Interaction of tetrameric silver with ammonia in AgCs-rho zeolite
Literature Information
Jaroslaw Sadlo, Marek Danilczuk, Jacek Michalik
Cationic silver clusters formed in γ-irradiated AgCs-rho zeolite have been studied by EPR spectroscopy. Tetrameric silver is formed efficiently in the dehydrated form of zeolite as well as in samples exposed to ammonia. However, the hyperfine splitting of the Ag43+ pentet in AgCs-rho/NH3 zeolite is distinctly smaller due to the shift of spin density from silver to nitrogen nuclei, suggesting the formation of an Ag43+–ammonia complex. The observed 14N and 15N superhyperfine splitting from interacting 14NH3 and 15NH3 molecules unequivocally proved the presence of a multicore Ag43+(NH3)n complex. Based on the simulation of 14N and 15N superhyperfine interactions a structure of the complex was proposed in which two ammonia molecules are located close to the octagonal windows of two neighboring α-cages and four further molecules are placed in next-neighboring α-cages interacting with the Ag tetramer through square windows. When dehydrated AgCs-rho zeolite containing radiation-induced Ag43+ clusters is exposed to ammonia the Ag hyperfine splitting of silver tetramer decreases from 13.9 to 10.7 mT proving that Ag43+ clusters are located in the sites accessible to adsorbates.
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Physical Chemistry Chemical Physics

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