129Xe NMR study of carbonaceous materials: effects of surface chemistry and nanotexture Original Research Article

Some aspects of the relationship between the physicochemical state of microcrystalline carbons and the 129Xe NMR parameters of adsorbed xenon have been investigated. No correlation between the values of the 129Xe chemical shift (δ0) and the substructural characteristics of the carbons (interlayer spacing, crystallite size, content of ordered or amorphous carbon of the samples), micropore volume and specific surface area was revealed. The δ0 values increase linearly with the surface concentrations of `strongʹ adsorption sites for H2PdCl4, and chemisorbed heteroatoms (O, Cl) as well. HREM studies of carbon surface microstructure revealed δ0 to be nanotexture-dependent. The lowest δ0 value (∼14 ppm) was detected for a graphitized carbon black, the surface of which consists primarily of exposed basal planes of carbon crystallites, and the highest δ0 value (∼100 ppm) for a carbon sample with exposed edge faces. Medium δ0 values (50±10 ppm) were found for carbons the surface of which was roughened by steps formed by carbon layers of different size. The 129Xe NMR technique, in combination with the common procedures for the determination of the surface area of solids, may open a way to estimate the contribution of the edge faces of carbon crystallites to the total surface area of unoxidized carbons.