Electronic Structure and Reactivity of TM-Doped La 1-x Sr x CoO 3 (TM=Ni, Fe) Heterogeneous Catalysts

TLDR: In this article, the catalytic properties of LaCoO3 in aqueous oxidation are explored as a function of doping, both Sr substitution for La and Fe/Ni substitution for Co are studied.

Abstract: The catalytic properties of LaCoO3 in aqueous oxidation are explored as a func- tion of doping. Both Sr substitution for La and Fe/Ni substitution for Co are studied. The re- action of interest is the aqueous epoxidation of crotyl alcohol with hydrogen peroxide. The reaction products are measured using GC, and the decomposition of hydrogen peroxide is studied using the volume of oxygen evolved during reaction. Strong variations in the activ- ity to epoxide formation are observed, with Fe-doped samples being rather inactive in the reaction. SR VUV photoemission is used to explore the surface reactivity of the ceramic catalysts in aqueous solution, using H2O as a p robe molecule. These measurements are complemented by XANES measurements designed to probe the local defect structure and XPS measurements of surface composition. We relate the observed catalytic activity to the defect structure of the doped materials. In Ni-doped materials, oxygen vacancies appear to be the predominant defect, whereas in Fe-doped samples, electron holes are stabilized on Fe, leading to very different catalytic behaviour. Surface studies in combination with AA measurements reveal some dissolution of the catalyst into solution during the reaction. The surface reactivity to water is influenced by the TM d electron count, with water binding more strongly to Fe-doped materials than to those containing Ni. The influence of these fac- tors on the rate of the unwanted hydrogen peroxide decomposition reaction and hence on ac- tivity in epoxidation is discussed.