Estimation of the catalytic centre in double metal cyanide catalysts by XAS

Double metal cyanide (DMC) catalysts are commonly applied at industrial ring opening polymerization of epoxides. Nevertheless, the knowledge on the molecular nature of their high activity and selectivity is limited. XAS studies were performed to look for the possible catalytic centre in this family of catalysts. DMC catalysts were synthesized from ZnCl2 and potassium hexacyanocobaltate(III) solution, in the presence of the different organic ligands and show significant fraction of the non-crystalline structure. Two ligands were analysed (tert-butanol (tBuOH) or glyme (CH3OCH2CH2OCH3)). EXAFS analysis established that only Zn atoms are the active metallic centers in DMC regardless the used ligand. The coordination around Zn was changed from octahedral in reference non catalytic material to tetrahedral in catalysts, and Cl atoms were detected near some of Zn atoms.