Structure sensitivity of propene oxidation over Co-Mn spinels

Single-phase cobalt–manganese spinel oxides (Co_3?nMn_nO₄, CMO) were studied for the catalytic oxidation of propene in a systematic optimization strategy. CMO films were synthesized by pulsed-spray evaporation chemical vapor deposition (PSE–CVD) and characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman and Ultraviolet–Visible (UV–Vis) spectroscopy. The effect of Co/Mn ratio in the mixed oxide systems on their catalytic activity was investigated in a fixed-bed reactor at T = 100–800 °C, with a space velocity of 90,000 mL/g_cat h and a feed of 2% C₃H₆/20% O₂/78% Ar. XRD patterns, FTIR and Raman spectroscopy reveal that a cubic single-phase spinel structure is obtained for n ? 1.23, while a tetragonal spinel structure is observed for n > 1.23. With increasing of the manganese content, the temperature–programmed analysis demonstrates a lower reducibility, a general decrease of the temperature required for the reduced samples to be re-oxidized and increasing thermal stability. The catalytic tests show that the involvement of cobalt–manganese oxides in propene oxidation suppresses the formation of reaction intermediates, favoring the selectivity toward CO₂ at low temperatures. Co_2.35Mn_0.65O₄ exhibits the best catalytic performance, which follows in line with its better reducibility compared with the other compositions in the series of CMO oxides. These results show the great potential of CMO for future industrial application as a low-temperature catalytic system which does not rely on precious metals.     

Improved stability of La0.5Sr0.5FeO3 by Ta-doping for oxygen separation membrane application

(La,Sr)FeO₃ mixed conducting perovskites are considered as interesting candidates for oxygen separation membranes but they suffer from limited structural stability in a large oxygen partial pressure (pO₂) gradient, because of their propensity for chemical expansion. Partial substitution of Fe with more stable elements tends to improve the stability while penalizing the electronic and ionic conductivities.In this study, we investigate the effect of 10% Ta substitution on the oxygen transport properties and stability of La_0.5Sr_0.5FeO₃. For this purpose, the material was evaluated as a membrane in a CPOX reactor. The oxygen permeation through a ~ 3 cm² pellet sample was first measured under air/Ar gradient in the temperature range of 800 to 1000 °C. The measured flux was 0.1 µmol cm^? 2 s^? 1 at 900 °C, which was a factor of 2 lower than for the Ta-free material. Methane was then introduced into the system and reacted in a catalytic bed with oxygen that has permeated through the membrane to form syngas (H₂, CO). As a result, the oxygen flux increased by a factor of 9, reaching 0.9 µmol cm^? 2 s^? 1 at 900 °C. The reactor was operated at 1000 °C for another 1000 h. During this time, the oxygen permeation flux decayed by ca. 4%/1000 h.The test was stopped after more than 2000 h of operation and the membrane analyzed by electron microscopy.     

Oxygen transport in La2NiO4 + δ: Assessment of surface limitations and multilayer membrane architectures

The steady-state oxygen permeation through dense La₂NiO_4 + δ ceramics, limited by both surface exchange and bulk ambipolar conduction, can be increased by deposition of porous layers onto the membrane surfaces. This makes it possible, in particular, to analyze the interfacial exchange kinetics by numerical modelling using experimental data on the oxygen fluxes and equilibrium relationships between the oxygen chemical potential, nonstoichiometry and total conductivity. The simulations showed that the role of exchange limitations increases on reducing oxygen pressure, and becomes critical at relatively large chemical potential gradients important for practical applications. The calculated oxygen diffusion coefficients in La₂NiO_4 + δ are in a good agreement with literature. In order to enhance membrane performance, the multilayer ceramics with different architecture combining dense and porous components were prepared via tape-casting and tested. The maximum oxygen fluxes were observed in the case when one dense layer, ~ 60 μm in thickness, is sandwiched between relatively thin (< 150 μm) porous layers. Whilst the permeability of such membranes is still affected by surface-exchange kinetics, increasing thickness of the porous supporting components leads to gas diffusion limitations.     

