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 828 毫秒
1.
[AlO4Al12(OH)24(H2O)12]7+ (Al13) formation in electrolysis process is studied. The results detected by27Al NMR spectroscopy show that high content of Al13 polymer is formed in the partially hydrolyzed aluminum solution prepared by controlled electrolysis process. In the produced electrolyte of total Al concentration ([AlT]) 2.0 mol · L−1 with a basicity (B = OH/Al molar ratios) of 2.0, the content of Al13 polymer is over 60% of total Al. Dynamic light scattering shows that the size distribution of the final electrolyte solutions ([AlT] = 2.0 mol · L−1) is trimodal with B = 2.0 and bimodal with B = 2.5. The aggregates of Al13 complexes increase the particle size of partially hydrolyzed aluminum solution.  相似文献   

2.
Aluminas resulting from sols prepared via a modified Yoldas procedure were studied with differential thermal analysis (DTA), differential thermal gravimetrie (DTG), 27Al nuclear magnetic resonance (27Al MAS NMR) and X-ray diffraction (XRD) concerning their thermal properties, aluminum speciation and phase content.Hydrolysis of aluminum-sec-butoxide in aluminum nitrate solutions allowed to prepare stable sols with varying molar ratios, solids contents and pH values. Resulting sols contained different aluminum species including also Al13 polycations. Sol preparation conditions also determined aluminum speciation in solid products obtained after thermal treatments of gels obtained from these sols. Al13 polycations and AlO5 species were found to play an important role for thermally induced transformation from amorphous products via eta-Al2O3 to alpha-Al2O3. Intermediately formed eta-Al2O3 promotes the phase transformation to alpha-Al2O3.  相似文献   

3.
The Er3+–Yb3+ codoped Al2O3 has been prepared by the sol–gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3 · 5H2O] and ytterbium nitrate [Yb(NO3)3 · 5H2O]. The phase structure, including only two crystalline types of doped Al2O3 phases, θ and γ, was obtained for the 1 mol% Er3+ and 5 mol% Yb3+ codoped Al2O3 at the sintering temperature of 1,273 K. By a 978 nm semiconductor laser diodes excitation, the visible up-conversion emissions centered at about 523, 545, and 660 nm were obtained. The temperature dependence of the green up-conversion emissions was studied over a wide temperature range of 300–825 K, and the reasonable agreement between the calculated temperature by the fluorescence intensity ratio (FIR) theory and the measured temperature proved that Er3+–Yb3+ codoped Al2O3 plays an important role in the application of high temperature sensor.  相似文献   

4.
A tetranuclear gold cluster has been synthesized by the reaction of [Au(PPh3)NO3] with the closo carborane diphosphine 1,2-(PPh2)2-1,2-C2B10H10 in THF, and characterized by elemental analysis, FT-IR, 1H and 13C?NMR spectroscopy and X-ray structure determination. The cluster crystallizes in the triclinic Pī, a?=?15.118(8)?Å, b?=?16.057(9)?Å, c?=?24.284(13)?Å, α?=?80.822(9)°, β?=?79.624(8)°, γ?=?81.938(8)°, Z?=?2, R 1?=?0.0626, wR 2?=?0.1894. A single crystal structure determination showed that four gold atoms form a tetrahedral framework. Among these four gold atoms, two were chelated by two nido carborane diphosphine [7,8-(PPh2)2-7,8-C2B9H10]? anions coming from the degradation of the initial closo ligand 1,2-(PPh2)2-1,2-C2B10H10, while the other two were ligated to two PPh3 groups. The luminescence of this cluster was also investigated in dichloromethane solution at room temperature.  相似文献   

5.
Single-pulse 13C NMR spectra and spin-lattice relaxation times T1(1H), detected indirectly via 13C carbons, and T1(13C) were measured at 31°C for virgin pelletized and annealed polylactic acid (PLA) samples using the magic-angle spinning technique. The structural relaxation resulting in more regular crystals with narrower conformation distribution and increase in the lamellae thickness and crystallinity brought about by annealing at 100°C was deduced from the narrowing of the 13C NMR lines and proton spin-lattice relaxation times T1(1H). The spin-lattice relaxation times T1(13C) related to the respective carbons of the α-polymorph of PLA are also discussed in the study.  相似文献   

