Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 21, Issue 25, Pages 13415-13427Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9cp01873e
Keywords
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Funding
- JSPS KAKENHI from the Japan Society for the Promotion of Science (JSPS) [17H01341, 18K14051, 18K14057]
- Japanese Ministry of Education, Culture, Sports, Science, and Technology (MEXT)
- JST-CREST [JPMJCR17J3, JPMJCR15P4]
- JST-PREST project [JPMJPR16S8]
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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.
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