title: Mutable Lewis and Brønsted acidity of aluminated SBA-15 as revealed by NMR of adsorbed pyridine-15N.
abstract: (1)H and variable-temperature (15)N NMR techniques have been used to study the effect of the gradual alumination of SBA-15 on the structure and adsorption properties of this mesoporous material. The interpretation of experimental spectra suggests that aluminum chlorhydrol most effectively reacts with silica surfaces in the confinement of the cavities of rough mesopore walls, instead of forming a homogeneous aluminum film. This first leads to a gradual filling of the cavities and finally results in aluminum islands on the inner surfaces of mesopores. In the sample with a Si/Al atomic ratio of 4.1, up to half of the inner surface area of the mesopores is covered with aluminum. The alumination produces Brønsted acid sites attributed to silanol groups interacting with aluminum but does not affect the proton-donating ability of isolated silanol groups. At high Si/Al ratios, the surface contains only one type of Lewis site attributed to tetracoordinated aluminum. At lower Si/Al ratios, Lewis acid sites with a lower electron-accepting ability appear, as attributed to pentacoordinated aluminum. The numerical values of the surface densities of all chemically active sites have been estimated after annealing at 420 and 700 K. We were surprised to observe that gaseous nitrogen can occupy Lewis acid sites and hinder the interaction of the aluminum with any other electron donor. As a result, aluminated surfaces saturated with nitrogen do not exhibit any Brønsted or Lewis acidity. At room temperature, it takes days before pyridine replaces nitrogen at the Lewis acid sites.
authors.affiliation: Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin, Germany.
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Gurinov
authors.forename: Yulia A
authors.initials: YA
authors.lastname: Rozhkova
authors.forename: Arnošt
authors.initials: A
authors.lastname: Zukal
authors.forename: Jiří
authors.initials: J
authors.lastname: Čejka
authors.forename: Ilya G
authors.initials: IG
authors.lastname: Shenderovich
mesh_terms: D000143:Acids / Q000737:chemistry*; D000327:Adsorption; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009587:Nitrogen Isotopes; D011725:Pyridines / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*; D013499:Surface Properties; D013696:Temperature
chemical_list: D000143:Acids; D009587:Nitrogen Isotopes; D011725:Pyridines; C509969:SBA-15; D012822:Silicon Dioxide; C023666:pyridine