6.
The Er3+-doped Al2O3 nanopowders have been prepared by the sol-gel method, using the aluminium isopropoxide [Al(OC3H7)3]-derived γ-AlOOH sols with addition of the erbium nitrate [Er(NO3)3·5H2O]. The five phases of γ-(Al,Er)2O3, θ-(Al,Er)2O3, α-(Al,Er)2O3, ErAlO3, and Al10Er6O24 were detected with the 0–20 mol% Er3+-doped Al2O3 nanopowders at the different sintering temperature of 600–1200°C. The average grain size was increased from about 5 to 62 nm for phase transformation of undoped γ-Al2O3→α-Al2O3 at the sintering temperature from 600 to 1200°C. At the same sintering temperature, average grain size was decreased with increase of the Er3+ doping concentration. Infrared absorption spectra of γ-Al2O3 and θ-Al2O3 nanopowders showed the two broad bands of 830–870 and 550–600 cm−1, the three broad bands of 830–870, 750–760, and 550–600 cm−1, respectively. The infrared absorption spectra for the α-Al2O3 nanopowder showed three characteristic bands, 640, 602, and 453 cm−1. The two characteristic bands of 669 and 418 cm−1 for Er2O3 clusters were observed for the Er3+-doped Al2O3 nanopowders when Er3+ doping concentration was increased up to 2 mol%. The 796, 788, 725, 692, 688, 669, 586, 509, 459, and 418 cm−1 are the characteristic bands of Al10Er6O24 phase.  相似文献   

7.
For the Er3+–Yb3+ codoped Al2O3 powders, the strong near-infrared photoluminescence (PL) centered at 1.535 μm derived from the energy transfer (ET) from Yb3+ to Er3+ was detected by a 978 nm laser diode excitation. Compared with that of Er3+ doped Al2O3 powders, the PL intensity enhanced about 9 times, the full width at half maximum (FWHM) extended from 82 to 90 nm, and the lifetime increased from 3.22 to 4.17 ms for Er3+–Yb3+ codoped Al2O3 powders at room temperature. The ET coefficient of 2.18 × 10−18 cm3 s−1 from Yb3+ to Er3+ was obtained based on the rate equations. The decrease of PL intensity with increasing temperature in the range of 298–733 K was observed, due to thermally enhanced nonradiative relaxation 4I13/2 → 4I15/2 dominated over thermally enhanced phonon-assisted ET in the Er3+–Yb3+ codoped Al2O3.  相似文献   

8.
The sol-gel process was applied to the preparation of Sm2+ ion-doped silicate glasses, which show persistent spectral hole burning at room temperature. The gels synthesized by the hydrolysis of metal alkoxides and SmCl3·6H2O were heated in air at 500°C, were then reacted with H2 gas to form the Sm2+ ion. The Al2O3−SiO22 glasses are appropriate to reduce the Sm3+ ion with H2 gas and show intense photoluminescence of Sm2+ ion. Persistent spectra hole burning was observed in the excitation spectrum for the7F05D0 transition of the Sm2+ ion by the irradiation of DCM dye laser. The hole width and depth were ∼16 cm−1 and ∼10% of the total intensity, respectively, at 20°C.  相似文献   

9.
SrAl2O4:Eu2+, Dy3+ powders were synthesized by sol–gel–combustion process using metal nitrates as the source of metal ions and citric acid as a chelating agent of metal ions. The amounts of citric acid in mole were two times those of the metal ions. By tracing the formation process of the sol–gel, it is found that decreasing the amount of NO3 in the solution is necessary for the formation of transparent sol and gel, and the dropping of ethanol into the precursor solution can decrease the amount of NO3 in the solution. By combusting citrate sol at 600 °C, followed by heating the resultant combustion ash at 1,100–1,300 °C in a weak reductive atmosphere containing active carbon, SrAl2O4:Eu2+, Dy3+ phosphors can prepared. X-ray diffraction, Thermogravimetry–differential thermal analysis, scanning electron microscopy and fluorescence spectrophotometer were used to investigate the formation process and luminescent properties of the as-synthesized SrAl2O4:Eu2+, Dy3+. The results reveal that the SrAl2O4 crystallizes completely when the combustion ash was sintered at 1,200–1,300 °C. The excitation and emission spectra indicate that excitation broadband mainly lies in a visible range and the phosphors emit strong light at 510 nm under the excitation of 348 nm. The afterglow of phosphors lasts for over 10 h when the excited source is cut off.  相似文献   

