Gold nanoparticle-based supramolecular approach for dye-sensitized H₂-evolving photocathodes

Solar conversion of water into the storable energy carrier H₂ can be achieved through photoelectrochemical water splitting using light adsorbing anodes and cathodes bearing O₂ and H₂ evolving catalysts, respectively. Herein a novel photocathode nanohybrid system is reported. This photocathode consists of a dye-sensitized p-type nickel oxide (NiO) with a perylene-based chromophore (PCA) and a tetra-adamantane modified cobaloxime reduction catalyst (Co) that photo-reduces aqueous protons to H₂. An original supramolecular approach was employed, using β-cyclodextrin functionalized gold nanoparticles (β-CD-AuNPs) to link the alkane chain of the PCA dye to the adamantane moieties of the cobaloxime catalyst (Co). This new architecture was investigated by photoelectrochemical measurements and via femtosecond-transient absorption spectroscopy. The results show that irradiation of the complete NiO|PCA|β-CD-AuNPs|Co electrode leads to ultrafast hole injection into NiO (π = 3 ps) from the excited dye, followed by rapid reduction of the catalyst, and finally H₂ evolution.