Inorganometallic Photocatalyst for CO 2 Reduction.

ConspectusDuring the last few decades, the design of catalytic systems for CO ₂ reduction has been extensively researched and generally involves (1) traditional approaches using molecular organic/organometallic materials and heterogeneous inorganic semiconductors and (2) combinatory approaches wherein these materials are combined as needed. Recently, we have devised a number of new TiO ₂ -mediated multicomponent hybrid systems that synergistically integrate the intrinsic merits of various materials, namely, molecular photosensitizers/catalysts and n -type TiO ₂ semiconductors, and lower the energetic and kinetic barriers between components. We have termed such multicomponent hybrid systems assembled from the hybridization of various organic/inorganic/organometallic units in a single platform inorganometallic photocatalysts . The multicomponent inorganometallic (MIOM) hybrid system onto which the photosensitizer and catalyst are coadsorbed efficiently eliminates the need for bulk-phase diffusion of the components and avoids the accumulation of radical intermediates that invokes a degradation pathway, in contrast to the homogeneous system, in which the free reactive species are concentrated in a confined reaction space. In particular, in energetic terms, we discovered that in nonaqueous media, the conduction band (CB) levels of reduced TiO ₂ (TiO ₂ (e ^- )) are positioned at a higher level (in the range -1.5 to -1.9 V vs SCE). This energetic benefit of reduced TiO ₂ allows smooth electron transfer (ET) from injected electrons (TiO ₂ (e ^- )) to the coadsorbed CO ₂ reduction catalyst, which requires relatively high reducing power (at least more than -1.1 V vs SCE). On the other hand, the existence of various shallow surface trapping sites and surface bands, which are 0.3-1.0 eV below the CB of TiO ₂ , efficiently facilitates electron injection from any photosensitizer (including dyes having low excited energy levels) to TiO ₂ without energetic limitation. This is contrasted with most photocatalytic systems, wherein successive absorption of single high-energy photons is required to produce excited states with enough energy to fulfill photocatalytic reaction, which may allow unwanted side reactions during photocatalysis. In this Account, we present our recent research efforts toward advancing these MIOM hybrid systems for photochemical CO ₂ reduction and discuss their working mechanisms in detail. Basic ET processes within the MIOM system, including intervalence ET in organic/organometallic redox systems, metal-to-ligand charge transfer of organometallic complexes, and interfacial/outer-sphere charge transfer between components, were investigated by conducting serial photophysical and electrochemical analyses. Because such ET events occur primarily at the interface between the components, the efficiency of interfacial ET between the molecular components (organic/organometallic photosensitizers and molecular reduction catalysts) and the bulk inorganic solid (mainly n -type TiO ₂ semiconductors) has a significant influence on the overall photochemical reaction kinetics and mechanism. In some TiO ₂ -mediated MIOM hybrids, the chemical attachment of organic or organometallic photosensitizing units onto TiO ₂ semiconductors efficiently eliminates the step of diffusion/collision-controlled ET between components and prevents the accumulation of reactive species (oxidatively quenched cations or reductively quenched anions) in the reaction solution, ensuring steady photosensitization over an extended reaction period. The site isolation of a single-site organometallic catalyst employing TiO ₂ immobilization promotes the monomeric catalytic pathway during the CO ₂ reduction process, resulting in enhanced product selectivity and catalytic performance, including lifetime extension. In addition, as an alternative inorganic solid scaffold, the introduction of a host porphyrin matrix (interlinked in a metal-organic framework (MOF) material) led to efficient and durable photocatalytic CO ₂ conversion by the new MOF-Re(I) hybrid as a result of efficient light harvesting/exciton migration in the porphyrinic MOF and rapid quenching of the photogenerated electrons by the doped Re(I) catalytic sites. Overall, the case studies presented herein provide valuable insights for the rational design of advanced multicomponent hybrid systems for artificial photosynthesis involving CO ₂ reduction.