10.
The extent of the epoxide ring-opening, the formation of ethyl ether groups as one reaction product of the ring-opening and the condensation degree of RSi(O0.5)3 units in sols and gels of the system 3-glycidoxypropyltrimethoxysilane (GPTS)-1.5H2O-0.01/0.1/1.0 metal alkoxide [Si(OEt)4, Sn(OBut)4, Al(OBus)3, Al(OEtOBu)3, Ta(OEt)5, Ti(OEt)4, Zr(OBun)4] in ethanol has been examined by means of liquid- and solid-state 13C and 29Si NMR spectroscopies. The results reveal a strong epoxide ring-opening effect of Al-alkoxides in hybrid sols after 24 h reaction time and of Zr-, Ta-, Al- and Sn-alkoxides in corresponding hybrid gels already at low concentration (1 mole%). The ring-opening rate increases in sols with higher metal alkoxide concentration (10 mole%) but decreases at 50 mole% concentration of Al-, Ti- and Zr-alkoxides. The ring-opening activity of metal alkoxides in 10 mole% hybrid sols increases after 24 h reaction time in the order Si(OEt)4 < Ti(OEt)4 < Zr(OBun)4 < Ta(OEt)5, Sn(OBut)4, Al(OBus)3, Al(OEtOBu)3. The 24 h hybrid sols and gels contain considerable amounts (up to 90%) of ethyl ether groups as reaction product of the ring-opening reaction which lowers the formation of polyether bonds. The condensation degree (c.d.) of RSi(O0.5)3 units of GPTS-1.5H2O sols with 10 mole% of metal alkoxides increases up to 80% after 7 h reaction time in the order: Si(OEt)4 Sn(OBut)4 < Zr(OBun)4 < Al(OBus)3 < Al(OEtOBu)3 < Ta(OEt)5 < Ti(OEt)4. An additional increase in c.d. up to 90% follows after the thermal sol-gel transformation. Generally, maximum activity of metal alkoxides in ring-opening and condensation reactions was found in sols and gels with 10 mole% additives. The effect of water on the epoxide ring-opening and on c.d. is discussed. Furthermore, the activity of metal alkoxides is compared with corresponding nanoscaled metal oxides.  相似文献   

11.
Three thermal effects on heating/cooling of K2TaF7 in the temperature interval of 680–800°C were investigated by the DSC method. The values determined for the enthalpy change of the individual processes are: ΔtransIIHm(K2TaF7; 703°C) = 1.7(2) kJ mol−1, ΔtransIHm(K2TaF7; 746°C) = 19(1) kJ mol−1 and ΔtransIIIHm(K2TaF7; 771°C) = 13(1) kJ mol−1. The first thermal effect was attributed to a solid-solid phase transition; the second to the incongruent melting of K2TaF7 and the third to mixing of two liquids. These findings are supported by in situ neutron powder diffraction experiments performed in the temperature interval of 654–794°C.   相似文献   

12.
Chromium(III)-carbonate reactions are expected to be important in managing high-level radioactive wastes. Extensive studies on the solubility of amorphous Cr(III) hydroxide solid in a wide range of pH (3–13) at two different fixed partial pressures of CO2(g) (0.003 or 0.03 atm.), and as functions of K2CO3 concentrations (0.01 to 5.8 mol⋅kg−1) in the presence of 0.01 mol⋅dm−3 KOH and KHCO3 concentrations (0.001 to 0.826 mol⋅kg−1) at room temperature (22±2 °C) were carried out to obtain reliable thermodynamic data for important Cr(III)-carbonate reactions. A combination of techniques (XRD, XANES, EXAFS, UV-Vis-NIR spectroscopy, thermodynamic analyses of solubility data, and quantum mechanical calculations) was used to characterize the solid and aqueous species. The Pitzer ion-interaction approach was used to interpret the solubility data. Only two aqueous species [Cr(OH)(CO3)22− and Cr(OH)4CO33−] are required to explain Cr(III)-carbonate reactions in a wide range of pH, CO2(g) partial pressures, and bicarbonate and carbonate concentrations. Calculations based on density functional theory support the existence of these species. The log 10 K° values of reactions involving these species [{Cr(OH)3(am) + 2CO2(g)Cr(OH)(CO3)22−+2H+} and {Cr(OH)3(am) + OH+CO32− Cr(OH)4CO33−}] were found to be −(19.07±0.41) and −(4.19±0.19), respectively. No other data on any Cr(III)-carbonato complexes are available for comparisons.  相似文献   

