Catalytic behavior of YBa2Cu3O7-x in the partial oxidation of ethanol to acetaldehyde

The partial oxidation of ethanol to acetaldehyde was performed over YBa₂Cu₃O_7-x in a flow reactor. The catalytic characteristics of YB₂Cu₃O_7-x were compared with those of an individual oxide comprising the YBa₂Cu₃O_7-x . The structural change of YBa₂Cu₃O_7-x and the other catalysts after the reaction was measured by means of XRD and XPS, and it was found that the high oxidation state of copper in YBa₂Cu₃O_7-x was responsible for the higher activity and the higher selectivity for acetaldehyde.     

The catalytic oxidation of CO on superconductor Ba2YCu3O7–8

The measurements of MS-TPD, TPRS, the electrical conductivity and kinetics on Ba₂YCu₃O_7-8 show that the catalytic activity of CO oxidation is closely related to properties such as the amounts and sites of oxygen, and electrical conductivity. Based on the experimental results a reaction mechanism has been suggested.     

Preparation and characterization of magnesium diboride superconductor by melting process

The recent discovery of the binary metallic magnesium diboride (MgB₂) superconductor having a remarkably high transition temperature (T_c) of 39 K has generated excitement among the scientist worldwide and gained great scientific interest. Various methods (viz. PLD, solid state reaction etc.) are reported for the preparation of this material in different forms (bulk, wire, thin film) which require a high processing temperature (750 to 950 °C). In this paper, we report a new method of processing MgB₂ superconductor that meets all the properties when compared with other processes. In this work, polycrystalline MgB₂ was prepared by using melting process at low temperature (660 °C). The stoichiometric mixture of Mg-rich and B-rich was pressed into pellets and piled to form Mg-rich/B-rich/Mg-rich system. The piled specimen was then heated up to 800 °C for four hrs with a heating rate of 5 °C/min. The sample was then kept at 660 °C for 12 hrs after cooling from 800 to 660 °C in 30 min. For comparison, the sample was also sintered at 660 °C for 24 hrs. The samples were characterized by using XRD, EDX, SEM, four probe AC methods and magnetization measurements using SQUID magnetometer. The critical temperature was found to be 39 K which shifts towards lower temperature with increasing applied field (0 to 9T). The critical current density, according to Bean’s critical state model was estimated and found to be ∼10₅ A/cm₂, which is comparable to the reported data.     

Catalytic behavior of YBa2Cu3O7-x in the partial oxidation of methanol to formaldehyde

The partial oxidation of methanol to formaldehyde was studied over YBa₂Cu₃O_7-x catalyst in a flow reactor. The structural change of YBa₂Cu₃O_7-x before and after the reaction was measured by means of XRD and iodometric titration method. The catalytic characteristics of YBa₂Cu₃O_7-x for the partial oxidation of methanol to formaldehyde was due to copper ions. It was found that Cu⁺² was responsible for the higher selectivity for formaldehyde.     

The Synergistic Effect of Adsorption-Photocatalysis for Removal of Organic Pollutants on Mesoporous Cu2V2O7/Cu3V2O8/g-C3N4 Heterojunction

Cu₂V₂O₇/Cu₃V₂O₈/g-C₃N₄ heterojunctions (CVCs) were prepared successfully by the reheating synthesis method. The thermal etching process increased the specific surface area. The formation of heterojunctions enhanced the visible light absorption and improved the separation efficiency of photoinduced charge carriers. Therefore, CVCs exhibited superior adsorption capacity and photocatalytic performance in comparison with pristine g-C₃N₄ (CN). CVC-2 (containing 2 wt% of Cu₂V₂O₇/Cu₃V₂O₈) possessed the best synergistic removal efficiency for removal of dyes and antibiotics, in which 96.2% of methylene blue (MB), 97.3% of rhodamine B (RhB), 83.0% of ciprofloxacin (CIP), 86.0% of tetracycline (TC) and 80.5% of oxytetracycline (OTC) were eliminated by the adsorption and photocatalysis synergistic effect under visible light irradiation. The pseudo first order rate constants of MB and RhB photocatalytic degradation on CVC-2 were 3 times and 10 times that of pristine CN. For photocatalytic degradation of CIP, TC and OTC, it was 3.6, 1.8 and 6.1 times that of CN. DRS, XPS VB and ESR results suggested that CVCs had the characteristics of a Z-scheme photocatalytic system. This study provides a reliable reference for the treatment of real wastewater by the adsorption and photocatalysis synergistic process.     

Structure Characteristics and NO Selective Catalytic Reduction Property of Sn x Zr1-x O2 Solid Solution Catalysts

Novel catalysts, Sn_xZr_1-xO₂ solid solutions, for NO selective catalytic reduction:NO SCR) are reported. They have much higher activity and selectivity than SnO₂ and ZrO₂. Sn⁴⁺ is the main reductive sites as proved by TPR. The dilution of Sn sites by the coexisting Zr causes a suppression of propene combustion and consequently promoted the selective reduction of NO. The rutile structure might be beneficial to NO SCR.     

