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A Mn­(I)-based hybrid system (OrgD-|TiO2|-MnP) for photocatalytic CO2 reduction is designed to be a coassembly of Mn­(4,4′-Y2-bpy)­(CO)3Br (MnP; Y = CH2PO­(OH)2) and (E)-3-[5-(4-(diphenylamino)­phenyl)-2,2′-bithiophen-2′-yl]-2-cyanoacrylic acid (OrgD) on TiO2 semiconductor particles. The OrgD-|TiO2|-MnP hybrid reveals persistent photocatalytic behavior, giving high turnover numbers and good product selectivity (HCOO– versus CO). As a typical run, visible-light irradiation of the hybrid catalyst in the presence of 0.1 M electron donor (ED) and 0.001 M LiClO4 persistently produced HCOO– with a >99% selectivity accompanied by a trace amount of CO; the turnover number (TONformate) reached ∼250 after 23 h of irradiation. The product selectivity (HCOO–/CO) was found to be controlled by changing the loading amount of MnP on the TiO2 surface. In situ FTIR analysis of the hybrid during photocatalysis revealed that, at low Mn concentration, the Mn–H monomeric mechanism associated with HCOO– formation is dominant, whereas at high Mn concentration, CO is formed via a Mn–Mn dimer mechanism.

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