Visible-Light-Driven Hydrogen Release from Dye-Sensitized Hydrogen Boride Nanosheets.

Hydrogen boride (HB) nanosheets are expected to be safe and lightweight hydrogen carriers because of their high gravimetric hydrogen density (8.5 wt %) and photon-driven hydrogen release under mild conditions. However, previously reported HB nanosheets respond only to ultraviolet (UV) light to release hydrogen. In this study, we develop dye-modified HB nanosheets that can release hydrogen under visible light irradiation (>470 nm) without heat input. Hydrogen generation is initiated by electron injection from excited dye molecules into the conduction band of the HB nanosheets. The conduction band of the HB nanosheets is formed by the antibonding states of the B 2p and H 1s atomic orbitals, and the electrons injected from the dye molecules react with the protons of the HB nanosheets to release gaseous hydrogen molecules. Although the hydrogen production is terminated after long-term light irradiation owing to dye oxidation and/or loss of protons in HB nanosheets, the total amount of the released hydrogen molecules corresponds to approximately 25% of the protons in HB nanosheets even under the extra mild conditions. The addition of a sacrificial agent like iodine ions and a proton source like formic acid sustained the H generation from the dye-modified HB nanosheets under visible light irradiation for long term.