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1.
The synthesis of cancrinite in the system Na2O–SiO2–Al2O3–Na2CO3–H2O was studied under low-temperature hydrothermal conditions in the 353 K<T<473 K interval. The aim was to reveal the suitable range for the crystallization of pure-phase carbonate cancrinite with the ideal composition Na8[AlSiO4]6CO3(H2O)2 without cocrystallization of sodalite or intermediate disordered phases between cancrinite and sodalite. It was found that cancrinite formation reacts very sensitive on the temperature within the autoclaves whereas the concentration of reactants and the alkalinity of the hydrothermal solution have a much lower influence on the phase formation. Thus the temperature of crystallization of carbonate cancrinite without any by-products should not remain below 473 K. At the lower reaction temperature of 353 K the formation of a disordered intermediate phase between the cancrinite and the sodalite structure has been obtained in every case, independent of the template concentrations and the base. Some problems to detect this in a typical powder product mixture are discussed. Besides the 29Si and 27Al MAS NMR characterization of the products, the crystal structure refinement of pure carbonate cancrinite of ideal composition Na8[AlSiO4]6CO3(H2O)3.4, has been carried out from X-ray powder data using the Rietveld method: P63, a=1271.3(1) pm, c=518.6(1) pm, RWP=0.073, RF=0.016 for 347 structure factors and 45 variable positional parameters.  相似文献   

2.
A novel sol–gel method based on V2O5·nH2O hydro-gel was developed to synthesize nanocrystalline Li3V2(PO4)3/carbon composite material. In this route, V2O5·nH2O hydro-gel, NH4H2PO4, Li2CO3 and high-surface-area carbon were used as starting materials to prepare precursor, and the Li3V2(PO4)3/carbon was obtained by sintering precursor at 750 °C for 4 h in flowing argon. The sol–gel synthesis ensures homogeneity of the precursors and improved reactivity. The sample was characterized by XRD, SEM and TEM. X-ray diffraction results show Li3V2(PO4)3 sample is monoclinic structure with the space group of P21/n. The TEM image indicates that the Li3V2(PO4)3 particles modified by conductive carbon are about 70 nm in diameter. The Li3V2(PO4)3/carbon system showed that the discharge capacities in the first and 50th cycle are about 155.3 and 143.6 mAh/g, respectively, in the range of 3.0–4.8 V. The sol–gel method is fit for the preparation of Li3V2(PO4)3/carbon composite material which may offer some favorable properties for commercial application.  相似文献   

3.
A new proton-conductive composite of NH4PO3–(NH4)2Mn(PO3)4 was synthesized and characterized as a potential electrolyte for intermediate temperature fuel cells that operated around 250 °C. Thermal gravimetric analysis and X-ray diffraction investigation showed that (NH4)2Mn(PO3)4 was stable as a supporting matrix for NH4PO3. The composite conductivity, measured using impedance spectroscopy, improved with increasing the molar ratio of NH4PO3 in both dry and wet atmospheres. A conductivity of 7 mS cm−1 was obtained at 250 °C in wet hydrogen. Electromotive forces measured by hydrogen concentration cells showed that the composite was nearly a pure protonic conductor with hydrogen partial pressure in the range of 102–105 Pa. The proton transference number was determined to be 0.95 at 250 °C for 2NH4PO3–(NH4)2Mn(PO3)4 electrolyte. Fuel cells using 2NH4PO3–(NH4)2Mn(PO3)4 as an electrolyte and the Pt–C catalyst as an electrode were fabricated. Maximum power density of 16.8 mW/cm2 was achieved at 250 °C with dry hydrogen and dry oxygen as the fuel and oxidant, respectively. However, the NH4PO3–(NH4)2Mn(PO3)4 electrolyte is not compatible with the Pt–C catalyst, indicating that it is critical to develop new electrode materials for the intermediate temperature fuel cells.  相似文献   

