Dual-Site Cooperation for High Benzyl Alcohol Oxidation Activity of MnO2 in Biphasic MnOx–CeO2 Catalyst Using Aerial O2 in the Vapor Phase

Abstract

Selective oxidation of benzyl alcohol to benzaldehyde in the vapor phase has drawn growing interest recently. In this work, MnOx–CeO2 mixed oxide compositions have been prepared by a coprecipitation method and tested for their oxidation activities of benzyl alcohol to benzaldehyde in the vapor phase. Detailed structural analyses have indicated that MnOx–CeO2 catalysts contain two phases, namely, α-MnO2 and fluorite CeO2 phases. The benzyl alcohol oxidation activity of pure MnO2 is more than 7 times higher compared to that of CeO2, indicating a much higher intrinsic oxidation ability of the MnO2 phase. Further, enhancement of the benzyl alcohol oxidation rate over MnO2 in 10%MnOx–CeO2 catalyst by 13 times is observed in relation to pure MnO2. The role of CeO2 in the MnOx–CeO2 catalyst has also been investigated, which indicates that the oxidation activity is almost independent of CeO2. However, stronger adsorption of benzyl alcohol over the MnOx–CeO2 catalysts compared to that of MnO2 points to the role of CeO2 in adsorption. Thus, both the CeO2 and the MnO2 components have different roles in the catalytic process—adsorption of benzyl alcohol on the CeO2 surface and its oxidation on MnO2 at the interface. The cooperation between the two sites toward oxidation could happen due to jumping of adsorbed benzyl alcohol from the surface of the CeO2 phase to the closest Mn4+ site in the MnO2 phase at the contact surface with MnO2 by thermal motion.