Changes in Ba Phases in BaO/Al2O3 upon Thermal Aging and H2O Treatment

The effects of thermal aging and H₂O treatment on the physicochemical properties of BaO/Al₂O₃ (the NO_x storage component in the lean NO_x trap systems) were investigated by means of X-ray diffraction (XRD), BET, TEM/EDX and NO₂ TPD. Thermal aging at 1000 °C for 10 h converted dispersed BaO/BaCO₃ on Al₂O₃ into low surface area crystalline BaAl₂O₄. TEM/EDX and XRD analysis showed that H₂O treatment at room temperature facilitated a dissolution/reprecipitation process, resulting in the formation of a highly crystalline BaCO₃ phase segregated from the Al₂O₃ support. Crystalline BaCO₃ was formed from conversion of both BaAl₂O₄ and a dispersed BaO/BaCO₃ phase, initially present on the Al₂O₃ support material after calcinations at 1000 and 500 °C, respectively. Such a phase change proceeded rapidly for dispersed BaO/BaCO₃/Al₂O₃ samples calcined at relatively low temperatures with large BaCO₃ crystallites observed in XRD within 10 min after contacting the sample with water. Significantly, we also find that the change in barium phase occurs even at room temperature in an ambient atmosphere by contact of the sample with moisture in the air, although the rate is relatively slow. These phenomena imply that special care to prevent the water contact must be taken during catalyst synthesis/storage, and during realistic operation of Pt/BaO/Al₂O₃ NO_x trap catalysts since both processes involve potential exposure of the material to CO₂ and liquid and/or vapor H₂O. Based on the results, a model that describes the behavior of Ba-containing species upon thermal aging and H₂O treatment is proposed.     

ZnO/Cr2O3 catalyst for reverse-water-gas-shift reaction of CAMERE process

The stability and the activity of Fe₂O₃/Cr₂O₃ and ZnO/Cr₂O₃ catalysts were examined for a reverse-watergas-shift reaction (RWReaction). The initial activities of those catalysts were quite high so that the conversion reached close to equilibrium. The activity of Fe₂O₃/Cr₂O₃ catalyst decreased from 33.5 to 29.8% during the RWReaction for 75 h at 873 K with GHSV (ml/gcat · h) of 100,000. Moreover, the coke formation on the Fe₂O₃/Cr₂O₃ catalyst caused clogging in the RWReactor of the CAMERE process. On the other hand, the ZnO/Cr₂O₃ catalyst showed no coke formation and no deactivation for the RWReaction at 873 K with GHSV (ml/gcat · h) of 150,000. The ZnO/Cr₂O₃ was a good catalyst for the RWReaction of the CAMERE process.     

Ambient temperature oxidation of carbon monoxide using a Cu2Ag2O3 catalyst

The mixed copper–silver oxide, Cu₂Ag₂O₃, has been prepared by co-precipitation and tested for ambient temperature carbon monoxide oxidation. The catalyst demonstrated appreciable low temperature oxidation activity and the catalyst aged for 4 h was the most active. Carbon monoxide conversion increased with time-on-stream, reaching steady state after ca. 1000 min. Acomparison of the catalytic activity has been made with a representative sample of a high activity hopcalite, mixed copper/manganese oxide catalyst. On the basis of CO oxidation rate data corrected for the effect of catalyst surface area the Cu₂Ag₂O₃, aged for 4 h was at least as active as the hopcalite.     

Nanostructured Y2O3 plasma coating for high temperature oxidation protection

This paper investigates the effect of nano-size and micron-size Y₂O₃ powder-coated specimen on high-temperature oxidation resistance of low-alloy Cr–Mo steel (2.25 Cr-1 Mo steel). Both are powder coated by plasma spray coating method. The oxidation rate and reaction kinetics are studied and the post-corroded scales are characterized in Field Emission Scanning Electron Microscope and X-ray Diffraction. The results clearly indicate that nanosize Y₂O₃-coated (nanostructured) specimen improves the high-temperature oxidation resistance in comparison to the micron-size Y₂O₃-coated specimen. The detail mechanism of the oxidation of both the coated specimen is discussed in detail in this paper.     

