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1.
NixMg6?xAl2 and NixMg6?xAl1.8La0.2 (x = 2, 4 or 6) catalysts were prepared via a co-precipitation method and calcined under an air flow at 800 °C. X-ray diffraction (XRD) results showed that the NixMg6?xAl1.8La0.2 catalysts contained different lanthanum oxide species after calcination. Fourier Transform Infrared Spectroscopy (FTIR) spectra demonstrated that the lanthanum doped catalysts adsorbed more CO2 compared to the lanthanum free solids. This improved basicity was verified in the CO2-TPD profiles. Temperature programmed reduction (TPR) analyses proved that the addition of lanthanum affected nickel species distribution in the catalysts and strengthened NiO-MgO interactions inside the solid matrix. The CO2 reforming of methane reaction (Ar/CO2/CH4:60/20/20; GHSV 60000 mL g?1 h?1) was carried out over the different catalysts in the temperature range of 600 °C–800 °C. Lanthanum addition improved the catalytic activity particularly by favoring the methane dry reforming reaction over all the other secondary reactions in addition to the creation of more basic sites that enhanced CO2 adsorption and contributed to the removal of carbon deposits. The most active lanthanum containing catalyst kept a constant catalytic performance for 14 h on stream despite the formation of carbon deposits. These carbon deposits can be removed under an oxidative atmosphere at moderate temperature due to the presence of lanthanum oxide species in the catalyst.  相似文献   

2.
In this study, the oxygen reduction activity of PrBaCo2O5+δ (PBC) double perovskite is remarkably enhanced by rationally tuning the calcination temperatures of the cathode precursor for solid oxide fuel cells (SOFCs). Effects of the calcination temperatures on the phase structure, microstructure, surface area and oxygen reduction reaction (ORR) activity of PBC cathode is systematically investigated. The cathode with optimized calcination temperature (900 °C, PBC-900) shows excellent activity and stability for ORR at 600 °C in terms of area specific resistances (ASRs). A distinctive low ASR of 0.068 Ω cm2 is obtained at 600 °C for PBC-900, which is 92.6%, 34.6% and 15.0% lower than PBC-800, PBC-1000 and PBC-1100, respectively. After operating for 250 h in air at 600 °C, the ASR value of PBC-900 is not significantly reduced. Furthermore, a single cell with PBC-900 cathode delivers attractive peak power density of 1.60 W cm−2 at 600 °C. The present study suggests that the ORR activity of PBC cathode can be greatly boosted by rationally tailoring the calcination temperatures, which may bring new avenue for the design of highly active cathodes for SOFCs.  相似文献   

3.
Mg-2.7Ni-x wt.% Sn(x = 0–2) alloys were fabricated to promote hydrogen generation kinetics of Mg-2.7Ni alloy. The Sn in Mg-2.7Ni-Sn alloys exists as Mg2Sn phase at the grain boundary and solid solution at the Mg matrix. The Mg2Sn at the grain boundary acts as the initiation site for pitting corrosion and the dissolved Sn in the alloy causes pitting corrosion by locally breaking the surface oxide film in the Mg matrix in seawater. The Mg-2.7Ni-1Sn alloy showed an excellent hydrogen generation rate of 28.71 ml min?1 g?1, which is 1700 times faster than that of pure Mg due to the combined action of galvanic and intergranular corrosion as well as pitting corrosion in seawater. As the solution temperature was increased from 30 to 70 °C, the hydrogen generation rate from the hydrolysis of the Mg-2.7Ni-1Sn alloy was dramatically increased from 34 to 257.3 ml min?1 g?1. The activation energy for the hydrolysis of Mg was calculated to be 43.13 kJ mol?1.  相似文献   

