Modelling of solid oxide proton conducting reactor-cells: thermodynamics and kinetics

A model is prepared for hydro- and dehydrogenation reactions that are carried out in solid electrolyte cell-reactors. Hydrogen is supplied in the form of H⁺ through the proton conducting wall and the thermodynamic activity of hydrogen on the catalyst surface is controlled electrochemically. Three reactor types are considered, a plug flow reactor, a well-mixed reactor and a “single-chamber” cell in which both electrodes are exposed to the same reacting mixture. Under certain conditions, the yield of the cell-reactor is orders of magnitude higher than that of the corresponding conventional catalytic reactor. The key parameters that affect the product yield as well as the conditions that must be met, are discussed. Experimental results for the reaction of methane dimerization studied with a strontia-ceria-ytterbia electrolyte on palladium electrodes, are presented and compared to model predictions. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Electrochemical promotion of environmentally important catalytic reactions

The performance of conventional heterogeneous metal catalysts may be enhanced by the addition of so-called promoter species that are used to modify the intrinsic metal surface chemistry with respect to activity and/or selectivity. Electrochemical methods provide an alternative, radically different and uniquely efficacious method of catalyst promotion. Substantial and reversible changes in catalyst perfomance can be induced by back-spillover ions pumped from a solid electrolyte to the surface of a catalytically active electrode: one hasin situ control of the working catalyst. Studies of the electrochemical promotion of NO reduction over Pt films supported on β″-alumina (a sodium ion conductor) demonstrate that major enhancements in activity are possible when Na is pumped to the catalyst surface. We have examined the NO+CO reaction and the reaction of NO with propene. Both reactions are relevant to control of automotive and other emissions, and both exhibit strong electrochemical promotion. By simulating lean-burn engine conditions, we have also demonstrated that EP of a Pt catalyst very substantially enhances the ability of NO to oxidise propene in an oxygen-rich atmosphere. Reaction kinetic data obtained as a function of catalyst potential, temperature and gas composition indicate that Na increases the strength of NO chemisorption relative to CO or propene, a process that is accompanied by weakening of the N-O bond, thus facilitating NO dissociation, which is the critical reaction-initiating step. XP spectroscopy under the appropriate conditions of temperature and catalyst potential confirms that the mode of operation of the elctrochemically promoted Pt film does indeed involve reversible pumping of Na to or from the solid electrolyte. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

1-Methylimidazolium hydrogen sulfate catalyzed convenient synthesis of 2,5-dimethyl-N-substituted pyrroles under ultrasonic irradiation

Ionic liquid [HMIM]HSO₄ was found to be an efficient catalyst for the synthesis of N-substituted pyrroles through the reaction of 2,5-hexanedione with amines under ultrasonic irradiation at room temperature. These reactions proceed with good yields under short reaction time. Furthermore, the green catalytic system can be recycled specific times with no decreases in yields and reaction rates.     

The effect of catalyst-electrode potential and work function on the chemisorptive bond of oxygen on Pt interfaced with YSZ

Controlled variation in catalyst-electrode potential of metals interfaced with solid electrolytes leads to the effect of Non-faradaic Modification of Catalytic Activity (NEMCA) which causes dramatic changes in the catalytic activity and selectivity. Its origin was shown to lie in the controlled variation of the work function upon polarization of the catalyst-solid electrolyte interface which is due to ion spillover over the entire gas exposed catalyst surface. In the present work the effect of induced work function changes on the kinetics and energetics of the interaction of oxygen with polycrystalline Pt, interfaced with an yttria stabilized zirconia solid electrolyte, were studied, by means of the temperature programmed desorption technique. It was found that by increasing catalyst potential and work function the O₂ desorption peak shifts towards lower temperatures, showing that the binding strength of chemisorbed oxygen species weakens by increasing catalyst work function. The activation energy of desorption of adsorbed O species was measured by the “temperature rate variation technique” and was found to decrease linearly with slope -1 with increasing catalyst work function. This straightforward experimental correlation between catalyst work function and the binding energy of chemisorbed O species is in absolute agreement with previous NEMCA studies which show that the apparent activation energy of all reactions studied, depends linearly on catalyst potential and work function. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Spt. 1994     

Synthesis and characterization of high temperature proton conductors of type Ba3Ca1+xNb2−xO9−δ

High temperature proton conductors (HTPCs) of composition Ba₃Ca_1+xNb_2−xO₉ have recently attracted considerable interest for possible applications in sensors, fuel cells etc. We give here a preliminary account of the synthesis of compounds with x=−0.03, 0.0, 0.12, 0.18 and 0.35. Both, the oxide and the sol-gel route were successfully used. Calcination and densification were systematically investigated supported by particle size measurements. The resulting samples were characterized using a) x-ray techniques for structural details, b) TEM techniques to search for domain boundaries and foreign phases, c) density measurements to check the results of various densification procedures and d) temperature programmed desorption (TPD) to elucidate the evolution of gases with temperature. The thermal expansion coefficient was determined in selected cases and dilatometry was used to determine the temperature range in which the density saturates. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Acetaldehyde oxidation at elevated pressure

