Ag catalysts supported on CeO2, MnO2 and CeMnOx mixed oxides for selective catalytic reduction of NO by C3H6

In the present study CeO2, MnO2 and CeMnOx mixed oxide (with molar ratio Ce/Mn = 1) were prepared by sol-gel method using citric acid as a chelating agent and calcined at 500 °C. The silver catalysts (1 wt.% Ag) over the obtained supports were synthesized by the incipient wetness impregnation method with [Ag(NH3)2]NO3 aqueous solution. The selective catalytic reduction of NO by C3H6 was investigated in a fixed-bed quartz reactor using a reaction mixture composed of 1000 ppm NO, 3600 ppm C3H6, 10 vol.% O2, 2.9 vol.% H2 and He as a balance gas, at WHSV of 25,000 mL g−1 h−1.The physical-chemical properties of the as-prepared catalysts were studied by several characterization techniques, such as X-ray fluorescence analysis, nitrogen adsorption/desorption, X-ray analysis, Raman spectroscopy, transmission electron microscopy with analysis of the surface composition by X-ray energy dispersive spectroscopy and X-ray photo-electron spectroscopy. Silver oxidation state and its distribution on the catalysts surface as well as the support microstructure are the main factors determining the low temperature activity in NO selective catalytic reduction. The most active Ag/CeMnOx catalyst (NO conversion at 300 °C is 44% and N2 selectivity is ~90%) is characterized by the presence of the fluorite-type phase with high dispersion and distortion. The characteristic “patchwork” domain microstructure of the mixed oxide along with the presence of dispersed Ag+/Agnδ+ species improve the low-temperature catalyst of NO reduction by C3H6 performance compared to Ag/CeO2 and Ag/MnOx systems

Influence of Titania Synthesized by Pulsed Laser Ablation on the State of Platinum during Ammonia Oxidation

A set of physicochemical methods, including X-ray photoelectron spectroscopy (XPS), X-ray diffraction, electron microscopy and X-ray absorption spectroscopy, was applied to study Pt/TiO$_{2}$ catalysts prepared by impregnation using a commercial TiO$_{2}$-P25 support and a support produced by pulsed laser ablation in liquid (PLA). The Pt/TiO$_{2}$-PLA catalysts showed increased thermal stability due to the localization of the highly dispersed platinum species at the intercrystalline boundaries of the support particles. In contrast, the Pt/TiO$_{2}$-P25 catalysts were characterized by uniform distribution of the Pt species over the support. Analysis of Pt4f XP spectra shows that oxidized Pt$^{2+}$ and Pt$^{4+}$ species are formed in the Pt/TiO$_{2}$-P25 catalysts, while the platinum oxidation state in the Pt/TiO$_{2}$-PLA catalysts is lower due to stronger interaction of the active component with the support due to strong interaction via Pt-O-Ti bonds. The Pt4f XP spectra of the samples after reaction show Pt$^{2+}$ and metallic platinum, which is the catalytically active species. The study of the catalytic properties in ammonia oxidation showed that, unlike the catalysts prepared with a commercial support, the Pt/TiO$_{2}$-PLA samples show higher stability during catalysis and significantly higher selectivity to N$_{2}$ in a wide temperature range of 200–400 °C

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

The partial hydrogenation of butadiene over Al13Fe4: A surface-science study of reaction and deactivation mechanisms

SSCI-VIDE+ECI2D+LPIInternational audienc

Intermetallic compounds as potential alternatives to noble metals in heterogeneous catalysis: The partial hydrogenation of butadiene on alpha-Al4Cu9(110)

SSCI-VIDE+ECI2D+LPIInternational audienceNon-noble intermetallic compounds have recently shown promising catalytic performances for the partial hydrogenation of alkynes and alkenes. In this work, the properties of alpha-Al4Cu9(110) toward the gas-phase hydrogenation of butadiene have been investigated at total pressures of 2-20 mbar and temperatures of 110-180 °C. The model catalyst is active and 100% selective to butenes. Moreover, although less active than Al13Fe4(010), which had been previously evaluated for the same reaction, it is more selective and more stable. The combination of catalytic tests with pre- and postreactionAuger electron spectroscopy measurements, and comparative tests with Cu(110), shows that copper governs the reaction on alpha-Al4Cu9(110). However, the lower activity of the (Curicher) sputtered Al4Cu9 surface with respect to the annealed one, and the differences between Al4Cu9 and Cu surfaces in terms of butene isomer distribution, butene conversion kinetics and sensitivity to poisons, demonstrate the unique character of the intermetallic compound

