title: Relative activity of La2O3, LaOCl, and LaCl3 in reaction with CCl4 studied with infrared spectroscopy and density functional theory calculations.
abstract: Relative activity of La2O3, LaOCl, and LaCl3 in the destructive adsorption of CCl4 to CO2 was studied with density-functional theory calculations and temperature-programmed reaction experiments monitored with IR spectroscopy. Integral absorbance of the IR peak for phosgene, which is a reaction intermediate, was obtained as a function of temperature, and initial reaction temperatures were compared for different sample amounts of La2O3 and LaOCl. The initial reaction temperatures of about 390 K for La2O3 and 365 K for LaOCl were practically independent of the tested sample weights, and the lower temperature for LaOCl was attributed to a higher activity of surface sites on this material. Calculations suggest that CCl4 decomposition proceeds through a stepwise Cl donation from CCl4 to the surface and that the overall rate is controlled by the first step: CCl4 splitting into a Cl anion and CCl3 cation over an acid-base pair of surface sites. A lanthanum acid site in the pair initiates the split by interacting with one of the chlorine atoms in CCl4, and an oxygen base site stabilizes the remaining CCl3 fragment. Transition state estimates suggest that the relative activity of surface sites can be ranked in the following order: LaOCl > LaCl3 with a partially dechlorinated surface > La2O3. Surface Lewis acidity and basicity of these materials are summarized in terms of the vibrational frequency for adsorbed CO, energy of the lowest unoccupied molecular orbital, and proton affinity. Higher activity of LaOCl is attributed to the higher acidity of the lanthanum site, the higher basicity of the oxygen site, and the geometry of the acid-base pair of sites that allows them to interact with CCl4 simultaneously.
authors.affiliation: The Dow Chemical Company, Core Research and Development, Midland, Michigan 48674, USA.
authors.forename: Simon G
authors.initials: SG
authors.lastname: Podkolzin
authors.forename: Olga V
authors.initials: OV
authors.lastname: Manoilova
authors.forename: Bert M
authors.initials: BM
authors.lastname: Weckhuysen