Characterization of nanohybrid membranes for direct methanol fuel cell applications

A series of sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (S-PPO) and sulfonated poly(ether ether ketone) (S-PEEK) at various sulfonation degrees were prepared and characterized for their degree of sulfonation, water uptake, ion exchange capacity, proton conductivity and methanol permeability. Based on the obtained results, the optimum samples were determined and subsequently blended together at different compositions. A single glass transition temperature (T_g) was determined for all blend samples, which was attributed to the presence of sulfonate groups on polymer backbones resulting in the formation of electrostatic cross-linking besides phenyl–phenyl interactions. Moreover, the molecular level of mixing in blends was verified through WAXS patterns. According to the membrane selectivity and hydrolytic stability measurements, 75 wt.% of S-PPO and 25 wt.% of S-PEEK was selected as the optimum composition. Afterwards, different amounts of an organically modified montmorillonite (MMT) were incorporated into the predetermined optimum composition matrices to reduce the methanol permeability of the resulted nanocomposite proton exchange membranes. The XRD patterns of nanocomposites revealed the exfoliated microstructure of the clay nanolayers in the polymeric matrices. Transport property measurements of nanohybrid membranes showed that the maximum selectivity parameter of 75 wt.% S-PPO/25 wt.% S-PEEK composition appeared in the presence of 1.5 wt.% of MMT, which is 1.53 times higher than the corresponding value for Nafion^® 117. The DMFC single cell test of the optimum nanohybrids membrane at 5 M methanol feed showed an open circuit voltage of 0.77 V and maximum power density of 135 mW cm^? 2 in comparison with 0.67 V and 108 mW cm^? 2 for Nafion^® 117, respectively. Fabricated nanohybrid membranes, thanks to their high selectivity, desirable transport properties and tenability, could be considered as promising polyelectrolytes for direct methanol fuel cell applications.     

Preparation and characterization of iron–molybdate thin films

Mixed Fe–Mo oxides are used in industrial catalytic processes of selective oxidation of methanol to formaldehyde. For better understanding of the structure-reactivity relationships of these catalysts we aim to prepare well-ordered iron–molybdate thin films as model catalysts. Here we have studied Mo deposition onto Fe₃O₄ (111) thin films produced on Pt(111) as a function of Mo coverage and annealing temperature using LEED, AES, STM and IRAS. At low temperatures, the iron oxide film is covered by Mo = O terminated molybdena nanoparticles. Upon oxidation at elevated temperatures (T > 900 K), Mo species migrate into the film and form new bonds with oxygen in the film. The resulting films maintain the crystal structure of Fe₃O₄, and the surface undergoes a (√3 × √3)R30° reconstruction. The structure is rationalized in terms of Fe substitution by Mo in the surface layers.     

Electrical conductivity and oxygen permeation properties of SrCoFeOx membranes

The total conductivity and oxygen permeation properties of dense SrCoFeO_x membranes synthesized from the solid state method were studied in the temperature range of 700–900 °C. The SrCoFeO_x membranes consist of an intergrowth (Sr₄Fe_6 − xCo_xO_13 ± δ), perovskite (SrFe_1 − xCo_xO_3 − δ), and spinel (Co_3 − xFe_xO₄) phase. SrCoFeO_x exhibits n-type and p-type conduction at low and high oxygen partial pressures, respectively, and has a total conductivity of 16.5 S/cm at 900 °C in air. The oxygen permeation fluxes for SrCoFeO_x and SrFeCo_0.5O_x membranes were measured with either an inert or carbon monoxide sweep gas. The oxygen permeation fluxes were higher through SrCoFeO_x membranes than SrFeCo_0.5O_x membranes and can be attributed to a difference in the amount and makeup of the perovskite phase present in each composition. The oxygen permeation fluxes with a carbon monoxide sweep gas were approximately two orders of magnitude larger than the fluxes measured with an inert sweep gas for both compositions. The large oxygen permeation fluxes observed with a carbon monoxide sweep are due to a higher driving force for oxygen transport and a reaction on the sweep side of the membrane that maintains a low oxygen partial pressure.     