A detailed chemical kinetic model for oxidation of CH₃CHO at intermediate to high temperature and elevated pressure has been developed and evaluated by comparing predictions to novel high-pressure flow reactor experiments as well as shock tube ignition delay measurements and jet-stirred reactor data from literature. The flow reactor experiments were conducted with a slightly lean CH₃CHO/O₂ mixture highly diluted in N₂ at 600–900 K and pressures of 25 and 100 bar. At the highest pressure, the oxidation of CH₃CHO was in the NTC regime, controlled to a large extent by the thermal stability and reactions of peroxide species such as HO₂, CH₃OO, and CH₃C(O)OO. Model predictions were generally in good agreement with the experimental data, even though the predicted temperature for onset of reaction was overpredicted at 100 bar. This discrepancy was attributed mainly to uncertainties in the CH₃C(O)OO reaction subset. Predictions of ignition delays in shock tubes and species profiles in JSR experiments were also satisfactory. At temperatures above the NTC regime, acetaldehyde ignition and oxidation is affected mainly by the competition between dissociation of CH₃CHO and reaction with the radical pool, and by reactions in the methane subset.     

用低温电催化重整方法和CoZnAl催化剂进行低温生物油重整制氢

利用电化学催化重整方法和CoZnAl催化剂实现了高效的生物油重整制氢过程．研究了电流强度对氢气产率、碳转化率以及产物分布的影响．结果表明,通过催化剂的电流对氢气产量和碳转化率都有明显的促进作用,在500 oC低温重整条件下氢气产率和碳转化率分别达到大约70%和85%．此外,用XRD、XPS、TGA和BET研究了电流对催化剂的结构和性能的影响．结果表明,通电催化床中热电子对生物油中含氧有机物的重整反应起着重要的促进作用．     

Neutron cross-sections above 20 MeV for design and modeling of accelerator driven systems

One of the outstanding new developments in the field of partitioning and transmutation (P&T) concerns accelerator-driven systems (ADS) which consist of a combination of a high-power, high-energy accelerator, a spallation target for neutron production and a sub-critical reactor core. The development of the commercial critical reactors of today motivated a large effort on nuclear data up to about 20 MeV, and presently several million data points can be found in various data libraries. At higher energies, data are scarce or even non-existent. With the development of nuclear techniques based on neutrons at higher energies, nowadays there is a need also for higher-energy nuclear data. To provide alternative to this lack of data, a wide program on neutron-induced data related to ADS for P&T is running at the 20–180 MeV neutron beam facility at ‘The Svedberg Laboratory’ (TSL), Uppsala. The programme encompasses studies of elastic scattering, inelastic neutron production, i.e., (n, xn′) reactions, light-ion production, fission and production of heavy residues. Recent results are presented and future program of development is outlined.      

Constraints of two-colour TiRe-LII at elevated pressures

The main objective of this work is to investigate the influence of high-pressure conditions on the determination of primary particle size distributions of laser-heated soot particles using pyrometrically determined temperature decays. The method is based on time-resolved laser-induced incandescence measurements carried out at two different wavelengths (two-colour TiRe-LII). The LII signals are transferred into a particle ensemble averaged (effective) temperature using Planck’s thermal radiation formula. Assuming that all particles within the size distribution possess a unique temperature at the end of the laser pulse, the size distribution can be determined by numerically simulating the measured temperature decay. From our investigations, for pressures up to a few bars it is obvious that this strategy can be successfully applied if standard laser pulses of nano-second duration are used as an LII-excitation source. At higher pressures the time scales of heat conduction are decreased to such an extent that a unique temperature for all particles within the ensemble cannot be assumed at the end of the nano-second laser pulse. However, further investigations show that the presented two-colour TiRe-LII technique can be successfully adopted under technical high-pressure conditions as well, if the pulse duration of the TiRe-LII-excitation source is reduced into the pico-second range.     

