Solvent-free oxidation of ethylbenzene over hierarchical flower-like core–shell structured Co-based mixed metal oxides with significantly enhanced catalytic performance

Herein, we reported the development of new and cost-effective cobalt-based metal oxide catalysts for the oxidation of ethylbenzene, which is considered to be of much importance for the production of high value-added raw materials. The heterogeneous Co-based catalyst system, hierarchical flower-like core–shell structured Co–Zn–Al mixed metal oxides supported on alumina (CoZnAl-MMO/Al 2 O 3 ), was reproducibly prepared by a two-step process, which involved in situ growth of a two-dimensional Co–Zn–Al layered double hydroxide precursor on amorphous alumina microspheres followed by calcination. The materials were characterized by XRD, SEM, TEM, HRTEM, TPR, XPS and nitrogen adsorption–desorption measurement. The results revealed that CoZnAl-MMO/Al 2 O 3 catalysts exhibited high dispersion of cobalt species due to well-developed three-dimensional flower-like CoZnAl-MMO platelets as well as the separating effect of the resulting ZnO phase. As-synthesized CoZnAl-MMO/Al 2 O 3 catalysts were studied in the oxidation of ethylbenzene without the addition of any solvent and additive using tert -butyl hydroperoxide as the oxygen source and showed much higher catalytic activity and selectivity for acetophenone compared with the conventional supported Co-based catalyst prepared by incipient impregnation. Furthermore, such cost-effective CoZnAl-MMO/Al 2 O 3 catalysts possessed high stability and could be reused at least three times without remarkable loss of the catalytic activity.