The Meaning of Surface Area and Porosity Measurements of Clays and Pillared Clays

Pillared clays (PC) generally present textural complexity, geometrical constraints and possible chemical heterogeneity by pillaring. As far as surface area and porosity measurements by physical adsorption of nitrogen are concerned, this overall complexity introduces interpretation difficulties. We consider two aspects of this problem in pillared clays. The textural complexity stems from the distribution of charge density, from the deformation of the host layers and from their entanglement. The microtexture is controlled by the wet preparation chemistry, to a large extent by the drying method as examplified by the titanium pillared montmorillonites. The geometrical constraints arise from the fact that the interlamellar space of the PC is (so far) microporous or just mesoporous. The small distance between the layers, of the order of one or a few molecular diameters, is therefore expected to perturb the arrangement of the pore filling molecules. The molecular confinement is a major source of underestimation of the total pore volume in the interlamellar space. It makes the surface area determination difficult and of little physical significance. Probably microporosity values are more valuable criterion of pillaring as shown in the titanium pillared samples. In addition to these two aspects, one has also to consider a possible chemical heterogeneity arising from the simultaneous presence of pillars, exchangeable ions and precipitated species. This can lead to a complex behaviour of surface area and microporosity as examplified by the mixed aluminium-iron pillared laponites.