Formation of reaction intermediates and primary volatiles during acid-catalysed fast pyrolysis of cellulose in a wire-mesh reactor

This study aims to understand the fundamental reaction mechanisms during fast pyrolysis of the acid-impregnated cellulose in a wire-mesh reactor at 40–450 °C and 20 °C/s, via quantifying key compounds in the reaction intermediates and primary volatiles. Acid impregnation reduces the onset reaction temperature of cellulose pyrolysis. During acid-catalysed cellulose pyrolysis, 1,6-anhydro-β-d-glucofuranose (AGF), levoglucosenone (LGO) and 5-hydroxymethylfurfural (5-HMF) are identified as major products in the primary volatiles, and the formation of levoglucosan is greatly suppressed. At temperatures < 100 °C, acid catalyses hydrolysis reactions to produce glucose, which is further dehydrated to AGF at 120 °C. At temperatures > 160 °C, acid enhances the dehydration of glucose, levoglucosan and AGF to produce 5-HMF and LGO as major primary products. Once produced, those products can be easily released into the vapour phase, as either aerosols via thermal ejection or vapours via evaporation. As the pyrolysis temperature increases to 240 °C, aromatic compounds can be identified in the primary volatiles, indicating condensation reactions also play important roles during acid-catalysed cellulose pyrolysis under the conditions. As a result, char formation becomes the favoured pathway during acid-catalysed cellulose pyrolysis at temperatures > 300 °C.     

Ultrasound assisted synthesis of performic acid in a continuous flow microstructured reactor

The present work establishes in depth study of ultrasound assisted preparation of performic acid (PFA) in a continuous flow microstructured reactor. The influence of various parameters viz. formic acid: hydrogen peroxide molar ratio, flow rate, temperature and catalyst loading on the PFA formation were studied in a continuous flow microstructured reactor. In a continuous microstructured reactor in the presence of ultrasonic irradiation, the formation of PFA was found to be dependent on the molar ratio of formic acid: hydrogen peroxide, flow rate of reactants, temperature and catalyst loading (Amberlite IR-120H). The optimized parameter values are 1:1 M ratio, 50 mL/h, 40 °C and 471 mg/cm³ respectively. Further, the performance of Amberlite IR-120H catalyst was evaluated for three successive cycles in continuous microstructured reactor. The performance of catalyst was found to be decreased with the usage of the catalyst and is attributed to neutralization of the sulfonic acid groups, catalyst shrinkage, or loss in pore sites. The experimental results revealed that, for an ultrasound assisted synthesis of PFA in continuous microstructured reactor the observed reaction time was even less than 10 min. The observed intensification in the PFA synthesis process can be attributed to the intense collapse of the cavities formed at low temperature during ultrasonic irradiations, which further improved the heat and mass transfer rates with the formation of H₂O₂ during the reaction. The combined use of ultrasound and a continuous flow microstructured reactor has proved beneficial process of performic acid synthesis.     

Electrochemical promotion in emission control catalysis

Electrochemical promotion for the catalytic reduction of NO by CO and of NO by ethylene over a Pt catalyst are reported for the first time. Both reactions are of importance in the catalytic control of automotive emissions and both exhibit strong rate enhancement when Na is pumped to the Pt catalyst electrode from a β″ solid electrolyte. Complementary data obtained with a Pt(111)/Na model system indicate that electrochemically-pumped Na acts by inducing dissociation of chemisorbed NO, which is the reaction initiating step. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994.     

Resistance to deformation and fracture of aluminum AD1 under shock-wave loading at temperatures of 20 and 600°C

The results of measurements of the dynamic elastic limit and spall strength under shock-wave loading of aluminum samples AD1 of thicknesses between 0.5 and 10.0 mm at room temperature and at temperature increased up to 600°C are presented. The anomalous thermal hardening of aluminum under high strain rate has been confirmed. An analysis of the decay of precursors at temperatures of 20 and 600°C has shown that the change in the main mechanism of drag of dislocations occurs at a strain rate equal approximately to 5 × 10³ s⁻¹, which agrees with the results of measurements by the Hopkinson split bar method. The results of measurements of the spall strength in a wide range of strain rates add the previously obtained data and agree with them.     

Alkylation of imidazole under ultrasound irradiation over alkaline carbons

N-Alkyl-imidazole has been synthesized by sonochemical irradiation of imidazole and 1-bromobutane using alkaline-promoted carbons (exchanged with the binary combinations of Na, K and Cs). The catalysts were characterized by X-ray photoelectron spectroscopy, thermal analysis and N₂ adsorption isotherms. Under the experimental conditions, N-alkyl-imidazoles can be prepared with a high activity and selectivity. It is observed that imidazole conversion increases in parallel with increasing the basicity of the catalyst. The influence of the alkaline promoter, the reaction temperature, and the amount of catalyst on the catalytic activity has been studied. For comparison, the alkylation of imidazole has also been performed in a batch reactor system under thermal activation.     