Preparation and luminescent properties of Tb3+ doped Y2O2SO4 microflakes

Abstract

Tb³⁺ doped Y₂O₂SO₄ (Y₂O₂SO₄:Tb³⁺) microflakes were prepared by a combination method of electrospinning and calcination. The two-dimensional microflakes had smooth surface and high radial/axial ratio. Crystal structures of the Y₂O₂SO₄:Tb³⁺ microflakes resulted in layer by layer growth in axial direction. A possible formation mechanism was proposed on the basis of experimental results, which indicated that poly(vinyl pyrrolidone) played the role of the nanostructure directing template and revealed the growth priority in radial direction. The microflakes showed a favourable fluorescent property symbolised by the characteristic green emission (541 nm) resulting from the ⁵D₄→⁷F₅ transition of Tb³⁺ ions under 229 nm ultraviolet excitation. The maximum intensity of Tb³⁺ emission of the Y₂O₂SO₄:Tb³⁺ microflakes was 2·3 times stronger than that of the Y₂O₂SO₄:Tb³⁺ bulk powders with the same doping concentration.     

Response surface methodology approach for the optimization of tartrazine removal by heterogeneous photo-Fenton process using mesostructured Fe2O3-suppoted ZSM-5 prepared by chitin-templating

A statistical optimization of tartrazine dye removal process from aqueous solution by heterogeneous photo–Fenton process using Fe₂O₃-supported ZSM-5 catalyst was performed. ZSM-5 support was prepared by chitin-templating technique to obtain a mesoporous structure. Thereafter, Fe₂O₃ was supported on ZSM-5 through wet impregnation method. This material was characterized by different techniques and posteriorly evaluated as a catalyst for the removal of tartrazine from aqueous solution. A central composite rotational design coupled with response surface methodology approach was used to evaluate the influence of different reaction conditions on the decolorization of a solution containing tartrazine and to obtain the optimum conditions. Under the optimum experimental conditions of dye decolorization, a mineralization experiment was conducted through analysis of total organic carbon. In these conditions, 95% of decolorization was achieved at 30?min of reaction and a significant mineralization of 80% was observed at 180?min. Therefore, the photo-Fenton process using Fe₂O₃-supported ZSM-5 prepared by chitin-templating was proved to be feasible for both the decolorization and mineralization of tartrazine in aqueous solution.     

The NO x reduction mechanism by H2 under near isothermal conditions over Pt–Ba/Al2O3 Lean NO x Trap systems

The study of the gas-phase NO reduction by H₂ and of the stability/reactivity of NO _x stored over Pt–Ba/Al₂O₃ Lean NO _x Trap systems allowed to propose the occurrence of a reduction process of the stored nitrates occurring via to a Pt-catalyzed surface reaction which does not involve, as a preliminary step, the thermal decomposition of the adsorbed NO _x species.     

Influence of magnesia doping on structure and electrical conductivity of pyrochlore type GdSmZr2O7

Abstract

Polycrystalline ceramic samples of magnesia doped GdSm_1–xMg_xZr₂O_7–x/2 have been prepared by conventional solid state reaction method using high purity oxides. The influence of magnesia dopant content on densification, microstructure and electrical properties of GdSm_1–xMg_xZr₂O_7–x/2 ceramics are investigated. Magnesia doping promotes the sintering densification behaviour of GdSm_1–xMg_xZr₂O_7–x/2 ceramics. GdSm_1–xMg_xZr₂O_7–x/2 (x?=?0, 0·05, 0·10) ceramics have a single phase of the pyrochlore type structure, while GdSm_1–xMg_xZr₂O_7–x/2 (x?=?0·15, 0·20) ceramics consist of the pyrochlore type structure and a small amount of magnesia as the second phase. The total conductivity of GdSm_1–xMg_xZr₂O_7–x/2 ceramics obeys the Arrhenius relation, and gradually increases with increasing temperature from 723 to 1173 K. GdSm_1–xMg_xZr₂O_7–x/2 ceramics are oxide-ion conductors in the oxygen partial pressure range of 1·0×10^–4 to 1·0 atm at each test temperature. The maximum value of the total conductivity is 1·29×10^–2 S cm^–1 at 1173 K for the GdSm_0·85Mg_0·15Zr₂O_6·925 ceramic.     

Microstructure and optical properties of nanocrystalline Cu2O thin films prepared by electrodeposition

Cuprous oxide (Cu₂O) thin films were prepared by using electrodeposition technique at different applied potentials (−0.1, −0.3, −0.5, −0.7, and −0.9 V) and were annealed in vacuum at a temperature of 100°C for 1 h. Microstructure and optical properties of these films have been investigated by X-ray diffractometer (XRD), field-emission scanning electron microscope (SEM), UV-visible (vis) spectrophotometer, and fluorescence spectrophotometer. The morphology of these films varies obviously at different applied potentials. Analyses from these characterizations have confirmed that these films are composed of regular, well-faceted, polyhedral crystallites. UV–vis absorption spectra measurements have shown apparent shift in optical band gap from 1.69 to 2.03 eV as the applied potential becomes more cathodic. The emission of FL spectra at 603 nm may be assigned as the near band-edge emission.     

