(Al)MCM-41 Molecular Sieves. Aluminium Distribution, Uniformity and Structure of Inner Surface

The effect of the framework Al content and synthesis procedure on the number of framework Al atoms located on the surface of (Al)MCM-41 channels and the distribution of the Al atoms between single Al atoms and various Al-O-(SiO)1,2-Al species was investigated. The total number of accessible framework Al atoms on the channel surface was obtained from the ion exchange capacity for Na+ ions and pyridine adsorption. The number of Al pairs on the surface and their distribution between different local arrangements of the channel surface was estimated using VIS spectroscopy of Co2+ ions. At low framework Al contents, Al atoms occupy only accessible T sites on the surface of the channel walls. In aluminium-rich (Al)MCM-41, a significant part of Al atoms is incorporated inside the channel walls and these Al atoms do not form cationic sites. Al atoms on the wall surface preferentially form Al-O-(SiO)1,2-Al sequences, enabling siting of divalent cations. Different synthesis procedures resulted in differences in Al distribution. The channel surface of the (Al)MCM-41 is formed by two regular local structures containing two types of deformed six-membered rings with Al-O-(SiO)1,2-Al sequences forming cationic sites.