The oxidative dehydrogenation (ODH) of isobutane over Cr_2O_3/La_2(CO_3)_3 has been investigated in a low-pressure Knudsen cell reactor, under conditions where the kinetics of the primary reaction steps can be accurat...The oxidative dehydrogenation (ODH) of isobutane over Cr_2O_3/La_2(CO_3)_3 has been investigated in a low-pressure Knudsen cell reactor, under conditions where the kinetics of the primary reaction steps can be accurately determined. By heating the catalyst at a constant rate from 150-300℃, temperature fluctuations due to non-equilibrium adsorption are minimized. The evolved gas profiles show that ODH to isobutene and water is a primary reaction pathway, while carbon dioxide, which forms from the catalyst during reaction, is the only other product. This CO2 evolution may enhance the activity of the catalyst. Isobutene formation proceeds with the participation of lattice oxygen from the Cr2O3/La2(CO3)3 catalyst. The intrinsic Arrhenius rate constant for the ODH of isobutane isk(s-1) = 1011.5±2.2exp{-((55±5) -ΔHads kJmol-1)/RT}The small pre-exponential factor is expected for a concerted mechanism and for such a catalyst with a small surface area and limited porosity.展开更多
The effects of rare-earth La_2O_3 addition on microstructures and electrical properties of SrTiO_3 ceramics were investigated. Semiconductor SrTiO_3-based voltage-sensing and dielectric dual functional ceramics was pr...The effects of rare-earth La_2O_3 addition on microstructures and electrical properties of SrTiO_3 ceramics were investigated. Semiconductor SrTiO_3-based voltage-sensing and dielectric dual functional ceramics was prepared by a single step sintering technology in this study, and the effects of the content of La_2O_3 on characteristics of the product were discussed in terms of microstructures and electrical properties of materials. The results show that SrTiO_3-based ceramics doped with La_2O_3 exhibits more homogeneous grain distribution, greater grain size, and excellent voltage sensing and dielectric characteristics than those without La_2O_3 doping. The samples doped with 1 1% La_2O_3 were sintered at 1420 ℃ in N_2+C weak reducing atmosphere. The average grain size of the samples doped with La_2O_3 is 40 μm, the breakdown voltage of 19.7 V·mm^(-1), the nonlinear exponent of 7.2, and dielectric constant of 22500. The results reveal that final products are suitable to use in low operating voltage.展开更多
The recrystallization behavior of Mo wires doped with various contents of La2O3,which were prepared by powder metallurgy method,was investigated using TEM and SEM in detail.It is shown that the recrystallization tempe...The recrystallization behavior of Mo wires doped with various contents of La2O3,which were prepared by powder metallurgy method,was investigated using TEM and SEM in detail.It is shown that the recrystallization temperature and recrystallized microstructure of Mo-La2O3 wires are strongly dependent on the La2O3 contents.An interlocked large grain structure is formed in Mo-La2O3 wires with contents of 0.2-0.4 wt% La2O3,on the other hand,Mo─La2O3 wires containing less than 0.1 or more than 0.8 wt% La2O3 show equiaxed grain structure.The reason for this is the difference between the longitudinal interparticle spacing and the transverse spacing of La2O3 particles in various Mo-La2O3 wires,which was observed by using TEM.展开更多
The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were studied. The emissions spectra of Eu2+ and Eu3+ were observed in BaO-La2O3-B2O3-Eu2O3 glasses. The resu...The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were studied. The emissions spectra of Eu2+ and Eu3+ were observed in BaO-La2O3-B2O3-Eu2O3 glasses. The results show that the broad emission peaks at 430 nm correspond to 5d→4f emission transition of Eu2+, the sharp emission peaks at 592, 616, 650 and 750 nm correspond to 5D0→7Fj（j=1-4） emission transition of Eu3+, respectively, which indicates that the BaO-La2O3-B2O3-Eu2O3 glass can convert ultraviolet and green components of sunlight into blue and red light so as to increase the intensity of blue and red light, respectively. The luminescent intensity of Eu2+ increases with increasing the molar ratio of Tb3+ in BaO-La2O3-B2O3-Eu2O3-Tb4O7 glasses, whereas the luminescent intensity of Eu3+ decreases. So the luminescent intensity of Eu（III, II） is influenced by Tb3+. These phenomena can be explained by electron transfer mechanism: Eu3+（4f6）+Tb3+（4f8）→Eu2+（4f7）+Tb4+（4f7）. Taking advantage of the luminescent properties of BaO-La2O3-B2O3-Eu2O3 glasses, light-conversion glass for agriculture can be produced.展开更多