Ru Catalysts Supported on Bamboo-like N-Doped Carbon Nanotubes: Activity and Stability in Oxidizing and Reducing Environment

The catalysts with platinum-group metals on nanostructured carbons have been a very active field of research, but the studies were mainly limited to Pt and Pd. Here, Ru catalysts based on nitrogen-doped carbon nanotubes (N-CNTs) have been prepared and thoroughly characterized; Ru loading was kept constant (3 wt.%), while the degree of N-doping was varied (from 0 to 4.8 at.%) to evaluate its influence on the state of supported metal. Using the N-CNTs afforded ultrafine Ru particles (<2 nm) and allowed a portion of Ru to be stabilized in an atomic state. The presence of Ru single atoms in Ru/N-CNTs expectedly increased catalytic activity and selectivity in the formic acid decomposition (FAD) but had no effect in catalytic wet air oxidation (CWAO) of phenol, thus arguing against a key role of single-atom catalysis in the latter case. A remarkable difference between these two reactions was also found in regard to catalyst stability. In the course of FAD, no changes in the support or supported species or reaction rate were observed even at a high temperature (150 °C). In CWAO, although 100% conversions were still achievable in repeated runs, the oxidizing environment caused partial destruction of N-CNTs and progressive deactivation of the Ru surface by carbonaceous deposits. These findings add important new knowledge about the properties and applicability of Ru@C nanosystems

Nitrogen Doped Carbon Nanotubes and Nanofibers for Green Hydrogen Production: Similarities in the Nature of Nitrogen Species, Metal–Nitrogen Interaction, and Catalytic Properties

The effect of nitrogen doped bamboo-like carbon nanotubes (N&ndash;CNTs) on the properties of supported platinum (0.2 and 1 wt %) catalysts in formic acid decomposition for hydrogen production was studied. It was shown that both impregnation and homogeneous precipitation routes led to the formation of electron-deficient platinum stabilized by pyridinic nitrogen sites of the N&ndash;CNTs. The electron-deficient platinum species strongly enhanced the activity and selectivity of the Pt/N&ndash;CNTs catalysts when compared to the catalysts containing mainly metallic platinum nanoparticles. A comparison of bamboo-like N&ndash;CNTs and herring-bone nitrogen doped carbon nanofibers (N&ndash;CNFs) as the catalyst support allowed us to conclude that the catalytic properties of supported platinum are determined by its locally one-type interaction with pyridinic nitrogen sites of the N&ndash;CNTs or N&ndash;CNFs irrespective of substantial structural differences between nanotubes and nanofibers

Pd-Ceria/CNMs Composites as Catalysts for CO and CH₄ Oxidation

The application of composite materials as catalysts for the oxidation of CO and other toxic compounds is a promising approach for air purification. In this work, the composites comprising palladium and ceria components supported on multiwall carbon nanotubes, carbon nanofibers and Sibunit were studied in the reactions of CO and CH4 oxidation. The instrumental methods showed that the defective sites of carbon nanomaterials (CNMs) successfully stabilize the deposited components in a highly-dispersed state: PdO and CeO2 nanoparticles, subnanosized PdOx and PdxCe1−xO2−δ clusters with an amorphous structure, as well as single Pd and Ce atoms, are formed. It was shown that the reactant activation process occurs on palladium species with the participation of oxygen from the ceria lattice. The presence of interblock contacts between PdO and CeO2 nanoparticles has an important effect on oxygen transfer, which consequently affects the catalytic activity. The morphological features of the CNMs, as well as the defect structure, have a strong influence on the particle size and mutual stabilization of the deposited PdO and CeO2 components. The optimal combination of highly dispersed PdOx and PdxCe1−xO2−δ species, as well as PdO nanoparticles in the CNTs-based catalyst, makes it highly effective in both studied oxidation reactions