4.
Nanocrystalline powders of co-doped ceria oxides Ce0.85La0.10Sr0.05O2-δ (CLSO) and Ce0.85Gda0.10Sr0.05O2-δ (CGSO) have been synthesized by auto combustion method at 100°C using sucrose as fuel. Thermal analysis (TGA/DSC) of as-prepared powders indicated calcination above 400°C to remove organic residue. The average grain size of the pellets sintered at 1200°C for 4 hours is 436 and 683 nm for CLSO and CGSO, respectively. The electrical conductivity of the sintered samples was determined by impedance measurements in the temperature range 300°C to 600°C and the frequency range 20 Hz to 2 MHz. At 600°C, the total electrical conductivity (σt) of CGSO is 6.78 × 10−3 S cm−1, 2.5 times higher than 2.72 × 10−3 S cm−1 of CLSO. Further, it is found that the value of grain boundaries blocking factor (αgb) of CGSO is 0.47 which is 30% lesser than 0.68 of CLSO at 600°C. The higher value of electrical conductivity of CGSO as compared to CLSO is attributed to the lesser blocking effect of grain boundaries, smaller lattice distortion and denser microstructure of CGSO as compared to CLSO. The electrical conductivity of synthesized samples has been compared with the electrical conductivity of similar compositions of co-doped CeO2 oxides. Our study indicated that the sintering temperature, and hence, the morphology of sintered samples has a significant role in determining the electrical conductivity. The presence of oxygen vacancies in the synthesized samples is experimentally supported by using UV-visible spectroscopy, Raman spectroscopy, and thermal analysis techniques.  相似文献   

5.
Optimal synthesis parameters of YBaCo4O7 had been done. The X-ray diffraction (XRD) results show that YBaCo4O7 samples are all single phase. The Scanning electron microscope (SEM) results indicate that with increasing calcination temperature, calcination time, and decreasing cooling rate, grain transformed from porous agglomerates of sphere or sphere-like to agglomerates of irregular polyhedron, as well as the grain size increased. YBaCo4O7+δ with oxygen storage capacity of 102.52 wt.%, maximum rate of intaking oxygen temperature of 339.7°C, and maximum rate of releasing oxygen temperature of 369.8°C can be obtained by the optimal synthesis parameters, calcination temperature of 1100°C, calcination time of 30 h, air-cooling, and solid-state reaction method.  相似文献   

6.
A facile and simple method was developed to prepare amorphous titanium oxalate from nonaqueous reaction of tetrabutyl titanate and oxalic acid in ethanol at room temperature. This complex was converted to mixed-phase TiO2 (anatase/rutile) by calcinations. The mixed-phase TiO2 obtained at the optimum calcination temperature (600 °C) consisting of 67 wt% anatase and 33 wt% rutile exhibited superior photocatalytic hydrogen production activity (1026 μmol h?1) with high stability, which can be ascribed to the phase-junctions (anatase/rutile) and high crystalline.  相似文献   

7.
The solar driven hydrogen production was successfully investigated in a glycerol-based photoelectrochemical cell (PEC) over nanostructured TiO2 supported bimetallic Cu and Ni by adjusting total metal loading (5, 10, and 15 mol%) and calcination temperature (400, 450, 500, and 600 °C). The effects of the mentioned parameters on physicochemical and photoelectrochemical properties of prepared Cu–Ni/TiO2 photoanodes were explored by using different characterization techniques. The hydrogen evolution was experimentally found to be affected total metal loading and calcination temperature. The calcined photocatalyst with the total metal loading of 5 mol% at 450 °C was identified as the most efficient photocatalyst by producing maximum accumulative hydrogen of 694.84 μmol. A high performance of this photocatalyst is mainly attributed to its proper particle size and great ratio of Ti3+:Ti4+ and Cu+:Cu2+ in TiO2 matrix. These better physicochemical properties enhanced charge carrier separation, which retarded the charge recombination and enhanced the transportation of photo-induced electrons at the photoelectrode/electrolyte interface. The intermediates from photooxidation of glycerol were verified using high performance liquid chromatography, indicating a partial oxidation of glycerol with selective pathway in KOH (1 M) solution. This work demonstrates that optimization Cu–Ni/TiO2 photoanode has the practical potential in PEC cell to generate hydrogen from solar and biomass energy.  相似文献   