4.
Tetrahydroborate sodalite formation was investigated in the system Na2O–SiO2–Al2O3–NaBH4–H2O under mild hydrothermal conditions. Due to the high degree of decomposition of hydroborates in aqueous solutions synthesis conditions were tuned by variation of the parameters alkalinity, liquid/solid ratio, reaction temperature and reaction time. The insertion of 8–16 molar NaOH solution was crucial for the higher stability of pure tetrahydroborate salt under strong alkaline conditions. Synthesis at 393 K and 24 h reaction time reveal tetrahydroborate sodalite Na8[AlSiO4]6(BH4)2 beside a small amount of amorphous material within the total batch. Structure, composition and thermal stability of this new sodalite was investigated using XRD, NMR, infrared and TG/DTA methods. The crystal structure of tetrahydroborate sodalite has been refined in the space group P-43n with a = 891.61(2) pm. The Si- and Al-atoms of the aluminosilicate framework are completely ordered. The boron atoms of the tetrahydroborate anions are located at the centre of the sodalite cage whereas the hydrogen atoms are positionally disordered. Na8[AlSiO4]6(BH4)2 shows a high stability under inert gas conditions. At atmospheric conditions the group can be oxidized to borate and boroxide anions suggesting the formation of hydrogen which leaves the sodalite cages. Future investigation of reloading properties of the oxidized form could be highly interesting for the hydrogen storage capabilities of these sodalites.  相似文献   

5.
In this study, we examine the interaction of N2O with TiO2(1 1 0) in an effort to better understand the conversion of NOx species to N2 over TiO2-based catalysts. The TiO2(1 1 0) surface was chosen as a model system because this material is commonly used as a support and because oxygen vacancies on this surface are perhaps the best available models for the role of electronic defects in catalysis. Annealing TiO2(1 1 0) in vacuum at high temperature (above about 800 K) generates oxygen vacancy sites that are associated with reduced surface cations (Ti3+ sites) and that are easily quantified using temperature programmed desorption (TPD) of water. Using TPD, X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS), we found that the majority of N2O molecules adsorbed at 90 K on TiO2(1 1 0) are weakly held and desorb from the surface at 130 K. However, a small fraction of the N2O molecules exposed to TiO2(1 1 0) at 90 K decompose to N2 via one of two channels, both of which are vacancy-mediated. One channel occurs at 90 K, and results in N2 ejection from the surface and vacancy oxidation. We propose that this channel involves N2O molecules bound at vacancies with the O-end of the molecule in the vacancy. The second channel results from an adsorbed state of N2O that decomposes at 170 K to liberate N2 in the gas phase and deposit oxygen adatoms at non-defect Ti4+ sites. The presence of these O adatoms is clearly evident in subsequent water TPD measurements. We propose that this channel involves N2O molecules that are bound at vacancies with the N-end of the molecule in the vacancy, which permits the O-end of the molecule to interact with an adjacent Ti4+ site. The partitioning between these two channels is roughly 1:1 for adsorption at 90 K, but neither is observed to occur for moderate N2O exposures at temperatures above 200 K. EELS data indicate that vacancies readily transfer charge to N2O at 90 K, and this charge transfer facilitates N2O decomposition. Based on these results, it appears that the decomposition of N2O to N2 requires trapping of the molecule at vacancies and that the lifetime of the N2O–vacancy interaction may be key to the conversion of N2O to N2.  相似文献   

6.
Three compounds, K2(H2O)4H2SiMo12O40 · 7H2O (1), K2Na2(H2O)4SiW12O40 · 4H2O (2), and Na4(H2O)8SiMo12O40 · 6H2O (3) have been synthesized and structurally characterized by single-crystal X-ray analysis, IR, and thermogravimetry. Compounds 1 and 2 both show the high symmetry trigonal space group P3221 and a novel 3D network structure. The Keggin anions [SiM12O40]4−(M = Mo, W) are linked by potassium or sodium cations to generate hexagon-shaped channels along the c-axis, in which water molecules are accommodated. Compound 3 is tetragonal, space group P4/mnc constructed from [SiMo12O40]4− anions and Na ions.  相似文献   

7.
利用固相烧结法制备出基础配方为ZnO–A12O3–MgO–TiO2–SiO2–Fe2O3的ZnO线性电阻。研究了Fe2O3掺杂量对ZnO线性电阻微观结构、阻温特性和阻频特性的影响。结果表明:当Fe2O3掺杂量为0.75%(质量分数)时,氧化锌线性电阻的非线性系数为1.12,阻温系数取得–8.23×103/℃,此时样品的综合性能最好。  相似文献   

