首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Highly oriented (100) diamond films have been successfully grown on SixGe1−x (100) thin films by bias enhanced nucleation (BEN) in microwave plasma chemical vapor deposition (MPCVD) system. Raman spectra show the 1332 cm−1 peak which proves the formation of diamond. Diamond nucleation density on SixGe1−x substrate estimated by scanning electron microscopy is higher than 109 cm−2. The interface between diamond and SixGe1−x substrate was characterized by transmission electron microscopy (TEM). About 20 nm decrease in thickness of the SixGe1−x film was observed after bias enhanced nucleation step. TEM shows the existence of silicon carbide and heteroepitaxial diamond grains grown on SixGe1−x substrate. Characterization from high-resolution TEM on the specimen of short time deposition reveals that a number of epitaxial diamond grains were directly nucleated on SixGe1−x with {111} interplanar spacing ratio of diamond and SixGe1−x of 2:3. The diamond nucleation is found to be preferred on the ridge position of the rough substrate surface. Diamond {100} facets were quickly developed in the early stage of growth.  相似文献   

2.
In this work, a series of Fe3−xTixO4 (0 ≤ x ≤ 0.78) was synthesized using a new soft chemical method. The synthetic Fe3−xTixO4 were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Mössbauer spectroscopy, thermogravimetric and differential scanning calorimetry (TG–DSC) analyses. The results showed that they were spinel structures and Ti was introduced into their structures.Then, decolorization of methylene blue (MB) by Fe3−xTixO4 in the presence of H2O2 at neutral pH values was studied using UV–vis spectra, dissolved organic carbon (DOC) and element C analyses. Furthermore, the degradation products remained in reaction solution after the decolorization were identified using ionic chromatography (IC), 13C nuclear magnetic resonance spectra (NMR), liquid chromatography and mass spectrometry (LC–MS). Although small amounts of MB were mineralized, the aromatic rings in MB were destroyed completely after the decolorization. Decolorization of MB by Fe3−xTixO4 in the presence of H2O2 was promoted remarkably with the increase of Ti content in Fe3−xTixO4 due to the enhancement of both adsorption and degradation of MB on Fe3−xTixO4.  相似文献   

3.
Powders of spinel Li4Ti5−xVxO12 (0 ≤ x ≤ 0.3) were successfully synthesized by solid-state method. The structure and properties of Li4Ti5−xVxO12 (0 ≤ x ≤ 0.3) were examined by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electronic microscope (SEM), galvanostatic charge–discharge test and cyclic voltammetry (CV). XRD shows that the V5+ can partially replace Ti4+ and Li+ in the spinel and the doping V5+ ion does almost not affect the lattice parameter of Li4Ti5O12. Raman spectra indicate that the Raman bands corresponding to the Li–O and Ti–O vibrations have a blue shift due to the doping vanadium ions, respectively. SEM exhibits that Li4Ti5−xVxO12 (0.05 ≤ x ≤ 0.25) samples have a relative uniform morphology with narrow size distribution. Charge–discharge test reveals that Li4Ti4.95V0.05O12 has the highest initial discharge capacity and cycling performance among all samples cycled between 1.0 and 2.0 V; Li4Ti4.9V0.1O12 has the highest initial discharge capacity and cycling performance among all samples cycled between 0.0 and 2.0 V or between 0.5 and 2.0 V. This excellent cycling capability is mainly due to the doping vanadium. CV reveals that electrolyte starts to decompose irreversibly below 1.0 V, and SEI film of Li4Ti5O12 was formed at 0.7 V in the first discharge process; the Li4Ti4.9V0.1O12 sample has a good reversibility and its structure is very advantageous for the transportation of lithium-ions.  相似文献   

4.
Fe1−xCox nanowires in self-assembled arrays with varying compositions were produced by the template-assisted pulsed electrochemical deposition method. The structural and magnetic properties of the arrays were investigated using several experimental techniques. TEM analyses indicated that the nanowires were regular, uniform, 8 μm in length and 50 nm in diameter. The results of X-ray diffraction indicated that the body-centered-cubic (bcc) (α), face-centered-cubic (fcc) (γ), and hexagonal-close-packed (hcp) () Fe–Co phases appeared in different compositions. Magnetic measurements showed that the coercivity and squareness of the hysteresis loops of the Fe1−xCox changed with their compositions, which may be attributable to shape anisotropy. The room temperature 57Fe Mössbauer spectra of the arrays of the Fe1−xCox nanowires revealed strong shape anisotropy.  相似文献   

