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Abstract: The photochromic process of nanocomposite film containing nanometer-sized Keggin type phosphotungstic acid uniformly dispersed in polyacrylamide matrix was studied by in situ AFM and spectroscopy. Under UV irradiation, the film was reduced photochemically to yield blue species. With the increase of irradiation time, the photoreduction proceeded from one-electron to two-electron blue stage. During the photochromism, the size and morphology of composite particles changed due to the cross-linked reactions of polymeric radicals. The XPS studies indicated that the chemical environment of tungsten changed and the W5+/W ratio increased as irradiation time prolonged. FT-IR results showed that the Keggin geometry of phosphotungstic acid was still preserved inside the composite during photochromism, and the interactions between polyanions and polymer matrix increased with the irradiation time. It was suggested that the degree of the photoreduction process depended on the varying of interactions between phosphotungstic acid and polymer. [Copyright &y& Elsevier]

A series of photochromic hybrid films were prepared through entrapping tungsten heteropolyoxometallate (PW12O403−) and molybdenum heteropolyoxometallate (PMo12O403−) in polyacrylamide (PAM) matrix, the corresponding structure and photochromic behaviors of the films were investigated with Fourier transform infrared (FT-IR), UV–Vis–near-infrared (NIR) absorption spectra (UV–Vis–NIR) and electron spin resonance (ESR). FT-IR results showed that the Keggin geometry of heteropolyoxometallate was still preserved inside the composites and strong Coulombic interaction was built between heteropolyoxometallate and PAM via hydrogen bonding. Irradiated with ultraviolet light, the transparent films changed from colorless to blue and showed reversible photochromism. The bleaching process occurred when the films were in contact with air or O2 in the dark. The molybdenum heteropolyoxometallate hybrid film had higher photochromic efficiency and slower bleaching reaction than tungsten heteropolyoxometallate hybrid film. The characteristic signals of radical and W(V) or Mo(V) in ESR spectra indicated that PAM is a hydrogen donor and the photoreduced process is in accordance with the radical mechanism. [Copyright &y& Elsevier]