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.     

Catalytic Oxidation of CO Gas over Nanocrystallite Cu x Mn1−x Fe2O4

The catalytic oxidation of CO over nanocrystallite Cu _x Mn_(1−x)Fe₂O₄ powders was studied using advanced quadruple mass gas analyzer system. The oxidation of CO to CO₂ was investigated as a function of reactants ratio and firing temperature of ferrite powders. The maximum CO conversion was observed for ferrite powders which have equal amount of Cu²⁺ and Mn²⁺ (Cu_0.5Mn_0.5Fe₂O₄). The high catalytic activity of Cu_0.5Mn_0.5Fe₂O₄ can be attributed to the changes of the valence state of catalytically active components of the ferrite powders. The firing temperature plays insignificant role in the catalytic activity of CO over nanocrystallite copper manganese ferrites. The mechanism of catalytic oxidation reactions was studied. It was found that the CO catalytic oxidation reactions on the surface of the Cu _x Mn_1−x Fe₂O₄ was done by the reduction of the ferrite by CO to the oxygen deficient lower oxide then re-oxidation of this phase to the saturated oxygen metal ferrite again.     

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.     

Carbon dioxide hydrogenation to methanol over the pre-reduced LaCr0.5Cu0.5O3 catalyst

The synthesis of methanol from CO₂ hydrogenation was carried out over the pre-reduced Cu-based LaCr_0.5Cu_0.5O₃ catalyst. It showed a much higher catalytic performance (X_CO2 = 10.4% and S_MeOH = 90.8%) at 250 °C than over 13% Cu/LaCrO₃ prepared by wet-impregnation method (X_CO2 = 4.8% and S_MeOH = 46.6%). XRD, H₂/CO₂-TPD and XPS measurements illustrated that hydrogen was adsorbed on the Cu^α+ sites and that CO₂ was activated on the medium basic sites for the reduced LaCr_0.5Cu_0.5O₃. This phenomenon was responsible for its catalytic activity.     

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.     

Solid-State Construction of CuOx/Cu1.5Mn1.5O4 Nanocomposite with Abundant Surface CuOx Species and Oxygen Vacancies to Promote CO Oxidation Activity

Carbon monoxide (CO) oxidation performance heavily depends on the surface-active species and the oxygen vacancies of nanocomposites. Herein, the CuO_x/Cu_1.5Mn_1.5O₄ were fabricated via solid-state strategy. It is manifested that the construction of CuO_x/Cu_1.5Mn_1.5O₄ nanocomposite can produce abundant surface CuO_x species and a number of oxygen vacancies, resulting in substantially enhanced CO oxidation activity. The CO is completely converted to carbon dioxide (CO₂) at 75 °C when CuO_x/Cu_1.5Mn_1.5O₄ nanocomposites were involved, which is higher than individual CuO_x, MnO_x, and Cu_1.5Mn_1.5O₄. Density function theory (DFT) calculations suggest that CO and O₂ are adsorbed on CuO_x/Cu_1.5Mn_1.5O₄ surface with relatively optimal adsorption energy, which is more beneficial for CO oxidation activity. This work presents an effective way to prepare heterogeneous metal oxides with promising application in catalysis.     

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.     

Theoretical and experimental study on the emission characteristics of waste plastics incineration by modified O2/RFG combustion technology

For mitigating the emission of greenhouse gas CO₂ from general air combustion systems, a clean combustion technology O₂/RFG is in development. The O₂/RFG combustion technology can significantly enhance the CO₂ concentration in the flue gas; however, using almost pure oxygen or pure CO₂ as feed gas is uneconomic and impractical. As a result, this study proposes a modified O₂/RFG combustion technology in which the minimum pure oxygen is mixed with the recycled flue gas and air to serve as the feed gas. The effects of different feed gas compositions and ratios of recycled flue gas on the emission characteristics of CO₂, CO and NO_x during the plastics incineration are investigated by theoretical and experimental approaches.Theoretical calculations were carried out by a thermodynamic equilibrium program and the results indicated that the emissions of CO₂ were increased with the O₂ concentrations in the feed gas and the ratios of recycled flue gas increased. Experimental results did not have the same trends with theoretical calculations. The best feed gas composition of the modified O₂/RFG combustion was 40% O₂ + 60% N₂ and the best ratio of recycled flue gas was 15%. As the O₂ concentration in feed gas and the ratio of recycled flue gas increased, the total flow rates and pressures of feed gas reduced. The mixing of solid waste and feed gas was incomplete and the formation of CO₂ decreased. Moreover, the emission of CO was decreased as the O₂ concentration in feed gas and the ratio of recycled flue gas increased. The emission of NO_x gradually increased with rising the ratio of recycled flue gas at lower O₂ concentration (<40%) but decreased at higher O₂ concentration (>60%).     

