The location of extra-framework Ni2+ cations in the hydrated and dehydrated nickel ion-exchanged zeolite ferrierite was determined from the analysis of synchrotron X-ray powder diffraction data. Rietveld refinements were performed in the Immm space group. One Ni2+ was found at the centre of the ferrierite cage coordinated to six water molecules in a quite regular octahedral coordination. The Ni(H2O)(6)(2+) octahedron assumes two equally probable statistical orientations, which differ by a rotation of about 45 degrees around the z axis. These two configurations of the Ni(H2O)(6)(2+) polyhedron show strong similarities with the two configurations of the Mg(H2O)(6)(2+) polyhedron found in natural Mg-rich ferrierite. However, whereas the cation site in natural Mg-ferrierite is fully occupied, in the Ni-exchanged form, this site is only half occupied. The unit cell volume of dehydrated Ni-ferrierite was 1.4% smaller than the unit cell volume of the hydrated phase. Two other Ni2+ extra-framework sites were found, one near the centre of the 10-ring channel, the other not far from the centre of the 8-ring window of the ferrierite cage. Four Ni2+ extra-framework sites were localised in dehydrated Ni-ferrierite. The first is near the centre of the 6-ring window of the ferrierite cage, the second is located on the walls of the cage, the third is in the 10-ring channel, and the last is at the intersection of the 10- and 8-ring channels. The last Ni2+ site is very close to the Cu(1) site found by Attfield et al. [M.P. Attfield, S.J. Weigel, A.K. Cheetham, J. Catal. 172 (1997) 274-280] in dehydrated Cu-ferrierite, whereas the other three Ni2+ sites resemble the alpha-, beta- and gamma-type sites of Kaucky et al. [D. Kaucky, J Dedecek, B. Wichterlova, Micropor. Mesopor. Mater. 31 (1999) 75-87] in dehydrated Co-ferrierite.
Ni2+ ion sites in hydrated and dehydrated forms of Ni-exchanged zeolite ferrierite
DALCONI, Maria Chiara;CRUCIANI, Giuseppe;ALBERTI, Alberto;
2000
Abstract
The location of extra-framework Ni2+ cations in the hydrated and dehydrated nickel ion-exchanged zeolite ferrierite was determined from the analysis of synchrotron X-ray powder diffraction data. Rietveld refinements were performed in the Immm space group. One Ni2+ was found at the centre of the ferrierite cage coordinated to six water molecules in a quite regular octahedral coordination. The Ni(H2O)(6)(2+) octahedron assumes two equally probable statistical orientations, which differ by a rotation of about 45 degrees around the z axis. These two configurations of the Ni(H2O)(6)(2+) polyhedron show strong similarities with the two configurations of the Mg(H2O)(6)(2+) polyhedron found in natural Mg-rich ferrierite. However, whereas the cation site in natural Mg-ferrierite is fully occupied, in the Ni-exchanged form, this site is only half occupied. The unit cell volume of dehydrated Ni-ferrierite was 1.4% smaller than the unit cell volume of the hydrated phase. Two other Ni2+ extra-framework sites were found, one near the centre of the 10-ring channel, the other not far from the centre of the 8-ring window of the ferrierite cage. Four Ni2+ extra-framework sites were localised in dehydrated Ni-ferrierite. The first is near the centre of the 6-ring window of the ferrierite cage, the second is located on the walls of the cage, the third is in the 10-ring channel, and the last is at the intersection of the 10- and 8-ring channels. The last Ni2+ site is very close to the Cu(1) site found by Attfield et al. [M.P. Attfield, S.J. Weigel, A.K. Cheetham, J. Catal. 172 (1997) 274-280] in dehydrated Cu-ferrierite, whereas the other three Ni2+ sites resemble the alpha-, beta- and gamma-type sites of Kaucky et al. [D. Kaucky, J Dedecek, B. Wichterlova, Micropor. Mesopor. Mater. 31 (1999) 75-87] in dehydrated Co-ferrierite.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
