TY - JOUR
T1 - Encapsulation of Two Potassium Cations in Preyssler-Type Phosphotungstates
T2 - Preparation, Structural Characterization, Thermal Stability, Activity as an Acid Catalyst, and HAADF-STEM Images
AU - Hayashi, Akio
AU - Ota, Hiromi
AU - López, Xavier
AU - Hiyoshi, Norihito
AU - Tsunoji, Nao
AU - Sano, Tsuneji
AU - Sadakane, Masahiro
N1 - Funding Information:
MS is grateful for Grants-in-Aid for Scientific Research (Scientific Research C, grant no. 26420787) from the Ministry of Education, Culture, Sports, and Science, Japan, and A-STEP program of the Japanese Science and Technology Agency (JST), and Furukawa Foundation for Promotion of Technology. XL is grateful to the Spanish Ministry of Science and Innovation (MICINN) (project CTQ2014-52774-P), the DGR of the Generalitat de Catalunya (grant no. 2014SGR199), and the XRQTC. The electron microscopy study by NH was supported by JSPS KAKENHI Grant Number JP16K06863. We thank T. Amimoto and N. Kawata at the Natural Science Center for Basic Research and Development (N-BARD), Hiroshima University, for the ESI-MS measurement and initial single crystal X-ray structure analysis, respectively.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/11/7
Y1 - 2016/11/7
N2 - Dipotassium cation (K+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110K2]13-, was prepared by heating monobismuth (Bi3+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110Bi(H2O)]12-, in acetate buffer in the presence of an excess amount of potassium cations. Characterization of the isolated potassium salt, K13[P5W30O110K2] (1a), and its acid form, H13[P5W30O110K2] (1b), by single crystal X-ray structure analysis, 31P and 183W nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, cyclic voltammetry (CV), high-resolution electrospray ionization mass spectroscopy (HR-ESI-MS), and elemental analysis revealed that two potassium cations are encapsulated in the Preyssler-type phosphotungstate molecule with formal D5h symmetry, which is the first example of a Preyssler-type compound with two encapsulated cations. Incorporation of two potassium cations enhances the thermal stability of the potassium salt, and the acid form shows catalytic activity for hydration of ethyl acetate. Packing of the Preyssler-type molecules was observed by high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).
AB - Dipotassium cation (K+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110K2]13-, was prepared by heating monobismuth (Bi3+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110Bi(H2O)]12-, in acetate buffer in the presence of an excess amount of potassium cations. Characterization of the isolated potassium salt, K13[P5W30O110K2] (1a), and its acid form, H13[P5W30O110K2] (1b), by single crystal X-ray structure analysis, 31P and 183W nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, cyclic voltammetry (CV), high-resolution electrospray ionization mass spectroscopy (HR-ESI-MS), and elemental analysis revealed that two potassium cations are encapsulated in the Preyssler-type phosphotungstate molecule with formal D5h symmetry, which is the first example of a Preyssler-type compound with two encapsulated cations. Incorporation of two potassium cations enhances the thermal stability of the potassium salt, and the acid form shows catalytic activity for hydration of ethyl acetate. Packing of the Preyssler-type molecules was observed by high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).
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U2 - 10.1021/acs.inorgchem.6b02116
DO - 10.1021/acs.inorgchem.6b02116
M3 - Article
AN - SCOPUS:84994642920
SN - 0020-1669
VL - 55
SP - 11583
EP - 11592
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -