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

Journal article (2020)

Authors

Lucas D. Dias Universidade de Coimbra, Universidade de São Paulo
Fábio M.S. Rodrigues Universidade de Coimbra
Mário J.F. Calvete Universidade de Coimbra
Sónia A.C. Carabineiro Universidade do Porto, New University of Lisbon
Marisa D. Scherer Universidade Federal de Mato Grosso do Sul
Anderson R.L. Caires University of Essex, Universidade Federal de Mato Grosso do Sul
J.G. Buijnsters Micro and Nano Engineering - Mechanical, Maritime and Materials Engineering
José L. Figueiredo Universidade do Porto
Vanderlei S. Bagnato Universidade de São Paulo, Texas A&M University
Mariette M. Pereira Universidade de Coimbra
Research Group
Micro and Nano Engineering (Mechanical, Maritime and Materials Engineering) (TU Delft)
Copyright: © 2020 Lucas D. Dias, Fábio M.S. Rodrigues, Mário J.F. Calvete, Sónia A.C. Carabineiro, Marisa D. Scherer, Anderson R.L. Caires, J.G. Buijnsters, José L. Figueiredo, Vanderlei S. Bagnato, Mariette M. Pereira
DOI: https://doi.org/10.3390/catal10121402
More Info
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Published Date

2020

Language

English

Faculty

Mechanical, Maritime and Materials Engineering

Department

Precision and Microsystems Engineering

Research Group

Micro and Nano Engineering

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.