Fluoride Retention During Low Temperature Organic Removal from Imidazolium-Containing Zeolites by Ozone Treatment

For zeolites synthesized using imidazolium cations, the organic matter can be extracted at very low temperatures (100 ºC) using ozone. This is possible for zeolites with 12-ring or larger pores, but requires higher temperatures in medium pore zeolites. The first chemical events in this process occur fast, even at room temperature, and imply the loss of aromaticity likely by formation of an adduct between ozone and the imidazole ring through carbons C4 and C5. Subsequent rupture of the imidazole ring provides smaller and more flexible fragments that can desorb more readily. This process has been studied experimentally, mainly through infrared spectroscopy, and theoretically by density functional theory. Amazingly, fluoride anions occluded in the small double four-ring units (d4r) during the synthesis remain inside the cage throughout the whole process when the temperature is not too high (≤ 150 oC). However, fluoride in larger cages in MFI ends up bonded to silicon in penta or hexacoordinated units, likely out of the cages, after ozone treatment at 150 ºC. For several germanosilicate zeolites, the process allows their subsequent degermanation to yield stable high-silica zeolites. Quaternary ammonium cations, require harsher conditions that eventually also extract fluoride from zeolite cages, including the d4r unit.