The electrochemical hydrogen evolution reaction（HER） on a non-precious electrocatalyst in an alkaline environment is of essential importance for future renewable energy. The design of advanced electrocatalysts for H...The electrochemical hydrogen evolution reaction（HER） on a non-precious electrocatalyst in an alkaline environment is of essential importance for future renewable energy. The design of advanced electrocatalysts for HER is the most important part to reduce the cost and to enhance the efficiency of water splitting. MoSis considered as one of the most promising electrocatalysts to replace the precious Pt catalyst.Herein, for the first time, we have successfully loaded MoSelectrocatalysts onto the CoOnanosheet array to catalyze HER with a low onset potential of6 mV. The high hydrogen evolution activity of MoSsupported on the CoOnanosheet array may be attributed to the increased active sites and the electronic interactions between MoSand CoO.展开更多
In-situ observation in high voltage electron microscope(HVEM) was used to investigate transformation from amorphous La(OH)3 to nanophase La2O3. Electron diffraction pattern indicates that the transition temperature fr...In-situ observation in high voltage electron microscope(HVEM) was used to investigate transformation from amorphous La(OH)3 to nanophase La2O3. Electron diffraction pattern indicates that the transition temperature from La(OH)3 to nanophase La2O3 is 400 ℃. Particle sizes for nanophase La2O3 are from 20 to 50 nm.展开更多
Photoelectrochemical and electrochemical reduction of CO_2 into organic chemicals is promising for directly or indirectly transforming solar energy into chemical energy for further utilization. However,research on the...Photoelectrochemical and electrochemical reduction of CO_2 into organic chemicals is promising for directly or indirectly transforming solar energy into chemical energy for further utilization. However,research on the electroactive species in these processes has been rather limited. In this work, we investigated possible electroactive species(CO_2 or HCO_3~– ) involved in the electrochemical reduction of KHCO_3 at elevated temperatures without CO_2 bubbling. The results showed that CO, CH_4, and C_2H_4 were produced after electrochemical reduction of 3.0 mol/L KHCO_3 at elevated temperature on a Cu electrode even without CO_2 bubbling, although their faradaic efficiencies were low(< 6 %). Measurements for CO_2 generation from the decomposition of HCO_3~– showed that elevated temperature and high HCO_3~– concentration strongly promoted this process. These results suggested that the in-situ produced CO_2 from the decomposition of HCO_3~– was probably the electroactive species in the electrochemical reduction of HCO_3~– without CO_2 bubbling. Changes of the Gibbs free energy, rate constant, and activation energy of the decomposition of HCO_3~– into CO_2 were also investigated and calculated from the experimental data.展开更多
CoO/CeOcomposites with high surface areas and ultrafine crystalline sizes for catalytic combustion of methane were firstly prepared by a new sol-gel method which combined ultrasonic impregnation treatment and calcinat...CoO/CeOcomposites with high surface areas and ultrafine crystalline sizes for catalytic combustion of methane were firstly prepared by a new sol-gel method which combined ultrasonic impregnation treatment and calcination in Natmosphere. The samples were characterized by various means such as nitrogen adsorption/desorption, X-ray diffraction(XRD), Htemperature-programmed reduction(H-TPR),X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). Results showed that the modified catalyst had the mesoporous structure, comparatively higher amount of surface oxygen and larger oxygen vacancies than others. As a result of the structure and surface composition merits, a high methane combustion conversion(50%) could be obtained at a low temperature of 262 °C for the modified CoO/CeOcomposites catalysts. The experimental results demonstrated that ultrasonic impregnation treatment combined with the Nthermal treatment prior to calcination in air had a promising application for preparation of CoO/CeOcomposites catalysts for low-temperature catalytic combustion of methane.展开更多