8.
We report a simple synthesis of La0.65Sr0.3MnO3 nanorods (LSM-R) through hydrothermal reaction followed by calcination at high temperature (700–850 °C). Thermogravimetric analysis and XRD study reveals that 850 °C is adequate for phase pure LSM-R formation. The microstructure of the powder has been clinically studied using FESEM and TEM. It is observed that the intermediate hydrothermal treatment plays key role in formation of such nanorods. Different bulk properties of LSM-R like sinteractivity, CTE, density, electrical conductivity etc. have been comprehensively studied. A maximum electrical conductivity of around 250 S/cm at 800 °C is obtained when LSM-R specimen is sintered at 1200 °C/2 h. The cathodic polarization of such LSM-R is measured using impedance analysis. It is observed that polarization value initially decreases attains minimum and then starts to increase with increase in cathode sintering temperature and dwelling time. A minimum cathodic polarization value of 0.32 Ω/cm2 at 800 °C is obtained at an optimized cathode sintering condition of 1000 °C/2 h.  相似文献   

9.
To develop the symmetrical electrode materials for solid oxide fuel cells (SOFCs) and to explore the facile cell fabrication technique are both meaningful and of great significance. Here a bi-functional hybrid material LaNi0.82Fe0.18O3 (LNF)/NiO was synthesized by a one-pot citrate method and further used as the quasi-symmetrical electrode catalysts for solid oxide fuel cells (SOFCs). LNF and Ni (reduced NiO) functioned as the cathode/anode catalysts. The La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) based asymmetrical tri-layered substrates were fabricated by a screen-printing assisted co-firing technique. The polarization resistances (Rp) of the infiltrated anode at 700, 650, 600 and 550 °C were only 0.08, 0.12, 0.18 and 0.3 Ω cm2, respectively. Comparably, the Rp of the infiltrated cathode were much larger, e.g., 0.18, 0.35, 0.875 and 2.55 Ω cm2 at 700, 650, 600 and 550 °C, respectively. Encouragingly, these cathode Rp values were largely reduced when discharge due to an activation process. The LNF and NiO reversibly formed and decomposed during the oxidation and reduction processes, suggesting that the LNF/NiO hybrid is a potential quasi-symmetrical SOFC electrode material. When using H2 as fuel and air as oxidant, the maximum power densities of the single cell at 650, 600 and 550 °C were as high as 928, 580 and 329 mW cm?2, respectively.  相似文献   

10.
Mg2AlNiXHZOY nano-oxyhydrides formation is evidenced during pre-treatment in H2 at 450 °C of Mg2AlNiXOY nano-compounds leading to highly performant catalysts in ethanol conversion and H2 formation, particularly at low temperature, through catalytic steam reforming (SRE) and oxidative steam reforming (OSRE). Total conversion of ethanol is obtained in SRE and OSRE with high stability. A higher production of H2 (60 L h?1 gcat?1) can be achieved at a reaction temperature of 300 °C in OSRE conditions compared to SRE (10 L h?1 gcat?1) mainly because of a beneficial use of a high concentration of ethanol (14 mol%) in presence of O2. Moreover, carbon formation is decreased and a much lower input of energy of 50 °C is used to get a temperature of 300 °C when O2 is added. Different physico-chemical characterizations and in particular in H2 (TPR, H2-XRD, INS) and after tests allow to conclude that the presence of Ni2+ cations in strong interaction with other cations, anionic vacancies and hydride species on and inside the solid play an important role in the catalytic performance (conversion and selectivity) and stability.  相似文献   

11.
Development of high proton conducting, chemically stable electrolyte for solid oxide fuel cell application still remains as a major challenge. In this work, yttrium (0, 5, 10, 15 and 20 mol%) doped barium zirconate synthesised by hydrothermal assisted coprecipitation exhibited highly crystalline cubic perovskite. The results demonstrate that the proton conductivity is higher than oxygen ion conductivity measured in the temperature range of 200–600 °C. The 20 mol% Y doped BaZrO3 exhibited higher protonic conductivity (6.1 mScm?1) with an activation energy 0.64 eV under the reducing atmosphere. The Mott–Schottky analysis carried out in hydrogen atmosphere at 200 °C revealed that the barrier height of doped BaZrO3 reduced from 0.6 to 0.2 V. The Schottky depletion layer width also decreased from 4 to 2 nm with the increase in yttrium concentration and the boiling water test showed good phase stability. Our study highlights the critical role of space charge in the grain boundary and its suppression with the increase in dopant concentration. The results demonstrate that Y doped BaZrO3 sintered at low temperature is a promising candidate as the electrolyte material for the intermediate temperature proton conducting solid oxide fuel cells.  相似文献   

