title: A Crucial Role of Rh Substituent Ion in Photoinduced Internal Electron Transfer and Enhanced Photocatalytic Activity of CdS-Ti(5.2-x)/6 Rhx /2 O2 Nanohybrids.
abstract: The photocatalytic activity and photostability of CdS quantum dot (QD) can be remarkably enhanced by hybridization with Rh-substituted layered titanate nanosheet even at very low Rh substitution rate (<1%). Mesoporous CdS-Ti(5.2-x)/6 Rhx/2O2 nanohybrids are synthesized by a self-assembly of exfoliated Ti(5.2-x)/6 Rhx/2O2 nanosheets with CdS QDs. The partial substitution of Rh(3+)/Rh(4+) ions for Ti(4+) ions in layered titanate is quite effective in enhancing an electronic coupling between hybridized CdS and titanate components via the formation of interband Rh 4d states. A crucial role of Rh substituent ion in the internal electron transfer is obviously evidenced from in situ X-ray absorption spectroscopy showing the elongation of (RhO) bond under visible light irradiation. This is the first spectroscopic evidence for the important role of substituent ion in the photoinduced electron transfer of hybrid-type photocatalyst. The CdS-Ti(5.2-x)/6 Rhx/2O2 nanohybrids show much higher photocatalytic activity for H2 production and better photostability than do CdS and unsubstituted CdS-TiO2 nanohybrid. This result is ascribable to the enhancement of visible light absorptivity, the depression of electron-hole recombination, and the enhanced hole curing of CdS upon Rh substitution. The present study underscores that the hybridization with composition-controlled inorganic nanosheet provides a novel efficient methodology to optimize the photo-related functionalities of semiconductor nanocrystal.
authors.affiliation: Department of Chemistry and Nanoscience, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Jang Mee
authors.initials: JM
authors.lastname: Lee
authors.affiliation: Department of Chemistry and Nanoscience, Ewha Womans University, Seoul, 03760, Korea.|Department of Chemistry, College of Natural Sciences, Yonsei University, Seoul, 03722, Korea.
authors.forename: Hyung Bin
authors.initials: HB
authors.lastname: Jin
authors.affiliation: Department of Chemistry and Nanoscience, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: In Young
authors.initials: IY
authors.lastname: Kim
authors.affiliation: Department of Chemistry and Nanoscience, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Yun Kyung
authors.initials: YK
authors.lastname: Jo
authors.affiliation: Department of Chemistry, College of Natural Sciences, Yonsei University, Seoul, 03722, Korea.
authors.forename: Jung-Wook
authors.initials: JW
authors.lastname: Hwang
authors.affiliation: Department of Chemistry, College of Natural Sciences, Yonsei University, Seoul, 03722, Korea.
authors.forename: Kang-Kyun
authors.initials: KK
authors.lastname: Wang
authors.affiliation: Pohang Light Sources, Pohang, 37673, Korea.
authors.forename: Min Gyu
authors.initials: MG
authors.lastname: Kim
authors.affiliation: Department of Chemistry, College of Natural Sciences, Yonsei University, Seoul, 03722, Korea.
authors.forename: Yong-Rok
authors.initials: YR
authors.lastname: Kim
authors.affiliation: Department of Chemistry and Nanoscience, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Seong-Ju
authors.initials: SJ
authors.lastname: Hwang
keywords: cation substitution; electronic coupling; hybrid materials; metal oxide nanosheets; photocatalysis, electron transfer