Photosensitized H₂ Evolution and NADPH Formation by Photosensitizer/Carbon Nitride Hybrid Nanoparticles

The broadband C₃N₄ semiconductor absorbs in the UV region, λ = 330-380 nm, a feature limiting its application for light-to-energy conversion. The unique surface adsorption properties of C₃N₄ allow, however, the binding of a photosensitizer, operating in the visible-solar spectrum to the surface of C₃N₄. Coupling of the energy levels of the photosensitizer with the energy levels of C₃N₄ allows effective photoinduced electron-transfer quenching and subsequent charge separation in the hybrid structures. Two methods to adsorb a photosensitizer on the C₃N₄ nanoparticles are described. One is exemplified by the adsorption of Zn(II)-protoporphyrin IX on C₃N₄ using π-π interactions. The second method utilizes the specific binding interactions of single-stranded nucleic acids on C₃N₄ and involves the binding of a Ru(II)-tris-bipyridine-modified nucleic acid on the C₃N₄ nanoparticles. Effective electron-transfer quenching of the photoexcited photosensitizers by C₃N₄ proceeds in the two hybrid systems. The two hybrid photosystems induce the effective photosensitized reduction of N,N'-dimethyl-4,4'-bipyridinium, MV²⁺, to MV^+•, in the presence of Na₂EDTA as a sacrificial electron donor. The generation of MV^+• is ca. 5-fold higher as compared to the formation of MV^+• in the presence of the photosensitizer alone (in the absence of C₃N₄). The effective generation of MV^+• in the photosystems is attributed to the efficient quenching of the photosensitizers, followed by effective charge separation of the electrons in the conduction band of C₃N₄ and the holes in the oxidized photosensitizer. The subsequent transfer of the conduction-band electrons to MV²⁺ and the oxidation of Na₂EDTA by the oxidized photosensitizers lead to the effective formation of MV^+•. The photogenerated MV^+• by the two hybrid photosystems is used to catalyze H₂ evolution in the presence of Pt nanoparticle catalysts and to mediate the reduction of NADP⁺ to NADPH, in the presence of ferredoxin-NADP⁺ reductase, FNR. The ability to couple the photogenerated NADPH to drive NADP⁺-dependent biocatalytic transformations is demonstrated.