8.
Complete Ni2+ exchange of a single crystal of zeolite X of composition Na92Si100Al92O384 per unit cell was attempted at 73°C with flowing aqueous 0.05 M NiCl2 (pH=4.3 at 23°C). After partial dehydration at 23°C and ≈10−3 Torr for two days, its structure, now of composition Ni2(NiOH)35(Ni4AlO4)2(H3O)46Si101Al91O384 per unit cell, was determined by X-ray diffraction techniques at 23°C (space group Fd , a0=24.788(5) Å). It was refined using all intensities; R1=0.080 for the 236 reflections for which Fo>4σ(Fo), and wR2=0.187 using all 1138 unique reflections measured. At four crystallographic sites, 45 Ni2+ ions were found per unit cell. Thirty of these are at two different site III′ positions. Twenty of those are close to the sides of 12-rings near O–Si–O sequences, where each coordinates octahedrally to two framework oxygens, to three water molecules which hydrogen bond to the zeolite framework, and to an OH ion. The remaining 10 are near O–Al–O sequences; only three members of a likely octahedral coordination sphere could be found. In addition, two Ni2+ ions are at site I, eight are at site I′, and five are at site II. Forty six H3O+ ions per unit cell, 24 at site II′ and 22 at site II, each hydrogen bond triply to six rings of the zeolite framework. Each of the 22 H3O+ ions also hydrogen bonds to a H2O molecule that coordinates to a site III′ Ni2+ ion. Six of the eight sodalite cages each contain four H3O+ ions at site II′; the remaining two each contains a tetrahedral orthoaluminate anion at its center. Each tetrahedral face of each orthoaluminate ion is centered by a site I′ Ni2+ ion to give two Ni4AlO4 clusters. The five site II Ni2+ ions each coordinate to a OH ion. With 46 H3O+ ions per unit cell, the great tendency of hydrated Ni2+ to hydrolyze within zeolite X is demonstrated. With a relatively weak single-crystal diffraction pattern, with dealumination of the zeolite framework, and with an apparent decrease in long-range Si/Al ordering likely due to the formation of antidomains, this crystal like others treated with hydrolyzing cations appears to have been damaged by Ni2+ exchange and partial dehydration.  相似文献   

9.
The hydrothermal transformation of calcium aluminate hydrates were investigated by in situ synchrotron X-ray powder diffraction in the temperature range 25 to 170 °C. This technique allowed the study of the detailed reaction mechanism and identification of intermediate phases. The material CaAl2O4·10H2O converted to Ca3Al2(OH)12 and amorphous aluminum hydroxide. Ca2Al2O5·8H2O transformed via the intermediate phase Ca4Al2O7·13H2O to Ca3Al2(OH)12 and gibbsite, Al(OH)3. The phase Ca4Al2O7·19H2O reacted via the same intermediate phase to Ca3Al2(OH)12 and mainly amorphous aluminum hydroxide. The powder pattern of the intermediate phase is reported.  相似文献   

10.
S.C. Lee  S.-H. Park  S.M. Lee  J.B. Lee  H.J. Kim   《Catalysis Today》2007,120(3-4):358-362
Monodispersed Cu2(OH)3Cl nanoplatelets, Cu(OH)2 nanowires, CuO nanoparticles and nanoribbons with a spherical morphology were synthesized using hydrothermal and heat-treatment reactions, and their H2 storage characteristics were examined. The Cu2(OH)3Cl nanoplatelets particles formed immediately after mixing the reactant, which subsequently formed larger uniform spherical particles in the submicron range. This procedure highlights a practical strategy for producing spherical Cu(OH)2 and CuO materials consisting of monodispersed nanocrystals. The spherical aggregates of Cu2(OH)3Cl nanoplatelets heat-treated at 473 K could reversibly store up to 2.35 wt.% H2 at 38 bar and 293 K.  相似文献   

11.
Phase changes in high temperature treated (>900 °C) 8 or 20 wt% BaO supported on γ-Al2O3 model lean NOx trap (LNT) catalysts, induced by NO2 and/or H2O adsorption, were investigated with powder X-ray diffraction (XRD), solid state 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and NO2 temperature programmed desorption (TPD) experiments. After calcination in dry air at 1000 °C, the XRD and solid state 27Al MAS NMR results confirm that stable surface BaO and bulk BaAl2O4 phases are formed for 8 and 20 wt% BaO/Al2O3, respectively. Following NO2 adsorption over these thermally treated samples, some evidence for nanosized Ba(NO3)2 particles are observed in the XRD results, although this may represent a minority phase. However, when water was added to the thermally aged samples after NO2 exposure, the formation of bulk crystalline Ba(NO3)2 particles was observed in both samples. Solid state 27Al MAS NMR is shown to be a good technique for identifying the various Al species present in the materials during the processes studied here. NO2 TPD results demonstrate a significant loss of uptake for the 20 wt% model catalysts upon thermal treatment. However, the described phase transformations upon subsequent water treatment gave rise to the partial recovery of NOx uptake, demonstrating that such a water treatment of thermally aged catalysts can provide a potential method to regenerate LNT materials.  相似文献   