5.
La(1−x)SrxCo(1−y)FeyO3 samples have been prepared by sol–gel method using EDTA and citric acid as complexing agents. For the first time, Raman mappings were achieved on this type of samples especially to look for traces of Co3O4 that can be present as additional phase and not detect by XRD. The prepared samples were pure perovskites with good structural homogeneity. All these perovskites were very active for total oxidation of toluene above 200 °C. The ageing procedure used indicated good thermal stability of the samples. A strong improvement of catalytic properties was obtained substituting 30% of La3+ by Sr2+ cations and a slight additional improvement was observed substituting 20% of cobalt by iron. Hence, the optimized composition was La0.7Sr0.3Co0.8Fe0.2O3. The samples were also characterized by BET measurements, SEM and XRD techniques. Iron oxidation states were determined by Mössbauer spectroscopy. Cobalt oxidation states and the amount of O electrophilic species were analyzed from XPS achieved after treatment without re-exposition to ambient air. Textural characterization revealed a strong increase in the specific surface area and a complete change of the shape of primary particles substituting La3+ by Sr2+. The strong lowering of the temperature at conversion 20% for the La0.7Sr0.3Co(1−y)FeyO3 samples can be explained by these changes. X photoelectron spectra obtained with our procedure evidenced very high amount of O electrophilic species for the La0.7Sr0.3Co(1−y)FeyO3 samples. These species able to activate hydrocarbons could be the active sites. The partial substitution of cobalt by iron has only a limited effect on the textural properties and the amount of O species. However, Raman spectroscopy revealed a strong dynamic structural distortion by Jahn–Teller effect and Mössbauer spectroscopy evidenced the presence of Fe4+ cations in the iron containing samples. These structural modifications could improve the reactivity of the active sites explaining the better specific activity rate of the La0.7Sr0.3Co0.8Fe0.2O3 sample. Finally, an additional improvement of catalytic properties was obtained by the addition of 5% of cobalt cations in the solution of preparation. As evidenced by Raman mappings and TEM images, this method of preparation allowed to well-dispersed small Co3O4 particles that are very efficient for total oxidation of toluene with good thermal stability contrary to bulk Co3O4.  相似文献   

6.
The generation of active chlorine on Ti/Sn(1−x)Ir x O2 anodes, with different compositions of Ir (x = 0.01, 0.05, 0.10 and 0.30 ), was investigated by controlled current density electrolysis. Using a low concentration of chloride ions (0.05 mol L−1) and a low current density (5 mA cm−2) it was possible to produce up to 60 mg L−1 of active chlorine on a Ti/Sn0.99Ir0.01O2 anode. The feasibility of the discoloration of a textile acid azo dye, acid red 29 dye (C.I. 16570), was also investigated with in situ electrogenerated active chlorine on Ti/Sn(1−x)Ir x O2 anodes. The best conditions for 100% discoloration and maximum degradation (70% TOC reduction) were found to be: NaCl pH 4, 25 mA cm−2 and 6 h of electrolysis. It is suggested that active chlorine generation and/or powerful oxidants such as chlorine radicals and hydroxyl radicals are responsible for promoting faster dye degradation. Rate constants calculated from color decay versus time reveal a zero order reaction at dye concentrations up to 1.0 × 10−4 mol L−1. Effects of other electrolytes, dye concentration and applied density currents also have been investigated and are discussed.  相似文献   

7.
InBaCo4−xZnxO7 oxides have been synthesized and characterized as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC). The effect of Zn substitution for Co on the structure, phase stability, thermal expansion, and electrochemical properties of the InBaCo4−xZnxO7 has been investigated. The increase in the Zn content from x = 1 to 1.5 improves the high temperature phase stability at 600 °C and 700 °C for 100 h, and chemical stability against a Gd0.2Ce0.8O1.9 (GDC) electrolyte. Thermal expansion coefficient (TEC) values of the InBaCo4−xZnxO7 (x = 1, 1.5, 2) specimens were determined to be 8.6 × 10−6 to 9.6 × 10−6/°C in the range of 80–900 °C, which provides good thermal expansion compatibility with the standard SOFC electrolyte materials. The InBaCo4−xZnxO7 + GDC (50:50 wt.%) composite cathodes exhibit improved cathode performances compared to those obtained from the simple InBaCo4−xZnxO7 cathodes due to the extended triple-phase boundary (TPB) and enhanced oxide-ion conductivity through the GDC portion in the composites.  相似文献   

