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1.
Diphasic boehmite derived unseeded and seeded (by either -Al2O3, -Fe2O3, or Fe(NO3)3) alumina gel planar monoliths were examined by DTA, XRD and photoluminescence spectroscopy. Luminescence spectra enable sensitive monitoring of the - and -Al2O3 crystallization in heat-treated gels due to Cr3+ impurity traces. Fe(NO3)3 unlike other seeds effectively influences crystallization of both - and -Al2O3. The present results are interpreted as prevailing solution or Fe3+ ion effect on the crystallization process.  相似文献   

2.
A V2O5/Al2O3 mixed solids sample was prepared with a molar ratio of 0.41 Na2O (4 and 10 mol%) was added in the form of sodium nitrate prior to calcination in air in the temperature range 500–1000C. Solid-solid interactions between V2O5 and Al2O3 were studied using DTA and TG curves and their derivatives together with XRD techniques.The results obtained showed that Na2O interacted with V2O5 at temperatures starting from 500C to yield a sodium/vanadium compound, Na0.3V2O5 which remained stable and decomposed in part by heating at 1000C. V2O5 exists in orthorhombic and monoclinic forms in the case of pure mixed solids and those containing 4 mol% of Na2O and preheated at 500C, and in monoclinic form in the case of the mixed solid doped with 10 mol% of Na2O.Heating of pure and doped mixed oxide solids at 650C resulted in the conversion of most of the V2O5 into AlVO4. Doping with sodium oxide enhanced the solid-solid interaction between V2O5 and Al2O3 at 650C to produce AlVO4. The produced AlVO4 decomposed completely on heating at 700C to form -Al2O3 and V2O5, (orthorhombic and monoclinic forms).The presence of Na2O was found to decrease the relative intensity of the diffraction lines of -Al2O3 (corundum) produced at 750C which indicated some kind of hindrance of the crystallization process.Heating of pure and doped mixed solids at 1000C resulted in a further crystallization of acorundum together with V2O5 and sodium vanadate, Na0.3V2O5. However, the intensities of diffraction lines relative to those of the sodium vanadium compound were found to decrease markedly by heating at 1000C, indicating partial thermal decomposition into vanadium and aluminium oxides.  相似文献   

3.
A novel nano-TiO2 polymer modified glassy carbon (GC) electrode was developed for the determination of an organophosphorous pesticide, fenitrothion (-NO2), in citrate buffer solution. The electrochemical behavior of fenitrothion was characterized by using cyclic voltammetry. An irreversible form, -NO2, was transformed into a reversible redox couple (-NHOH/-NO), and it can be used to determine trace fenitrothion by square wave voltammetry. The experimental parameters, such as film thickness, pH value, accumulation potential and time were optimized. Interestingly, a cyclic voltammetric scan was observed to be more effective than a constant potential for the accumulation of fenitrothion. A linear response over a fenitrothion concentration of 2.5×10–8 to 1.0×10–5M was exhibited, with a detection limit of 1.0×10–8M (S/N=3). The high sensitivity and selectivity of this film electrode was demonstrated by its practical application to the determination of trace amounts of fenitrothion in lake water and apple samples.  相似文献   

4.
Summary In this work, we search for the simplest complete surfaces of systems with three and four atoms, i.e. the minimal sets of critical points with their index, which are topologically consistent in the whole configuration space. Then we show the smallest change in the A2B2 system by requiring at least one stable acetylene configuration and one stable vinylidene configuration, like on the C2H2 surface. Finally, we give complete sets of minima, saddle points and maxima obtained for C2H2 with analytical potentials proposed in the literature and with a semi-empirical method at the CAS-CI level.  相似文献   

5.
Recent IR spectroscopic studies on the surface properties of fresh Mo2N/-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/-Al2O3, both Mo+ (0<<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm-1, due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/-Al2O3 catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/-Al2O3 catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites.  相似文献   

