Potential of Ceria-Zirconia-Based Materials in Carbon Soot Oxidation for Gasoline Particulate Filters

ZrO(2)and Ce(0.8)Zr(0.2)O(2)mixed oxides were prepared and tested in the oxidation of carbon soot at different oxygen partial pressures and degrees of catalyst/soot contact to investigate their activity under typical gasoline direct injection (GDI) operating conditions. Under reductive atmospheres, generation of oxygen vacancies occurs in Ce0.8Zr0.2O2, while no reduction is observed on ZrO2. Both materials can oxidize carbon under high oxygen partial pressures; however, at low oxygen partial pressures, the presence of carbon can contribute to the reduction of the catalyst and formation of oxygen vacancies, which can then be used for soot oxidation, increasing the overall performance. This mechanism is more efficient in Ce(0.8)Zr(0.2)O(2)than ZrO2, and depends heavily on the interaction and the degree of contact between soot and catalyst. Thus, the ability to form oxygen vacancies at lower temperatures is particularly helpful to oxidize soot at low oxygen partial pressures, and with higher CO(2)selectivity under conditions typically found in GDI engine exhaust gases

Ceria-zirconia particles wrapped in a 2D carbon envelope: improved low-temperature oxygen transfer and oxidation activity

Engineering the interface between different compo-nents of heterogeneous catalysts at nanometer level canradically alter their performances.This is particularly true forceria-based catalysts where the interactions are critical forobtaining materials with enhanced properties.Here we showthat mechanical contact achieved by high-energy milling ofCeO2–ZrO2powders and carbon soot results in the formationof acore of oxide particles wrapped in athin carbon envelope.This 2D nanoscale carbon arrangement greatly increases thenumber and quality of contact points between the oxide andcarbon. Consequently,the temperatures of activation andtransfer of the oxygen in ceria are shifted to exceptionally lowtemperatures and the soot combustion rate is boosted. Thestudy confirms the importance of the redox behavior of ceria-zirconia particles in the mechanism of soot oxidation andshows that the organization of contact points at the nanoscalecan significantly modify the reactivity resulting in unexpectedproperties and functionalities.Postprint (published version

Influence of nanoscale surface arrangements on the oxygen transfer ability of ceria-zirconia mixed oxide

Ceria-based materials, and particularly CeO2-ZrO2 (CZ) solid solutions are key ingredient in catalyst formulations for several applications due to the ability of ceria to easily cycling its oxidation state between Ce4+ and Ce3+. Ceria-based catalysts have a great soot oxidation potential and the mechanism deeply relies on the degree of contact between CeO2 and carbon. In this study, carbon soot has been used as solid reductant to better understand the oxygen transfer ability of ceria-zirconia at low temperatures; the effect of different atmosphere and contact conditions has been investigated. The difference in the contact morphology between carbon soot and CZ particles is shown to strongly affect the oxygen transfer ability of ceria; in particular, increasing the carbon-ceria interfacial area, the reactivity of CZ lattice oxygen is significantly improved. In addition, with a higher degree of contact, the soot oxidation is less affected by the presence of NOx. The NO oxidation over CZ in the presence of soot has also been analyzed. The existence of a core/shell structure strongly enhances reactivity of interfacial oxygen species while affecting negatively NO oxidation characteristics. These findings are significant in the understanding of the redox chemistry of substituted ceria and help determining the role of active species in soot oxidation reaction as a function of the degree of contact between ceria and carbon

NiO-nanoflowers decorating a plastic electrode for the non-enzymatic amperometric detection of H2O2 in milk: old issue, new challenge

In food supply chain, there are regulatory limitations on the use of chemicals for cleaning processing lines since the healthiness of the commodities must be guaranteed if accidentally traces of these detergents and sanitizers pass to them. Hydrogen peroxide, is a commonly used sanitizer in the cleaning of the food processing lines having both bactericidal and bacteriostatic properties, however, it produces inflammatory effects on the human body. The availability of rapid systems to detect its accidental presence is therefore useful to speed up the control and apply corrective actions. In the present work, a drop casting and easily prepared plastic graphite / PVC electrode decorated with NiO nanostructures has been investigated as electrochemical sensor for the non-enzymatic amperometric determination of H2O2. 24 The catalytic activity, dispersion, and stability of NiO nanostructures mixed with plastic nanocomposite electrode have been studied in detail. The preparation method, particularly the precipitating agents used in the synthesis of NiO nanostructures strongly influenced their morphology and porosity. Further, the electrochemical response of NiO-PE electrodes towards H2O2 resulted to be morphology-dependent. The non-enzymatic electrochemical sensor was optimized for the rapid and sensitive detection of H2O2 present in milk with no sample pre- treatments. NiO nanoflowers showed the best catalytic activity towards H2O2, a linear range that extends up to 4 mM and a LOD of 5 μM (3sd of the blank signal) were obtained