In this paper,various techniques including BET,XRD,SEM and XPS were used to study the sintering of pure and La_2O_3-doped titania.The experimental results show that sintering of titania proceeds via volume diffu- sion...In this paper,various techniques including BET,XRD,SEM and XPS were used to study the sintering of pure and La_2O_3-doped titania.The experimental results show that sintering of titania proceeds via volume diffu- sion.Adding of lanthanum oxide decreases the rate of sintering and hinders the phase transition from anatase to rutile crystal by strong surface interaction between the mixed crystals(La_4Ti_9O_(24),La_(0.66)TiO_(2.99))and TiO_2.展开更多
NiAl-La2O3 compostite coating was prepared by Ni-La2O3 electrodeposited and pack aluminized at 1173 K on Ni-base superalloy K38. The result of oxidation in air at 1273 K for 20 h shows that the oxidation rate of NiAl-...NiAl-La2O3 compostite coating was prepared by Ni-La2O3 electrodeposited and pack aluminized at 1173 K on Ni-base superalloy K38. The result of oxidation in air at 1273 K for 20 h shows that the oxidation rate of NiAl-La2O3 coating is remarkably lower than that of NiAl-La2O3 free coating. The oxide film surface morphology of NiAl-La2O3 composite coating was obviously modified after oxidation. HREM study of the fine structure of aluminum oxide on the composite coating shows that La2O3 particles with diameter of 10￣40 nm were incorporated into u-Al2O3 layer. It is believed that La2O3 dispersive particles improve NiAl coating oxidation resistance by a way to influence aluminum layer microstructure and to modify cationic transfer behavior of the layer growth.展开更多
The influence of La2O3 on stress in the scales of NiAl-type coatings were studied by a novel two-side oxidation bending method during isothermal and anisothermal oxidation. The results indicate that. differences of th...The influence of La2O3 on stress in the scales of NiAl-type coatings were studied by a novel two-side oxidation bending method during isothermal and anisothermal oxidation. The results indicate that. differences of thermal expansion coefficients of the coatings applied on the two sides of the bending sample can be analyzed by detecting the deflection behaviour of the sample, the growth stress in La2O3 added x-Al2O3 coating is reduced by some 350 kgf/ mm2 for 50 h isothermal oxidation at 900℃ . and the mechanism is that the grain size of scale is reduced due to addition of La2O3 and its plasticity is increased, the magnitude of thermal expansion coefficients of coatings influences the thermal stress developing during cooling. Stress in the scale on simple NiAl is relieved mainly in way of cracking and spalling of the scale at temperature 400￣ 600℃ ,but that on La2O3-added coating is relieved slightly due to good integrity and adherence of the scale.展开更多
文摘The oxidative dehydrogenation (ODH) of isobutane over Cr_2O_3/La_2(CO_3)_3 has been investigated in a low-pressure Knudsen cell reactor, under conditions where the kinetics of the primary reaction steps can be accurately determined. By heating the catalyst at a constant rate from 150-300℃, temperature fluctuations due to non-equilibrium adsorption are minimized. The evolved gas profiles show that ODH to isobutene and water is a primary reaction pathway, while carbon dioxide, which forms from the catalyst during reaction, is the only other product. This CO2 evolution may enhance the activity of the catalyst. Isobutene formation proceeds with the participation of lattice oxygen from the Cr2O3/La2(CO3)3 catalyst. The intrinsic Arrhenius rate constant for the ODH of isobutane isk(s-1) = 1011.5±2.2exp{-((55±5) -ΔHads kJmol-1)/RT}The small pre-exponential factor is expected for a concerted mechanism and for such a catalyst with a small surface area and limited porosity.
