Electrostatic self-assembled multilayers of tetrachromatedmetalloporphyrins/polyoxometalateand its electrocatalytic properties in oxygen reduction

Periodate-Mediated Aerobic Oxidation of Sulfides over a Bifunctional Porphyrin-polyoxometalate Catalyst: Photosensitized Singlet Oxygen Oxidation of Iodate to Periodate

“…Most terminal oxidants used in biomimetic oxidation of organic compounds are consumed in stoichiometrically equivalent amounts. − ,− Regeneration of the reduced terminal oxidant by molecular oxygen is a green chemistry strategy for the replacement of chemical terminal oxidants with air as the most abundant, sustainable, and greenest oxidant. Photosensitized regeneration of the reagents consumed in chemical and biological transformations is an efficient approach to achieve this goal.…”

“…43−52 Also, a synergic effect was observed between a cationic porphyrin electrostatically supported on SiW 12 O 40 4− and POM in the electrocatalytic reduction of oxygen in aqueous solution. 53 Polyoxometalates have been used for the activation of terminal oxidants such as oxone, 54 alkyl hydroperoxide, 55,56 molecular oxygen, 57,58 NaClO, 59,60 iodosyl benzene, 61,62 and hydrogen peroxide. 63−65…”

“…The functionalization of porphyrins at the meso positions with OH-containing substituents such as benzenephophate, − N -(1,3-dihydroxy-2-(hydroxymethyl)­propan-2-yl)­benzamide, and N -(1,3-dihydroxy-2-(hydroxymethyl)­propan-2-yl)­benzamide for covalent-bond formation with the metal center of POM is the most commonly used strategy for this purpose. Furthermore, anionic POMs form stable hybrids with cationic porphyrins such as meso -tetrakis­( N -methylpyridinium-4-yl)­porphyrin through electrostatic interactions. − Porphyrin-POM hybrids are promising multifunctional materials for photocatalytic and photovoltaic applications as well as the biomimetic oxidation of organic substrates. − The formation of hybrids was found to increase the oxidative stability of the POM-bound metalloporphyrin. − Also, a synergic effect was observed between a cationic porphyrin electrostatically supported on SiW 12 O 40 4– and POM in the electrocatalytic reduction of oxygen in aqueous solution . Polyoxometalates have been used for the activation of terminal oxidants such as oxone, alkyl hydroperoxide, , molecular oxygen, , NaClO, , iodosyl benzene, , and hydrogen peroxide. − …”

Electrocatalytic Transformation of Carbon Dioxide into Low Carbon Compounds on Conducting Polymers Derived from Multimetallic Porphyrins

“…This effect has also been corroborated by using al ayer by layer assembly of [FeTPyP{Cr-(phen) 2 Cl} 4 ] 8 + /SiW 12 O 40 4À on GC. [57] These resultss eem to be directly related to the intrinsic properties of the conducting polymer.I nt he case of Poly-NiTRP,t he high selectivity towardm ethanol production can be associated with the presence of av ery active redox center in the macrocycle core, and also to the formation of av ery compact and thin film. These factorss uggest that reduction takes place thanks to the possible coordination of carbon dioxide to the reduced metal center in the conducting polymer,w hich should occur in the conducting polymer/solventi nterphase.…”