Protonation-Induced Enhanced Optical-Light Photochromic Properties of an Inorganic-Organic Phosphomolybdic Acid/Polyaniline Hybrid Thin Film

• Main Authors: Qingrui Zeng, Suyue Guo, Yuanbo Sun, Zhuojuan Li, Wei Feng
• Format: Article
• Language: English
• Published: MDPI AG 2020-09-01
• Series: Nanomaterials
• Subjects: phosphomolybdic acid (PMoA); polyaniline (PANI); protonation; photochromism; nanocomposite thin film
• Online Access: https://www.mdpi.com/2079-4991/10/9/1839

A phosphomolybdic acid/polyaniline (PMoA/PANI) optical-light photochromic inorganic/organic hybrid thin film was successfully synthesized by protonation between the the multiprotonic acid phosphomolybdic acid (H₃PO₄·12MoO₃) and the conductive polymer polyaniline. The stable Keggin-type structure of PMoA was maintained throughout the process. Protonation and proton transfer successfully transformed the quinone structure of eigenstate PANI into the benzene structure of single-polarized PANI in the PMoA/PANI hybridized thin film, and proton transfer transformed the benzene structure of single-polarized PANI back to the quinone structure of eigenstate PANI in the PMoA/PANI hybrid thin film, as verified by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The average distribution of PMoA/PANI was observed by atom force microscopy (AFM). Interestingly, protonation of PMoA caused PANI to trigger transformation of the quinone structure into the single-polarized benzene structure, which enhanced the electron delocalization ability and vastly enhanced the maximum light absorption of the PMoA/PANI hybrid thin film as confirmed by density functional theory (DFT), electrochemistry, and ultraviolet-visible spectroscopy (UV-Vis) studies. Under optical-light illumination, the pale-yellow PMoA/PANI hybrid thin film gradually turned deep blue, thus demonstrating a photochromic response, and reversible photochromism was also observed in the presence of hydrogen peroxide (H₂O₂) or oxygen (O₂). After 40 min of optical-light illumination, 36% of the Mo⁵⁺ species in PMoA was photoreduced via a protonation-induced proton transfer mechanism, and this proton transfer resulted in a structural change of PANI, as observed by XPS, generating a dominant structure with high maximum light absorption of 3.46, when compared with the literature reports.