12.
A series of La(Co, Mn, Fe)1−x(Cu, Pd)xO3 perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O2, NO + O2, C3H6, in the absence or presence of 5% H2O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C3H6, 1% O2, 0 or 10% H2O, and 50,000 h−1 space velocity. The objective was to investigate the influence of H2O addition on catalytic behavior. A good performance (100% NO conversion, 77% N2 yield, and 90% C3H6 conversion) was achieved at 600 °C over LaFe0.8Cu0.2O3 under a dry feed stream. With the exposure of LaFe0.8Cu0.2O3 to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N2 yield, and 86% C3H6 conversion. A competitive adsorption between H2O vapor with O2 and NO molecules at anion vacancies over LaFe0.8Cu0.2O3 was found by means of TPD studies here. A deactivation mechanism was therefore proposed involving the occupation of available active sites by water vapor, resulting in an inhibition of catalytic activity in C3H6 + NO + O2 reaction. This H2O deactivation was also verified to be strictly reversible by removing steam from the feed.  相似文献   

13.
The reaction pathways, kinetics and mechanisms of 4-(naphthylmethyl)bibenzyl (NBBM) have been studied in order to resolve the fundamentals underlying the catalysis of coal liquefaction by Fe-based catalysts. Reactions of NBBM: ( 1 ) under nitrogen in the absence of catalyst, (2) under hydrogen in the absence of catalyst, (3) under nitrogen in the presence of the catalyst precursor Fe(CO)3(PPh3)2, and (4) under hydrogen in the presence of the catalyst precursor Fe(CO)3(PPh3)2 were accomplished. Thermolysis was selective for cleavage of the weak bibenzyl bond, whereas the catalyst precursor effected cleavage at the naphthyl moiety. The catalyst precursor was most effective in the presence of hydrogen, where the rate of consumption of NBBM and the selectivity of breaking the bond at the naphthalene ring both increased. Hydrogenation activity was also observed. Possible mechanisms are proposed to describe the pyrolytic and catalytic reactions of NBBM.  相似文献   

14.
Since the electromechanical devices move towards enhanced power density, high mechanical quality factor (Qm) and electromechanical coupling factor (kp) are commonly needed for the high powered piezoelectric transformer with Qm≥2000 and kp=0.60. Although Pb(Mn1/3Nb2/3)O3–PbZrO3–PbTiO3 (PMnN–PZ–PT) ceramic system has potential for piezoelectric transformer application, further improvements of Qm and kp are needed. Addition of 2CaO–Fe2O3 has been proved to have many beneficial effects on Pb(Zr,Ti)O3 ceramics. Therefore, 2CaO–Fe2O3 is used as additive in order to improve the piezoelectric properties in this study. The piezoelectric properties, density and microstructures of 0.07Pb(Mn1/3Nb2/3)O3–0.468PbZrO3–0.462PbTiO3 (PMnN–PZ–PT) piezoelectric ceramics with 2CaO–Fe2O3 additive sintered at 1100 and 1250 °C have been studied. When sintering temperature is 1250 °C, Qm has the maximum 2150 with 0.3 wt.% 2CaO–Fe2O3 addition. The kp more than 0.6 is observed for samples sintered at 1100 °C. The addition of 2CaO–Fe2O3 can significantly enhance the densification of PMnN–PZ–PT ceramics when the sintering temperature is 1250 °C. The grain growth occurred with the amount of 2CaO–Fe2O3 at both sintering temperatures.  相似文献   

15.
G. Centi  F. Vazzana 《Catalysis Today》1999,53(4):6695-693
The catalytic behavior in N2O reduction by propane in the presence of O2, H2O and SO2 of Fe/ZSM-5 catalysts prepared by ion exchange and chemical vapour deposition (CVD) is reported. The catalyst prepared by CVD shows a lower dependence of the rate of selective N2O reduction on the decrease in C3H8 to N2O ratio in the feed and a higher resistance to deactivation by SO2 in accelerated durability tests with high SO2 concentration (500 ppm). This catalyst shows stable catalytic behavior in the presence of SO2 for more than 600 h of time-on-stream. Characterization of the catalysts by UV–VIS–NIR diffuse reflectance indicates that the poor performances of the sample prepared by ion exchange could be related to the presence of highly clustered Fe3+ species, in this catalyst. On the other hand, Fe2O3 particles are not present in the sample prepared by CVD while mainly isolated Fe3+ ions and iron-oxide nanoclusters are present.  相似文献   