Microstructural and electrical characterization of bulk YBa2Cu3O7−δ ceramics

The value of critical current density at 77 K in “zero” applied field (J_c) characterizing the superconducting state for YBa₂Cu₃O_7−δ ceramics is closely related to the microstructure.The interrelationships between the microstructural factors such as pore volume fraction, oxygen content, average grain size, are complex. However, these factors also influence the normal state resistivity measured at room temperature (ρ₃₀₀). We demonstrate how the current carrying cross section influences Jc and ρ₃₀₀ in a similar way. Data, reported for two classes of YBa₂Cu₃O_7−δ: small grain porous ceramics and larger-grain denser ceramics, reveal an approximate linear relation between ρ_300 K and J_c. Extrapolation of this relation to a fully dense small grain YBa₂Cu₃O_7−δ ceramic yields values of ρ₃₀₀ = 0.4 mΩ cm and J_c = 10³ A cm⁻².     

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.     

Stable carbon dioxide reforming of methane over modified Ni/Al2O3 catalysts

CO₂ reforming of methane was studied over modified Ni/Al₂O₃ catalysts. The metal modifiers were Co, Cu, Zr, Mn, Mo, Ti, Ag and Sn. Relative to unmodified Ni/Al₂O₃, catalysts modified with Co, Cu and Zr showed slightly improved activity, while other promoters reduced the activity of CO₂ reforming. Mn-promoted catalyst showed a remarkable reduction in coke deposition, while entailing only a small reduction in catalytic activity compared to unmodified catalyst. The catalysts prepared at high calcination temperatures showed higher activity than those prepared at low calcination temperature. The Mn-promoted catalyst showed very low coke deposition even in the absence of diluent gas and the activity changed only slightly during 100 h operation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal and chemical stability of Cu–Zn–Cr-LDHs prepared by accelerated carbonation

Layered double hydroxides Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O with different molar ratios of Cu/Zn/Cr were synthesized by accelerated carbonation. The products were characterized by XRD, SEM, FT-IR and TG-DTG-DSC-MS. The chemical stability was tested by the modified Toxicity Characteristic Leaching Procedure (TCLP). The results showed that the products were the mixture of Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O and (CuZn)₂(CO₃)(OH)₂, with similar thermal behavior. All products were chemically stable with reduced leaching at pH > 6 (Cu²⁺, Zn²⁺) or > 5 (Cr³⁺).     

Highly Active CNT-Promoted Cu–ZnO–Al2O3 Catalyst for Methanol Synthesis from H2/CO/CO2

With types of in-house-synthesized multi-walled carbon nanotubes (CNTs) and the nitrates of the corresponding metallic components, highly active CNT-promoted Cu–ZnO–Al₂O₃ catalysts, symbolized as Cu _i Zn _j Al _k -x%CNTs, were prepared by the co-precipitation method. Their catalytic performance for methanol synthesis from H₂/CO/CO₂ was studied and compared with the corresponding CNT-free co-precipitated catalyst, Cu _i Zn _j Al _k . It was shown experimentally that appropriate incorporation of a minor amount of the CNTs into the Cu _i Zn _j Al _k could significantly increase the catalyst activity for methanol synthesis. Under the reaction conditions of 493 K, 5.0 MPa, H_2/CO/CO₂/N₂ = 62/30/5/3 (v/v), GHSV = 8000 h^-1, the observed CO conversion and methanol formation rate over a co-precipitated catalyst of Cu₆Zn₃Al₁-12.5%CNTs reached 36.8% and 0.291 mol CH₃OH s^-1 (m²-surf. Cu)^-1, which was about 44 and 25% higher than those (25.5% and 0.233 mol CH₃OH s^-1 (m²-surf. Cu)^-1) over the corresponding CNT-free co-precipitated catalyst, Cu₆Zn₃Al₁. Addition of a minor amount (10–15 wt%) of the CNTs to the Cu₆Zn₃Al₁ catalyst was found to considerably increase specific surface area, especially Cu surface area of the catalyst. H₂-TPD measurements revealed that the CNTs and the pre-reduced CNT-promoted catalyst systems could reversibly adsorb and store a considerably greater amount of hydrogen under atmospheric pressure at temperatures ranging from room temperature to 573 K. This unique feature would be beneficial for generating microenvironments with higher stationary-state concentration of active hydrogen adspecies on the surface of the functioning catalyst, especially at the interphasial active sites since the highly conductive CNTs might promote hydrogen spillover from the Cu sites to the Cu/Zn interphasial active sites, and thus be favorable for increasing the rate of the CO hydrogenation reactions. Alternatively, the operation temperature for methanol synthesis over the CNT-promoted catalysts can be 15–20 degrees lower than that over the corresponding CNT-free contrast system. This would contribute considerably to an increase in equilibrium CO conversion and CH₃OH yield. The results of the present work indicated that the CNTs could serve as an excellent promoter.     

