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The series of layered double hydroxides, MgnAl(OH)2n+2X (n = 2–5, X = NO3− or Cl−) and NinAl(OH) 2n+2X (n = 2–4, X = NO3− or Cl−), were pillared with polyoxometalate ions of the Keggin structure, ranging from [PW12O40]3− to [PV4W8O40]7−, in aqueous solution. Full exchange of the Keggin ions into the layers is achieved as evidenced by X-ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Also, partial exchange was observed for Ni5Al(OH)12NO3 The key factor that effects these reactions is the pre-swelling step. Thus, when the layered double hydroxides are thoroughly wet either by preparing wet solids or by soaking the dried products for an extended period, pillaring reactions proceed with great ease. Relations can be extracted between the water content and the separation between the layers, as well as between layer charge density and the charge of the Keggin ion. The pillared layered double hydroxides were found generally to have interlayer distances ranging from 11.0 to 13.5 Å, which is smaller than the numerical sum of the Keggin ion diameter and the ideal thickness of the hydroxide layer. This fact and the low crystallinity are attributed to strong interaction between the basic layered double hydroxides and the acidic Keggin ions. A more crystalline phase with the expected 14.5 Å interlayer spacing was also obtained as a mixture with the lower spaced products.

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