科研之友
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摘要
The reaction of nitric oxide with fully dehydrated, fully In-exchanged zeolite Y (In-Y, FAU with Si/Al = 1.69) yields zeolite Y with distorted cubic In4O44+ cations, one per sodalite cavity, and In3+-NO3- complexes with facially coordinating nitrate ions in the supercages. With only trigonal coordination, additional In3+ and In+ ions occupy supercage sites. vertical bar In3+ In-4.6(+) (17.9)(In4O44+)(8)(In3+-NO3-)(4.2)vertical bar- [Si121Al71O384]-FAU was prepared by the reaction of In-Y with 300 Torr of NO(g) at 673 K under anhydrous conditions. Its structure was determined by single-crystal crystallography with synchrotron X-radiation. It was refined in the space group Fd (3) over barm (a = 24.617(1) angstrom) with all 1145 unique data; the final error index, R-1 = 0.081, was calculated using only the 988 reflections with F-o > 4 sigma(F-o). Upon reaction with NO, most of the In+ ions and the few In2+ ions in In-Y were oxidized to In3+. Most of these In3+ ions are members of In4O44+ clusters and In3+-NO3- complexes; NO has reacted to form O-2(-), NO3-, and apparently N-2 and In2O. Each In3+ ion in In4O44+ is octahedral, bonding to three framework oxygen atoms of a double 6-ring at 2.182(7) angstrom and to three extra-framework oxide ions of its cluster at 2.229(5) angstrom. The In3+ ion in In3+-NO3- is capped octahedral, bonding to three framework oxygens at 2.208(11) angstrom and facially to the three oxygen atoms and the nitrogen atom of a NO3- anion (In3+-O = 1.91(7) angstrom, In3+-N = 1.68(13) angstrom, N-O = 1.47(8) angstrom). The nitrate ion is seen for the first time to behave as a tetradentate ligand to a single cation.
- 出版日期2011-10-20