基金Project supported by Science and Technology Foundation of Yunnan Province (2002GG-09)
文摘The effects of rare-earth La_2O_3 addition on microstructures and electrical properties of SrTiO_3 ceramics were investigated. Semiconductor SrTiO_3-based voltage-sensing and dielectric dual functional ceramics was prepared by a single step sintering technology in this study, and the effects of the content of La_2O_3 on characteristics of the product were discussed in terms of microstructures and electrical properties of materials. The results show that SrTiO_3-based ceramics doped with La_2O_3 exhibits more homogeneous grain distribution, greater grain size, and excellent voltage sensing and dielectric characteristics than those without La_2O_3 doping. The samples doped with 1 1% La_2O_3 were sintered at 1420 ℃ in N_2+C weak reducing atmosphere. The average grain size of the samples doped with La_2O_3 is 40 μm, the breakdown voltage of 19.7 V·mm^(-1), the nonlinear exponent of 7.2, and dielectric constant of 22500. The results reveal that final products are suitable to use in low operating voltage.
文摘The recrystallization behavior of Mo wires doped with various contents of La2O3,which were prepared by powder metallurgy method,was investigated using TEM and SEM in detail.It is shown that the recrystallization temperature and recrystallized microstructure of Mo-La2O3 wires are strongly dependent on the La2O3 contents.An interlocked large grain structure is formed in Mo-La2O3 wires with contents of 0.2-0.4 wt% La2O3,on the other hand,Mo─La2O3 wires containing less than 0.1 or more than 0.8 wt% La2O3 show equiaxed grain structure.The reason for this is the difference between the longitudinal interparticle spacing and the transverse spacing of La2O3 particles in various Mo-La2O3 wires,which was observed by using TEM.
文摘The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were studied. The emissions spectra of Eu2+ and Eu3+ were observed in BaO-La2O3-B2O3-Eu2O3 glasses. The results show that the broad emission peaks at 430 nm correspond to 5d→4f emission transition of Eu2+, the sharp emission peaks at 592, 616, 650 and 750 nm correspond to 5D0→7Fj（j=1-4） emission transition of Eu3+, respectively, which indicates that the BaO-La2O3-B2O3-Eu2O3 glass can convert ultraviolet and green components of sunlight into blue and red light so as to increase the intensity of blue and red light, respectively. The luminescent intensity of Eu2+ increases with increasing the molar ratio of Tb3+ in BaO-La2O3-B2O3-Eu2O3-Tb4O7 glasses, whereas the luminescent intensity of Eu3+ decreases. So the luminescent intensity of Eu（III, II） is influenced by Tb3+. These phenomena can be explained by electron transfer mechanism: Eu3+（4f6）+Tb3+（4f8）→Eu2+（4f7）+Tb4+（4f7）. Taking advantage of the luminescent properties of BaO-La2O3-B2O3-Eu2O3 glasses, light-conversion glass for agriculture can be produced.
基金support from the National Natural Science Foundation of China (51402100 and 21573066)the Provincial Natural Science Foundation of Hunan (2016JJ1006 and 2016TP1009)
文摘The electrochemical hydrogen evolution reaction（HER） on a non-precious electrocatalyst in an alkaline environment is of essential importance for future renewable energy. The design of advanced electrocatalysts for HER is the most important part to reduce the cost and to enhance the efficiency of water splitting. MoSis considered as one of the most promising electrocatalysts to replace the precious Pt catalyst.Herein, for the first time, we have successfully loaded MoSelectrocatalysts onto the CoOnanosheet array to catalyze HER with a low onset potential of6 mV. The high hydrogen evolution activity of MoSsupported on the CoOnanosheet array may be attributed to the increased active sites and the electronic interactions between MoSand CoO.
文摘In-situ observation in high voltage electron microscope(HVEM) was used to investigate transformation from amorphous La(OH)3 to nanophase La2O3. Electron diffraction pattern indicates that the transition temperature from La(OH)3 to nanophase La2O3 is 400 ℃. Particle sizes for nanophase La2O3 are from 20 to 50 nm.
