Pt/CeO2 and Pt/CeSnOx catalysts for low-temperature CO oxidation prepared by plasma-arc technique

We applied a method of plasma arc synthesis to study effects of modification of the fluorite phase of ceria by tin ions. By sputtering active components (Pt, Ce, Sn) together with carbon from a graphite electrode in a helium ambient we prepared samples of complex highly defective composite PtCeC and PtCeSnC oxide particles stabilized in a matrix of carbon. Subsequent high-temperature annealing of the samples in oxygen removes the carbon matrix and causes the formation of active catalysts Pt/CeOx and Pt/CeSnOx for CO oxidation. In the presence of Sn, X-Ray Diffraction (XRD) and High-Resolution Transmission Electron Microscopy (HRTEM) show formation of a mixed phase CeSnOx and stabilization of more dispersed species with a fluorite-type structure. These factors are essential for the observed high activity and thermic stability of the catalyst modified by Sn. X-Ray Photoelectron Spectroscopy (XPS) reveals the presence of both Pt2+ and Pt4+ ions in the catalyst Pt/CeOx, whereas only the state Pt2+ of platinum could be detected in the Sn-modified catalyst Pt/CeSnOx. Insertion of Sn ions into the Pt/CeOx lattice destabilizes/reduces Pt4+ cations in the Pt/CeSnOx catalyst and induces formation of strikingly high concentration (up to 50% at.) of lattice Ce3+ ions. Our DFT calculations corroborate destabilization of Pt4+ ions by incorporation of cationic Sn in Pt/CeOx. The presented results show that modification of the fluorite lattice of ceria by tin induces substantial amount of mobile reactive oxygen partly due to affecting geometric parameters of ceria by tin ions

States of Pt/CeO2 catalysts for CO oxidation below room temperature.

CO molecules can be efficiently oxidized over Pt/CeO2 catalysts, but the stability and reactivity of different states of Pt in the catalysts are still unclear. Here we combine experimental and computational methods to characterize Pt/CeO2 catalysts subjected to reductive and oxidative pre-treatments and exposed to CO oxidation reaction conditions. Particles of metallic Pt, known to be catalytically active at elevated temperature, are shown to be precursors for the formation, under operando conditions, of more stable PtOx particles that enable CO oxidation below room temperature. These PtOx particles are also similarly stable to - but more active than - atomically dispersed Pt2+ species. The results and approaches presented in this study illustrate the complex response of catalytic materials to reaction conditions and pave the way for future efforts to improve Pt/CeO2 and similar catalysts using dedicated pre-treatment strategies

Pt/CeO2 and Pt/CeSnOx Catalysts for Low-Temperature CO Oxidation Prepared by Plasma-Arc Technique

We applied a method of plasma arc synthesis to study effects of modification of the fluorite phase of ceria by tin ions. By sputtering active components (Pt, Ce, Sn) together with carbon from a graphite electrode in a helium ambient we prepared samples of complex highly defective composite PtCeC and PtCeSnC oxide particles stabilized in a matrix of carbon. Subsequent high-temperature annealing of the samples in oxygen removes the carbon matrix and causes the formation of active catalysts Pt/CeOx and Pt/CeSnOx for CO oxidation. In the presence of Sn, X-Ray Diffraction (XRD) and High-Resolution Transmission Electron Microscopy (HRTEM) show formation of a mixed phase CeSnOx and stabilization of more dispersed species with a fluorite-type structure. These factors are essential for the observed high activity and thermic stability of the catalyst modified by Sn. X-Ray Photoelectron Spectroscopy (XPS) reveals the presence of both Pt2+ and Pt4+ ions in the catalyst Pt/CeOx, whereas only the state Pt2+ of platinum could be detected in the Sn-modified catalyst Pt/CeSnOx. Insertion of Sn ions into the Pt/CeOx lattice destabilizes/reduces Pt4+ cations in the Pt/CeSnOx catalyst and induces formation of strikingly high concentration (up to 50% at.) of lattice Ce3+ ions. Our DFT calculations corroborate destabilization of Pt4+ ions by incorporation of cationic Sn in Pt/CeOx. The presented results show that modification of the fluorite lattice of ceria by tin induces substantial amount of mobile reactive oxygen partly due to affecting geometric parameters of ceria by tin ions