13.
Unsaturated heteropolyanions (HPA) [PW11O39]7− stabilize TiIV hydroxo complexes in aqueous solutions (Ti: PW11 [PW11O39]7−⪯12, pH 1–3). Spectral studies (optical,17O and31P NMR, and IR spectra) and studies by the differential dissolution method demonstrated that TiIV hydroxo complexes are stabilized through interactions of polynuclear TiIV hydroxo cations with heteropolyanions [PW11TiO40 5− formed. Depending on the reaction conditions, hydroxo cations Ti n−1O x H y m+ either add to oxygen atoms of the W−O−Ti bridges of the heteropolyanions to form the complex [PW11TiO40·Ti n−1O x H y ] k− (at [HPA]=0.01 mol L−1) or interact with TiIV of the heteropolyanions through the terminal o atom to give the polynuclear complexes [PW11O39Ti−O−Ti n−1O x H y ]q− (at [HPA]=0.2 mol L−1). When the complexes of the first type were treated with H2O2, TiIV ions added peroxo groups. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 914–920, May, 1997.  相似文献   

14.
The efflorescence and deliquescence processes of Mg(NO3)2 aerosol particles deposited on ZnSe substrate have been investigated through in situ Fourier transform infrared-attenuated total reflection (FTIR-ATR) technique at the molecular level. At relative humidity (RH) of ∼3%, Mg(NO3)2 particles existed as amorphous states. The amorphous Mg(NO3)2 particles were transformed into crystalline Mg(NO3)2 · nH2O (n ≤ 5) with slight increasing of RH. Thermodynamically stable Mg(NO3)2·6H2O crystals were gradually formed on the particle surface and started to be dissolved at the saturation point (∼53% RH). At the same time, a continuous phase transition from Mg(NO3)2 · nH2O (n≤5) to Mg(NO3)2·6H2O occurred on the particle surface. This led the solid particles to completely deliquesce at 76% RH, which was much higher than the saturation point of 53% RH. In the efflorescence process, Mg(NO3)2 droplets entered into the supersaturated region due to the gradual evaporation of water. Finally, amorphous particles were formed when RH decreased below 5%. In the FTIR-ATR spectra of the supersaturated Mg(NO3)2 droplets, the absorbance of the symmetric stretching vibration of NO 3 (v 1- NO 3 ) clearly became stronger. It resulted from the continuous formation of solvent share ion pairs (SIPs), and even the contact ion pairs (CIPs) between Mg2+ and NO 3 . Supported by the Trans-Century Program Foundation for the Talents by the Ministry of Education of China, the National Natural Science Foundation of China (Grant Nos. 20073004, 20473012, and 20673010), the 111 Project (B07012), and the State Key Laboratory of Physical Chemistry for Solid Surface of Xiamen University  相似文献   

15.
Synthesis and characterization of a new Pt(II) complex with the amino acid L-alliin (S-allyl-L-cysteine sulfoxide, C6H11NO3S) are described. Elemental and mass spectrometric analyses of the solid complex are consistent with [PtCl2(alliin)], or [PtCl2(C6H11NO3S)]. 13C nuclear magnetic resonance (NMR), [1H–15N] two dimensional (2D) NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and S atoms. The complex is very soluble in dimethyl sulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented moderate cytotoxic activity, inducing about 40% cell death at a concentration of 400 μmol ·?L?1.  相似文献   

