Embedding hexanuclear tantalum bromide cluster {Ta6Br12} into SiO2 nanoparticles by reverse microemulsion method
Wanghui Chen,
Maxence Wilmet,
Thai Giang Truong,
Noée Dumait,
Stéphane Cordier,
Yoshio Matsui,
Toru Hara,
Toshiaki Takei,
Norio Saito,
Thi Kim Ngan Nguyen,
Takeo Ohsawa,
Naoki Ohashi,
Tetsuo Uchikoshi,
Fabien Grasset
Affiliations
Wanghui Chen
CNRS-Saint Gobain, UMI 3629, Laboratory for Innovative Key Materials and Structures (LINK), National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Corresponding authors.
Maxence Wilmet
CNRS-Saint Gobain, UMI 3629, Laboratory for Innovative Key Materials and Structures (LINK), National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) – UMR 6226, F-35000 Rennes, France
Thai Giang Truong
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) – UMR 6226, F-35000 Rennes, France
Noée Dumait
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) – UMR 6226, F-35000 Rennes, France
Stéphane Cordier
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) – UMR 6226, F-35000 Rennes, France
Yoshio Matsui
Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Toru Hara
Research Center for Structural Materials, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki, 305-0047, Japan
Toshiaki Takei
Research Network and Facility Services Division, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Norio Saito
CNRS-Saint Gobain, UMI 3629, Laboratory for Innovative Key Materials and Structures (LINK), National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Thi Kim Ngan Nguyen
CNRS-Saint Gobain, UMI 3629, Laboratory for Innovative Key Materials and Structures (LINK), National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Takeo Ohsawa
NIMS-Saint-Gobain Center of Excellence for Advanced Materials, National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Naoki Ohashi
CNRS-Saint Gobain, UMI 3629, Laboratory for Innovative Key Materials and Structures (LINK), National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; NIMS-Saint-Gobain Center of Excellence for Advanced Materials, National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Tetsuo Uchikoshi
CNRS-Saint Gobain, UMI 3629, Laboratory for Innovative Key Materials and Structures (LINK), National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
Fabien Grasset
CNRS-Saint Gobain, UMI 3629, Laboratory for Innovative Key Materials and Structures (LINK), National Institute of Material Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Research Center for Functional Materials (RCFM), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan; Corresponding authors.
Hexanuclear tantalum bromide cluster units [{Ta6Bri12}La6] (i = inner, a = apical, L = ligand OH or H2O) are embedded into SiO2 nanoparticles by a reverse microemulsion (RM) based method. [{Ta6Bri12}Bra2 (H2O)a4]·nH2O (noted TBH) and tetraethyl orthosilicate (TEOS) are used as the starting cluster compound and the precursor of SiO2, respectively. The RM system in this study consists of the n-heptane (oil phase), Brij L4 (surfactants), ethanol, TEOS, ammonia solution and TBH aqueous sol. The size and morphology of the product namely {Ta6Br12}@SiO2 nanoparticles are analyzed by HAADF-STEM and EDS mappings. The presence and integrity of {Ta6Br12} in the SiO2 nanoparticles are evidenced by EDS mapping, ICP-OES/IC and XPS analysis. The optical properties of {Ta6Br12}@SiO2 nanoparticles are analyzed by diffuse reflectance UV-vis spectroscopy, further evidencing the integrity of the embedded {Ta6Br12} and revealing their oxidation state. Both {Ta6Br12}2+ and {Ta6Br12}3+ are found in SiO2 nanoparticles, but the latter is much more stable than the former. The by-products in this RM-based synthesis, as well as their related factors, are also discussed.