Membrane cleaning with ultrasonically driven bubbles

A laboratory filtration plant for drinking water treatment is constructed to study the conditions for purely mechanical in situ cleaning of fouled polymeric membranes by the application of ultrasound. The filtration is done by suction of water with defined constant contamination through a membrane module, a stack of five pairs of flat-sheet ultrafiltration membranes. The short cleaning cycle to remove the cake layer from the membranes includes backwashing, the application of ultrasound and air flushing. A special geometry for sound irradiation of the membranes parallel to their surfaces is chosen. Two frequencies, 35 kHz and 130 kHz, and different driving powers are tested for their cleaning effectiveness. No cleaning is found for 35 kHz, whereas good cleaning results are obtained for 130 kHz, with an optimum cleaning effectiveness at moderate driving powers. Acoustic and optic measurements in space and time as well as analytical considerations and numerical calculations reveal the reasons and confirm the experimental results. The sound field is measured in high resolution and bubble structures are high-speed imaged on their nucleation sites as well as during their cleaning work at the membrane surface. The microscopic inspection of the membrane surface after cleaning shows distinct cleaning types in the cake layer that are related to specific bubble behaviour on the membrane. The membrane integrity and permeate quality are checked on-line by particle counting and turbidity measurement of the permeate. No signs of membrane damage or irreversible membrane degradation in permeability are detected and an excellent water permeate quality is retained.     

Mixed conductivity and oxygen permeability of doped Pr2NiO4-based oxide

Pr₂NiO₄-based oxide was studied as a new mixed electronic and oxide ionic conductor for the oxygen permeation membrane. It was found that Pr₂NiO₄ doped with Cu and Fe for Ni site exhibits the relatively high oxygen permeation rate. Doping second cation to Ni site is effective for improving the oxygen permeation rate and the trivalent cation seems to be effective for increasing the oxygen permeation rate. Among the examined cation, the highest oxygen permeation rate was obtained by doping 5 mol% Fe. The oxygen permeation rate was also significantly affected by the surface catalyst and the highest oxygen permeation rate of 80 μmol·min^− 1·cm^− 2 at 1273 K was achieved by using La_0.1Sr_0.9Co_0.9Fe_0.1O₃ for the surface catalyst. Since the electrical conductivity slightly decreased with decreasing P_O2 and it dropped significantly at P_O2 = 10^− 19 atm, chemical stability of Pr₂NiO₄-based oxide seems to be reasonably high. Application of this new mixed conductor for the oxygen permeation membrane under the CH₄ partial oxidation was also studied and it was confirmed that the oxygen permeation rate much improved under the CH₄ oxidation condition and this Pr₂NiO₄ can be used for the oxygen permeation membrane for the CH₄ partial oxidation.     

Epitaxial growth of well-ordered ultra-thin Al2O3 film on NiAl (1 1 0) by a single-step oxidation

Well-ordered ultra-thin Al₂O₃ films were grown on NiAl (1 1 0) surface by exposing the sample at various oxygen absorption temperatures ranging from 570 to 1100 K at dose rates 6.6 × 10⁻⁵ and 6.6 × 10⁻⁶ Pa. From the results of low-energy electron diffraction (LEED), Auger electron spectrometer (AES) and X-ray photon spectroscopy (XPS) observations, it was revealed that oxidation mechanism above 770 K is different from well-known two-step process. At high temperature, oxidation and crystallization occurred simultaneously while in two-step process oxidation and crystallization occurred one after another. At high-temperature oxidation well-ordered crystalline oxide can be formed by a single-step without annealing. Well-ordered Al₂O₃ layer with thickness over 1 nm was obtained in oxygen absorption temperature 1070 K and a dose rate 6.6 × 10⁻⁶ Pa at 1200 L oxygen.     

Efficient H2O2/CH3COOH oxidative desulfurization/denitrification of liquid fuels in sonochemical flow-reactors

The oxidative desulfurization/denitrification of liquid fuels has been widely investigated as an alternative or complement to common catalytic hydrorefining. In this process, all oxidation reactions occur in the heterogeneous phase (the oil and the polar phase containing the oxidant) and therefore the optimization of mass and heat transfer is of crucial importance to enhancing the oxidation rate. This goal can be achieved by performing the reaction in suitable ultrasound (US) reactors. In fact, flow and loop US reactors stand out above classic batch US reactors thanks to their greater efficiency and flexibility as well as lower energy consumption. This paper describes an efficient sonochemical oxidation with H₂O₂/CH₃COOH at flow rates ranging from 60 to 800 ml/min of both a model compound, dibenzotiophene (DBT), and of a mild hydro-treated diesel feedstock. Four different commercially available US loop reactors (single and multi-probe) were tested, two of which were developed in the authors’ laboratory. Full DBT oxidation and efficient diesel feedstock desulfurization/denitrification were observed after the separation of the polar oxidized S/N-containing compounds (S ⩽ 5 ppmw, N ⩽ 1 ppmw). Our studies confirm that high-throughput US applications benefit greatly from flow-reactors.     

