A two-step reaction mechanism of oxygen release from Pd/CeO2: mathematical modelling based on step gas concentration experiments

Topics in Catalysis - A mathematical model has been developed to study the transient release of oxygen from a 1 wt% Pd/CeO2 catalyst in the 450–550 °C range based on alternate...     

Nucleation of isolated PO4 units on CeO2 driven by high temperatures and the effect on its oxygen storage and release properties

The chemical nature of P-containing species of varying concentration present in CeO₂ after impregnation with (NH₄)₂HPO₄ and calcination at 1273 K, and their effects on the oxygen storage and release (OSR) properties of ceria are reported for the first time. The samples were characterized by different techniques and the results were compared with those recently reported on the same samples but calcined at 873 K. When P-containing ceria solids were calcined at 1273 K, CePO₄ (monazite) was the predominant P-containing species on the surface of ceria, confirming previous studies that showed that monazite exists for those samples in which the surface P loading (P atoms per nm⁻²) is larger than 5.5. For lower surface P concentrations, isolated orthophosphate units are present at the surface and within the subsurface region of the solid. Severe sintering of CeO₂ after calcination at 1273 K resulted in P concentrations >5.5 P atoms·nm⁻² in all samples. Isolated PO₄ units that could initially be present in the samples calcined at 873 K nucleated and CePO₄ was formed when samples were calcined at 1273 K. OSR properties of CeO₂ deteriorated progressively when P loading increased due to the presence of larger crystals of the very stable Ce(III) phase of CePO₄ at the surface of the P-containing ceria solids.     

Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies

Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with mass spectrometry were performed for the first time to study essential mechanistic aspects of the water–gas shift (WGS) reaction over alumina-supported Pt, Pd, and Rh catalysts. In particular, the concentrations (μmol g⁻¹) of active intermediate species found in the carbon-path from CO to the CO₂ product gas (use of ¹³CO), and in the hydrogen-path from H₂O to the H₂ product gas (use of D₂O) of the reaction mechanism were determined. It was found that by increasing the reaction temperature from 350 to 500 °C the concentration of active species in both the carbon-path and hydrogen-path increased significantly. Based on the large concentration of active species present in the hydrogen-path (OH/H located on the alumina support), the latter being larger than six equivalent monolayers based on the exposed noble metal surface area (θ > 6.0), the small concentration of OH groups along the periphery of metal-support interface, and the significantly smaller concentration (μmol g⁻¹) of active species present in the carbon-path (adsorbed CO on the noble metal and COOH species on the alumina support and/or the metal-support interface), it might be suggested that diffusion of OH/H species on the alumina support towards catalytic sites present in the hydrogen-path of reaction mechanism might be considered as a slow reaction step. The formation of labile OH/H species is the result of dissociative chemisorption of water on the alumina support, where the role of noble metal is to activate the CO chemisorption and likely to promote formate decomposition into CO₂ and H₂ products. It was found that there is a good correlation between the surface concentration and binding energy of CO on the noble metal (Pt, Pd or Rh) with the activity of alumina-supported noble metal towards the WGS reaction.     

The CH4/NO/O2 “Lean-deNOx” Reaction on Mesoporous Mn-Based Mixed Oxides

High surface area Mn-based porous oxides (MANPO) containing additives like Ce, Sr and La were found to be very active and selective materials under 0.67% CH₄/0.2% NO/5% O₂ lean-deNO _x conditions in the 200–300°C low-temperature range. These materials perform also impressively in the presence of 4% H₂O in the feed stream, where a N₂ selectivity of 98% and an excellent stability over 24 h on stream have been observed. The MANPO materials can be considered serious competitors of noble metals for low-temperature lean-deNO _x applications.     

Direction-based adaptive data propagation for heterogeneous sensor mobility

We consider sensor networks where the sensor nodes are attached on entities that move in a highly dynamic, heterogeneous manner. To capture this mobility diversity we introduce a new network parameter, the direction-aware mobility level, which measures how fast and close each mobile node is expected to get to the data destination (the sink). We then provide local, distributed data dissemination protocols that adaptively exploit the node mobility to improve performance. In particular, “high” mobility is used as a low cost replacement for data dissemination (due to the ferrying of data), while in the case of “low” mobility either (a) data propagation redundancy is increased (when highly mobile neighbors exist) or (b) long-distance data transmissions are used (when the entire neighborhood is of low mobility) to accelerate data dissemination toward the sink. An extensive performance comparison to relevant methods from the state of the art demonstrates significant improvements, i.e. latency is reduced by even four times while keeping energy dissipation and delivery success at very satisfactory levels.     

Digital inclusion of people with disabilities: a qualitative study of intra-disability diversity in the digital realm

ABSTRACT

This paper presents an in-depth study of intra-disability diversity in the digital realm and the related role of individuality and selectiveness in the digital choices and experiences of people with disabilities (PwD). The study adopts the interactionist model of disability and problematises conceptual uniformity in research that focuses on the medical and socially-constructed features of disability as those determining digital constraints and affordances for PwD. Through primary qualitative evidence, it argues that individuality and selectiveness shape a complex terrain of intra-disability diversity, which forms the nuances and experiences of digital inclusion for PwD. Thus, it invites researchers to move beyond disability-fixed categorisations and offers a 3-tier recommendation for future research to explain the range of PwD’ perceptions and experiences in the digital realm.     

