Tailoring the electron density of cobalt oxide clusters to provide highly selective superoxide and peroxide species for aerobic cyclohexane oxidation

The catalytic aerobic cyclohexane oxidation to cyclohexanol and cyclohexanone (KA oil) is an industrially relevant reaction. This work is focused on the synthesis of tailor-made catalysts based on the well-known Co4O4 core in order to successfully deal with cyclohexane oxidation reaction. The catalytic activity and selectivity of the synthesized catalysts can be correlated with the electronic density of the cluster, modulated by changing the organic ligands. This is not trivial in cyclohexane oxidation. Furthermore, the reaction mechanism is discussed on the basis of kinetics and spin trapping experiments, confirming that the electronic density of the catalyst has a clear influence on the distribution of the reaction products. In addition, in situ Raman spectroscopy was used to characterize the oxygen species formed on the cobalt cluster during the oxidation reaction. Altogether, it can be concluded that the catalyst with the highest oxidation potential promotes the formation of peroxide and superoxide species, which is the best way to oxidize inactivated CH bonds in alkanes. Finally, based on the results of the mechanistic studies, the contribution of these cobalt oxide clusters in each single reaction step of the whole process has been proposed.The authors thank Prof. A. Corma for his support and discussion on this work. S. G.-T. thanks MINECO for an FPU Ph.D. contract FPU16/02117. P. O.-B. is grateful for the financial support given by the Spanish Government (RTI2018-096399-A-I00).Peer reviewe