The role of MCM-41 composition in the creation of basicity by alkali metal impregnation

Three types of mesoporous molecular sieves (silicate MCM-41, niobosilicate NbMCM-41, and aluminosilicate AlMCM-41) were impregnated with alkali metal acetates. The textural stability of the samples was estimated on the basis of XRD measurements and nitrogen adsorption/desorption methods. The acidic–basic properties of the obtained materials were tested in the cyclization of acetonylacetone and studied by FTIR spectroscopy after adsorption of methylacetylene (propyne) and pyridine. Two types of chemical reactions between mesoporous matrix and alkali metal salt/oxide were observed: the reaction between alkali metal salt and silica/silicate and the reaction between basic oxide and silanol groups or Na+ cations. In the first one the alkali metal silicate formation decreases from Li to Cs species and leads to the destruction of the material. The second reaction places alkali metal cations in extra framework positions, which increases from Li to Cs species and is only observed in the case of AlMCM-41 and NbMCM-41 materials. As a result of the second reaction Lewis acidity is generated. The average effect of these two interactions leads to the volcanic curve for basicity of M/AlMCM-41 and M/NbMCM-41 with the maximum for K-samples. In contrast, basicity of M/MCM-41 systematically increases from Li to Cs form since the second type of interaction does not occur for these samples.