Although the layer charge in 2:1 phyllosilicate minerals is known to result from the replacement of tetrahedral Si or octahedral Al, Fe and Mg by ions of lower charge, there is only limited information concerning the distribution of layer charge from X-ray crystallographic data1–3. Here we use 29Si and 27Al magic angle spinning (MAS) NMR spectroscopy to examine the site distribution of tetrahedral Si and Al in a series of synthetic trioctahedral clays with (Si/Al)tetr values in the range 2.74–7.69. Analysis of the 29Si spectra shows that Loewenstein's rule for Al occupancy of the tetrahedral sheet is obeyed and that there is some short-range ordering for Al sites. The nature of the ordering is explained in part by the results of electrostatic potential energy calculations. In general, strong 27Al resonances are observed for Al in tetrahedral sites, but the resonances due to Al in octahedral sites are considerably weaker than would be expected on the basis of chemical analysis. Consequently, no quantitative analysis of the 27Al spectra is possible.
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Lipsicas, M., Raythatha, R., Pinnavaia, T. et al. Silicon and aluminium site distributions in 2:1 layered silicate clays. Nature 309, 604–607 (1984). https://doi.org/10.1038/309604a0
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