Mechanochemical Redox: Calcination-free Synthesis of Ceria-hybrid Catalyst with Ultra-High Surface Area

Transition metal-doped CeO2 (MCeOx) is of great importance in industrial catalysis. However, current synthetic methods often result in the separation of MOx phases, which significantly decreases their catalytic activity. Toward this end, the chemistry of mechanochemical redox was introduced to prepare Ce1-xMnxO2-delta catalyst. The redox behavior between MnO4- and Ce3+ could in situ produces atomically dispersed Ce1-xMnxO2-delta solid solution without calcination. Moreover, the mechanochemical synthesis endows Ce1-xMnxO2-delta a surface area (302 m(2)/g) that is much higher than the counterparts prepared by traditional methods, such as co-precipitation method (66 m(2)/g) CTAB-assisted precipitation method (122 m(2)/g) and sol-gel method (136 m(2)/g). Importantly, the well dispersed heteroatoms and high porosity afford doped ceria excellent activity and stability during CO oxidation. The reaction mechanism was finally explored by DFT calculation, which reveals that Mn and Cu dopants facilitate electron transfer and oxygen releasing.

Automated summary

Transition metal-doped CeO2 prepared through mechanochemical redox chemistry exhibits higher surface area compared to traditional methods, leading to excellent catalytic activity and stability in CO oxidation due to well dispersed heteroatoms and high porosity. DFT calculations indicate that Mn and Cu dopants facilitate electron transfer and oxygen releasing in the reaction mechanism.