Platinized spherical supramolecular nanoassemblies of a porphyrin: facile synthesis and excellent catalytic recyclability

Abstract

Porphyrin-based supramolecular nanoassemblies of a spherical morphology have been attracting broad interest owing to their wide application possibilities in numerous fields of paramount significance. Most of the existing assembly protocols, however, either suffer from the requirement of elaborately-designed yet tediously-synthesized ad hoc porphyrins, the use of surfactant templates, or accurate consideration of the experimental parameters etc. The initiation of a facile surfactant-free fabrication protocol performable under ambient conditions using commercial porphyrins as building blocks is strongly desired. We herein report that a commercial metal-free porphyrins, 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TPPNH2), could be facilely organized to form well-defined discrete spherical nanoassemblies at room temperature by means of a simple reprecipitation method. We further find that the as-manufactured TPPNH2 nanospheres could work as photocatalysts towards the reduction of potassium tetrachloroplatinate(II), leading to their self-platinization and the production of platinum/porphyrin nanosphere nanocomposites, wherein ultrathin Pt nanoparticles of a size of ca. 3 nm are immobilized on the porphyrin nanospheres. Significantly, by taking the advantage of their easy sedimentation from aqueous suspensions, we show that the as-produced composites could serve as qualified heterogeneous nanocatalysts in terms of their excellent catalytic stability and recyclability towards the reduction of 4-nitrophenol, where the catalytic reactivity exhibits only trivial changes even after the reactions have been repeated 8 times continuously. Taking into account the general concerns of porphyrins- and Pt-based nanostructures, this might provide a facile method for the construction of spherical porphyrin nanostructures with self-platinization capability. Meanwhile, considering the high cost and scarcity of Pt, our nanocomposites with excellent stability and recyclability likely have a bright future of potential uses.