Synthetic metalloporphyrins have been developed as models of heme-enzimes (peroxidases, catalases and cytochrome P450). The introduction of electron-withdrawing substituents on mesoaryl and/or β-pyrrolic positions of the porphyrin has been a successful strategy to obtain more efficient and robust catalysts for oxidation reactions.

Another important approach in this sense has been the immobilisation of the metalloporphyrins in/on solid matrices, such as silica gel, zeolites, ion exchange resins, clays and hybrid inorganic-organic silicates obtained via sol gel process. The immobilisation of the catalysts allows site-isolation of the metalloporphyrin-catalyst from the bulk solution and, moreover, possibilities recovery and re-use of the catalyst, which is a desirable characteristic for future industrial applications. In this sense, the use of clean and cheap oxidants, such as O₂ and H₂O₂, is essential and then some aspects concerning to activation of these oxidants promoted by metalloporphyrins are discussed in this review.

In a posterior section of this paper will be discussed some studies related to generation and detection of short-lived intermediates formed during oxidation reactions metalloporphyrins-promoted in homogeneous and heterogeneous media. New perspectives and challenges concerned to oxidation reactions catalysed by synthetic metalloporphyrins are presented in the final section.