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 CeO 2 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 CeO 2 nanocubes, which are in the range of 15 ± 1.5 to 25 ± 1.5 nm. High concentration of Ce 3+ species are found in Co–Mn/CeO 2 (23.34%) compared with that in Mn/CeO 2 (21.41%), Co/CeO 2 (15.63%), and CeO 2 (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 Co 2+ to Co 3+ and simultaneously Mn 4+/3+ to Mn 2+ . The Co–Mn/CeO 2 catalyst exhibits the best performance in solvent-free oxidation of benzylamine (89.7% benzylamine conversion) compared with the Co/CeO 2 (29.2% benzylamine conversion) and Mn/CeO 2 (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 CeO 2 nanocubes as well as the abundant structural defects in cerium oxide plays a key role in the efficiency of the Co–Mn/CeO 2 catalyst for the aerobic oxidation of benzylamine.