The Effects of CO2 and H2O on the NO x Destruction Performance of a Model NO x Storage/Reduction Catalyst

The effects of CO₂ and H₂O on the NO _x storage and reduction characteristics of a Pt/Ba/Al₂O₃ catalyst were investigated. The presence of CO₂ and H₂O, individually or together, affect the performance and therefore the chemistry that occurs at the catalyst surface. The effects of CO₂ were observed in both the trapping and reduction phases of the experiments, whereas the effect of H₂O seems limited to the trapping phase. The data also indicate that multiple types of sorption sites (or mechanisms for sorption) exist on the catalyst. One mechanism is characterized by a rapid and complete uptake of NO _x . A second mechanism is characterized by a slower rate of NO _x uptake, but this mechanism is active for a longer time period. As the temperature is increased, the effect of H₂O decreases compared to that of CO₂. At the highest temperatures examined, the elimination of H₂O when CO₂ is present did not affect the performance.     

Thin films of Cu2Sb and Cu9Sb2 as anode materials in Li-ion batteries

Thin Cu₂Sb films have been prepared by heat-treating Sb films, electrodeposited on Cu substrates. The influence of the electrodeposition conditions and the heat-treatment period on composition and morphology of the films were investigated (SEM and XRD) and the obtained films were tested as anode materials for Li-ion batteries. The Cu₂Sb material showed a stable capacity of 290 mAh g⁻¹ (close to the theoretical capacity of 323 mAh g⁻¹) during more than 60 cycles. The presence of 9-11% (w/w) Sb₂O₃ in the electrodeposited films resulted in smaller particles but also slowed down formation of Cu₂Sb during the heat-treatment step. The presence of Sb₂O₃ was found to decrease the cycling stability although structural reversibility of Cu₂Sb was obtained both with and without Sb₂O₃. Longer heat-treatments of pure Sb films resulted in the formation of Cu₉Sb₂ which was shown to be reduced at a lower potential than Cu₂Sb. The Cu₉Sb₂ was converted to Cu₂Sb during repeated cycling and the capacity of the latter Cu₂Sb material was found to be 230 mAh g⁻¹. While reduction of the materials was complicated by simultaneous formation of an SEI layer, three plateaus could be identified during the oxidation of Li₃Sb, indicating the presence of three separate one-electron oxidation reactions.     

Rapid deposition of YBCO films by laser CVD and effect of lattice mismatch on their epitaxial growth and critical temperature

a-Axis- and c-axis-oriented YBa₂Cu₃O_7–δ (YBCO) films were grown on (100) SrTiO₃ substrate by laser chemical vapour deposition (laser CVD). The effect of lattice mismatch between films and substrates on in-plane and out-of-plane crystallinity and critical temperature (T_C) was investigated. The preferred orientation changed from a-axis to c-axis as the deposition temperature increased from 928 to 1049 K. The c-axis-oriented YBCO showed a minimum of full width at half maximum of 0.5° for the ω-scan and 1.0° for the φ-scan. A smaller mismatch between YBCO films and substrates led a higher crystallinity for in-plane and out-of-plane epitaxial growths. A high T_C of 90 K was obtained for the c-axis-oriented YBCO films. The deposition rate of the YBCO films was 58–101 μm h⁻¹, approximately 60–1000 times higher than that of conventional CVD.     

