| Summary: | Saponite is a trioctahedral 2:1 smectite with the ideal composition M<sub>x</sub>Mg<sub>3</sub>Al<sub>x</sub>Si<sub>4−x</sub>O<sub>10</sub>(OH,F)<sub>2</sub>.nH<sub>2</sub>O (M = interlayer cation). Both the success of the saponite synthesis and the determination of its applications depends on robust knowledge of the structure and composition of saponite. Among the routine characterization techniques, spectroscopic methods are the most common. This review, thus, provides an overview of various spectroscopic methods to characterize natural and synthetic saponites with focus on the extensive work by one of the authors (JTK). The Infrared (IR) and Raman spectra of natural and synthetic saponites are discussed in detail including the assignment of the observed bands. The crystallization of saponite is discussed based on the changes in the IR and Raman spectra and a possible crystallization model is provided. Infrared emission spectroscopy has been used to study the thermal changes of saponite in situ including the dehydration and (partial) dehydroxylation up to 750 °C. <sup>27</sup>Al and <sup>29</sup>Si magic-angle-spinning nuclear magnetic resonance spectroscopy is discussed (as well as <sup>11</sup>B and <sup>71</sup>Ga for B- and Ga-Si substitution) with respect to, in particular, Al(IV)/Al(VI) and Si/Al(IV) ratios. X-ray photoelectron spectroscopy provides chemical information as well as some information related to the local environments of the different elements in the saponite structure as reflected by their binding energies.
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