Photocatalytic Systems for CO(2) Reduction: Metal-Complex Photocatalysts and Their Hybrids with Photofunctional Solid Materials

[Image: see text] Photocatalytic CO(2) reduction is a critical objective in the field of artificial photosynthesis because it can potentially make a total solution for global warming and shortage of energy and carbon resources. We have successfully developed various highly efficient, stable, and selective photocatalytic systems for CO(2) reduction using transition metal complexes as both photosensitizers and catalysts. The molecular architectures for constructing selective and efficient photocatalytic systems for CO(2) reduction are discussed herein. As a typical example, a mixed system of a ring-shaped Re(I) trinuclear complex as a photosensitizer and fac-[Re(bpy)(CO)(3){OC(2)H(4)N(C(2)H(4)OH)(2)}] as a catalyst selectively photocatalyzed CO(2) reduction to CO with the highest quantum yield of 82% and a turnover number (TON) of over 600. Not only rare and noble metals but also earth abundant ones, such as Mn(I), Cu(I), and Fe(II) can be used as central metal cations. In the case using a Cu(I) dinuclear complex as a photosensitizer and fac-Mn(bpy)(CO)(3)Br as a catalyst, the total formation quantum yield of CO and HCOOH from CO(2) was 57% and TON(CO+HCOOH) exceeded 1300. Efficient supramolecular photocatalysts for CO(2) reduction, in which photosensitizer and catalyst units are connected through a bridging ligand, were developed for removing a diffusion control on collisions between a photosensitizer and a catalyst. Supramolecular photocatalysts, in which [Ru(N(∧)N)(3)](2+)-type photosensitizer and Re(I) or Ru(II) catalyst units are connected to each other with an alkyl chain, efficiently and selectively photocatalyzed CO(2) reduction in solutions. Mechanistic studies using time-resolved IR and electrochemical measurements provided molecular architecture for constructing efficient supramolecular photocatalysts. A Ru(II)–Re(I) supramolecular photocatalyst constructed according to this molecular architecture efficiently photocatalyzed CO(2) reduction even when it was fixed on solid materials. Harnessing this property of the supramolecular photocatalysts, two types of hybrid photocatalytic systems were developed, namely, photocatalysts with light-harvesting capabilities and photoelectrochemical systems for CO(2) reduction. Introduction of light-harvesting capabilities into molecular photocatalytic systems should be important because the intensity of solar light shone on the earth’s surface is relatively low. Periodic mesoporous organosilica, in which methyl acridone groups are embedded in the silica framework as light harvesters, was combined with a Ru(II)–Re(I) supramolecular photocatalyst with phosphonic acid anchoring groups. In this hybrid, the photons absorbed by approximately 40 methyl acridone groups were transferred to one Ru(II) photosensitizer unit, and then, the photocatalytic CO(2) reduction commenced. To use water as an abundant electron donor, we developed hybrid photocatalytic systems combining metal-complex photocatalysts with semiconductor photocatalysts that display high photooxidation powers, in which two photons are sequentially absorbed by the metal-complex photosensitizer and the semiconductor, resulting in both high oxidation and reduction power. Various types of dye-sensitized molecular photocathodes comprising the p-type semiconductor electrodes and the supramolecular photocatalysts were developed. Full photoelectrochemical cells combining these dye-sensitized molecular photocathodes and n-type semiconductor photoanodes achieved CO(2) reduction using only visible light as the energy source and water as the reductant. Drastic improvement of dye-sensitized molecular photocathodes is reported. The results presented in this Account clearly indicate that we can construct very efficient, selective, and durable photocatalytic systems constructed with the metal-complex photosensitizers and catalysts. The supramolecular-photocatalyst architecture in which the photosensitizer and the catalyst are connected to each other is useful especially on the surface of solid owing to rapid electron transfer from the photosensitizer to the catalyst. On basis of these findings, we successfully constructed hybrid systems of the supramolecular photocatalysts with photoactive solid materials. These hybridizations can add new functions to the metal-complex photocatalytic systems, such as water oxidation and light harvesting.