8.
The CO2 reforming of CH4 to synthesis gas by using praseodymium modified hexaaluminate La1−xPrxNiAl11O19 (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) as catalysts was studied. The modifier Pr improved the reducibility and catalytic activity of Ni ions as active component in the hexaaluminate lattices, especially the conversion of CH4 and CO2 reached 89.62% and 92.94%, respectively over La0.8Pr0.2NiAl11O19. It was found that the addition of Pr can promote the electronic transformation between the Ni ions and the La ions to maintain Ni at a lower valence, which promotes the activation of CH4.  相似文献   

9.
Mesoporous BixTi1−xO2 spheres with core–shell chamber were prepared by alcoholysis under solvothermal conditions. The cross-condensation between Ti–OH and Bi–OH ensured complete incorporation of Bi-dopants into TiO2 lattice, though Bi atom is much bigger than Ti. Meanwhile, the aggregation of titania building clusters into spheres and their subsequent reactions including dissolution and re-deposition processes lead to the hollow spheres with tunable interior structure. The Bi-doping induced strong spectral response in visible region owing to the formation of narrow intermediate energy band gaps. Meanwhile, multiple reflections within the sphere interior voids promoted the light absorbance. As a result, the as-prepared BixTi1−xO2 spheres exhibited much higher activity than the undoped TiO2, the Bi2O3/TiO2 obtained by impregnating the TiO2 with Bi(NO3)3 solution, and the BixTi1−xO2 after being ground during photodegradation of p-chlorophenol under visible light irradiation. Meanwhile, the BixTi1−xO2 could be used repetitively for 10 times owing to the high hydrothermal stability and the absence of Bi-leaching.  相似文献   

10.
LiCoxMn1−xPO4/C nanocomposites (0 ≤ x ≤ 1.0) were prepared by a combination of spray pyrolysis at 300 °C and wet ball-milling followed by heat treatment at 500 °C for 4 h in 3% H2 + N2 atmosphere. X-ray diffraction analysis indicated that all samples had the single phase olivine structures indexed by orthorhombic Pmna. The lattice parameters linearly decreased with increasing cobalt content, which confirmed the existence of solid solutions. It was clearly seen from the scanning electron microscopy observation that the LiCoxMn1−xPO4/C samples were agglomerates with approximately 100 nm primary particles. The LiCoxMn1−xPO4/C nanocomposites were used as cathode materials for lithium batteries, and electrochemical performance was comparatively investigated with cyclic voltammetry and galvanostatic charge–discharge test using the Li?1 M LiPF6 in EC:DMC = 1:1?LiCoxMn1−xPO4/C cells at room temperature. The cells at 0.05 C charge–discharge rate delivered first discharge capacities of 165 mAh g−1 (96% of theoretical capacity) at x = 0, 136 mAh g−1 at x = 0.2, 132 mAh g−1 at x = 0.5, 125 mAh g−1 at x = 0.8 and 132 mAh g−1 (79% of theoretical capacity) at x = 1.0, respectively. While the first discharge capacity increased with the cobalt content at high charge–discharge rates more than 0.5 C due to higher electronic conductivity of LiCoPO4 in comparison with LiMnPO4, the cycleability of cell became worse with increasing the amount of cobalt. The existence of Mn2+ seemed to enhance the cycleability of LiCoxMn1−xPO4/C nanocomposite cathode.  相似文献   

11.
The catalytic activities of ceria–zirconia mixed oxides CexZr1−xO2 (x = 0.17, 0.62 and 0.8) rhodium catalysts were determined by isothermal steady-state experiments using a representative mixture of exhaust gases of coal combustion. Results show that all supports are active in deNOx reaction in the presence of the mentioned gas mixture. However, their catalytic activity varies with the content of cerium and goes through a maximum for x = 0.62, leading to 27% NOx consumption. The effect of rhodium on Ce0.62Zr0.38O2 considerably improves the catalytic activity during the deNOx process assisted by hydrocarbons. The rhodium addition decreases by about 34 °C the temperature of NOx consumption, which goes up to 57%. A mechanism of hydrocarbon (HC) assisted reduction of NO is proposed on ceria–zirconia-supported rhodium catalysts. This mechanism is divided in three catalytic cycles involving (i) the oxidation of NO into NO2, (ii) the reaction of NO2 and the hydrocarbons leading to RNOx species and CxHyOz, and finally (iii) the decomposition of NO assisted by these latter CxHyOz species.  相似文献   

