Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts

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

doi:10.3390/catal10121402

Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts

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

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Abstract

The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso 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@NH₂ ) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF₃ ) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF₃-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 O₂ as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF₃-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.

Original language	English
Article number	1402
Pages (from-to)	1-13
Number of pages	13
Journal	Catalysts
Volume	10
Issue number	12
DOIs	https://doi.org/10.3390/catal10121402
Publication status	Published - Dec 2020

Keywords

Allylic oxidation
Copper (II) porphyrin
Nanodiamonds

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@article{8cc58a8925f1459991c6c0d5e41cadbe,

title = "Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts",

abstract = "The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso 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@NH2 ) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF3 ) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF3-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 O2 as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF3-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.",

keywords = "Allylic oxidation, Copper (II) porphyrin, Nanodiamonds",

author = "Dias, {Lucas D.} and Rodrigues, {F{\'a}bio M. S.} and Calvete, {M{\'a}rio J. F.} and Carabineiro, {S{\'o}nia A. C.} and Scherer, {Marisa D.} and Caires, {Anderson R.L.} and Buijnsters, {Josephus G.} and Figueiredo, {Jos{\'e} L.} and Bagnato, {Vanderlei S.} and Pereira, {Mariette M.}",

note = "funded by FCT-Foundation for Science and Technology, I.P., under projects UIDB/00313/2020; PTDC/QUI-OUT/27996/2017 (DUALPI); POCI-01-0145-FEDER-027996; POCI-01-0145-FEDER-016387; UIDB/50006/2020 (Associate Laboratory for Green Chemistry-LAQV); MATIS (CENTRO-010145-FEDER-00014); Base Funding-UIDB/50020/2020 of the Associate Laboratory LSRE-LCM-funded by national funds through FCT/MCTES (PIDDAC); and 5625-DRI-DAAD-2020/21. SACC also acknowledges FCT Investigador FCT program (IF/01381/2013/CP1160/CT0007) and Scientific Employment Stimulus -Institutional Call (CEECINST/00102/2018). The authors also thank Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) for CEPOF 2013/07276-1, and INCT {"}Basic Optics and Applied to Life Sciences{"} (FAPESP 2014/50857-8, CNPq 465360/2014-9). A.R.L. Caires acknowledges CAPES-PrInt funding program (grant number 88887.353061/2019-00 and 88881.311921/2018-01). J.G.B. thanks the Dutch Research Council (NWO) for funding as a part of the Open Technology Programme (project number 16361). L.D. Dias thanks FAPESP for the Post-doc grant 2019/13569-8. F.M.S.R. thanks FCT for the PhD grant (PD/BD/114340/2016).",

year = "2020",

month = dec,

doi = "10.3390/catal10121402",

language = "English",

volume = "10",

pages = "1--13",

journal = "Catalysts",

issn = "2073-4344",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

number = "12",

}

TY - JOUR

T1 - Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts

AU - Dias, Lucas D.

AU - Rodrigues, Fábio M. S.

AU - Calvete, Mário J. F.

AU - Carabineiro, Sónia A. C.

AU - Scherer, Marisa D.

AU - Caires, Anderson R.L.

AU - Buijnsters, Josephus G.

AU - Figueiredo, José L.

AU - Bagnato, Vanderlei S.

AU - Pereira, Mariette M.

N1 - funded by FCT-Foundation for Science and Technology, I.P., under projects UIDB/00313/2020; PTDC/QUI-OUT/27996/2017 (DUALPI); POCI-01-0145-FEDER-027996; POCI-01-0145-FEDER-016387; UIDB/50006/2020 (Associate Laboratory for Green Chemistry-LAQV); MATIS (CENTRO-010145-FEDER-00014); Base Funding-UIDB/50020/2020 of the Associate Laboratory LSRE-LCM-funded by national funds through FCT/MCTES (PIDDAC); and 5625-DRI-DAAD-2020/21. SACC also acknowledges FCT Investigador FCT program (IF/01381/2013/CP1160/CT0007) and Scientific Employment Stimulus -Institutional Call (CEECINST/00102/2018). The authors also thank Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) for CEPOF 2013/07276-1, and INCT "Basic Optics and Applied to Life Sciences" (FAPESP 2014/50857-8, CNPq 465360/2014-9). A.R.L. Caires acknowledges CAPES-PrInt funding program (grant number 88887.353061/2019-00 and 88881.311921/2018-01). J.G.B. thanks the Dutch Research Council (NWO) for funding as a part of the Open Technology Programme (project number 16361). L.D. Dias thanks FAPESP for the Post-doc grant 2019/13569-8. F.M.S.R. thanks FCT for the PhD grant (PD/BD/114340/2016).

PY - 2020/12

Y1 - 2020/12

N2 - The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso 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@NH2 ) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF3 ) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF3-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 O2 as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF3-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.

AB - The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso 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@NH2 ) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF3 ) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF3-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 O2 as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF3-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.

KW - Allylic oxidation

KW - Copper (II) porphyrin

KW - Nanodiamonds

UR - http://www.scopus.com/inward/record.url?scp=85097216183&partnerID=8YFLogxK

U2 - 10.3390/catal10121402

DO - 10.3390/catal10121402

M3 - Article

AN - SCOPUS:85097216183

SN - 2073-4344

VL - 10

SP - 1

EP - 13

JO - Catalysts

JF - Catalysts

IS - 12

M1 - 1402

ER -

Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts

Abstract

Keywords

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