In situ probing of Pt/TiO2_{2} activity in low-temperature ammonia oxidation

The improvement of the low-temperature activity of the supported platinum catalysts in selective ammonia oxidation to nitrogen is still a challenging task. The recent developments in in situ/operando characterization techniques allows to bring new insight into the properties of the systems in correlation with their catalytic activity. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando X-ray absorption spectroscopy (XAS) techniques were applied to study Pt/TiO$_{2}$ catalysts in ammonia oxidation (NH$_{3}$ + O$_{2}$ reaction). Several synthesis methods were used to obtain samples with different size of Pt particles, oxidation state of Pt, and morphology of the support. Metal platinum particles on titania prepared by pulsed laser ablation in liquids exhibited the highest activity at lower temperatures with the temperature of 50% conversion of NH$_{3}$ being 150 °C. The low-temperature activity of the catalysts synthesized by impregnation can be improved by the reductive pretreatment. NAP-XPS and operando XANES data do not show formation of PtO$_{x}$ surface layers or PtO/PtO$_{2}$ oxides during NH$_{3}$ + O$_{2}$ reaction. Despite the differences in the oxidation state of platinum in the as-prepared catalysts, their treatment in the reaction mixture results in the formation of metallic platinum particles, which can serve as centers for stabilization of the adsorbed oxygen species. Stabilization of the bulk platinum oxide structures in the Pt/TiO$_{2}$ catalysts seems to be less favorable due to the metal–support interaction

Society, State, Nation and the People in the Democratic South Africa: Two Decades of Illusions in The Practice of Public Administration, Development Planning and Management

The purpose of this article is to provide a conceptual argument in that as South Africa transcended beyond its democratic dispensation, an opportunity was missed in the process leading to transition to define a society, state, nation and the people for sustaining the democratic founding for purposes of public administration practice, development planning and management. That is done by critically portraying South Africa as a society, state, nation and locating the people for governance purposes within a democratic founding. It is argued that attempts are made to rewrite the history of the country with a view of bolstering its societal status, nation, state and the people without a profound context. South Africa has become what it is today due to its history that remains its defining factor if it has to locate its society, state, nation and the people. Having lost that opportunity during transition, governance has become so unwieldy in that those assigned with authority in the governance landscape, tend to confuse the roles of society, nation, state and the people and that eventually strain the fragile democracy by distorting the facts and the role of constitutional apparatus that are instrumental to the country’s democratic founding. The conclusion is rather pessimistic in that as long as these issues are not properly located within the governance landscape; the democratic dispensation remains vulnerable for demise just like other democracies within the African continent with the potential of the middle class hijacking it from the vulnerable poor majority being the people that public administration practice has to serve. DOI: 10.5901/mjss.2015.v6n2s1p61

Effect of the type of active component–support interaction on the low-temperature activity of metal-oxide catalysts in CO oxidation

The Pt–SnOx, Pd–SnOx, and Au–SnOx composite catalysts were synthesized by pulsed laser ablation. The catalyst testing in the CO + O2 reaction showed that the action of the reaction medium can induce both partial deactivation (Pt–SnOx) and activation (Au–SnOx) of the catalysts. The Pd–SnOx catalyst has a high activity even in the initial state, and the effect of the reaction medium is slight. It was shown that gold and platinum mainly exist in the metallic state, while palladium exists as PdO nanoparticles. Electron transfer between the active component and support particles was detected for the Pt–SnOx and Au–SnOx catalysts. Electron donation effect from the support, enhanced by the action of the reaction medium, was found for Au–SnOx. This effect was assumed to determine the low-temperature activity of the catalyst towards the CO oxidation

A study of Pt/al2O3 nanocomposites obtained by pulsed laser ablation to be used as catalysts of oxidation reactions

Pulsed laser ablation (PLA) in liquids is an effective high-energy method for the synthesis of functional nanomaterials. In the present work, a nanocomposite catalyst Pt/Al2O3(PLA) is prepared by mixing solutions of platinum and aluminium nanodispersions obtained by the PLA method in alcohol and water, respectively. After being dried out, the obtained nanocomposite is thermally treated in air at 400 °C and 550 °C. It is shown by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction that platinum in the composition of the calcined samples stabilizes on the Al2O3 surface in the form of metal nanoparticles. The main crystal structure of η-Al2O3 is determined and impurity phases of Al(OH)3 hydroxide and metallic aluminium are revealed using X-ray powder diffraction (XRPD). The Pt/Al2O3 nanocomposite samples obtained by the PLA method are found to be highly prospective for the use in reactions of catalytic oxidation of CO and NH3. The Pt/Al2O3(PLA) nanocomposites are compared with the Pt/Al2O3 (IMP) catalyst synthesized by the method of solution chemistry. The Pt/Al2O3(IMP) sample containing highly dispersed platinum nanoparticles (1–2 nm) on the γ-Al2O3 surface has a lower T50 value (188 °C) in the reaction of CO oxidation that the PLA catalyst (T50 = 198 °C). At the same time, in the reaction of NH3 oxidation, the PLA catalyst is more active (T50 = 167 °C) than the IMP sample (T50 = 180 °C). The observed regularities are discussed in terms of the dispersion and the oxidation depth of platinum particles in the composition of Pt/Al2O3 catalysts

