Visible-light photochromic nanocomposite thin films based on polyvinylpyrrolidone and polyoxometalates supported on clay minerals

摘要

A novel reversible photochromic nanocomposite film was prepared by entrapping phosphomolybdic acid supported on the sodium bentonite (PMoA/Na-MMT) into polyvinylpyrrolidone (PVPd). The microstructure, thermal stability, photochromic behavior and mechanism of the hybrid film were investigated. Fourier transform infrared spectroscopy (FT-IR) results illustrated that the Keggin geometry of polyoxometalates (PMoA) and organic groups of PVPd were still preserved inside the composites and non-covalent bond interaction was built between PMoA/Na-MMT and PVPd polymer matrix. Transmission electron microscopy (TEM) image showed that PMoA nanoparticles were finely dispersed in Na-MMT which exhibited fine stratified structure. Atomic force microscopy (AFM) images indicated that the surface topography of polymeric matrix changed after adding PMoA/Na-MMT, and the surface appearance of nanocomposite film was different before and after visible-light irradiation. The stability of the hybrid film and the effect of the perturbation of Na-MMT on the stability were determined by means of the thermogravimetric analysis (TG) and differential thermal analysis (DTA). Irradiated with visible light, the ultraviolet-visible spectra (UV-vis) showed that the hybrid films changed from colorless to blue and could recover the colorless state gradually in air, where oxygen played an important role during the bleaching process. The hybrid films exhibited excellent bleaching ability during the heating. According to the X-ray photoelectron spectroscopy (XPS) analysis, the appearance of Mo~(5+) species indicated the photo-reduction reaction between PMoA/Na-MMT and PVPd matrix occurred according to the proton transfer mechanism, and the photochromic reactions were found to exhibit first-order kinetics.