Synthesis of hydrophobic molecular sieves by hydrothermal treatment with acetic acid

A series of calcined borosilicate molecular sieves are treated hydrothermally with aqueous acetic acid and subsequently characterized in detail. The acid treatments are shown to expel boron from the molecular sieves, and the defects created by the boron removal are subsequently healed with silicon dissolved from other parts of the crystal. By use of this procedure, highly crystalline, hydrophobic all-silica CIT-1 and SSZ-33 (CON topology) molecular sieves are synthesized for the first time. Si-29 Bloch decay (BD) and crosspolarization magic-angle spinning (CPMAS) NMR spectra indicate that the materials have few internal defects and allow for structural characterization of CON materials by Si-29 MAS NMR. Seven unique tetrahedral silicon species are identified in the spectra in agreement with the published crystal structure. The effects of treatment conditions such as acid type, solution pH, and temperature are studied in detail. Conditions near the isoelectric point of silica (pH = 0-2) are found to be efficient for the production of a variety of hydrophobic materials with few structural defects including molecular sieves of the *BEA, CON, and MWW topologies. Detailed control studies using SSZ-33 show that the nearly defect-free materials contain triangular mesopores that are clearly distinguishable in field-emission electron microscopy images. The silica that previously inhabited the mesopores is a likely source for the species required to heal the defects created by boron expulsion: In addition to healing the vacancies previously inhabited by boron with dissolved silicon, an additional aluminum or gallium source can be added to the acetic acid solution and the ions are incorporated into the framework. Many of the defects that are not filled with the Al3+ or Ga2+ species are filled with silicon during the treatment to produce a more hydrophobic metallosilicate than the one containing internal silanol defects.