Identification of single Ru(II) ions on ceria as a highly active catalyst for abatement of NOx pollutants

Atom trapping allows to prepare catalysts with atomically dispersed Ru ions anchored to the ceria support. The resulting catalysts free of expensive noble metals such as Pt, Pd, Rh (whose prices are ~8-60 times higher than Ru on the per-molar basis) with Ru loadings of only 0.25-0.5 wt% show excellent activity in industrially important catalytic NO oxidation reaction, a critical step that requires use of relatively large loadings of expensive noble metals in diesel aftertreatment systems. Ru1/CeO2 catalysts are stable during continuous cycling, ramping and cooling as well as presence of moisture. Furthermore, Ru1/CeO2 shows excellent NOx storage properties during cold start, with improved NO adsorption compared with the best described Pd/Zeolite NO adsorbers with ~2-3 times higher Pd loadings. We clarify the location of Ru(II) ions on the ceria surface and identify mechanism of NO oxidation (as well as reactive storage) using DFT calculations and in-situ DRIFTS/Mass-spectroscopy measurements. Furthermore, we show the possible applications of Ru1/CeO2 in gasoline engines for NO reduction by CO: only 0.1 wt% of atomically dispersed Ru is sufficient to achieve high activity at low temperatures. With the aid of excitation-modulation in-situ infra-red measurements, we uncover the elementary steps of NO reduction by CO on an atomically dispersed ceria-supported catalyst. Our study highlights the potential applicability of single-atom catalysts to industrially relevant NO and CO abatement.

The Sintering of Au Nanoparticles on Flat {100}, {111} and Zigzagged {111}-Nanofacetted Structures of Ceria and Its Influence on Catalytic Activity in CO Oxidation and CO PROX

The thermal stability of Au nanoparticles on ceria support of various morphology (nanocubes, nanooctahedra, and {111}-nanofacetted nanocubes) in oxidizing and reducing atmospheres was investigated by electron microscopy. A beneficial effect of the reconstruction of edges of ceria nanocubes into zigzagged {111}-nanofacetted structures on the inhibition of sintering of Au nanoparticles was shown. The influence of different morphology of Au particles on various ceria supports on the reducibility and catalytic activity in CO oxidation, and CO PROX of Au/ceria catalysts was also investigated and discussed. It was shown, that ceria nanocubes with flat {110} terminated edges are more suitable as a support for Au nanoparticles, used to catalyze CO oxidation, than zigzagged {111}- nanofacetted structures. Graphic Abstract

Ultra-Small Pd Nanoparticles on Ceria as an Advanced Catalyst for CO Oxidation

In this study, we demonstrate the preparation and characterization of small palladium nanoparticles (Pd NPs) on modified ceria support (Pd/CeO2) using wet impregnation and further reduction in an H2/Ar flow. The obtained particles had a good dispersion, but their small size made it difficult to analyze them by conventional techniques such as transmission electron microscopy (TEM) and X-ray powder diffraction (XRPD). The material demonstrated a high catalytic activity in the CO oxidation reaction: the 100% of CO conversion was achieved at ~50 °C, whereas for most of the cited literature, such a high conversion usually was observed near 100 °C or higher for Pd NPs. Diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy in combination with CO probe molecules was used to investigate the size and morphology of NPs and the ceria support. On the basis of the area ratio under the peaks attributed to bridged (B) and linear (L) carbonyls, high-dispersion Pd NPs was corroborated. Obtained results were in good agreement with data of X-ray absorption near edge structure analysis (XANES) and CO chemisorption measurements.

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.