Nanosized cationic and anionic manganese porphyrins as mesoporous catalysts for the oxidation of olefins: Nano versus bulk aggregates

In this study, catalytic activity of bulk and nano‐sized meso‐tetrakis(4‐sulfonatophenyl)porphyrinatomanganese(III) acetate, MnTPPS₄(OAc), (ammonium salt) and meso‐tetrakis(3‐methylpyridyl)porphyrinatomanganese(III) acetate, MnT(3‐MePy)P(OAc) (tosylate salt) for the oxidation of olefins with tetra‐n‐butylammonium Oxone has been studied and compared with that of the bulk counterparts. The nanoparticles were prepared by mixing solvent techniques using water, (triethyleneglycol) monomethyl ether and dimethylsulfoxide or acetonitrile. The formation of nano‐sized catalysts was confirmed by UV‐Vis spectroscopy, DLS and AFM. Nitrogen porosimetry measurements indicated the homogeneous pore size distribution in the bulk and nano‐sized manganese porphyrins. In spite of the high oxidizability of Oxone, the heterogenized manganese porphyrins showed a significantly higher oxidative stability relative to their homogeneous counterparts within a reaction time of 6 h. The increase in the catalytic activity induced by the formation of nano‐sized catalysts was more pronounced in the case of MnT(3‐MePy)P(OAc). MnT(3‐MePy)P(OAc) may be recovered and reused for at least 4 times without any significant decrease in the catalyst efficiency. In the case of MnTPPS₄(OAc) a large decrease in the catalytic activity was observed after the first use of the catalyst. The latter was attributed to higher degrees of catalyst degradation in the case of MnTPPS₄(OAc).