title: Organic-inorganic hybrid photocatalyst for carbon dioxide reduction.
abstract: Efficient hybrid photocatalysts for carbon dioxide reduction were developed from dye-sensitized TiO2nanoparticles and their catalytic performance was optimized by ternary organic/inorganic components. Thus, the hybrid system consists of (E)-2-cyano-3-(5'-(5''-(p-(diphenylamino)phenyl)thiophen-2''-yl)thiophen-2'-yl)-acrylic acid as a sensitizer and fac-[Re(4,4'-bis(diethoxyphosphorylmethyl)-2,2'-bipyridine)(CO)3Cl] as a reduction catalyst (ReP), both of which have been fixed onto TiO2semiconductors (s-TiO2, h-TiO2, d-TiO2). Mott-Schottky analysis on flat-band potential (Efb) of TiO2mesoporous films has verified that Efbcan be finely modulated by volume variation of water (0 to 20 vol%). The increase of added water resulted in substantial positive shifts of Efbfrom -1.93 V at 0 vol% H2O, to -1.74 V (3 vol% H2O), to -1.56 V (10 vol% H2O), and to -1.47 V (20 vol% H2O). As a result, with addition of 3-10 vol% water in the photocatalytic reaction, conversion efficiency of CO2to CO increased significantly reaching a TON value of ∼350 for 30 h. Catalytic activity enhancement is mainly attributed to (1) the optimum alignment of Efbby 3-10 vol% water with respect to the of the dye and Eredof ReP for smooth electron transfer from photo-excited dye to RePvia the TiO2semiconductor and (2) the water-induced acceleration of chemical processes on the fixed ReP. In addition, the energy level was further tuned by variation of the dye and ReP amounts. We also found that the intrinsic properties of TiO2sources (morphology, size, agglomeration) exert a great influence on the overall photocatalytic activity of this hybrid system. Implications of the present observations and reaction mechanisms are discussed in detail.
authors.affiliation: Department of Advanced Materials Chemistry, Korea University, Sejong 30019, Korea. hjson@korea.ac.kr.
authors.forename: Dong-Il
authors.initials: DI
authors.lastname: Won
authors.forename: Jong-Su
authors.initials: JS
authors.lastname: Lee
authors.forename: Ha-Yeon
authors.initials: HY
authors.lastname: Cheong
authors.forename: Minji
authors.initials: M
authors.lastname: Cho
authors.forename: Won-Jo
authors.initials: WJ
authors.lastname: Jung
authors.forename: Ho-Jin
authors.initials: HJ
authors.lastname: Son
authors.forename: Chyongjin
authors.initials: C
authors.lastname: Pac
authors.forename: Sang Ook
authors.initials: SO
authors.lastname: Kang