Preparation of excessively Ni²⁺-exchanged zeolite Y (FAU, Si/Al = 1.70) and its single-crystal structure

A single crystal of excessively Ni²⁺-exchanged zeolite Y (FAU, Si/Al = 1.70) was prepared by exchange of |Na₇₁|[Si₁₂₁Al₇₁O₃₈₄]-FAU with an aqueous stream 0.05 M Ni(NO₃)₂ at 293 K and pH 4.9, followed by vacuum evacuation at room temperature and 1.3 × 10⁻⁴ Pa. Its crystal structure was determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group Fd3m and was refined to the final error indices R₁/wR₂ = 0.0554/0.1557 for |Ni_24.7(NiOH)_12.1(Ni₂O(OH)₂)_4.8(Ni₄AlO₄)_1.7Na_17.0(H₃O)_6.9|[Si₁₁₇Al₇₅O₃₈₄]-FAU. Crystal has about 53 Ni²⁺ ions per unit cell, indicating the uptake of excess Ni(OH)₂, perhaps as NiOH⁺ ions. Some dealumination of the framework occurred during Ni²⁺ exchange. In this structure, Ni²⁺ ions occupy sites I, I′, II′, II, and III′. The residual Na⁺ ions are found at sites II′ and II. Due to the low pH of the Ni²⁺ exchange solution, some H₃O⁺ ions are observed. Nonframework oxygen atoms as oxide and hydroxide ions and orthoaluminate coordinate to some of Ni²⁺ ions to give NiOH⁺, Ni₂O(OH)₂, and Ni₄AlO₄ ³⁺ groups.