16.
The germanate KF·2[Ca6(SO4) (GeO4)2O] was synthesized by solid state reactions; comparison of the observed and calculated powder pattern, assuming an isostructural relationship with the silicate phase, gives good agreement. Sulphate groups may also be substituted by CrO42− to give the isostructural KF·2[Ca6(CrO4)(SiO4)2O].  相似文献   

17.
In an attempt to better understand interactions occuring at hydrated cement/organic polymer interfaces, the reaction mechanism and products formed at the interfaces between poly(acrylic acid), p(AA) or poly(acrylamide), p(AM), and Ca(OH)2 or gibbsite, Al2O3·3H2O, were explored using x-ray photoelectron spectroscopy (XPS). It was estimated that at p(AA)/Ca(OH)2 interfaces, a Ca-complexed carboxylate interfacial reaction product was formed by an ionic reaction between the COOH in p(AA) and Ca2+ ions from Ca(OH)2. A similar reaction product was formed at p(AM)/Ca(OH)2 interfaces as a result of an inter-facial transformation of amide in p(AM) into carboxylic acid, caused by the alkali-catalyzed hydrolysis of the amide. The proton-accepting hydroxyl groups existing at the outermost surface sites of Al2O2·3H2O react favorably with proton-donating COOH groups in p(AA). This acidbase interaction at the p(AA)/Al2O3·3H2O joint formed hydrogen bonds. Whereas, when the p(AM) was applied on Al2O3·3H2O surfaces, interfacial electrostatic bonds were formed through charge-transferring reaction mechanisms in which the charge density was transferred from the Al in Al2O3·3H2O to the C=0 oxygen in p(AM).  相似文献   

18.
Layered double hydroxide pillared by Paratungstate A ion, Mg12Al6(OH)36(W7O24)·4H2O, was prepared via anion exchange reaction of the synthetic precursor, Mg4Al2(OH)12TA·xH2O (TA2−=terephthalate), and [W7O24]6− ion. Some physico-chemical properties were measured and the preparation conditions were studied. Trace aqueous organocholorine pesticide, hexachlorocyclohexane (HCH), was totally degraded and mineralized into CO2 and HCl by irradiating a Mg12Al6(OH)36(W7O24)·4H2O suspension in the near UV area. Disappearance of trace HCH follows Langmuir–Hinshelwood first-order kinetics. The model and mechanism for the photocatalytic degradation of HCH on the Mg12Al6(OH)36(W7O24)·4H2O were proposed, indicating that the interlayer space is the reaction field, and that photogeneration of OH√ radicals are responsible for the degradation pathway.  相似文献   

19.
The synthesis and structure of (CH3CH[NH3]CH2NH3)1/2·ZnPO4, an organically templated zincophosphate (ZnPO) analogue of aluminosilicate zeolite thomsonite (THO), are described. The ZnPO framework is built up from an alternating, vertex-sharing, network of ZnO4 and PO4 groups (dav(Zn–O)=1.944 (8) Å, dav(P–O)=1.535 (9) Å, θav(Zn–O–P)=130.5°) involving distinctive 4=1 secondary building units. The 1,2-diammonium propane cations are highly disordered in the [0 0 1] 8-ring channels. Crystal data: (CH3CH[NH3]CH2NH3)1/2·ZnPO4, Mr=198.42, orthorhombic, space group Pncn (no. 52), a=14.119 (6) Å, b=14.136 (5) Å, c=12.985 (5) Å, V=2591 (3) Å3, Z=10, R(F)=0.057, Rw(F)=0.061 (for a twinned crystal).  相似文献   

20.
Conductivity of molten Mg(NO3)2. 6H2O + NH4NO3 system containing up to 80 mole percent of the latter was measured in the temperature range 320–400 K. Temperature dependence of conductivity exhibited Arrhenian behaviour. Conductivity—composition isotherms were non-linear indicating weak ordering tendencies. Equivalent conductivity data did not obey Markov equation; deviations have been interpreted in terms of the Tobolsky parameter (θ). Constancy of θ indicate that the water of hydration in the system remains with Mg2+ ions and is unaffected by the addition of NH+4 ions.  相似文献   

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