Nanoscale Cobalt-Manganese Oxide Catalyst Supported on Shape-Controlled Cerium Oxide: Effect of Nanointerface Configuration on Structural, Redox, and Catalytic Properties.

Understanding the role of nanointerface structures in supported bimetallic nanoparticles is vital for the rational design of novel high-performance catalysts. This study reports the synthesis, characterization, and the catalytic application of Co-Mn oxide nanoparticles supported on CeO2 nanocubes with the specific aim of investigating the effect of nanointerfaces in tuning structure-activity properties. High-resolution transmission electron microscopy analysis reveals the formation of different types of Co-Mn nanoalloys with a range of 6 ± 0.5 to 14 ± 0.5 nm on the surface of CeO2 nanocubes, which are in the range of 15 ± 1.5 to 25 ± 1.5 nm. High concentration of Ce3+ species are found in Co-Mn/CeO2 (23.34%) compared with that in Mn/CeO2 (21.41%), Co/CeO2 (15.63%), and CeO2 (11.06%), as evidenced by X-ray photoelectron spectroscopy (XPS) analysis. Nanoscale electron energy loss spectroscopy analysis in combination with XPS studies shows the transformation of Co2+ to Co3+ and simultaneously Mn4+/3+ to Mn2+ . The Co-Mn/CeO2 catalyst exhibits the best performance in solvent-free oxidation of benzylamine (89.7% benzylamine conversion) compared with the Co/CeO2 (29.2% benzylamine conversion) and Mn/CeO2 (82.6% benzylamine conversion) catalysts for 3 h at 120 °C using air as the oxidant. Irrespective of the catalysts employed, a high selectivity toward the dibenzylimine product (97-98%) was found compared with the benzonitrile product (2-3%). The interplay of redox chemistry of Mn and Co at the nanointerface sites between Co-Mn nanoparticles and CeO2 nanocubes as well as the abundant structural defects in cerium oxide plays a key role in the efficiency of the Co-Mn/CeO2 catalyst for the aerobic oxidation of benzylamine.