12.
LiCoO2-based materials are well-known cathode materials used in lithium ion batteries. Moreover, these materials are currently utilized in low-temperature proton-conducting solid oxide fuel cells (SOFCs). Various dopants, such as Mn, Sr, and Zn, are introduced into LiCo2-based materials to improve their properties and performance for proton-conducting SOFC applications. In this regard, Mn-, Sr-, and Zn-doped LiCoO2 and LiCo0.6X0.4O2 (X = Mn, Sr, or Zn) powders are synthesized via the glycine-nitrate combustion method. Their properties are characterized using different techniques. The precursor cathode powder is dried at 100°C and subjected to thermogravimetric analysis (TGA). The phase formation and morphology of calcined LiCo0.6Mn0.4O2 (LCMO), LiCo0.6Sr0.4O2 (LCSO), and LiCo0.6Zn0.4O2 (LCZO) powders at 600°C to 700°C are examined via X-ray diffraction. At 600°C, both calcined LCSO and LCZO powders show few secondary phases, but these phases greatly decrease as calcination temperature increases to 700°C. By contrast, calcined LCMO powders exhibit a single phase structure at both calcination temperatures of 600°C and 700°C. The measured crystallite sizes of LCMO, LCSO, and LCZO powders are 23.32 ± 0.20, 21.08 ± 0.72, and 21.24 ± 0.32 nm, respectively. TEM images indicate that the particles in LCMO and LCZO powders highly agglomerate compared with those in LCZO powders. This result confirms that LCSO cathodes have the highest electrical conductivity (356.66 S cm−1) and the lowest area specific resistance (0.29 Ω cm2 in humidified [3%] air) at 700°C. In conclusion, LCSO materials are the best cathodes with high potential for proton-conducting SOFC applications.  相似文献   

13.
Cubic ytterbium scandium stabilized zirconium oxide (1Yb10ScSZ) nanoparticles with highly uniform sizes were synthesized using basic amino acid as organic precursor in aqueous medium. The 1Yb10ScSZ materials were prepared by precipitation (P-YbScSZ) and sol–gel (SG-YbScSZ) using l-arginine as the basic amino acid. l-Arginine can form complex gel with metal cation and increase the solution pH. The calcination temperatures were varied from 600 to 700 °C to study the effect of calcination temperature on particle size. The stable cubic phase ensured the high ionic conductivity of the zirconia-based electrolyte material for solid-oxide fuel cells (SOFC). The crystal structures of the nanoparticles obtained from the precipitation and sol–gel methods were cubic, but the nanoparticles obtained from the precipitation method calcined at 600 °C were more uniformly sized. However, the symmetrical cell with SG-YbScSZ powder sintered at 1550 °C/5 h showed a higher ionic conductivity value of 0.012 Ω cm2 at 800 °C and a lower activation energy than the cell using the P-YbScSZ powder. This finding demonstrated that the 1Yb10ScSZ electrolyte prepared by the sol–gel method had better properties, higher sinter ability, and ability to obtain sufficient density with better electrical property than that prepared by the precipitation method.  相似文献   

14.
Ni–Sn porous metals with different concentrations of Sn were prepared as potential current collectors for solid oxide fuel cells (SOFCs). The weight increase of these species was evaluated after heat-treatment under elevated temperatures in air for thousands of hours to evaluate the long-term oxidation resistance. Ni–Sn porous metals with 5–14 wt% of Sn exhibited excellent oxidation resistance at 600 °C, although oxidation became significant above 700 °C. Intermetallic Ni3Sn was formed at 600 °C due to phase transformation of the initially solid solutions of Sn in Ni in the porous metals. For the porous metal with 10 wt% of Sn, the oxidation rate constant at 600 °C in air was estimated to be 8.5 × 10?14 g2 cm?4 s?1 and the electrical resistivity at 600 °C was almost constant at approximately 0.02 Ω cm2 up to an elapsed time of 1000 h. In addition, the gas diffusibility and the power-collecting ability of the porous metal were equivalent to those of a platinum mesh when applied in the cathode current collector of a SOFC operated at 600 °C. Ni–Sn porous metals with adequate contents of Sn are believed to be promising cathode current collector materials for SOFCs for operation at temperatures below 600 °C.  相似文献   