6.
The three copper(II)-arsenates were synthesized under hydrothermal conditions; their crystal structures were determined by single-crystal X-ray diffraction methods:Cu3(AsO4)2-III:a=5.046(2) Å,b=5.417(2) Å,c=6.354(2) Å, =70.61(2)°, =86.52(2)°, =68.43(2)°,Z=1, space group ,R=0.035 for 1674 reflections with sin / 0.90 Å–1.Na4Cu(AsO4)2:a=4.882(2) Å,b=5.870(2) Å,c=6.958(3) Å, =98.51(2)°, =90.76(2)°, =105.97(2)°,Z=1, space group ,R=0.028 for 2157 reflections with sin / 0.90 Å–1.KCu4(AsO4)3:a=12.234(5) Å,b=12.438(5) Å,c=7.307(3) Å, =118.17(2)°,Z=4, space group C2/c,R=0.029 for 1896 reflections with sin / 0.80 Å–1.Within these three compounds the Cu atoms are square planar [4], tetragonal pyramidal [4+1], and tetragonal bipyramidal [4+2] coordinated by O atoms; an exception is the Cu(2)[4+1] atom in Cu3(AsO4)2-III: the coordination polyhedron is a representative for the transition from a tetragonal pyramid towards a trigonal bipyramid. In KCu4(AsO4)3 the Cu(1)[4]O4 square and the As(1)O4 tetrahedron share a common O—O edge of 2.428(5) Å, resulting in distortions of both the CuO4 square and the AsO4 tetrahedron. The two Na atoms in Na4Cu(AsO4)2 are [6] coordinated, the K atom in KCu4(AsO4)3 is [8] coordinated by O atoms.Die drei Kupfer(II)-Arsenate wurden unter Hydrothermalbedingungen gezüchtet und ihre Kristallstrukturen mittels Einkristall-Röntgenbeugungsmethoden ermittelt:Cu3(AsO4)2-III:a = 5.046(2) Å,b = 5.417(2) Å,c = 6.354(2) Å, = 70.61 (2)°, = 86.52(2)°, = 68.43(2)°,Z = 1, Raumgruppe ,R = 0.035 für 1674 Reflexe mit sin / 0.90 Å–1.Na4Cu(AsO4)2:a = 4.882(2) Å,b = 5.870(2) Å,c = 6.958(3) Å, = 98.51(2)°, = 90.76(2)°, = 105.97(2)°,Z = 1, Raumgruppe ,R = 0.028 für 2157 Reflexe mit sin / 0.90 Å–1.KCu4(AsO4)3:a = 12.234(5) Å,b = 12.438(5) Å,c = 7.307(3) Å, = 118.17(2)°,Z = 4, Raumgruppe C2/c,R = 0.029 für 1896 Reflexe mit sin / 0.80 Å–1.Die Cu-Atome in diesen drei Verbindungen sind durch O-Atome quadratisch planar [4], tetragonal pyramidal [4 + 1] und tetragonal dipyramidal [4 + 2]-koordiniert; eine Ausnahme ist das Cu(2)[4 + 1]-Atom in Cu3(AsO4)2-III: Das Koordinationspolyeder stellt einen Vertreter des Übergangs von einer tetragonalen Pyramide zu einer trigonalen Dipyramide dar. In KCu4(AsO4)3 haben das Cu(1)[4]O4-Quadrat und das As(1)O4-Tetraeder eine gemeinsame O—O-Kante von 2.428(5) Å, was eine Verzerrung der beiden Koordinationsfiguren CuO4-Quadrat und AsO4-Tetraeder bedingt. Die zwei Na-Atome in Na4Cu(AsO4)3 sind durch O-Atome [6]-koordiniert, das K-Atom in KCu4(AsO4)3 ist [8]-koordiniert.
Zur Kristallchemie dreier Kupfer (II)-Arsenate: Cu3(AsO4)2-III, Na4Cu(AsO4)2 und KCu4(AsO4)3
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7.
Summary Computer based methods for the processing of chronoamperometric datavia convolutions are discussed. On the example of the quasi-reversible Fe3+/Fe2+ couple, their application for data acquisition and determination of the heterogeneous electrochemical parameters is demonstrated. The plot of Q/i vs. t/i is superior to that employingi/I 1, being less sensitive to distortions by charging currents once these have died away and by the effects of damping on the initially rapidly varying currents. Cyclic voltammetry is often combined with convolution or deconvolution, and digital simulation studies are also frequently performed to confirm the results.
