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Experimental and theoretical study of multinuclear indium-oxo clusters in CHA zeolite for CH4 activation at room temperature
Title: | Experimental and theoretical study of multinuclear indium-oxo clusters in CHA zeolite for CH4 activation at room temperature |
Authors: | Maeno, Zen Browse this author →KAKEN DB | Yasumura, Shunsaku Browse this author | Liu, Chong Browse this author | Toyao, Takashi Browse this author →KAKEN DB | Kon, Kenichi Browse this author | Nakayama, Akira Browse this author | Hasegawa, Jun-ya Browse this author →KAKEN DB | Shimizu, Ken-ichi Browse this author →KAKEN DB |
Issue Date: | 7-Jul-2019 |
Publisher: | Royal Society of Chemistry |
Journal Title: | Physical chemistry chemical physics |
Volume: | 21 |
Issue: | 25 |
Start Page: | 13415 |
End Page: | 13427 |
Publisher DOI: | 10.1039/c9cp01873e |
Abstract: | We have carried out an experimental and theoretical study of CHA-zeolite supported indium (In)-oxo clusters that promote CH4 activation at room temperature. X-ray absorption fine structure (XAFS) measurements indicate the formation of multinuclear In-oxo clusters by the O-2 activation of the In(I)-exchanged CHA zeolite prepared through reductive solid-state ion exchange (RSSIE). The structure of the In-oxo clusters and their locations were investigated in detail using ab initio thermodynamic analysis. The redox properties of the In species during RSSIE and the formation of the In-oxo clusters were also studied by temperature programmed reaction and in situ XAFS measurements. The reaction of CH4 on the O-2-activated In-CHA zeolite was monitored using IR spectroscopy where adsorbed formic acid was generated at room temperature. The adsorption and C-H activation of CH4 on our plausible model of the In-oxo clusters were theoretically investigated using density functional theory calculations. We found that CH4 is likely to adsorb and react more easily on dinuclear In-oxo ions than on monomeric In-oxo ions and that the C-H bond cleavage reaction occurs via a heterolytic pathway rather than a homolytic pathway. This study reveals the potential of multinuclear In-oxo clusters as active sites for the transformation of CH4 to oxygenates under mild reaction conditions. |
Type: | article (author version) |
URI: | http://hdl.handle.net/2115/78825 |
Appears in Collections: | 触媒科学研究所 (Institute for Catalysis) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 前野 禅
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