Synthesis and properties of nanoparticle forms saponite clay, cancrinite zeolite and phase mixtures thereof

The low-temperature synthesis (90 °C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure-phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al = 1.25) is crystallized at low temperature from a silica-rich synthesis gel, as evidenced by 29Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m2/g) and zeolite end members (8.9–40 m2/g), as well as their unique mixed phase composites (124–329 m2/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils.