Effect of particle size on the photochromic response of PWA/SiO₂ nanocomposite

A series of photochromic phosphotungstic acid (PWA)/SiO₂ composites were synthesized using the sol-gel method. Depending on the feeding schedule of PWA during synthesis, the size of the formed PWA/SiO₂ particles varied considerably from as small as 1.2 nm to ca. 10 nm. With decreasing silica particle size, the total contact area/interaction between SiO₂ and PWA increases, as revealed by FT-IR and solid-state ²⁹Si-NMR analyses. Particularly, when the size of PWA/SiO₂ is ~1 nm, crystallization of PWA is inhibited, and PWA presents as amorphous molecular entities distributing uniformly in the SiO₂ host, which is in evidence in the XRD spectroscopy and HR-TEM imaging. In contrast, substantial crystallization of PWA takes place when PWA/SiO₂ particles are as large as 10 nm, in which case less amount of surface free Si-OH is available for PWA to make bonds with. Photochromism occurs activated by ultraviolet light irradiation. The rate of coloration/bleaching is found to depend strongly on the particle size of PWA/SiO₂; specifically, the rate increases twice when the particle size is reduced from 10 nm to 1.2 nm.