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Despite the myriad studies on polybenzimidazole based polymer electrolyte membranes for fuel cells operating above 100 °C, the development of membranes with higher proton conductivity without compromising mechanical stability has continued to be the prime challenge. In this article, organic/inorganic hybrid nanocomposites of poly (4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI) were prepared with surface functionalized silica nanoparticles to address this key issue. Structural and morphological studies probed by SAXS, WAXD and TEM, respectively revealed the formation of self-assembled clusters of nanoparticles when the OPBI nanocomposites were made with amine modified silica (AMS) whereas a well dispersed structure was obtained for OPBI and the unmodified silica (UMS) composite. The OPBI/AMS nanocomposites displayed a significant enhancement in the thermal stabilities compared to the pristine OPBI and OPBI/UMS nanocomposite. The OPBI/AMS nanocomposite membranes exhibited a larger mechanical reinforcement than the pristine OPBI and OPBI/UMS nanocomposite. The formation of nanoparticle clusters in the OPBI matrix in the case of OPBI/AMS was found to be the driving force for the higher thermal and mechanical stability of OPBI/AMS than those of OPBI/UMS. The incorporation of AMS in the OPBI matrix shielded the polymer chains from the attack of oxidative radicals, resulting in a huge enhancement of oxidative stability of the nanocomposite membranes compared to the pure OPBI membrane. The OPBI/AMS nanocomposite membranes have significantly higher phosphoric acid (PA) loading compared to the pure OPBI membrane which resulted in the higher proton conductivities of the former. The self-assembled clusters of AMS in the OPBI matrix facilitated the proton transport process.

We report the development of a new photonic crystal hydrogel for the sensing of highly toxic mercury ion (Hg2+) in water. This new sensing material optically reports the Hg2+ concentration in watervia diffraction of visible light from polymerized crystalline colloidal array (PCCA). The PCCA consists of light diffracting crystalline colloidal array (CCA) of monodisperse, highly charged polystyrene particles, which are polymerized within the polyacrylamide hydrogel. The changes in hydrogel surroundings trigger the volume change of hydrogel, which alters the lattice spacing of CCA and hence shifts the diffraction wavelength of light. The ions responsive urease coupled PCCA (UPCCA) hydrolyzes the urea and produces the HCO3− and NH4+ ions inside the hydrogel. These ions induce the charge-screening of the polyacrylamide carboxylates by decreasing the electrostatic repulsion between carboxylates and the polyacrylamide backbone relaxes, causing the shrinkage of hydrogel. Hence the UPCCA exhibits the blue shift of the diffracted wavelength. Hg2+ being the principal inhibitor of the urease-urea hydrolysis perturbs urea hydrolysis by the UPCCA when UPCCA is exposed to Hg2+ along with urea and hence suppresses the production of ions. This intervenes the shrinkage of hydrogel and does not allow the hydrogel to shrink as it shrinks in absence of Hg2+. Therefore the PCCA net blue shift decreases in the presence of Hg2+ along with urea compared to only urea. The extent of this hydrogel volume change is a function of Hg2+ concentrations. This UPCCA photonic crystal sensor detects ultra low (1 ppb) concentration of Hg2+ in water, exhibits reversibility and displays very high selectivity towards Hg2+. The uncompetitive inhibition nature of the urease enzyme, when it is covalently attached in the polymer hydrogel backbone, is the driving force for the very high selectivity and reversibility of the UPCCA sensor.