Bestimmung kinetischer Parameter des Systems FeCl3/FeCl2 mittels einer neuen Verarbeitung chronoamperometrischer Daten
Zusammenfassung Computerunterstützte Verfahren zur Verarbeitung chronoamperometrischer Daten mittels Faltungsintegralen werden diskutiert. Am Beispiel des quasireversiblen Systems Fe3+/Fe2+ wird die Anwendung der neuen Methoden zur Datenerfassung und zur Bestimmung der heterogenen elektrochemischen Parameter gezeigt. Der Plot von Q/i gegen t/i ist dem voni/I 1 überlegen, da er durch Ladeströme und Dämpfung der ursprünglich stark variierenden Ströme weniger stark beeinflußt wird. Cyclische Voltammetrie wird häufig im Zusammenhang mit Konvolutions- und Dekonvolutionsmethoden angewandt; digitale Simulation zur Überprüfung der Ergebnisse wird ebenfalls oft eingesetzt.
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8.
The effects of feed composition on the adsorption dynamics and the optimal process design were studied from the experimental and simulated results in the H2 layered bed PSA with activated carbon and zeolite 5A. The breakthrough results using the base composition (56.4 vol% H2; 26.6 vol% CH4; 8.4 vol% CO; 5.5 vol% N2; and 3.1 vol% CO2) in various layered beds were compared with those using the higher nitrogen composition and the no nitrogen composition. In the breakthrough dynamics, the propagation velocity of wave front of each component was closely related to the slope of isotherm estimated at its concentration in the feed. Breakthrough behavior at each layered bed in the higher nitrogen composition showed similar trends as that in the base composition. However, the no nitrogen composition showed different breakthrough behavior from the other groups. In this feed composition, it was observed that the order of CO and CH4 breakthrough times was reversed with a change in the carbon-to-zeolite ratio. Based on the adsorption dynamics and breakthrough behavior of each feed composition group in various layered beds, the effect of feed composition on a seven-step two-bed PSA process for the H2 recovery from coke oven gas was investigated numerically to develop a well-designed H2 PSA process under various operating conditions. As expected from the breakthrough results, the trends of the PSA performance in the higher nitrogen composition were similar to those in the base composition except for the slight decrease in the optimal carbon-to-zeolite ratio. However, in case of the no nitrogen composition, high purity product was obtained from the activated carbon-rich layered bed PSA because the adsorption capacity of the activated carbon for impurities was superior to that of zeolite. As a result, the optimum carbon-to-zeolite ratio at each operating condition was slightly changed depending on the propagation velocity of each component on each layer.  相似文献   