Detailed profiling of CNTs arrays along the growth window in a floating catalyst reactor

We report a detailed longitudinal and depth profiles of multi-wall carbon nanotubes (CNTs) arrays synthesized using xylene and ferrocene in a floating catalyst reactor. Point to point analyses of the CNTs grown in a “growth window” with CNTs arrays longer than 0.5 mm were performed using optical microscopy, Raman spectroscopy, FESEM, high-resolution TGA/DTA, and TEM techniques. The heights of the CNTs arrays show a maximum at a mid point of the growth window, while a reverse trend of minimum is observed for iron-to-CNTs atomic ratios. The ratio of amorphous carbon to CNTs sharply increases along the growth window and from the bottom to top of CNTs arrays. The CNTs diameter also increases along the growth window, due to deposition of the amorphous carbon, which can be almost removed by temperature programmed oxidation up to around 500 °C. A base growth mechanism, the variations of catalyst content, residence time and temperature profile along the growth window, the adsorption and decomposition of polycyclic aromatic hydrocarbons to amorphous carbon, and a limited diffusion of hydrocarbon species through the arrays covered by excessive amorphous carbon may explain the results.     

费-托合成制清洁燃料用担载纳米钴基催化剂制备中热处理对其结构和催化性能的影响

" 应用浸渍法在不同的焙烧条件(90~500 ℃)制备了一系列Al2O3担载钴基催化剂(质量含量为15%);采用XRD、XPS、程序升温还原对其进行了结构表征和分析,考察其在一氧化碳选择加氢制备清洁燃料用长链烷烃的反应中的催化性能．XPS结果表明,对于在90~200 ℃焙烧的催化剂,仍可观察到未完全分解的硝酸钴的存在;对于在200~500 ℃焙烧的几个催化剂可观察到Co3O4的物相．对于经过几种热处理制备的氧化铝担载的四个纳米钴基催化剂(200~500 ℃热处理),XRD和XPS结果表明四个样品中主要是9     

Electrochemical promotion of propane deep oxidation on doped lanthanum manganites

Electrochemical catalysts based on LSM deposited on YSZ were used for propane deep oxidation. Electrochemical characterizations such as impedance spectroscopy and current–overpotential measurements were performed. Different thicknesses of LSM films were catalytically characterized and EPOC experiments were carried out on those electrochemical catalysts. It was found that the reaction rates can be in situ tuned by applying an anodic polarization but with weak promotional effects. The faradaic efficiency decreased as the applied potential, the temperature, and the thickness of the catalyst increased. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

The thermal contact problem in nano- and micro-scale photothermal measurements

Thermal contact resistance between two solids is discussed with regard to its influence on the measurements of temperature and thermo-physical parameters in micro- and nano-structures. Two important applications are considered: thin film coatings on substrates and local measurements with a nano-probe in scanning thermal microscopy. The mechanical contact of a copper layer on carbon is measured by adhesion strength experiments and correlated to the thermal transport across the interface deduced from infrared radiometric measurements. A novel quantity the thermal wave contrast is introduced which takes into account the interface resistance and modifications of the coating and substrates at the interface. With regard to scanning thermal microscopy the contact resistance problem is discussed for 3ω-measurements in the active mode and for temperature measurements in the passive mode. It is shown that the thermo-elastic response can offer a means to avoid the influence of the thermal contact resistance on local temperature measurements.     

Surface modification of layered silicates. II. Factors affecting thermal stability

Different aluminosilicates, such as montmorillonite, vermiculite and mica, were surface-treated with a variety of organic modifiers to quantify factors affecting the thermal stability of the modified fillers. Montmorillonites with different cation exchange capacities were also used. Thermal characterisation was carried out via high resolution thermogravimetric analysis and the results were correlated with X-ray diffraction measurements. Modified substrates, such as montmorillonite, vermiculite and mica, differed in their thermal behaviour even when modified with the same surface modifiers. Phosphonium-based modifiers were the most thermally stable, compared to pyridinium and ammonium ions. Mixed brushes from the modifiers also influenced the thermal behaviour of the modified substrates. When further modified using physical adsorption or chemical reactions on the surface, the modified minerals also displayed alterations in the thermal behaviour of the fillers. The results can be used as a guide for the selection of surface modifiers in the nanocomposite synthesis process where compounding of the filler with the polymer at high temperature and shear is required.     

Laser-induced desorption of Na-dimers

We find that Na-dimers are desorbed in a thermal process if rough Na surfaces are irradiated with pulsed laser light of λ=532 nm. In contrast, for light of λ=355 nm, Na₂ can be detached in a non-thermal reaction at low laser fluences. This is concluded from the kinetic energy distributions of the dimers determined by time-of-flight measurements using a second laser at λ=248 nm for photoionization. The transition from non-thermal to thermal desorption at large fluences of the laser light can also be identified. Received: 23 July 1996 / Accepted: 26 August 1996