Improved Pd/CeO2 Catalysts for Low-Temperature NO Reduction: Activation of CeO2 Lattice Oxygen by Fe Doping: Activation of CeO₂Lattice Oxygen by Fe Doping

Developing better three-way catalysts with improved low-temperature performance is essential for cold start emission control. Density functional theory in combination with microkinetics simulations is used to predict reactivity of CO/NO/H2 mixtures on a small Pd cluster on CeO2(111). At low temperatures, N2O formation occurs via a N2O2 dimer over metallic Pd3. Part of the N2O intermediate product re-oxidizes Pd, limiting NO conversion and requiring rich conditions to obtain high N2 selectivity. High N2 selectivity at elevated temperatures is due to N2O decomposition on oxygen vacancies. Doping CeO2 by Fe is predicted to lead to more oxygen vacancies and a higher N2 selectivity, which is validated by the lower onset of N2 formation for a Pd catalyst supported on Fe-doped CeO2 prepared by flame spray pyrolysis. Activating ceria surface oxygen by transition metal doping is a promising strategy to improve the performance of three-way catalysts.