Experimental and theoretical study of multinuclear indium–oxo clusters in CHA zeolite for CH₄ activation at room temperature

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 O2 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 O2-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.