9.
Dielectric measurements of SO2 quinol clathrates show that the reorientation of encaged SO2 molecules is very rapid and depends greatly on the degree of cage occupancy. For a-quinol sample of cage occupancy = 0.57, the reorientation rate was 1 MHz at 6 K, with a reorientational activation energy of 673 J/mol. For a sample identified by13C NMR as-quinol, and for a-quinol sample with most cages filled with Xe, SO2 reorientation rates are even greater, with activation energies of only some tens of J/mol. The low temperature dielectric studies show that some ethanol may be enclathrated in-quinol recrystallized from this solvent. The13C NMR spectra confirm the X-ray results that the lattice becomes distorted with increased SO2 content.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.  相似文献   

10.
The combinations and disproportionations of the CH3 and 2-propyl (iP) radicals with the 1,1,2-trimethylallyl (TMA) radical have been studied in the gas phase in the temperature interval of 389–451 K and 490–540 K, respectively. For the ratios of the terminal (t) and non-terminal (n) combinations of the CH3 and iP radicals with the TMA radical, values of 1.9±0.1 and 2.84±±0.10 were obtained, respectively. The ratios of the tt and tn and nn to tn combinations of the TMA radical were 1.59 and 0.46, respectively. The disproportionation-combination rations were (CH3 , TMA)=0.022±±0.012 and (iP, TMA)=0.026±0.011.
CH 3 2- (iP) 1,1,2- (TMA) : 389–451 K 490–540 K. (t) (n) TMA 1,9±0,1 2,84±0,10, . tt tn nn tn TMA 1,59 0,46, . (CH 3 , TMA)=0,022±0,012 (iP, TMA)=0,026±0,011.
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11.
Vapour phase treatment at elevated temperatures with an activating agent is an effective method of synthesis and purposeful modification of amorphous and fine-grained crystalline substances. In the systems amorphous silica-quartz and amorphous Al(OH)3 -crystalline-Al2O3 different forms of bound water are of prime importance. DTA, TG, DSC, NMR1H,29Si,27Al, IR spectroscopy, electron- and optical microscopy methods have been used. The interaction of water molecules with the base skeleton and with hydroxide groups on the surface and in the bulk of the silica is of primary significance for modification of the silica structure. The proportion of different forms of the bound water determines the integral evaporation enthalpy of water. Various properties of silica are determined by weak bound water in the surface layer of the material. In the sequence Al(OH)3-Al2O3 the structure transformation is observed according to the following scheme:-Al(OH)3-AlOOH- -Al2O3, which takes place during the vapour phase treatment with activator.
Zusammenfassung Eine Dampfphasenbehandlung bei höheren Temperaturen mit einem Aktivierungsmittel ist eine effektive Methode zur Synthese und zielgerichteten Modifizierung von amorphen und feinkörnigen kristallinen Substanzen. In den Systemen amorphes Siliziumdioxid-Quarz sowie amorphes Al(OH)3-kristallines-Al2O3 hat verschiedenartig gebundenes Wasser eine primäre Bedeutung. Bei den Untersuchungen kamen DTA, TG, DSC,1H-,29Si-,27Al-NMR, IR-Spektroskopie sowie Elektronen- und optische Mikroskopie zur Anwendung. Die Wechselwirkung von Wassermolekülen mit dem Grundgerüst und mit Hydroxidgruppen an der Oberfläche und im Innern von Silika ist für die Modifizierung der Silikastruktur von primärer Bedeutung. Der Anteil der verschiedenartig gebundenen Wasserformen bestimmt die vollständige Verdampfungsenthalpie des Wassers. Die verschiedenen Eigenschaften von Silika werden durch schwach gebundenes Wasser in der Oberflächenschicht der Substanz bestimmt. Die Umwandlung Al(OH)3-Al2O3 durchläuft folgendes Schema:-Al(OH)3--AlOOH--Al2O3, nach dem der Vorgang bei der Gasphasenbehandlung mit Aktivator abläuft.
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12.
Summary Spots of citrinin, ochratoxin A, aflatoxin M1 and penicillic acid on thin-layer chromatograms can be semi-quantitatively estimated by using a grey scale, commonly used in photo laboratories. The detection limits are 0.01 g for citrinin, 0.006 g for ochratoxin A, 0.002 g for aflatoxin M1 and 0.01 g for penicillic acid. Standard curves for these mycotoxins are given.
Halbquantitative Bestimmung der Mycotoxine Citrinin, Ochratoxin A, Aflatoxin M1 und Penicillinsäure auf Dünnschicht-Chromatogrammen mit Hilfe eines Graukeils
Zusammenfassung Mit Hilfe eines in Photolabors gebräuchlichen Graukeils können dünnschicht-chromatographische Flecke der obengenannten Mycotoxine halbquantitativ bestimmt werden. Die Nachweisgrenzen betragen 0,01 g für Citrinin, 0,006 g für Ochratoxin A, 0,002 g für Aflatoxin M1 und 0,01 g für Penicillinsäure. Eichkurven werden angegeben.
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13.
Summary Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgMnCoZnNiCu(EDTA) · 6H2O where + + + + + =2, 01, 0,,2, 0, 1.This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure.Due to this preference, and also to the structural features, the heterobimetallic MM(EDTA) · 6H2O compounds constitute a structurally new class of materials which can be described as ordered alternating-heterobimetallic polymeric coordination complexes.  相似文献   

14.
    
