Excited-State Dynamics of Graphitic Carbon Nitride Photocatalyst and Ultrafast Electron Injection to a Ru(II) Mononuclear Complex for Carbon Dioxide Reduction

We have previously developed photocatalytic CO, reduction systems using graphitic carbon nitride (g-C3N4) and a Ru(II) mononuclear complex (e.g., trans(Cl)-[Ru-II{4,4'-(H2PO3)(2) bpy}(2)(CO)(2)Cl-2] bpy = 2,2'-bipyridine, abbreviated as RuP) hybrids and demonstrated its high activities under visible light (lambda > 400 nm). To understand the excited-state dynamics of C3N4 and electron-transfer process to RuP, here we examined the photophysical properties of g-C3N4 as well as mesoporous g-C3N4 (mpg-C3N4) by means of time-resolved emission and/or time-resolved infrared absorption (TR-IR) spectroscopy. The emission decay measurements showed that g-C3N4 (as well as mpg-C3N4) has at least three emissive excited states with different lifetimes (g-C3N4; 1.3 +/- 0.4, 3.9 +/- 0.9, and 15 +/- 4 ns at 269 nm photoexcitation) in aqueous suspension. These excited states were not quenched upon addition of a hole scavenger (e.g., disodium dihydrogen ethylenediamine tetraacetate dehydrate) and/or an electron acceptor (RuP), even though photochemical electron-transfer processes from/to g-C3N4 has been experimentally confirmed by photocatalytic reactions. On the other hand, TR-IR spectroscopy clearly indicated that mobile electrons photogenerated in mpg-C3N4, which are shallowly trapped and/or free electron in the conduction band, are able to move into RuP with a timescale of a few picoseconds. These results suggest that main emission centers and reaction sites (including charge-transfer interfaces) are separately located in the C3N4 materials, and that electron transfer from C3N4 to RuP progresses through less- or non-luminescent sites, in which mobile electrons exist with a certain lifetime.