Structure of Co(II) Species Formed on the Surface of γ-Alumina Upon Interfacial Deposition

ABSTRACT

The mode of retention of Co(H2O)6 2+ species at the “γ-alumina/aquatic solution” interface is refined using simulations, adsorption isotherm, potentiometric mass titrations and mainly proton - ion titrations jointly with diffuse reflectance spectroscopy. It was found that the increase in the Co(II) surface concentration affects considerably the kind of the Co(II) species deposited. Mononuclear/mono-substituted inner sphere Co(II) complexes are formed at extremely low Co(II) surface concentration. A mixed surface state involving mononuclear/mono-substituted and binuclear/bi-substituted Co(II) complexes is formed at relatively low Co(II) surface concentration. Only binuclear/bi-substituted Co(II) complexes are formed at intermediate Co(II) surface concentration. Finally, oligo-nuclear inner sphere Co(II) species are formed at relatively high Co(II) surface concentration, in addition to the bi-nuclear ones. The above species concern a range of surface Co(II) concentration extending from zero to 2.7 theoretical surface layers of [Co(H2O)6]2+. The formation of Co(II) surface precipitate starts above these theoretical surface layers. The above indicates that one may control the surface Co(II) concentration, by adjusting the Co(II) concentration in the impregnating solution, and thus the Co(II) surface species formed. This control allows tailoring the preparation of cobalt catalysts supported on γ-alumina and thus the development of effective Co/γ-alumina catalysts.

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