Oxygen species on the silver surface oxidized by MW-discharge: Study by photoelectron spectroscopy and DFT model calculations

A polycrystalline silver surface has been studied by synchrotron radiation photoelectron spectroscopy after deep oxidation by microwave discharge in an O₂ atmosphere. Oxidized structures with high oxygen content, AgO_x with x > 1, have been found on the silver surface after oxidation at 300–400 K. The line shapes observed in the O1s spectra were decomposed into five components and indicated that complex oxidized species were formed. An analysis of the oxidized structures with binding energies, Е_b(O1s), greater than 530 eV pointed to the presence of both Ag–O and O–O bonds. We have carried out a detailed experimental study of the valence band spectra in a wide spectral range (up to 35 eV), which has allowed us to register the multicomponent structure of spectra below Ag4d band. These features were assigned to the formation of Ag–O and O–O bonds composed of molecular (associative) oxygen species. DFT model calculations showed that saturation of the defect oxidized silver surface with oxygen leads to the formation of associative oxygen species, such as superoxides, with electrophilic properties and covalent bonding. The high stability of oxygen-rich silver structures, AgO_x, can be explained by the formation of small silver particles during the intensive MW oxidation, which can stabilize such oxygen species.     

Fluorescent microscope system to monitor real-time interactions between focused ultrasound,echogenic drug delivery vehicles,and live cell membranes

Rapid development in the field of ultrasound triggered drug delivery has made it essential to study the real-time interaction between the membranes of live cells and the membranes of echogenic delivery vehicles under exposure to focused ultrasound. The objective of this work was to design an analysis system that combined fluorescent imagining, high speed videography, and definable pulse sequences of focused ultrasound to allow for real time observations of both cell and vehicle membranes. Documenting the behavior of the membranes themselves has not previously been possible due to limitations with existing optical systems used to understand the basic physics of microbubble/ultrasound interaction and the basic interaction between microbubbles and cells. The performance of this new system to monitor membrane behavior was demonstrated by documenting the modes of vehicle fragmentation at different ultrasound intensity levels. At 1.5 MPa the membranes were shown to completely fragment while at intensities below 1 MPa the membranes pop open and slowly unfold. The interaction between these vehicles and cell membranes was also documented by the removal of fluorescent particles from the surfaces of live cells out to 20 μm from the microbubble location. The fluid flow created by microstreaming around ensonated microbubbles was documented at video recording speeds from 60 to 18,000 frames per second. This information about membrane behavior allows the chemical and physical properties of the drug delivery vehicle to be designed along with the ultrasound pulse sequence to cause the most efficient drug delivery.     

Mixed oxygen ion and electron conducting hollow fiber membranes for oxygen separation

Phase inversion spinning technique was employed to prepare dense perovskite hollow fiber membranes made from composition BaCo_xFe_yZr_zO_3−δ (BCFZ, x + y + z = 1.0). Scanning electron microscope (SEM) shows that such hollow fibers have an asymmetric structure, which is favored to the oxygen permeation. An oxygen permeation flux of 7.6 cm³/min cm² at 900 °C under an oxygen gradient of 0.209 × 10⁵ Pa/0.065 × 10⁵ Pa was achieved. From the Wagner Theory, the oxygen permeation through the hollow fiber membrane is controlled by both bulk diffusion and surface exchange. The elements composition of fresh fiber and the fiber after long-term experiments were analyzed by energy-dispersive X-ray spectra (EDXS). Compared to the fresh fiber, sulphur was found on the tested hollow fiber membrane surface exposed to the air side and in the bulk, and Ba segregations occur on the tested hollow fiber membrane surface exposed to the air side. A decrease of the oxygen permeation flux was observed, which was probably due to the sulphur poisoning.     

