Thermo-reversible sol–gel transition of TiO2 nanoparticles with surface modified by p-toluene sulfonic acid

In this paper an unprecedent thermo-reversible sol–gel transition for titania nanoparticles dispersed in a solution of p-toluene sulfonic acid (PTSH) in isopropanol is reported. The sol formed by the thermo-hydrolysis at 60 °C of titanium tetraisopropoxide (Ti(OiPr)4) reversibly changes into a turbid gel upon cooling to room temperature. Turbidimetric measurements performed for samples containing different nominal acidity ratios (A = [PTSH]/[Ti]) have evidenced that the gel transformation temperature increases from 20 to 35 °C as the [PTSH]/[Ti] ratio increases from 0.2 to 2.0. SAXS results indicate that the thermo-reversible gelation is associated to a reversible aggregation of a monodisperse set of titania nanoparticles with average gyration radius of ≈2 nm. From the different PTSH species evidenced by Raman spectroscopy and TG/DTA of dried gels we proposed that the thermo-reversible gelation in this systems is induced by the formation of a supramolecular network, in which the protonated surface of nanoparticles is interconnected through cooperative hydrogen bonds between –SO3 groups of p-toluene sulfonic acid.