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

Abstract

We have previously developed photocatalytic CO2 reduction systems using graphitic carbon nitride (g-C3N4) and a Ru(II) mononuclear complex (e.g., trans(Cl)–[RuII{4,4′-(H2PO3)2bpy}2(CO)2Cl2] bpy = 2,2′-bipyridine, abbreviated as RuP) hybrids and demonstrated its high activities under visible light (λ > 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 phot...