsters José L. Figueiredo Vanderlei S. Bagnato Mariette M. Pereira
spellingShingle	Lucas D. Dias Fábio M. S. Rodrigues Mário J. F. Calvete Sónia A. C. Carabineiro Marisa D. Scherer Anderson R. L. Caires Josephus G. Buijnsters José L. Figueiredo Vanderlei S. Bagnato Mariette M. Pereira Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts Catalysts nanodiamonds copper (II) porphyrin allylic oxidation
author_facet	Lucas D. Dias Fábio M. S. Rodrigues Mário J. F. Calvete Sónia A. C. Carabineiro Marisa D. Scherer Anderson R. L. Caires Josephus G. Buijnsters José L. Figueiredo Vanderlei S. Bagnato Mariette M. Pereira
author_sort	Lucas D. Dias
title	Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts
title_short	Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts
title_full	Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts
title_fullStr	Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts
title_full_unstemmed	Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts
title_sort	porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts
publisher	MDPI AG
series	Catalysts
issn	2073-4344
publishDate	2020-12-01
description	The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via <i>ipso</i> nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, infrared spectroscopy (IR) and thermogravimetry-differential scanning calorimetry (TG-DSC). The amine-functionalized nanodiamonds (ND@NH<sub>2</sub>) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPP<i>p</i>CF<sub>3</sub>) were tested using <i>Allium cepa</i> as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPP<i>p</i>CF<sub>3</sub>-Cu(II) was also evaluated as a reusable catalyst in cyclohexene allylic oxidation, and displayed a remarkable turnover number (TON) value of ≈265,000, using O<sub>2</sub> as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPP<i>p</i>CF<sub>3</sub>-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.
topic	nanodiamonds copper (II) porphyrin allylic oxidation
url	https://www.mdpi.com/2073-4344/10/12/1402
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Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts

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