Magnetic studies of zeolites. Part 2.—Magnetic properties of NiA, NiX and NiY

Abstract

The bulk susceptibilities of nickel-exchanged forms of zeolites A, X and Y measured over a wide range of temperature show that in the fully hydrated zeolites the nickel ions are octahedrally coordinated. On dehydration, the octahedral coordination is retained by the nickel ions of NiA and NiCaX. However, highly dehydrated NiA was found to be unstable.

For NiX and NiY, the reciprocal susceptibility passed through a maximum when the number of residual water molecules were 4 to 6 per Ni²⁺ ion. This is believed to arise from a distorted octahedral or pentahedral coordination around the Ni²⁺ ions, where some of the ligands are residual water molecules and the other ligands are lattice oxygen ions. Further dehydration causes a decrease in the reciprocal susceptibility, this being attributed to many of the Ni²⁺ ions being in tetrahedral coordination, where three of the ligands are lattice oxygen and the fourth is derived from residual water. A tendency for Ni²⁺ to occupy the hexagonal prisms in preference to sites I′ and II′ is evident in dehydrated CaNiX but not in NiX or NiY. The Ni²⁺ ions may move out of the hexagonal sites of dehydrated NiX, NiY and CaNiX at T>400 K; this behaviour is reversible.

We suggest that where most of the Ni²⁺ ions in a dehydrated zeolite are tetrahedrally coordinated, the nickel ions are less susceptible to reduction.