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| Type |
Symposium |
| Area |
Material Design and Applications for Artificial Photosynthesis |
| Room No. |
Room 405+406 |
| Time |
FRI 15:55-16:20 |
| Code |
MAT3-4 |
| Subject |
Highly Selective and Durable Photochemical CO2 Reduction by Molecular Mn(I) Catalyst Fixed on Particular Dye-Sensitized TiO2 Platform |
| Authors |
Ho-Jin Son
Department of Advanced Materials Chemistry, Korea University , Korea |
| Abstract |
A new Mn(I)-based hybrid system (OrgD-|TiO2|-MnP) for photocatalytic CO2 reduction is designed to be a co-assembly 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 excellent product selectivity (HCOO– versus CO) that surpass the catalytic activities of the related homogeneous and other heterogenized Mn photocatalytic systems reported so far. 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 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 an Mn‒Mn dimer mechanism. |
| E-mail |
hjson@korea.ac.kr |
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123rd General Meeting of the KCS