Potential of Ceria-Based Catalysts for the Oxidation of Landfill Leachate by Heterogeneous Fenton Process

In this study, ceria and ceria-zirconia solid solutions were tested as catalyst for the treatment of landfill leachate with a Fenton-like process. The catalysts considered in this work were pure ceria and ceria-zirconia solid solutions as well as iron-doped samples. All the catalysts were extensively characterized and applied in batch Fenton-like reactions by a close batch system, the COD (chemical oxygen demand) and TOC (total organic carbon) parameters were carried out before and after the treatments in order to assay oxidative abatement. Results show a measurable improvement of the TOC and COD abatement using ceria-based catalysts in Fenton-like process and the best result was achieved for iron-doped ceria-zirconia solid solution. Our outcomes point out that heterogeneous Fenton technique could be effectively used for the treatment of landfill leachate and it is worth to be the object of further investigations

Possible Recycling of End-of-Life Dolomite Refractories by the Production of Geopolymer-Based Composites: Experimental Investigation

Production and characterization of geopolymers prepared by mixing metakaolin, end-of-life dolomite refractories, sodium silicate solution, and sodium hydroxide solution have been performed. The as-received refractory was crumbled in order to obtain products having, respectively, 250\ua0\u3bcm, 1 mm, and 2.5\ua0mm maximum particles size. Each batch of powder was added in different proportions to a blank geopolymeric matrix. It has been observed that the addition of waste refractory reduces workability of the reference refractory-free slurry. After hardening, only the set of samples prepared with powders with maximum size of 250\ua0\u3bcm maintain integrity while the others resulted affected by the presence of fractures caused by volumetric instabilities; samples with composition R100 showed the highest compressive strength, whereas higher refractory addition lowers strength. Specific surface area appears independent by materials composition; conversely pore volume slightly increases with the addition of dolomite refractory powder. During the thermodilatometric tests all compositions display a shrinkage of about 0.1% between 170 and 400\ua0\ub0C; however, sintering starts at higher temperature (above 600\ua0\ub0C) and samples melt in the range between 650 and 750\ua0\ub0C as a function of their composition, thus showing that the resulting materials loose refractoriness with respect to both the reference geopolymer and the dolomite refractory. Graphical Abstract: [Figure not available: see fulltext.

Pincer and Carbonyl Ruthenium Complexes for Transfer Hydrogenation Reactions

The transfer hydrogenation (TH) catalyzed by ruthenium complexes is a cost-effective and environmentally benign way for the reduction of carbonyl compounds. On account of the reversibility of the TH process, ruthenium catalysts have attracted a great deal of interest for a number of C-H activation organic transformations. To improve the catalytic activity and to retard decomposition, the design of suitable chelating and non-innocent ligands appears crucial. We report here the preparation of pincer, carbonyl and acetate ruthenium complexes, displaying high productivity for the TH of carbonyl compounds, including flavanones and biomass-derived molecules (5-HMF, ethyl levulinate). The alkylation of amines with alcohols and the preliminary results on the photochemical TH of carbonyl compounds are also presented

Surface faceting and reconstruction of ceria nanoparticles

The surface atomic arrangement of metal oxides determines their physical and chemical properties, and the ability to control and optimize structural parameters is of crucial importance for many applications, in particular in heterogeneous catalysis and photocatalysis. Whereas the structures of macroscopic single crystals can be determined with established methods, for nanoparticles (NPs), this is a challenging task. Herein, we describe the use of CO as a probe molecule to determine the structure of the surfaces exposed by rod-shaped ceria NPs. After calibrating the CO stretching frequencies using results obtained for different ceria single-crystal surfaces, we found that the rod-shaped NPs actually restructure and expose {111} nanofacets. This finding has important consequences for understanding the controversial surface chemistry of these catalytically highly active ceria NPs and paves the way for the predictive, rational design of catalytic materials at the nanoscale.Postprint (author's final draft

The Effect of the P/Si Ratio on the Preparation and Properties of Phosphoric Acid-Metakaolin Geopolymers

The present research deals with the production and characterization of geopolymers prepared by mixing metakaolin, different amounts of phosphoric acid solution and water. Hardening was performed by aging the geopolymeric pastes in a climatic chamber. The workability of the pastes has been improved while the H2O/total solid content has been kept constant and the P/Si ratio increased. However, such a benefit implies considerable heat output, which must be controlled in order to limit the formation of extended fractures. The compressive strength of the hardened materials increases with increasing P/Si ratio at a constant H2O/total solid content, whereas their strength decreases with increasing H2O/ total solid content at a constant P/Si ratio. The open macroporosity, which is directly dependent on the total amount of water added to the geopolymeric pastes, may explain the above results better than the nano/microporosity and/or chemical bonds that contribute to building up the materials\u2019 textural features