Biologically Inspired and Magnetically Recoverable Copper Porphyrinic Catalysts: A Greener Approach for Oxidation of Hydrocarbons with Molecular Oxygen

Abstract

An efficient synthetic method for magnetically recoverable hybrid copper porphyrinic nanomaterials is reported. These functionalized magnetic materials prove to be efficient bioinspired oxidation catalysts of olefins and thiols, using molecular oxygen as oxidant, in total absence of reductants and solvents, with the highest TON (turnover number) yet achieved for this reaction (≈200 000). A comparative study between homogeneous and heterogeneous oxidation of cyclohexene is discussed, revealing the heterogeneous system to be the most promising concerning stability and reusability of the catalysts. The full characterization of the magnetic hybrid porphyrinic nanomaterials, by transmission electron microscopy, flame atomic absorption spectrometry, thermogravimetry, N2 sorption, and infrared spectroscopy, is also described.

A Green Route to Produce Adipic Acid on TiO2–Fe2O3 Nanocomposites

“…For cyclohexene oxidation, the traditional oxidants are t ‐butyl hydroperoxide, H 2 O 2 , and molecular oxygen, the last one being the greenest and the most abundant . Cyclohexene oxidation with H 2 O 2 is another alternative to producing adipic acid (Scheme ), which is one of the most widely used dicarboxylic acids in the chemical industry.…”

Magnetic HMS silica as a Support to Immobilization of Catalysts Based on Cationic Manganese Porphyrins

“…Magnetic porous silica solids appeared as promising supports to MP immobilization as they combine the advantages of the ordered porous silica with the magnetic properties of the magnetite (Fe 3 O 4 ) core, which makes separation of the catalyst from the solution fast and easy. This tends to minimize process costs, by increasing separation efficiency without significant catalyst mass loss, and enables the future development of technological products, as it allows the reuse of the catalyst for several cycles.…”

A Cost-Efficient Method for Unsymmetrical Meso-Aryl Porphyrin Synthesis Using NaY Zeolite as an Inorganic Acid Catalyst

“…Owing to porphyrin’s myriad of applications, including biomedicine [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 ], catalysis [ 9 , 10 , 11 , 12 ], and materials [ 13 , 14 , 15 , 16 , 17 , 18 ], the preparation of unsymmetrically substituted porphyrins, bearing bridgeable groups for further linkage to other chemical entities and materials, is of utmost interest [ 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 ]. Unsymmetrically substituted porphyrin design has been applied for several decades, at first, using porphyrin β-pyrrolic substituting patterns such as the 3+1 route [ 27 , 28 , 29 ], employing the chemistry proposed in the well-known MacDonald 2+2 method [ 30 ], which essentially relied on the cumbersome synthesis of tripyrranes [ 31 ], later mitigated by Sessler’s advances on their syntheses [ 32 ].…”