Atomic scale insights on chlorinated gamma-alumina surfaces.

The thermochemistry of chlorinated gamma-alumina surfaces is explored by means of density functional calculations as a function of relevant reaction conditions used in experiments and in high-octane fuel production in the refining industry such as hydrocarbon isomerization and reforming. The role of chlorine as a dope of the Brønsted acidity of gamma-alumina surfaces is investigated at an atomic scale. Combining infrared spectroscopy and density functional theory calculations, the most favorable location of chlorine atoms on the (110), (100) and (111) surfaces of gamma-alumina is found to result either from direct adsorption or from the exchange of basic hydroxyl groups. Moreover, the modification of the hydrogen bond network upon chlorine adsorption is put forward as a key parameter for changing the Brønsted acidity. In a second step, we use a thermodynamic approach based on DFT total energy calculations corrected by the chemical potentials of HCl and H2O to determine the adsorption isotherms of chlorine and the relative surface concentration of hydroxyl groups and chlorine species on the gamma-alumina surfaces. The determination of chlorine content as a function of temperature and partial pressures of H2O and HCl offers new quantitative data required for optimizing the state of the support surface in industrial conditions. The mechanisms of chlorination are also discussed as a function of reaction conditions.