Structural insight into strong Pt-CeO 2 interaction: from single Pt atoms to PtOx clusters

Pt-CeO2 nanocomposites were obtained by coprecipitation, varying the Pt loading over a wide range of 1-30 wt %. The samples were calcined in air at 450-1000 °C. The Pt-CeO2 nanocomposites were investigated by a set of structural (X-ray diffraction, extended X-ray absorption fine structure (EXAFS), pair distribution function (PDF), and transmission electron microscopy) and spectroscopic (X-ray photoelectron spectroscopy and Raman spectroscopy) methods. Over the whole range of Pt loading, the main species were Pt2+ and Pt4+. They were localized either in a single-atom state or in the form of PtOx clusters on the ceria surface. The joint PDF and EXAFS modeling based on the combination of [Pt2+O4] single-atom and Pt3O4 structural fragments allowed us to propose the local structure of the PtOx clusters. The formation of such surface structures is associated with a distorted ceria surface on the Pt-CeO2 nanocomposites. We assume that the close arrangement of platinum ions in the PtOx clusters could be responsible for the effective redox properties of the samples

Unraveling the low-temperature activity of Rh–CeO2 catalysts in CO oxidation: probing the local structure and Red-Ox transformation of Rh3+ species

The local structure of the active sites is one of the key aspects of establishing the nature of the catalytic activity of the systems. In this work, a detailed structural investigation of the Rh–CeO2 catalysts prepared by the co-precipitation method was carried out. The application of a variety of physicochemical methods such as XRD, Raman spectroscopy, XPS, TEM, TPR-H2, and XAS revealed the presence of highly dispersed Rh3+ species in the catalysts: Rh3+ single ions and RhOx clusters. The substitution of Ce4+ ions by Rh3+ species, which provided a strong distortion of the CeO2 lattice, is shown. XAS data ensured the refinement of the Rh local structure. It was shown that single Rh3+ sites located next to each other can merge the formation of RhOx clusters with Rh local environment close to the one in Rh2O3 and CeRh2O5 oxides. The distortion of the CeO2 lattice around single and cluster rhodium species had a beneficial effect on the catalytic activity of the samples in low-temperature CO oxidation (LTO-CO). TEM, XAS, and in situ XRD data allowed establishing the structural transformations of the catalysts under Red-Ox treatments. The reduction treatment led to Rhn metallic cluster formation localized on defects of the reduced CeO2d. The reduced sample demonstrated efficient CO conversion at 0 1C. However, this system was not stable: its contact with air led to ceria reoxidation and partial reoxidation of Rh to highly dispersed Rh3+ species at room temperature, while heating in an oxidizing atmosphere resulted in the complete reoxidation of metallic rhodium species. The results of the work shed light on the structural aspects of the reversibility of the Rh–CeO2 catalysts based on the highly dispersed Rh3+ species under treatment in the reaction conditions

Pd/CeO2-SnO2 catalysts with varying tin content: Promotion of catalytic properties and structure modification

1%Pd/CeO2-SnO2 catalysts with varying Ce/Sn ratio were synthesized by counter-precipitation followed by calcination in a wide temperature range. The catalysts with Ce/Sn < 3/1 possess high thermal stability after calcination up to 1000 ◦C while maintaining low-temperature activity in CO oxidation. The PdOx clusters serving as active centers in CO oxidation are modified by Sn upon calcination. High tin content (Ce/Sn = 1/3) provides the activity of the catalysts in CH4 oxidation due to stabilization of PdO nanoparticles in the form of core@shell PdO@(CeO2 + SnO2) structures. Formation of the nanoheterophase structure upon calcination plays a key role in the stabilization of Pd-active centers of different types