Construction of Porous Organic/Inorganic Hybrid Polymers Based on Polyhedral Oligomeric Silsesquioxane for Energy Storage and Hydrogen Production from Water

In this study, we used effective and one-pot Heck coupling reactions under moderate reaction conditions to construct two new hybrid porous polymers (named OVS-P-TPA and OVS-P-F HPPs) with high yield, based on silsesquioxane cage nanoparticles through the reaction of octavinylsilsesquioxane (OVS) with different brominated pyrene (P-Br(4)), triphenylamine (TPA-Br(3)), and fluorene (F-Br(2)) as co-monomer units. The successful syntheses of both OVS-HPPs were tested using various instruments, such as X-ray photoelectron (XPS), solid-state (13)C NMR, and Fourier transform infrared spectroscopy (FTIR) analyses. All spectroscopic data confirmed the successful incorporation and linkage of P, TPA, and F units into the POSS cage in order to form porous OVS-HPP materials. In addition, the thermogravimetric analysis (TGA) and N(2) adsorption analyses revealed the thermal stabilities of OVS-P-F HPP (T(d)(10) = 444 °C; char yield: 79 wt%), with a significant specific surface area of 375 m(2) g(–1) and a large pore volume of 0.69 cm(3) g(–1). According to electrochemical three-electrode performance, the OVS-P-F HPP precursor displayed superior capacitances of 292 F g(−1) with a capacity retention of 99.8% compared to OVS-P-TPA HPP material. Interestingly, the OVS-P-TPA HPP showed a promising HER value of 701.9 µmol g(−1) h(−1), which is more than 12 times higher than that of OVS-P-F HPP (56.6 µmol g(−1) h(−1)), based on photocatalytic experimental results.