AbstractThe structure of synthetic aluminosilicates prepared at pH 6 has been investigated by 29Si and 27Al high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy. Fourier transform infrared (FTIR) spectroscopy and electron microscopy have also been used to characterize the products. The amount of Si and Al in protoimogolite, disordered allophane and other structures has been measured. There is a fair correlation between the intensity of the 349 cm−1 band in the FTIR spectra and the proportion by weight of protoimogolite Si measured by NMR. It is shown that disordered allophanes have similar structures to those proposed by van Reeuwijk and de Villiers (Soil Sci. Soc. Am. Proc. 32 (1968) 238–240), i.e. octahedral Al surrounding a tetrahedral core. Moreover, it is clear that at high Al:Si ratios (⩾1:1), protoimogolite can compete with disordered allophane precursors for aluminum. The driving forces for formation of protoimogolite rather than allophane appear to be long range Al-Al repulsive forces through oxygen.