Improved Low-Temperature CO Oxidation Performance
of Pd Supported on La-Stabilized Alumina
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Abstract
Simulated diesel oxidation catalysts
(DOCs) consisting of 2.5% Pd were prepared on γ-Al<sub>2</sub>O<sub>3</sub> and lanthana-stabilized γ-Al<sub>2</sub>O<sub>3</sub>; it was found that the La-containing catalyst had higher
CO conversion and lower onset temperature for CO oxidation (∼100
°C). Aberration-corrected STEM showed that the La–alumina
support helped to stabilize Pd in smaller particles and clusters,
increasing dispersion from 17 to 26%. The higher dispersion was responsible,
in part, for the improved CO oxidation rate; at 140 °C, the
turnover frequency (TOF) was improved from 0.0019 to 0.0095 s<sup>–1</sup> with the addition of La. This TOF increase appears
to be tied to facile redox behavior of the Pd/La–alumina catalyst,
which was evident in the results of in situ X-ray absorption spectroscopy
(XAS) and FTIR spectroscopy. In these experiments, both catalysts
were calcined at 500 °C to form PdO and then reduced to Pd metal
at 140 °C in the presence of CO. When the CO-covered catalyst
was exposed to CO oxidation reaction conditions at 140 °C, the
2.5% Pd/Al<sub>2</sub>O<sub>3</sub> catalyst remained nearly fully
reduced, and the surface coverage of CO did not change, indicating
irreversible CO adsorption and very low reactivity toward oxygen.
On the other hand, the more active 2.5% Pd/La–Al<sub>2</sub>O<sub>3</sub> catalyst was more reactive toward oxygen, with a portion
of the Pd becoming oxidized when the gas phase was switched from pure
CO to the reaction mixture. There was a drop in surface coverage of
CO when switching from pure CO to the reaction mixture on the Pd/La–alumina.
The results suggest that the role of the La–alumina support
is 2-fold, increasing the dispersion of Pd by forming small, stable
Pd particles and allowing a portion of the Pd to exhibit facile redox
behavior at low temperatures, making the Pd less susceptible to poisoning
by CO. This work provides insights into factors that could lead to
improved low-temperature CO oxidation reactivity in Pd-based automotive
exhaust catalysts