Semiconductive and Redox Properties of Ti and Zr Pyrophosphate Catalysts (TiP2O7 and ZrP2O7). Consequences for the Oxidative Dehydrogenation of n-Butane

The electrical conductivity of titanium and zirconium pyrophosphates used as catalysts in n-butane oxidative dehydrogenation has been measured under oxygen and n-butane at 400 and 500 °C and under subsequent exposures to both gases at the catalytic reaction temperature. The two compounds appeared to be p-type semiconductors under air with positive holes as the main charge carriers but became n-type when contacted with n-butane. If their conductivities are comparable as p-type semiconductors (within one order of magnitude), by contrast, they differ by 3 orders of magnitude when being n-type semiconductors. These results explain the difference in catalytic reaction mechanism encountered on the two solids. The alkane activation was proposed to be related in both cases to the p-type semiconducting properties of the solids, likely through hydrogen abstraction by a surface O^- species, forming a C₄H₉ radical which will similarly undergo a second hydrogen abstraction to form butenes. The changes in activation energy and in selectivity on TiP₂O₇ at higher temperatures (>450 C) are indicative of a change in mechanism, possibly with the transient formation of an alkoxide species.     

Kinetic evaluation of mechanistic models for O2 release from ZSM-5-supported [Cu2+ –O–Cu2+] ions by thermal reduction or chemical interaction with impinging N2O molecules

For a series of oxidized Cu-ZSM-5 catalysts which were characterized in the catalytic amounts of the oxygen-bridged Cu²⁺-dimers, [Cu²⁺–O–Cu²⁺], activation energies required for the reduction of the Cu²⁺-dimer species by O₂ release were determined using the temperature-programmed experiments of thermal O₂ desorption (TPD) and N₂O decomposition reaction. The activation energy for the thermal reduction of the Cu²⁺-dimers during the TPD decreased linearly with increasing molar number of the Cu²⁺-dimers available on the ZSM-5, suggesting that the energy barrier of the O₂ formation via a Langmuir-Hinshelwood (LH) mechanism increased in proportion to the distance between the two Cu²⁺-dimers in the nearest neighbor. Activation energies of thermal O₂ release were comparable to the literature-reported binding energies of the differently spaced Cu²⁺-dimers. It was also revealed that the activation energy of O₂ release during the temperature programmed N₂O decomposition reaction over an oxidized catalyst was generally low as compared to that in the TPD, and that the degree of reduction of the Cu²⁺-dimers was much greater in the N₂O decomposition reaction than in the TPD at the same temperatures. These beneficial effects N₂O decomposition on the reduction of the Cu²⁺-dimers were discussed in respect of the removal mechanism of the Cu²⁺-dimer bridged oxygen.     

Color-tunable properties of Eu3+- and Dy3+-codoped Y2O3 phosphor particles

Rare-earth phosphors are commonly used in display panels, security printing, and fluorescent lamps, and have potential applications in lasers and bioimaging. In the present study, Eu³⁺- and Dy³⁺-codoped uniform-shaped Y₂O₃ submicron particles were prepared using the urea homogeneous precipitation method. The structure and morphology of the resulting particles were characterized by X-ray diffraction, field emission scanning electron microscope, and field emission transmission electron microscope, whereas their optical properties were monitored by photoluminescence spectroscopy. The room-temperature luminescence color emission of the synthesized particles can be tuned from red to yellow by switching the excitation wavelength from 254 to 350 nm. The luminescence intensities of red and yellow emissions could be altered by varying the dopant concentration. Strong quenching was observed at high Eu³⁺ and Dy³⁺ concentrations in the Y₂O₃ host lattice.     

Partial oxidation of methane catalyzed by YBa2Cu3Ox in a solid state electrochemical reactor

The catalytic oxidation of methane was studied between 840 and 1110 K on a YBa₂Cu₃O* mixed-conducting electrode deposited on an yttria stabilized zirconia solid electrolyte. The lattice oxygen supplied electrochermically to the catalyst surface actively participated in the oxidation reaction, with CO as the major product, and CO₂, CH₃OH and HCHO as the minor products. The reaction rate was found to be of first order with respect to methane. The rate constant depended strongly on the electrochemically imposed bias. Under DC bias condition, the reaction rate was enhanced by as much as two orders of magnitude over that observed under open-circuit conditions. An Eley-Rideal mechanism for the interaction of CH₄ with surface oxygen is proposed as the rate-determining step.     

Revisiting Ga2O3/H-ZSM-5 propane aromatization catalysts

Oxidative or reducing treatments at 873 K of Ga₂O₃/H-ZSM-5 (Si/Al = 13 or 60) cause a change in H⁺ concentration as evidenced by IR spectroscopy of OH groups at 3610 cm^–1; this change is nicely correlated to the variation ofm-xylene isomerisation rate.