Unraveling defect chemistry in doped-ceria catalyst for oxidative coupling of lignin-based aniline and benzyl alcohol

[Display omitted] •Zr-doped CeZrxOy solid solutions with a cubic fluorite structure were synthesized.•Lattice distortion and oxygen defects of CeZrxOy promoted redox property of pristine CeO2.•Defective Ce3+, Osurf. and Vö sites enabled effective adsorption and activation of alcohol and O2.•CeZr1Oy showed a superior yield and productivity of bio-imine among CeO2-based catalysts.•Satisfying gram-scaled synthesis, wide substrate scope and stable reusability were reported. The defect chemistry of doped-ceria is vital but tangled for sustainable conversion of biomass resources. In this work, a group of Zr-doped CeO2 solid solutions were prepared and the defect chemistry in CeZrxOy (0.02 ≤ x ≤ 5) catalyst was elucidated over the oxidative coupling of lignin-based aniline and benzyl alcohol. Varying the Zr molar fraction enabled to successfully adjust the defect sites of catalysts and further influence their catalytic performances. In addition, the optimal CeZr1Oy catalyst exhibited a flexible temperature adaptability, wide substrate scope and superior reusability. Various characterizations, kinetic investigations, controlled experiments, DFT calculations and in situ DRIFT-IR technique were used to unravel the roles of Ce3+ and oxygen defects and the reaction mechanism. It was disclosed that Zr-doped defects can obviously increase surface Ce3+ cations, oxygen species (peroxide and superoxide anions) and oxygen vacancies. These coordinatively unsaturated sites were shown to play critical roles in absorbing and activating substrates hence can accelerate the formation rate of bio-based imines.