12.
Effect of cobalt and rhodium promoter on NOx storage and reduction (NSR) kinetics was investigated over Pt/BaO/Al2O3. Kinetics of 2% cobalt loading over Pt/BaO/Al2O3 demonstrated highest NOx uptake during lean cycle, while reduction efficiency during rich cycle appeared most poor. In contrast to this, rhodium showed suppressing effect of NOx uptake during lean cycle and demonstrated an enhanced effect for the higher efficiency of NOx reduction during rich cycle. DRIFT study for NOx uptake and regeneration confirmed formation of surface BaNOx from the band at 1300 cm−1 and formation of bulk BaNOx from the band at 1330 cm−1.  相似文献   

13.
Electrical conductivity measurements on EUROCAT V2O5–WO3/TiO2 catalyst and on its precursor without vanadia were performed at 300°C under pure oxygen to characterize the samples, under NO and under NH3 to determine the mode of reactivity of these reactants and under two reaction mixtures ((i) 2000 ppm NO + 2000 ppm NH3 without O2, and (ii) 2000 ppm NO + 2000 ppm NH3 + 500 ppm O2) to put in evidence redox processes in SCR deNOx reaction.It was first demonstrated that titania support contains certain amounts of dissolved W6+ and V5+ ions, whose dissolution in the lattice of titania creates an n-type doping effect. Electrical conductivity revealed that the so-called reference pure titania monolith was highly doped by heterovalent cations whose valency was higher than +4. Subsequent chemical analyses revealed that so-called pure titania reference catalyst was actually the WO3/TiO2 precursor of V2O5–WO3/TiO2 EUROCAT catalyst. It contained an average amount of 0.37 at.% W6+dissolved in titania, i.e. 1.07 × 1020 W6+ cations dissolved/cm3 of titania. For the fresh catalyst, the mean amounts of W6+ and V5+ ions dissolved in titania were found to be equal to 1.07 × 1020 and 4.47 × 1020 cm−3, respectively. For the used catalyst, the mean amounts of W6+ and V5+ ions dissolved were found to be equal to 1.07 × 1020 and 7.42 × 1020 cm−3, respectively. Since fresh and used catalysts have similar compositions and similar catalytic behaviours, the only manifestation of ageing was a supplementary progressive dissolution of 2.9 × 1020 additional V5+ cations in titania.After a prompt removal of oxygen, it appeared that NO alone has an electron acceptor character, linked to its possible ionosorption as NO and to the filling of anionic vacancies, mostly present on vanadia. Ammonia had a strong reducing behaviour with the formation of singly ionized vacancies. A subsequent introduction of NO indicated a donor character of this molecule, in opposition to its first adsorption. This was ascribed to its reaction with previously adsorbed ammonia strongly bound to acidic sites. Under NO + NH3 reaction mixture in the absence of oxygen, the increase of electrical conductivity was ascribed to the formation of anionic vacancies, mainly on vanadia, created by dehydroxylation and dehydration of the surface. These anionic vacancies were initially subsequently filled by the oxygen atom of NO. No atoms, resulting from the dissociation of NO and from ammonia dehydrogenation, recombined into dinitrogen molecules. The reaction corresponded to
. In the presence of oxygen, NO did not exhibit anymore its electron acceptor character, since the filling of anionic vacancies was performed by oxygen from the gas phase. NO reacted directly with ammonia strongly bound on acidic sites. A tentative redox mechanism was proposed for both cases.  相似文献   

14.
The phase stability of SrCo0.8Fe0.2O3−d perovskite doped with niobium was studied by in situ high-temperature X-ray diffraction in the temperature range of 30–1000 °C and oxygen partial pressure 0.2–10−5 atm. The stability of the cubic perovskite structure in a wide range of oxygen partial pressures is the main advantage of SrCo0.8−xFe0.2NbxO3−d (x = 0.1–0.3) system in comparison with SrCo0.8Fe0.2O3−d. It is suggested that equilibrium of the thermal expansion with changes of the oxygen non-stoichiometry leading to the same lattice parameters in the oxidizing and reducing environments at the catalytic temperatures is a necessary requirement for stable operation of perovskite as an oxygen-conducting membrane. In the case of SrCo0.8−xFe0.2NbxO3−d perovskite this condition is met at x = 0.2. This makes the SrCo0.6Fe0.2Nb0.2O3−d composition promising for application as oxygen-conducting membrane.  相似文献   

15.
Catalytic CO oxidation and C3H6 combustion have been studied over La1−xSrxCrO3 (x = 0.0–0.3) oxides prepared by solid-state reaction and characterised by X-ray diffraction (XRD), nitrogen adsorption (BET analysis) and X-ray photoelectron spectroscopy (XPS). The expected orthorhombic perovskite structure of the chromite is observed for all levels of substitution. However, surface segregation of strontium along with a chromium oxidation process, leading to formation of Cr6+-containing phases, is produced upon increasing x and shown to be detrimental to the catalytic activity. Maximum activity is achieved for the catalyst with x = 0.1 in which mixed oxide formation upon substitution of lanthanum by strontium in the chromite becomes maximised.  相似文献   

