P-derived organic cations as structure-directing agents: Synthesis of a high-silica zeolite (ITQ-27) with a two-dimensional 12-ring channel system

Recently, efforts have been made to synthesize large-pore, multidimensional zeolite frameworks as a basis for new catalysts to improve various hydrocarbon conversions. A new aluminosilicate zeolite, ITQ-27, has been prepared using the phosphorus-containing structure-directing agent, dimethyldiphenylphosphonium. Its crystal structure was determined in its calcined form by direct methods ( FOCUS) on synchrotron powder diffraction data (lambda = 0.8702 angstrom) after the unit cell and space group were determined from tilt electron diffraction experiments on individual microcrystals. The material crystallizes in space group Fmmm, where a = 27.7508(5) angstrom, b = 25.2969(7) angstrom, and c = 13.7923(4) angstrom. The final model, refined by Rietveld methods, comprises seven unique T-sites forming a framework with straight 12-MR channels that are connected by 14-MR openings between them. ( Corresponding 12-ring pore dimension is 6.94 angstrom x 6.20 angstrom.) Since access from one 14-MR opening to the next is through the 12-MR channel, the structure is best described as a two-dimensional, 12-MR framework.