Key Properties and Parameters of Pd/CeO₂ Passive NO<i>_x</i> Adsorbers

In this paper, a series of Pd/CeO2 catalysts prepared by different synthesis routes and showing different morphological and textural properties have been investigated for passive NOx adsorption (PNA) applications. The results obtained by NOx adsorption/desorption tests demonstrated that NOx storage capacity and NOx storage efficiency of Pd/CeO2 materials depend strictly on their surface area, whereas the morphology of the support and the Pd deposition method do not seem to play a key role. In contrast, the Pd deposition method does impact the dynamics of NOx desorption by affecting the amount of NOx desorbed at different temperatures. This seems to be connected to Pd–Ce interactions at the nanoscale that favor NOx desorption at higher temperatures suitable for PNA application. These findings are relevant in designing and optimizing the properties of Pd/CeO2 materials for their function as passive NOx adsorbers

Tuning Chemical and Morphological Properties of Ceria Nanopowders by Mechanochemistry

Cerium oxide powders are widely used and are of fundamental importance in catalytic pollution control and energy production due to the unique chemical properties of CeO2. Processing steps involved in catalyst preparation, such as high-temperature calcination or mechanical milling processes, can alter the morphological and chemical properties of ceria, heavily affecting its final properties. Here, we focus on the tuning of CeO2 nanopowder properties by mild- and high-energy milling processes, as the mechanochemical synthesis is gaining increasing attention as a green synthesis method for catalyst production. The textural and redox properties were analyzed by an array of techniques to follow the aggregation and comminution mechanisms induced by mechanical stresses, which are more prominent under high-energy conditions but strongly depend on the starting properties of the ceria powders. Simultaneously, the evolution of surface defects and chemical properties was followed by Raman spectroscopy and H2 reduction tests, ultimately revealing a trade-off effect between structural and redox properties induced by the mechanochemical action. The mild-energy process appears to induce the largest enhancement in surface properties while maintaining bulk properties of the starting materials, hence confirming its effectiveness for its exploitation in catalysis

Identification of Highly Selective Surface Pathways for Methane Dry Reforming Using Mechanochemical Synthesis of Pd–CeO₂

The methane dry reforming (DRM) reaction mechanism was explored via mechanochemically prepared Pd/CeO2 catalysts (PdAcCeO2M), which yield unique Pd–Ce interfaces, where PdAcCeO2M has a distinct reaction mechanism and higher reactivity for DRM relative to traditionally synthesized impregnated Pd/CeO2 (PdCeO2IW). In situ characterization and density functional theory calculations revealed that the enhanced chemistry of PdAcCeO2M can be attributed to the presence of a carbon-modified Pd0 and Ce4+/3+ surface arrangement, where distinct Pd–CO intermediate species and strong Pd–CeO2 interactions are activated and sustained exclusively under reaction conditions. This unique arrangement leads to highly selective and distinct surface reaction pathways that prefer the direct oxidation of CHx to CO, identified on PdAcCeO2M using isotope labeled diffuse reflectance infrared Fourier transform spectroscopy and highlighting linear Pd–CO species bound on metallic and C-modified Pd, leading to adsorbed HCOO [1595 cm–1] species as key DRM intermediates, stemming from associative CO2 reduction. The milled materials contrast strikingly with surface processes observed on IW samples (PdCeO2IW) where the competing reverse water gas shift reaction predominates