Ceria Nanoparticles’ Morphological Effects on the N2O Decomposition Performance of Co3O4/CeO2 Mixed Oxides

Ceria-based oxides have been widely explored recently in the direct decomposition of N2O (deN2O) due to their unique redox/surface properties and lower cost as compared to noble metal-based catalysts. Cobalt oxide dispersed on ceria is among the most active mixed oxides with its efficiency strongly affected by counterpart features, such as particle size and morphology. In this work, the morphological effect of ceria nanostructures (nanorods (ΝR), nanocubes (NC), nanopolyhedra (NP)) on the solid-state properties and the deN2O performance of the Co3O4/CeO2 binary system is investigated. Several characterization methods involving N2 adsorption at −196 °C, X-ray diffraction (XRD), temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (ΤΕΜ) were carried out to disclose structure–property relationships. The results revealed the importance of support morphology on the physicochemical properties and the N2O conversion performance of bare ceria samples, following the order nanorods (NR) > nanopolyhedra (NP) > nanocubes (NC). More importantly, Co3O4 impregnation to different carriers towards the formation of Co3O4/CeO2 mixed oxides greatly enhanced the deN2O performance as compared to bare ceria samples, without, however, affecting the conversion sequence, implying the pivotal role of ceria support. The Co3O4/CeO2 sample with the rod-like morphology exhibited the best deN2O performance (100% N2O conversion at 500 °C) due to its abundance in Co2+ active sites and Ce3+ species in conjunction to its improved reducibility, oxygen kinetics and surface area

Facet-Dependent Reactivity of Fe₂O₃/CeO₂ Nanocomposites: Effect of Ceria Morphology on CO Oxidation

Ceria has been widely studied either as catalyst itself or support of various active phases in many catalytic reactions, due to its unique redox and surface properties in conjunction to its lower cost, compared to noble metal-based catalytic systems. The rational design of catalytic materials, through appropriate tailoring of the particles’ shape and size, in order to acquire highly efficient nanocatalysts, is of major significance. Iron is considered to be one of the cheapest transition metals while its interaction with ceria support and their shape-dependent catalytic activity has not been fully investigated. In this work, we report on ceria nanostructures morphological effects (cubes, polyhedra, rods) on the textural, structural, surface, redox properties and, consequently, on the CO oxidation performance of the iron-ceria mixed oxides (Fe2O3/CeO2). A full characterization study involving N2 adsorption at –196 °C, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), temperature programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) was performed. The results clearly revealed the key role of support morphology on the physicochemical properties and the catalytic behavior of the iron-ceria binary system, with the rod-shaped sample exhibiting the highest catalytic performance, both in terms of conversion and specific activity, due to its improved reducibility and oxygen mobility, along with its abundance in Fe2+ species

CO2 Hydrogenation over Nanoceria-Supported Transition Metal Catalysts: Role of Ceria Morphology (Nanorods versus Nanocubes) and Active Phase Nature (Co versus Cu)

In this work we report on the combined impact of active phase nature (M: Co or Cu) and ceria nanoparticles support morphology (nanorods (NR) or nanocubes (NC)) on the physicochemical characteristics and CO2 hydrogenation performance of M/CeO2 composites at atmospheric pressure. It was found that CO2 conversion followed the order: Co/CeO2 > Cu/CeO2 > CeO2, independently of the support morphology. Co/CeO2 catalysts demonstrated the highest CO2 conversion (92% at 450 °C), accompanied by 93% CH4 selectivity. On the other hand, Cu/CeO2 samples were very selective for CO production, exhibiting 52% CO2 conversion and 95% CO selectivity at 380 °C. The results obtained in a wide range of H2:CO2 ratios (1–9) and temperatures (200–500 °C) are reaching in both cases the corresponding thermodynamic equilibrium conversions, revealing the superiority of Co- and Cu-based samples in methanation and reverse water-gas shift (rWGS) reactions, respectively. Moreover, samples supported on ceria nanocubes exhibited higher specific activity (µmol CO2·m−2·s−1) compared to samples of rod-like shape, disclosing the significant role of support morphology, besides that of metal nature (Co or Cu). Results are interpreted on the basis of different textural and redox properties of as-prepared samples in conjunction to the different impact of metal entity (Co or Cu) on CO2 hydrogenation process