15.
In this paper, Co2C/MoN/NF at different calcination temperatures (T = 500, 550, 600, 650, 700 °C) was prepared in situ on 3D foam nickel (NF) by hydrothermal treatment and high-temperature calcination. The experimental results show that the sample synthesized at 600 °C (Co2C/MoN-600/NF) has the best catalytic capacity and the maximum electrochemical active area. For the hydrogen evolution reaction (HER), the potential is only ?176 mV at 100 mA cm?2, meanwhile, only 1.42 V is needed for urea oxidation reaction (UOR). Furthermore, a two-electrode electrolyze cell of Co2C/MoN-600/NF6Co2C/MoN-600/NF was constructed. And the voltage required for overall urea splitting (OUS) is 1.507 V at 50 mA cm?2, which is 171 mV lower than that of overall water splitting (OWS, 1.678 V). Moreover, the prepared catalyst not only can treat urea in wastewater but also catalyze the production of hydrogen. Therefore, it will be a promising green electrocatalyst.  相似文献   

16.
A series of wet sludge samples with different moisture contents were pyrolyzed in situ steam in a bench-scale fixed bed reactor in order to examine the influence of moisture and temperature on product distribution and gas composition. The results demonstrated that inherent moisture in wet sludge had a great effect on the product yield. The pyrolysis of wet sludge (43.38% moisture content) at 800 °C exhibited maximum H2 yield (7.76 mol kg?1 dry basis wet sludge) and dry gas yield (0.61 Nm3 kg?1) and H2 content of 42.13 vol%. When the moisture exceeded 43.38%, H2 yield and gas yield both tended to decline. It was also shown that the elevated temperature exhibited a significant influence on gas content increase and tar reduction; at the same time, H2 yield and H2 content were increased from 1.83 mol kg?1 dry basis wet sludge and 16.67 vol% to 9.15 mol kg?1 dry basis wet sludge and 45.67 vol%, respectively, as temperature increased from 600 °C to 850 °C. LHV of fuel gas varies from 15.49 MJ Nm?3 to 11.65 MJ Nm?3 because of decrease in CH4 and C2H4 content as temperature increasing. In conclusion, hydrogen rich gas production by pyrolysis of wet sludge which avoided pre-drying process and utilized in situ steam agent from wet sludge is an economic method.  相似文献   

17.
SmBa0.5Sr0.5Co2O5+δ (SBSC55) impregnated with nano-sized Ce0.8Sm0.2O1.9 (SDC) powder has been investigated as a candidate cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The cathode chemical compatibility with electrolyte, thermal expansion behavior, and electrochemical performance are investigated. For compatibility, a good chemical compatibility between SBSC55 and SDC electrolyte is still kept at 1100 °C in air. For thermal dilation curve, it could be divided into two regions, one is the low temperature region (100–265 °C); the other is the high temperature region (265–850 °C). In the low temperature region (100–265 °C), a TEC value is about 17.0 × 10?6 K?1 and an increase in slope in the higher temperatures region (265–800 °C), in which a TEC value is around 21.1 × 10?6 K?1. There is an inflection region ranged from 225 to 330 °C in the curve of d(δL/L)/dT vs. temperature. The peak inflection point located about 265 °C is associated to the initial temperature for the loss of lattice oxygen and the formation of oxygen vacancies. For electrochemical properties, the polarization resistances (Rp) significantly reduced from 4.17 Ω cm2 of pure SBSC55 to 1.28 Ω cm2 of 0.65 mg cm?2 of SDC-impregnated SBSC55 at 600 °C. The single cell performance of SBSC55∣SDC∣Ni-SDC loaded with 0.65 mg cm?2 SDC exhibited the optimum power density of 823 mW cm?2 at operating temperature of 800 °C. Based on above-mentioned properties, SBSC55 impregnated with an appropriate SDC is a potential cathode for IT-SOFCs.  相似文献   