Electrode materials for potentiometric hydrogen sensors

Due to their relatively high sensitivity, improved long-term stability, possibilities for miniaturization and low cost products, mixed potential solid electrolyte sensors can be competitive for the in situ measurement of hydrogen trace concentrations in oxygen containing gases. Their response behavior in non-equilibrated oxygen containing gas mixtures is mainly determined by the catalytic activity of the measuring electrode and depends strongly on preparation and measuring conditions. In this work the sensitivity of electrodes made of composites (Au/MeO) has been investigated in hydrogen containing gases in the concentration range φ(H₂) = 0…800 vol.-ppm using a two-chamber setup with Pt-air reference. Electrodes made of Au/Nb₂O₅ composites show the highest sensitivities of up to 20 mV/vol.-ppm at φ(H₂) = 10 vol.-ppm and the lowest catalytic activity for hydrogen oxidation. Selected composite materials were tested additionally in self-heated solid electrolyte sensors with both electrodes exposed to the same atmosphere (gas-symmetrical sensor).     

Characterization of Sr2.7Ln0.3Fe1.4Co0.6O7 (Ln = La,Nd, Sm,Gd) intergrowth oxides as cathodes for solid oxide fuel cells

Perovskite-related intergrowth oxides Sr_2.7Ln_0.3Fe_1.4Co_0.6O_7 ? δ (Ln = La, Nd, Sm, and Gd) have been investigated as cathode materials for solid oxide fuel cells (SOFC). With decreasing size of the Ln³⁺ ions, the unit cell volume, oxygen content, thermal expansion coefficient (TEC), and total electrical conductivity decrease from Ln = La to Gd. The decreasing unit cell volume and oxygen content is attributed to the decreasing size of Ln³⁺ ions from Ln = La to Gd and a consequent preference for lower coordination numbers. While the decrease in the ionicity of the Ln–O bonds from Ln = La to Gd causes a decrease in the TEC, the increasing amount of oxygen vacancies leads to a decrease in electrical conductivity arising from a thermally activated semiconducting behavior. The cathode polarization conductance (R_p^? 1) measured using the ac-impedance spectroscopy and the catalytic activity for the oxygen reduction reaction in SOFC decrease from Ln = La to Gd partly due to the decrease in electrical conductivity.     

A new way to apply ultrasound in cross-flow ultrafiltration: Application to colloidal suspensions

A new coupling of ultrasound device with membrane process has been developed in order to enhance cross-flow ultrafiltration of colloidal suspensions usually involved in several industrial applications included bio and agro industries, water and sludge treatment. In order to reduce mass transfer resistances induced by fouling and concentration polarization, which both are main limitations in membrane separation process continuous ultrasound is applied with the help of a vibrating blade (20 kHz) located in the feed channel all over the membrane surface (8 mm between membrane surface and the blade). Hydrodynamic aspects were also taking into account by the control of the rectangular geometry of the feed channel.Three colloidal suspensions with different kinds of colloidal interaction (attractive, repulsive) were chosen to evaluate the effect of their physico-chemical properties on the filtration.For a 90 W power (20.5 W cm⁻²) and a continuous flow rate, permeation fluxes are increased for each studied colloidal suspension, without damaging the membrane. The results show that the flux increase depends on the initial structural properties of filtered dispersion in terms of colloidal interaction and spatial organizations.For instance, a Montmorillonite Wyoming–Na clay suspension was filtered at 1.5 × 10⁵ Pa transmembrane pressure. Its permeation flux is increased by a factor 7.1, from 13.6 L m⁻² h⁻¹ without ultrasound to 97 L m⁻² h⁻¹ with ultrasound.     