16.
Mesoporous TiO2 was prepared by simply controlling the hydrolysis of Ti(OBu)4 with the help of acetic acid. The mesoporous TiO2 had a well-crystallized anatase phase and a high surface area of 290 m2 g−1 with a pore size of about 4 nm. The anatase phase and the mesoporous structure were maintained in the VOx/TiO2 catalyst with a monolayer dispersion of V2O5, however, the surface area decreased to 126 m2 g−1. The catalyst was highly active and selective for methanol oxidation, giving about 55% conversion of methanol and 85% selectivity to dimethoxymethane at 423 K.  相似文献   

17.
Catalytic light-off of a stream of NO, H2, CO in an excess O2 has been studied over various metal oxides loading 1 wt% Pt. Because a low-surface area Y2O3 (<5 m2 g−1) was found to exhibit the highest de-NOx activity, a mesoporous Y2O3 was then synthesized from an yttrium-based surfactant mesophase templated by dodecyl sulfate , which was anion-exchanged by acetate (AcO = CH3COO). The product showed a 3-D mesoporosity with a large surface area (396 m2 g−1) and the Pt-supported catalyst achieved much improved light-off characteristics suitable for the low-temperature de-NOx in the presence of CO and excess O2.  相似文献   

18.
A novel N and F co-doped TiO2 (TiO2−xyNxFy) photocatalyst is prepared by treating the TiO2 precursor in NH4F/ethanol fluid under supercritical conditions. During photocatalytic degradation of methylene blue under visible light irradiation, the as-prepared TiO2−xyNxFy exhibits higher activity than the undoped TiO2, N-doped TiO2 (TiO2−xNx), and F-doped TiO2 (TiO2−yFy). Based on the characterizations including XRD, Raman, FTIR, TEM, PLS, UV–vis DRS, N2 adsorption–desorption isotherms, XPS and NH3-TPD, the synergetic promotions of N- and F-dopants incorporated into the TiO2 lattice are discussed based on the enhanced spectral response in visible region, oxygen vacancies, and surface acidic sites. Meanwhile, the supercritical treatment also promotes the activity owing to the increase in both the surface area and the crystallization degree of anatase, and the enhanced incorporation of N- and F-dopants into the TiO2 lattice.  相似文献   

19.
Ammonium nitrate is thermally stable below 250 °C and could potentially deactivate low temperature NOx reduction catalysts by blocking active sites. It is shown that NO reduces neat NH4NO3 above its 170 °C melting point, while acidic solids catalyze this reaction even at temperatures below 100 °C. NO2, a product of the reduction, can dimerize and then dissociate in molten NH4NO3 to NO+ + NO3, and may be stabilized within the melt as either an adduct or as HNO2 formed from the hydrolysis of NO+ or N2O4. The other product of reduction, NH4NO2, readily decomposes at ≤100 °C to N2 and H2O, the desired end products of DeNOx catalysis. A mechanism for the acid catalyzed reduction of NH4NO3 by NO is proposed, with HNO3 as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNOx systems could help mitigate catalyst deactivation at low operating temperatures (<150 °C).  相似文献   

20.
Pt on ceria (CeOx) particles supported on carbon black (CB) were synthesized using the combined process of hot precipitation and impregnation methods. During 30 cycles of cyclic voltammetry pre-treatment in the potential ranging from −0.2 to 1.3 V (V vs. Ag/AgCl), it was observed that a small amount of CeOx, which consisted of the interface region between Pt and CeOx, remained on Pt particles. Other free CeOx particles were dissolved into H2SO4 aqueous solution. To develop the Pt-CeOx/CB catalyst, the surface chemical states, the net chemical composition, morphology and electrochemical behavior in H2SO4 aqueous solution were characterized. Our microanalysis and electrochemical analysis indicate that the active CeO2 with high specific surface area provides the continuous amorphous cerium oxide (Ce3+, Ce4+) layer with pores on the surface of Pt particles. It is concluded that the amorphous cerium oxide layer on Pt inhibits the oxidation of Pt surface and contributes to enhancement of the activity on Pt cathode. The single cell performance was also improved using the Pt-CeOx/CB cathode. Based on all data, it is expected that the design based on characterization of the interface between Pt and small amount of amorphous cerium oxide layer could help in preparation of more active Pt catalyst.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号