16.
An experimental study on the removal of NOx in a simulated vehicle exhaust gas has been carried out using point to plane and multipoint to plane DBD corona reactors. Hydrocarbon (C3H6) and NOx by-products were systematically investigated with a Gas Chromatography coupled to a Mass Spectrometry (GC/MS). NOx (NO and NO2) and CO output were also monitored with a gas analyzer in order to complete the mass balance. 18O tracer technique analyzes is applied to investigate the mechanism of propylene decomposition. From the plasma chemical reaction pathway proposed, it is apparent that the oxygen activation is one of the important steps for initiating the oxidation processes and the R-NOx formation. We present data for the reaction of the (N2/O2/C3H6/CO2NO/H2O system in the corona discharge reactors mentioned above. This system has been shown to generate a significant amount of aldehyde. CH3NO2 and CH3ONO2 are the main R-NOx compounds produced. Reactant composition and discharge energy densities (controlled by a numerical oscilloscope) were the operating parameters under study in wet and dry air mixture. Water vapors played an important role in NOx removal (especially in NO2 removal) via the reaction forming HNO3. Therefore, in wet-gas mixture supplied reactors the highest removal rates of NOx were as high as 30%, while in dry-gas only 15%. Different dielectric materials such as Al2O3/SiO2 and TiO2 on Al2O3/SiO2 support have been used.  相似文献   

17.
Abstract

The fully deprotonated anion of 1,3,5-benzene-triphosphonic acid 1,3,5-C6H3[PO32?]3 gives rise to deceptively simple 1H and 31P NMR spectra due to a corresponding [AX]3 spin system. The 13C{1H} NMR spectrum reveals two 13C isotopomers which are identified via AXX′2 systems. Results from analysis and iteration are described.  相似文献   

18.
A new platinum(II) complex with deoxyalliin was synthesized and characterized by chemical and spectroscopic techniques. Elemental and mass spectrometry analyses of the solid complex fit to the composition [Pt(C6H11NO2S)Cl2]·H2O. 13C NMR, 15N NMR and infrared spectra of the complex are consistent with coordination of deoxyalliin to Pt(II) through the nitrogen and sulfur atoms forming a square-planar geometry. The complex is soluble in dimethylsulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells, a human cervix adenocarcinoma-derived cell line. The results were compared with those of a palladium(II) complex previously described.  相似文献   

19.
Stabilised titania sols were prepared using an additive free particulate sol-gel route, via electrostatic stabilisation mechanism, with various processing parameters. Peptisation temperature, 50°C and 70°C, and TiO2 concentration, 0.1, 0.2 and 0.4 molar, were chosen as processing parameters during sol preparation. Results from TiO2 particle size and zeta potential of sols revealed that the smallest titania hydrodynamic diameter (13 nm) and the highest zeta potential (47.7 mV) were obtained for the sol produced at the lower peptisation temperature of 50°C and lower TiO2 concentration of 0.1 M. On the other hand, between the sols prepared at 70°C, smaller titania particles (20 nm) and higher zeta potential (46.3 mV) were achieved with increasing TiO2 concentration up to 0.4 M. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) results of produced powders annealed at different temperatures showed that the 300°C annealed powder made from 0.1 M sol prepared at 50°C was a mixture of anatase and brookite, corresponding to a major phase of anatase (∼95% estimated), with the smallest average crystallite size of 1.3 nm and the highest specific surface area (SSA) of 193 m2/g. Furthermore, increasing TiO2 concentration up to 0.4 molar for the sols prepared at 70°C resulted in decreasing the average crystallite size (1.9 nm at 300°C) and increasing SSA (116 m2/g at 300°C) of the powders annealed at different temperatures. Anatase-to-rutile phase transformation temperature was increased with decreasing peptisation temperature down to 50°C, whereas TiO2 concentration had no effect on this transition. Anatase percentage increased with decreasing both peptisation temperature and TiO2 concentration. Such prepared powders can be used in many applications in areas from photo catalysts to gas sensors.  相似文献   

20.
A new red-emitting long afterglow Sr3Al2O6: Eu2+, Pr3+ phosphor was synthesized by sol–gel methods using Sr(NO3)2, Al(NO3)3·9H2O, Eu(NO3)3 and Pr(NO3)3 as raw materials. The crystalline structure of the phosphor powders were characterized by X-ray diffraction. Luminescent properties of the phosphor powders were analyzed by the fluorescence spectrophotometer. Sr3Al2O6: Eu2+, Pr3+ phosphor powders with single Sr3Al2O6 phase were prepared at 1200 °C for 2 h in the reducing atmosphere. Pr3+ doped made the light intensity and the light-lasting time of Sr3Al2O6: Eu2+, Pr3+ phosphors improved. The emission peaks of the Sr3Al2O6: Eu2+, Pr3+ phosphor powders lay at 612 nm with the excitation of 472 nm and the longest afterglow time could last for about 15 min at Pr3+ content of 0.06.  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