Reversible Hydrogen Releasing and Fixing with Poly(Vinylfluorenol) through a Mild Ir-Catalyzed Dehydrogenation and Electrochemical Hydrogenation

The radical polymerization of 2-vinylfluorenol, an alcohol derivative of vinylfluorene, gives poly(vinylfluorenol), which quantitatively releases hydrogen gas (≈110 mL per gram polymer at standard temperature and pressure) by simply warming at 100 °C with an iridium catalyst. A high population of fluorenol units in the polymer accomplishes a large formula-weight-based theoretical hydrogen density (1.0 wt%). The dehydrogenated ketone derivative, poly(vinylfluorenone), exhibits reversible negative-charge storage with a high density of 260 mAh g⁻¹. The electrolytically reduced poly(vinylfluorenone) is momentarily hydrogenated in the presence of an electrolyte with water as the hydrogen source to be converted to the original poly(vinylfluorenol). The formed poly(vinylfluorenol) almost quantitatively evolves hydrogen gas similar to the starting poly(vinylfluorenol). Both hydrogen and charge storage with the organic fluorenol/fluorenone polymer suggest a new type of energy-storage configuration.