Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Outros Autores: | , , , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/105855 https://doi.org/10.3390/catal10121402 |
Resumo: | 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@ NH-TPPpCF3) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@ NH-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@ NH-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. |
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Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalystsnanodiamondscopper (II) porphyrinallylic oxidationThe 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@ NH-TPPpCF3) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@ NH-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@ NH-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.This research was 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 Fundação de Amparo à Pesquisa do Estado de São 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).MDPI2020info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/105855http://hdl.handle.net/10316/105855https://doi.org/10.3390/catal10121402eng2073-4344Dias, Lucas DaniloRodrigues, Fábio M.S.Calvete, Mário J. F.Carabineiro, Sónia A. C.Scherer, Marisa D.Caires, Anderson R. L.Buijnsters, Josephus G.Figueiredo, José L.Bagnato, Vanderlei S.Pereira, Mariette M.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-04-06T10:19:51Zoai:estudogeral.uc.pt:10316/105855Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:22:21.145464Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts |
title |
Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts |
spellingShingle |
Porphyrin–Nanodiamond Hybrid Materials—Active, Stable and Reusable Cyclohexene Oxidation Catalysts Dias, Lucas Danilo nanodiamonds copper (II) porphyrin allylic oxidation |
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 |
author |
Dias, Lucas Danilo |
author_facet |
Dias, Lucas Danilo Rodrigues, Fábio M.S. Calvete, Mário J. F. Carabineiro, Sónia A. C. Scherer, Marisa D. Caires, Anderson R. L. Buijnsters, Josephus G. Figueiredo, José L. Bagnato, Vanderlei S. Pereira, Mariette M. |
author_role |
author |
author2 |
Rodrigues, Fábio M.S. Calvete, Mário J. F. Carabineiro, Sónia A. C. Scherer, Marisa D. Caires, Anderson R. L. Buijnsters, Josephus G. Figueiredo, José L. Bagnato, Vanderlei S. Pereira, Mariette M. |
author2_role |
author author author author author author author author author |
dc.contributor.author.fl_str_mv |
Dias, Lucas Danilo Rodrigues, Fábio M.S. Calvete, Mário J. F. Carabineiro, Sónia A. C. Scherer, Marisa D. Caires, Anderson R. L. Buijnsters, Josephus G. Figueiredo, José L. Bagnato, Vanderlei S. Pereira, Mariette M. |
dc.subject.por.fl_str_mv |
nanodiamonds copper (II) porphyrin allylic oxidation |
topic |
nanodiamonds copper (II) porphyrin allylic oxidation |
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 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@ NH-TPPpCF3) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@ NH-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@ NH-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. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10316/105855 http://hdl.handle.net/10316/105855 https://doi.org/10.3390/catal10121402 |
url |
http://hdl.handle.net/10316/105855 https://doi.org/10.3390/catal10121402 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
2073-4344 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
MDPI |
publisher.none.fl_str_mv |
MDPI |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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