Oxygen permeation characteristics of zirconia with surface modification

Yttria-stabilized zirconia (YSZ) can be used as an oxygen-permeating membrane at elevated temperature (> 1400 °C) due to its chemical and mechanical stability. It was previously shown that the oxygen transport through YSZ membrane in reducing oxygen partial pressure (P_O2) was highly influenced by the surface-exchange kinetics that can be improved by porous surface coating layers such as YSZ, GDC (Gd-doped ceria) or YSZ–GDC mixture [H.J. Park, G.M. Choi, J. Eur. Ceram. Soc. 25 (2005) 2577]. However, the increased oxygen flux was still lower than that estimated assuming bulk-diffusion limit and rapidly decreased with time due to the sintering of coating layers and the reaction between bulk YSZ and coating layers. In this study, the oxygen fluxes through YSZ with LaCrO₃, GDC + LaCrO₃ (bilayer), LaCrO₃ + 5 wt.% GDC (mixture), or LaCr_0.7Co_0.3O₃ coatings were measured under controlled P_O2 gradient (permeate-side P_O2: ∼ 3 × 10^− 12 atm, feed-side P_O2: 2 × 10^− 10–2 × 10^− 8 atm) at 1600 °C. The oxygen flux drastically increased with these coatings. The highest increase in oxygen flux was shown with GDC + LaCrO₃ (bilayer) coating and was maintained for a long time. The presence of highly catalytic Ce ions while maintaining porous structure in the coating layer may explain the observation. The prevention of formation of resistive layer due to ceria coating may also be partly responsible for the observation.     

Reversible and irreversible reactions of three oxygen precursors on InAs(0 0 1)-(4 × 2)/c(8 × 2)

The substrate reactions of three common oxygen sources for gate oxide deposition on the group III rich InAs(0 0 1)-(4 × 2)/c(8 × 2) surface are compared: water, hydrogen peroxide (HOOH), and isopropyl alcohol (IPA). Scanning tunneling microscopy reveals that surface atom displacement occurs in all cases, but via different mechanisms for each oxygen precursor. The reactions are examined as a function of post-deposition annealing temperature. Water reaction shows displacement of surface As atoms, but it does not fully oxidize the As; the reaction is reversed by high temperature (450 °C) annealing. Exposure to IPA and subsequent low-temperature annealing (100 °C) show the preferential reaction on the row features of InAs(0 0 1)-(4 × 2)/c(8 × 2), but higher temperature anneals result in permanent surface atom displacement/etching. Etching of the substrate is observed with HOOH exposure for all annealing temperatures. While nearly all oxidation reactions on group IV semiconductors are irreversible, the group III rich surface of InAs(0 0 1) shows that oxidation displacement reactions can be reversible at low temperature, thereby providing a mechanism of self-healing during oxidation reactions.     

Kinetic demixing and decomposition of oxygen permeable membranes

Oxygen flux through La_0.5Sr_0.5Fe_1−xCo_xO_3−δ (x = 0, 0.5 and 1) membranes has been determined as a function of oxygen partial pressure, temperature and time. The flux was diffusion controlled for low pO₂ gradients while larger pO₂ gradients caused a surface exchange controlled flux. The activation energy of the oxygen flux varied in the range 67–105 kJ/mol. After about 1 month at 1150 °C in an O₂/N₂ gradient the membranes were examined for kinetic demixing and decomposition. On the reducing side only the original perovskite phase was observed at the surface, while on the oxidizing side various secondary phases were observed dependent on the composition at the Fe/Co-site and the Sr + La/Fe + Co ratio of the materials. Moreover, kinetic demixing of the main perovskite phase was also observed, particularly near the surfaces. Grain growth and pore coalescence resulting in membrane expansion were also observed in some cases. The present findings are discussed with regard to the long term chemical stability of the membranes.     

Role of sub-surface oxygen in Cu(100) oxidation

Density functional theory (DFT) calculations are used to investigate the role of sub-surface oxygen in Cu(100) oxidation. We find that the presence of sub-surface oxygen atoms causes the top copper layer of the missing-row reconstructed surface to rise by 1.7 Å compared to the bare surface. This prediction compares well to an earlier scanning tunneling microscopy measurement of 1.8 Å [Lampimaki et al. Journal of Chemical Physics 126 (2007) 034703]. When the missing-row reconstructed surface is exposed to an additional oxygen molecule, surface restructuring that leads to oxide-like structures is only observed when sub-surface oxygen is present. The oxide-like nature of these structures is confirmed through structural, Bader, and electron density of states analyses. These findings, combined with our previous DFT results that predicted low energy barriers for the embedment of oxygen atoms into the sub-surface [Lee and McGaughey, Surface Science 603 (2009) 3404], demonstrate the key role played by sub-surface oxygen in Cu(100) oxidation.