122nd General Meeting of the KCS

Type Poster Presentation
Area Inorganic Chemistry
Room No. Grand Ballroom
Time 10월 19일 (금요일) 11:00~12:30
Code INOR.P-51
Subject Highly Selective and Durable Photochemical CO2 Reduction by Molecular Mn(I) Catalyst Fixed on Particular Dye-Sensitized TiO2 Platform
Authors Pil Soo Kim, Sunghan Choi, So-Yoen Kim, Chul Hoon Kim, Sang Ook Kang, 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)3Cl (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 (HCOOH versus CO) which surpass the catalytic activities of 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 produced persistently HCOOH with a >99% selectivity accompanied by a trace amount of CO; the turnover number (TONHCOOH) reaches ~210 after 25 h irradiation. The product selectivity (HCOOH/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 the Mn‒H monomeric mechanism associated with HCOOH formation is dominated at low Mn concentration whereas CO is formed via an Mn‒Mn dimer mechanism at high Mn concentration.
E-mail kevin2shc@gmail.com