Abstract
Solar energy can be converted into chemical energy by photocatalytic water splitting to produce molecular hydrogen. Details of the photo-induced reaction mechanism occurring on the surface of a semiconductor are not fully understood, however. Herein, we employ a model photocatalytic system consisting of single atoms deposited on quantum dots that are anchored on to a primary photocatalyst to explore fundamental aspects of photolytic hydrogen generation. Single platinum atoms (Pt(1)) are anchored onto carbon nitride quantum dots (CNQDs), which are loaded onto graphitic carbon nitride nanosheets (CNS), forming a Pt(1)@CNQDs/CNS composite. Pt(1)@CNQDs/CNS provides a well-defined photocatalytic system in which the electron and proton transfer processes that lead to the formation of hydrogen gas can be investigated. Results suggest that hydrogen bonding between hydrophilic surface groups of the CNQDs and interfacial water molecules facilitates both proton-assisted electron transfer and sorption/desorption pathways. Surface bound hydrogen atoms appear to diffuse from CNQDs surface sites to the deposited Pt(1) catalytic sites leading to higher hydrogen-atom fugacity surrounding each isolated Pt(1) site. We identify a pathway that allows for hydrogen-atom recombination into molecular hydrogen and eventually to hydrogen bubble evolution.