Summary An atomic-absorption determination of beryllium in-Al2O3 ceramics is described. The sample is dissolved rapidly and completely at 300 ± 50°C in "strong phosphoric acid. The determination is carried out by means of a N2O/C2H2 flame after dilution. The effects of phosphoric acid and aluminium(III) on the signal for beryllium at optimal flame stoichiometry and various burner heights are investigated. Phosphoric acid enhances the atomization and minimizes the interference effects. The proposed method allows the determination of beryllium in the range of 0.01–20% with a variation coefficient of 0.6% (at 0.7% Be in -Al2O3 ceramics).
AAS-Bestimmung von Beryllium in -Al2O3-Keramik
Zusammenfassung Die Probe wird schnell bei 300 ± 50° C in starker Phosphorsäure aufgeschlossen. Nach entsprechendem Verdünnen wird Beryllium mittels AAS unter Verwendung einer N2O/C2H2-Flamme bestimmt. Die Methode ist für die Bestimmung von 0,01–20% Be im -Al2O3 geeignet. Der Variationskoeffizient beträgt 0,6% (bei 0,7% Be in der Probe). Bei verschiedenen Brennerhöhen wurde die Wirkung von Al(III) und von Phosphorsäure auf die Atomisation von Beryllium untersucht. Phosphorsäure verringert die chemischen Störungen (Aluminat- und Carbidbildung) und begünstigt die Atomisierung.
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15.
Summary Crystals of Co2(X 2O7)·2H2O,X=P/As were synthesized under hydrothermal conditions. Their crystal structures were determined by single crystal X-ray diffraction:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2)Å, =94.77(2)/94.74(2)°, space group P21/n,R=0.032/0.046,R w=0.028/0.034 for 2423/2042 reflections and 131/119 variables. Within the twoXO4 tetrahedra connected via a common corner to anX 2O7 group the average P-O bond lengths are approximately equal (1.540 and 1.543 Å), but As-O differs significantly (1.685 and 1.696 Å). A comparison with the isotypic Mn and Mg pyrophosphates shows a correlation between the ratio Me-O/X-O and the angle O-X-O.
Vergleich der Kristallstrukturen von Co2(X 2O7)·2H2O,X=P und As
Zusammenfassung Kristalle von Co2(X 2O7)·2H2O,X=P/As wurden unter Hydrothermalbedingungen synthetisiert. Ihre Kristallstrukturen wurden mittels Röntgenbeugung an Einkristallen bestimmt:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2) Å, =94.77(2)/97.74(2)°, Raumgruppe P21/n,R=0.032/0.046,R w=0.028/0.034 für 2423/2042 Reflexe und 131/119 Variable. In den beiden über eine gemeinsame Ecke zuX 2O7-Gruppen verknüpftenXO4-Tetraedern sind die mittleren P-O-Abstände ungefähr gleich (1.540 und 1.543 Å), hingegen differiert As-O signifikant (1.685 und 1.696 Å). Ein Vergleich mit den isotypen Mn- und Mg-Pyrophosphaten zeigt eine Korrelation zwischen dem Quotienten Me-O/X-O und dem WinkelX-O-X.
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16.
Using synchrotron radiation LIII absorption spectra of rhenium in Re/SiO2 and (Re+Pt)/SiO2 catalysts prepared via triethoxyrhenium have been studied. The conclusion has been drawn that reduced catalysts contain lowvalent rhenium ions and their composition is more uniform than that of the previously examined catalysts Re/Al2O3 and (Re+Pt)/Al2O3 prepared by a conventional impregnation technique.
LIII- Re/SiO2 (Re+Pt)/SiO2, . , , Re/Al2O3 (Re+Pt)/Al2O3, .
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17.
The phase equilibria in the total range of component concentrations in the V2O5-Cr2O3 system up to 1000 °C were studied by means of phase powder diffraction and DTA. Two compounds exist in the system: CrVO4, melting incongruently at 860±5 °C, and Cr2V4O13, which decomposes in the solid state at 640±5 °C to CrVO4(s) and V2O5(s). At 645±5 °C, CrVO4 and V2O5 form a eutectic mixture with the CrVO4 content not exceeding 2% mol.
Zusammenfassung Mittels DTA und Pulverdiffraktionsaufnahmen wurde das Phasengleichgewicht des Systems V2O5-Cr2O3 bis 1000 °C im gesamten Konzentrationsbereich untersucht. Innerhalb des Systemes existieren zwei Verbindungen: CrVO4 mit einem inkongruentem Schmelzpunkt bei 860±5 °C und Cr2V4O13, das sich in festem Zustand bei 640±5 °C in CrVO4(s) und V2O5(s) zersetzt. Bei 645±5 °C bilden CrVO4 und V2O5 ein eutektisches Gemisch mit einem maximalen CrVO4-Gehalt von 2 mol%.

DTA V25-Cr23 1000° . : CrVO4, 860±5° Cr2V4O13, 640±5° CrVO4 V2O5, 645±5° CrVO4, 2 %.
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18.
A study has been made of temperature programmed desorption (TPD) of NH3 and H2O from samples of NH4X and CoNH4X zeolites of various degree of exchange. NH3 TPD peaks could be explained by interaction of NH3 with different Brönsted and Lewis acidic centers. Moreover a water peak at high temperatures allowed interpretations of the dehydroxylation, and by reason of the characteristic desorption temperatures a particular state of the Co2+ ions in the CoNH4X zeolites is postulated.
- () NH3 H2O NH4X CoNH4X . NH3 NH3 =qs . . Co2+ CoNH4X.
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19.
Certain features of the chemist's molecular structure model, viz. size and shape, are retrieved even in the best non-adiabatic variational calculations thus far carried out for ground states of H 2 + and H2. Those features do not conflict with the full symmetry of exact molecular eigenstates, once they are properly understood as correlation effects.  相似文献   

20.
Studies of the effect of zinc chloride and aluminium additives on the activity of a Pd/Al2O3 catalyst (5 wt.%Pd) in the isomerization of heptene-1, allylbenzene,p-allylphenol and 4-allyl-2-methoxyphenol (eugenol) indicate that the rate and selectivity of isomerization depend on the sequence of addition of salts and reagent to the catalytic system. The simultaneous addition of ZnCl2 or AlCl3 with olefin, produces a 2–3 fold increase in the isomer yield compared to ethanol.
Pd/Al2O3- (5 .% Pd) -1, , -, 4--2- (). , . ZnCl2 AlCl3 2–3 .
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