Two calcium–cobalt silicates were synthesized in which cobalt occupies different structural positions. The crystal phases belong to two main structural silicate types. In the Co-åkermanite structure (Ca2CoSi2O7), cobalt cations take tetrahedral coordination toward oxygen atoms. In the Co-pyroxene structure of CaCoSi2O6, cobalt displays octahedral coordination. Ca2CoSi2O7 was prepared by solid-phase synthesis and CaCoSi2O6 was prepared by sol–gel method. The synthesis of the phases was confirmed by XRD, FTIR, and EPR data. On the basis of the XPS analysis, it can be concluded that Co2+ cations exist in the studied silicates. Thus, it is possible to study the catalytic activity of two silicate phases containing Co2+ cations in different coordinations: tetrahedral and octahedral. It was found that cobalt silicates with crystal structures corresponding to pyroxene and åkermanite possess catalytic activity in the reactions of complete oxidation of CO and toluene. Co-pyroxene exhibits higher catalytic activity than Co-åkermanite, but the higher cobalt content on the surface of Co-pyroxene should also be taken into account. Then, it turns out that catalytically active complexes with Со2+ ions in tetrahedral coordination are more efficient than those with such ions in octahedral coordination when equal concentrations of cobalt were used on the surface of the catalysts.
