Highly Selective and Durable Photochemical CO<SUB>2</SUB> Reduction by Molecular Mn(I) Catalyst Fixed on Particular Dye-Sensitized TiO<SUB>2</SUB> Platform
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초록
내용
A new Mn(I)-based hybrid system for photocatalytic CO2 reduction is designed to be a co-assembly of Mn(4,4′-Y2-bpy)(CO)3Br and (E)-3-[5-(4-(diphenylamino)phenyl)-2,2′-bithiophen-2′-yl]-2-cyanoacrylic acid (OrgD) on TiO2 semiconductor particles. The hybrid system reveals persistent photocatalytic behavior, giving high turnover numbers and excellent product selectivity of CO. As a typical run, visible-light irradiation of the hybrid catalyst in the presence of 0.1 M electron donor and 0.001 M LiClO4 persistently produced HCOO– with a ＞99% selectivity accompanied by a trace amount of CO; the turnover number (TON formate) reached ~250 after 23 h 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, the Mn‒H monomeric mechanism associated with HCOO– formation is dominant, whereas at high Mn concentration, CO is formed via an Mn‒Mn dimer mechanism.