Organophosphonate bridged anatase mesocrystals: low temperature crystallization, thermal growth and hydrogen photo-evolution

Abstract

The sol–gel co-condensation of organo-phosphonates to titanium alkoxides enables access to novel organic–inorganic hybrids based on phosphonate-bridged titanium dioxide. In this contribution, we bring new perspectives to the long established sol–gel mineralization of titanium alkoxide species, by harnessing the virtues of the well-designed phosphonate-terminated phosphorus dendrimers as reactive amphiphilic nanoreactor, confined medium and cross-linked template to generate discrete crystalline anatase nanoparticles at low temperature (T = 60 °C). An accurate investigation on several parameters (dendrimer generation, dendrimer-to-titanium alkoxide ratio, precursor reactivity, temperature, solvent nature, salt effect) allows a correlation between the network condensation, the opening porous framework and the crystalline phase formation. The evolution of the dendrimer skeleton upon heat treatment has been deeply monitored by means of ³¹P NMR, XPS and Raman spectroscopy. Increasing the heteroatom content within a titania network provides the driving force for enhancing their photocatalytic water splitting ability for hydrogen production.