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Crystallographic Evidence for the Reduction of CO in Partially Dehydrated Silver Zeolite A

  • Kim, Yang (Department of Chemistry, Pusan National University) ;
  • Song, Seong-Hwan (Department of Chemistry, Pusan National University) ;
  • Seff, Karl (Department of Chemistiry, University of Hawaii)
  • Published : 1989.06.20

Abstract

The crystal structure of $Ag^+$-exchanged zeolite A vacuum-dehydrated at $370^{\circ}C$ and then treated with carbon monoxide at $$23^{\circ}C$ has been determined by single crystal x-ray diffraction methods in the cubic space group Pm3m at $23^(1){\circ}C$ ; a = 12.116 (2)${\AA}$. The structure was refined to the final error indices $R_1\;=\;0.061\;and\;R_2$(weighted) = 0.068 using 349 independent reflections for which I > 3${\sigma}(I).\;3.6\;Ag_+-CO$ complexes, where -CO may represent -CHO or -$CH_2OH$, were found in each large cavity. By coordination to silver atoms followed by reaction with $Ag^{\circ}and\;H^+$ within the zeolite, carbon monoxide has been partially reduced. In about 28% of the sodalite units, a $Ag_6(Ag^+)_2$ cluster may be present. In about 37% of the sodalite units, three $Ag^+$ ions are found on threefold axes where they may be bridged by three water molecules. The remaining 35% of the sodalite units are empty of silver species. Two $Ag^+$ ions per unit cell are associated with 8-ring oxygens. The remaining ca $$3Ag^+$ ions per unit cell have been reduced during the synthesis and have migrated to form small silver crystallities on the surface of the zeolite single crystal.

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References

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  1. Crystal structure of a carbon monoxide sorption complex of dehydrated fully manganese(II)-exchanged zeolite X vol.26, pp.1, 1989, https://doi.org/10.1016/s1387-1811(98)00220-0
  2. Surprising Intrazeolitic Chemistry of Silver vol.120, pp.10, 2016, https://doi.org/10.1021/acs.jpcc.5b11490