文摘Photoelectrochemical and electrochemical reduction of CO_2 into organic chemicals is promising for directly or indirectly transforming solar energy into chemical energy for further utilization. However,research on the electroactive species in these processes has been rather limited. In this work, we investigated possible electroactive species(CO_2 or HCO_3~– ) involved in the electrochemical reduction of KHCO_3 at elevated temperatures without CO_2 bubbling. The results showed that CO, CH_4, and C_2H_4 were produced after electrochemical reduction of 3.0 mol/L KHCO_3 at elevated temperature on a Cu electrode even without CO_2 bubbling, although their faradaic efficiencies were low(< 6 %). Measurements for CO_2 generation from the decomposition of HCO_3~– showed that elevated temperature and high HCO_3~– concentration strongly promoted this process. These results suggested that the in-situ produced CO_2 from the decomposition of HCO_3~– was probably the electroactive species in the electrochemical reduction of HCO_3~– without CO_2 bubbling. Changes of the Gibbs free energy, rate constant, and activation energy of the decomposition of HCO_3~– into CO_2 were also investigated and calculated from the experimental data.
文摘CoO/CeOcomposites with high surface areas and ultrafine crystalline sizes for catalytic combustion of methane were firstly prepared by a new sol-gel method which combined ultrasonic impregnation treatment and calcination in Natmosphere. The samples were characterized by various means such as nitrogen adsorption/desorption, X-ray diffraction(XRD), Htemperature-programmed reduction(H-TPR),X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). Results showed that the modified catalyst had the mesoporous structure, comparatively higher amount of surface oxygen and larger oxygen vacancies than others. As a result of the structure and surface composition merits, a high methane combustion conversion(50%) could be obtained at a low temperature of 262 °C for the modified CoO/CeOcomposites catalysts. The experimental results demonstrated that ultrasonic impregnation treatment combined with the Nthermal treatment prior to calcination in air had a promising application for preparation of CoO/CeOcomposites catalysts for low-temperature catalytic combustion of methane.
文摘In this paper,various techniques including BET,XRD,SEM and XPS were used to study the sintering of pure and La_2O_3-doped titania.The experimental results show that sintering of titania proceeds via volume diffu- sion.Adding of lanthanum oxide decreases the rate of sintering and hinders the phase transition from anatase to rutile crystal by strong surface interaction between the mixed crystals(La_4Ti_9O_(24),La_(0.66)TiO_(2.99))and TiO_2.
文摘NiAl-La2O3 compostite coating was prepared by Ni-La2O3 electrodeposited and pack aluminized at 1173 K on Ni-base superalloy K38. The result of oxidation in air at 1273 K for 20 h shows that the oxidation rate of NiAl-La2O3 coating is remarkably lower than that of NiAl-La2O3 free coating. The oxide film surface morphology of NiAl-La2O3 composite coating was obviously modified after oxidation. HREM study of the fine structure of aluminum oxide on the composite coating shows that La2O3 particles with diameter of 10￣40 nm were incorporated into u-Al2O3 layer. It is believed that La2O3 dispersive particles improve NiAl coating oxidation resistance by a way to influence aluminum layer microstructure and to modify cationic transfer behavior of the layer growth.
文摘The influence of La2O3 on stress in the scales of NiAl-type coatings were studied by a novel two-side oxidation bending method during isothermal and anisothermal oxidation. The results indicate that. differences of thermal expansion coefficients of the coatings applied on the two sides of the bending sample can be analyzed by detecting the deflection behaviour of the sample, the growth stress in La2O3 added x-Al2O3 coating is reduced by some 350 kgf/ mm2 for 50 h isothermal oxidation at 900℃ . and the mechanism is that the grain size of scale is reduced due to addition of La2O3 and its plasticity is increased, the magnitude of thermal expansion coefficients of coatings influences the thermal stress developing during cooling. Stress in the scale on simple NiAl is relieved mainly in way of cracking and spalling of the scale at temperature 400￣ 600℃ ,but that on La2O3-added coating is relieved slightly due to good integrity and adherence of the scale.
