Interaction of surface hydroxyls with adsorbed molecules. A quantum-chemical study

Journal Article · Thu Nov 08 04:00:00 EST 1984 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j150667a058· OSTI ID:6061599

Geerlings, P; Tariel, N; Botrel, A; Lissillour, R; Mortier, W J

A study has been conducted to explain the interaction mechanisms of (bridging and terminal) surface hydroxyl groups with molecules, using ab initio, EHT, and CNDO/2-FA quantum-chemical calculations. Bond strength variations and charge shifts were found to be in complete agreement with Gutmann's rules, and provide a basis for the understanding of the Bronsted acid properties of zeolites and amorphous silica-alumina. A quantitative measure of the interaction strength is possible by referring to the experimentally determined donor number (Gutmann) following many molecules, but care should be taken for those molecules for which the donor strength was determined by indirect methods. Only a few exceptions to Gutmann's rules should exist, e.g., in those cases where the atom interacting with the proton is not the most electronegative of the donor molecule (such as for CO). Individual bonds in a given complex are more susceptible to perturbations (changes in composition and interactions with adsorbing molecules) if the coordination number increases. These rules are in agreement with the observations and apply to all reactions (inter- or intramolecular) involving a change in coordination. 52 references, 6 figures, 4 tables.

• Research Organization: Vrije Universiteit, Brussels, Belgium
• OSTI ID: 6061599
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 88:8; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400600 -- Radiation Chemistry
ADSORBENTS
ALUMINIUM COMPOUNDS
ALUMINIUM OXIDES
AMMONIA
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
COMPLEXOMETRY
CONFIGURATION INTERACTION
CORRELATIONS
EXTRAPOLATION
FORECASTING
HYDRIDES
HYDROGEN COMPOUNDS
HYDROXYL RADICALS
INORGANIC ION EXCHANGERS
ION EXCHANGE MATERIALS
MATERIALS
MATHEMATICAL MODELS
MECHANICS
MINERALS
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL SOLUTION
OXIDE MINERALS
OXIDES
OXYGEN COMPOUNDS
QUANTUM MECHANICS
RADICALS
SILICA
SILICA GEL
SILICON COMPOUNDS
SILICON OXIDES
SURFACE PROPERTIES
WATER
ZEOLITES