The Design of a New Cobalt Sulfide Nanoparticle Implanted Porous Organic Polymer Nanohybrid as a Smart and Durable Water-Splitting Photoelectrocatalyst.

Development of an inexpensive, efficient and robust nanohybrid catalyst as a substitute for platinum in photoelectrocatalytic hydrogen production has been considered intriguing and challenging. In this study, the design and sequential synthesis of a novel cobalt sulfide nanoparticle grafted Porous Organic Polymer nanohybrid (CoSx @POP) is reported and used as an active and durable water-splitting photoelectrocatalyst in the hydrogen evolution reaction (HER). The specific textural and relevant chemical properties of as-synthesised nanohybrid materials (Co3 O4 @POP &CoSx @POP) were investigated by means of XRD, XPS, FTIR,13 C CP MAS NMR, spectroscopy, HR-TEM, HAADF-STEM with the corresponding elemental mapping, FE-SEM and nitrogen physisorption studies. CoSx @POP has been evaluated as a superior photoelectrocatalyst in HER, achieving a current density of 6.43 mA cm-2 at 0 V versus the reversible hydrogen electrode (RHE) in a 0.5 m Na2 SO4 electrolyte which outperforms its Co3 O4 @POP analogue. It was found that the nanohybrid CoSx @POP catalyst exhibited a substantially enhanced catalytic performance of 1.07 μmol min-1 cm-2 , which is considered to be ca. 10 and 1.94 times higher than that of pristine POP and CoSx , respectively. Remarkable photoelectrocatalytic activity of CoSx @POP compared to Co3 O4 @POP toward H2 evolution could be attributed to intrinsic synergistic effect of CoSx and POP, leading to the formation of a unique CoSx @POP nanoarchitecture with high porosity, which permits easy diffusion of electrolyte and efficient electron transfer from POP to CoSx during hydrogen generation with a tunable bandgap, that straddles between the reduction and oxidation potential of water.