Highly efficient complete oxidation of dilute benzene over ultrafine Cu0.1Ce0.5Zr0.4O2−δ catalyst in a fluidized bed reactor

Ultrafine Cu_0.1Ce_0.5Zr_0.4O_2−δ catalyst operated in a fluidized bed reactor was found to be very effective for complete oxidation of dilute benzene in air. The complete conversion of benzene could be achieved at reaction temperature as low as 220 °C. The mechanism of benzene oxidation over the Cu_0.1Ce_0.5Zr_0.4O_2−δ catalyst was investigated by conducting pulse reaction of pure benzene in the absence of O₂ over the catalyst and the results indicated the involvement of lattice oxygen from the catalyst in benzene oxidation.     

Hydrogenation of phenol with supported Rh catalysts in the presence of compressed CO2: Its effects on reaction rate, product selectivity and catalyst life

Hydrogenation of phenol to cyclohexanone and cyclohexanol in/under compressed CO₂ was examined using commercial Rh/C and Rh/Al₂O₃ catalysts to investigate the effects of CO₂ pressurization on the total conversion and the product selectivity. Although the total rate of phenol hydrogenation with Rh/C was lowered by the presence of CO₂, the selectivity to cyclohexanone was improved at high conversion levels >70%. On the other hand, the activity of Rh/Al₂O₃ was completely lost in an early stage of reaction. The features of these multiphase catalytic hydrogenation reactions using compressed CO₂ were studied in detail by phase behavior and solubility measurements, in situ high-pressure FTIR for molecular interactions of CO₂ with reacting species and formation/adsorption of CO on the catalysts, and simulation of reaction kinetics using a simple model. The CO₂ pressurization was shown to suppress the hydrogenation of cyclohexanone to cyclohexanol, improving the selectivity to cyclohexanone. The formation and adsorption of CO were observed for the two catalysts at high CO₂ pressures in the presence of H₂, which was one of important factors retarding the rate of hydrogenation in the presence of CO₂. It was further indicated that the adsorption of CO on Rh/Al₂O₃ was strong and caused the complete loss of its activity.     

Microwave fabrication of Cu2ZnSnS4 nanoparticle and its visible light photocatalytic properties

Cu₂ZnSnS₄ nanoparticle with an average diameter of approximately 31 nm has been successfully synthesized by a time effective microwave fabrication method. The crystal structure, surface morphology, and microstructure of the Cu₂ZnSnS₄ nanoparticle were characterized. Moreover, the visible light photocatalytic ability of the Cu₂ZnSnS₄ nanoparticle toward degradation of methylene blue (MB) was also studied. About 30% of MB was degraded after 240 min irradiation when employing Cu₂ZnSnS₄ nanoparticle as a photocatalyst. However, almost all MB was decomposed after 90 min irradiation when introducing a small amount of H₂O₂ as a co-photocatalyst. The enhancement of the photocatalytic performance was attributed to the synergetic effect between the Cu₂ZnSnS₄ nanoparticle and H₂O₂. The detailed photocatalytic degradation mechanism of MB by the Cu₂ZnSnS₄ was further proposed.     

Influence of low concentration of SO2 for selective reduction of NO by C3H8 in lean-exhaust conditions on the activity of Ag/Al2O3 catalyst

The effect of SO₂ for the selective reduction of NO by C₃H₈ on Ag/Al₂O₃ was investigated in the presence of excess oxygen and water vapor. The NO_x conversion decreased permanently even in the presence of a low concentration of SO₂ (0.5–10 ppm) at <773 K. The increase in SO₂ concentration resulted in a large decrease in NO_x conversion at 773 K. However, when the reaction temperature was more than 823 K, the activity of Ag/Al₂O₃ remained constant even in the presence of 10 ppm of SO₂. The sulfate species formed on the used Ag/Al₂O₃ were characterized by a temperature programmed desorption method. The sulfated species formed on silver should mainly decrease the deNO_x activity on the Ag/Al₂O₃. The sulfated Ag/Al₂O₃ was appreciably regenerated by thermal treatment in the deNO_x feed at 873 K. The moderate activity remains at 773 K in the presence of 1 ppm SO₂ for long time by the heat treatment at every 20 h intervals.