18.
It is attempted to optimize preparation of ZrO2 as support of the nickel catalysts for selective methanation of CO in H2-rich gas (CO-SMET). Therefore, the supports ZrO2 were prepared at first by thermal decomposition method from zirconium oxynitrate and zirconium oxychloride at the calcination temperature of 400 °C and 800 °C, respectively. It is illustrated that the salt kind and calcination temperature affected phase state (tetragonal, monoclinic), crystallite size and specific surface area (SSA) of the supports. The difference in property of the supports influenced catalytic performance of the catalysts Ni/ZrO2 for CO-SMET reaction. Especially, the chlorine ion residues in the support ZrO2 prepared from zirconium oxychloride was beneficial for CO removal selectively. Furthermore, a precipitation method was adopted to prepare ZrO2 for comparison with the thermal decomposition method with use of the zirconium oxychloride as starting material. It is found that the supports ZrO2 prepared by the precipitation method induced a better dispersion of metallic Ni on its surface. The catalyst Ni/ZrO2 with use of the support ZrO2 prepared by the precipitation method and calcination at 400 °C exhibited a good performance at the reaction temperature of 220 °C in the 100 h durability test, where CO outlet concentration was kept below 10 ppm and the selectivity remained constant at 100%. Relation of Ni crystallite size and chlorine ion residues with the catalytic performance was discussed.  相似文献   

19.
Perovskite Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3-δ (BSCFNi) oxide is synthesized and characterized as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The X-ray diffraction (XRD) spectra show that BSCFNi is chemical compatible with La0.9Sr0.1Ga0.83Mg0.17O2.865(LSGM) electrolyte below 950 °C, but weak reaction is observed between BSCFNi cathode and Sm0.2Ce0.8O1.9 (SDC) electrolyte after calcined at 950 °C for 10 h. The XPS results indicate that transition metal cations in BSCFNi sample exist two different valence states, i.e., Co4+/3+, Fe4+/3+ and Ni3+/2+. The average thermal expansion coefficient (TEC) of BSCFNi is 18.7 × 10?6 K?1 between 200 °C and 850 °C in air. The maximum electrical conductivity reaches 35.3 Scm?1 at 425 °C in air. The polarization resistance of BSCFNi cathode on LSGM and SDC electrolytes are 0.033 and 0.066 Ωcm2 at 800 °C, respectively. The maximum power density of LSGM electrolyte-supported single cell with BSCFNi cathode reaches 690 mWcm?2 at 800 °C. These primarily results indicate that BSCFNi is a candidate cathode material for IT-SOFCs.  相似文献   

20.
A mixture of MgH2 and Mg2FeH6 was synthesized by reactive ball milling of magnesium hydride and iron in hydrogen atmosphere. The material is highly nanocrystalline, with typical dimensions of the order of 10 nm; after hydrogen cycling at ~400 °C, well defined XRD peaks of Mg2FeH6 can be observed. Volumetric measurements of hydrogenation/dehydrogenation provide clear evidence of the presence of both hydrides even at lower temperatures. The relative content of magnesium-iron hydride increases on increasing H2 cycling temperature, passing from ~44% at 335 °C to ~54% at 390 °C. Already at 250 °C the composite releases ~3wt% H2 in ~1000 s, while above 340 °C, more than 4wt% H2 can be discharged in less than 100s, following the Johnson-Mehl-Avrami-Kolmogorov equation, with an exponent n = 1, compatible with a reaction controlled transformation. Finally, also the electrochemical performances in a lithium cell have been investigated: the material is able to undergo a conversion reaction and gives on the first discharge more than 1400 mAhg?1. The overpotentials decrease after materials activation by H2 sorption treatments. Moreover, for the first time, the partial reversibility of the conversion reaction for materials containing magnesium iron hydride is here reported.  相似文献   

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