Catalytic behavior of La–Sr–Ce–Fe–O mixed oxidic/perovskitic systems for the NO+CO and NO+CH4+O2 (lean-NOx) reactions

Mixed oxides of the general formula La_0.5Sr_xCe_yFeO_z were prepared by using the nitrate method and characterized by XRD and Mössbauer techniques. The crystal phases detected were perovskites LaFeO₃ and SrFeO_3−x and oxides -Fe₂O₃ and CeO₂ depending on x and y values. The low surface area ceramic materials have been tested for the NO+CO and NO+CH₄+O₂ (“lean-NO_x”) reactions in the temperature range 250–550°C. A noticeable enhancement in NO conversion was achieved by the substitution of La³⁺ cation at A-site with divalent Sr⁺² and tetravalent Ce⁺⁴ cations. Comparison of the activity of the present and other perovskite-type materials has pointed out that the ability of the La_0.5Sr_xCe_yFeO_z materials to reduce NO by CO or by CH₄ under “lean-NO_x” conditions is very satisfying. In particular, for the NO+CO reaction estimation of turnover frequencies (TOFs, s⁻¹) at 300°C (based on NO chemisorption) revealed values comparable to Rh/-Al₂O₃ catalyst. This is an important result considering the current tendency for replacing the very active but expensive Rh and Pt metals. It was found that there is a direct correlation between the percentage of crystal phases containing iron in La_0.5Sr_xCe_yFeO_z solids and their catalytic activity. O₂ TPD (temperature-programmed desorption) and NO TPD studies confirmed that the catalytic activity for both tested reactions is related to the defect positions in the lattice of the catalysts (e.g., oxygen vacancies, cationic defects). Additionally, a remarkable oscillatory behavior during O₂ TPD studies was observed for the La_0.5Sr_0.2Ce_0.3FeO_z and La_0.5Sr_0.5FeO_z solids.     

Low-temperature H2-SCR of NO on a novel Pt/MgO-CeO2 catalyst

The selective catalytic reduction of NO by H₂ under strongly oxidizing conditions (H₂-SCR) in the low-temperature range of 100–200 °C has been studied over Pt supported on a series of metal oxides (e.g., La₂O₃, MgO, Y₂O₃, CaO, CeO₂, TiO₂, SiO₂ and MgO-CeO₂). The Pt/MgO and Pt/CeO₂ solids showed the best catalytic behavior with respect to N₂ yield and the widest temperature window of operation compared with the other single metal oxide-supported Pt solids. An optimum 50 wt% MgO-50wt% CeO₂ support composition and 0.3 wt% Pt loading (in the 0.1–2.0 wt% range) were found in terms of specific reaction rate of N₂ production (mols N₂/g_cat s). High NO conversions (70–95%) and N₂ selectivities (80–85%) were also obtained in the 100–200 °C range at a GHSV of 80,000 h⁻¹ with the lowest 0.1 wt% Pt loading and using a feed stream of 0.25 vol% NO, 1 vol% H₂, 5 vol% O₂ and He as balance gas. Addition of 5 vol% H₂O in the latter feed stream had a positive influence on the catalytic performance and practically no effect on the stability of the 0.1 wt% Pt/MgO-CeO₂ during 24 h on reaction stream. Moreover, the latter catalytic system exhibited a high stability in the presence of 25–40 ppm SO₂ in the feed stream following a given support pretreatment. N₂ selectivity values in the 80–85% range were obtained over the 0.1 wt% Pt/MgO-CeO₂ catalyst in the 100–200 °C range in the presence of water and SO₂ in the feed stream. The above-mentioned results led to the obtainment of patents for the commercial exploitation of Pt/MgO-CeO₂ catalyst towards a new NO_x control technology in the low-temperature range of 100–200 °C using H₂ as reducing agent. Temperature-programmed desorption (TPD) of NO, and transient titration of the adsorbed surface intermediate NO_x species with H₂ experiments, following reaction, have revealed important information towards the understanding of basic mechanistic issues of the present catalytic system (e.g., surface coverage, number and location of active NO_x intermediate species, NO_x spillover).     

Construction and Applications of a Microcomputer Controlled Pulsed Amperometric Detector System

ABSTRACT

The construction of a microcomputer controlled pulsed amperometric detector system is described. It includes a potentiostat, a flow-through cell and a sample injection unit. The microcomputer generates the appropriate waveform of the applied potential and controls the overall sequence of the measurement. The system is suitable for general studies on the detection of various classes of organic compounds with the pulsed amperometric technique. The detectability of various hydroxycompounds has been studied.     

Implementation of a high speed frequency synthesizer employing a dual input phase accumulator

We present a new PLL based frequency synthesizer, in which we have replaced the conventional phase frequency detector and the dividers (programmable counters) with a sequential dual input phase accumulator (DIPA), consisting of a digital circuit employing adders, registers and a ladder. The main feature of the DIPA is that the two input frequencies are not required to be normalized (divided down) to the step frequency of the synthesizer. Instead, the two different high frequencies, that is the reference and the output frequency of the synthesizer, are applied directly. The DIPA samples and normalizes their phases at very high rates, calculates their phase difference, producing an output that consists of a dc component proportional to the phase difference and harmonics of the two input high frequencies. These harmonics are high frequencies and can easily be rejected by a wide bandwidth filter of the loop, without affecting the high convergence speed of the loop. Moreover, these harmonics do not generate spurs near the output frequency. The resolution of the DIPA based synthesizer depends only on the length of the digital word of the DIPA, and its convergence speed depends on the lower of the two input frequencies. The output of the DIPA is a linear function of the phase difference of the two input frequencies and its dynamic range exceeds the limit of ±2π that governs the conventional phase detectors. Thus, the proposed frequency synthesizer based on the DIPA has low phase noise, no spurs nearby the output frequency, high resolution and fast convergence rate. Additionally, the output frequency can be digitally modulated under the control of the closed loop, either by phase or frequency modulation.