Preparation and structure of a single Au atom on the TiO2(110) surface: control of the Au–metal oxide surface interaction

Kiyotaka Asakura; Satoru Takakusagi; Hiroko Ariga; Wang-Jae Chun; Shushi Suzuki; Yuichiro Koike; Hiromitsu Uehara; Kotaro Miyazaki; Yasuhiro Iwasawa

doi:10.1039/C2FD20131C

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Preparation and structure of a single Au atom on the TiO₂(110) surface: control of the Au–metal oxide surface interaction

Kiyotaka Asakura,*^a Satoru Takakusagi,^a Hiroko Ariga,^a Wang-Jae Chun,^b Shushi Suzuki,^c Yuichiro Koike,^a Hiromitsu Uehara,^a Kotaro Miyazaki^a and Yasuhiro Iwasawa^d

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Catalysis Research Center, Hokkaido University Kita 21-10, Kita Sapporo 001-0021, Japan
E-mail: askr@cat.hokudai.ac.jp ;
Fax: +81-11-706-9113 ;
Tel: +81-11-706-9113

Graduate School of Arts and Sciences, International Christian University, Mitaka, Japan
E-mail: wchun@icu.ac.jp ;
Fax: +81-422-33-1449 ;
Tel: +81-422-33-3293

Department of Crystalline Materials Science, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
E-mail: shushi@apchem.nagoya-u.ac.jp ;
Fax: +81- 52-789-5299 ;
Tel: +052-789-5299

Innovation Research Center for Fuel Cells, Department of Engineering Science, Graduate School of Information Engineering Science, The University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Japan
E-mail: iwasawa@pc.uec.ac.jp ;
Fax: +81-(0)42-443-5483 ;
Tel: +81-(0)42-443-5921

Faraday Discuss., 2013, Advance Article

DOI: 10.1039/C2FD20131C
Received 23 Nov 2012, Accepted 12 Dec 2012
First published online 18 Dec 2012

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Three-dimensional Au structures on bare and organic-compound-modified TiO₂(110) surfaces were interrogated by Au L₃-edge polarization dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS) spectroscopy. On the bare TiO₂(110) surface, icosahedral Au₅₅ nanoclusters were the main product found. When the surfaces were modified with ortho or meso mercaptobenzoic acid (o-MBA or m-MBA), Au was atomically dispersed. Sulfur atoms in the o- and m- MBA formed strong covalent bonds with Au to produce stable Au-MBA (o- and m- forms) surface complexes. On the other hand, only oxygen atoms on the surface did not make a strong enough interaction to stabilize the Au species. We discuss how the Au species formed on the modified TiO₂(110) surface and the possibility to control the Au structure by the surface modification method.

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Kiyotaka Asakura
Satoru Takakusagi
Hiroko Ariga
Wang-Jae Chun
Shushi Suzuki
Yuichiro Koike
Hiromitsu Uehara
Kotaro Miyazaki
Yasuhiro Iwasawa

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Preparation and structure of a single Au atom on the TiO₂(110) surface: control of the Au–metal oxide surface interaction