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1.
Cation-deficient lanthanum manganite oxides with 0.8  La/Mn  1.25 were synthesized using a multi-step decomposition of gel precursors and investigated from experimental and theoretical point of view. The XRD (X-Ray Diffraction) analysis of the mixed LaMnO3 oxide crystal concludes to a hexagonal structure, space group R-3c, excluding the presence of pure oxides such as La2O3, Mn2O3, or MnO2 whatever the ratio La/Mn is. Oxides with nominal formulae La1?xMnO3+y and LaMn1?xO3+y contain more than one defect structure involving valence defect (holes h), anionic vacancies as well as cationic vacancies in A and B sublattices of the perovskite structure. With the increase of La or Mn non-stoichiometry, the oxygen content y decreases more with La-deficient compositions than with Mn-deficient ones. The La/Mn ratio influences strongly the relationship between [h], [VO], [VLa?] and [VMn?].The DFT-GGA (Density functional Theory, Generalized-Gradient Approximation) simulation of these compounds using VASP (Vienna Ab-initio Simulation Package) concludes that the electronic structure for the optimized stoichiometric La6Mn6O18 is not optimal, relative to that expected considering Mn(III) ions with four alpha electrons each. The non-stoichiometry is the easiest way of reducing the Jahn–Teller instability by depopulating the half-filled eg orbitals. A partial oxidation is then stabilizing. Creation of defects, either an O insertion or a cationic vacancy, allows finding an ideal count. In the case of pure cationic defects (missing a La(III) or a Mn(III) cation), the amount of vacancies is one missing cation upon twelve. The compact nature of lanthanum manganite oxide does not allow oxygen insertion within the bulk structure and oxidation can only be achieved at the surface without O penetration. The formation of antisites is endothermic. The creation of mixed vicinal vacancies, one oxygen and one cationic vacancy (La or Mn), is exothermic for a concentration of defects of one defect per twelve cations.  相似文献   

2.
MgCuAl layered double hydroxides (LDHs) with a hydrotalcite like structure containing different proportions of Mg2+ and Cu2+ cations have been prepared. Thermogravimetry and X-ray diffraction data indicated that the transformation of LDH into mixed oxides is effective after calcination at 723 K, irrespective of the composition. The acid-base properties of these mixed oxides have been investigated using adsorption microcalorimetry and X-ray photoelectron spectroscopy with NH3 (for acidity) and SO2 (for basicity) as probe molecules. Their catalytic behaviour for the conversion of cyclohexanol has been tested. The acid-base properties and the selectivity of catalysts has been related to their composition. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

3.
采用了BET、XRD、TG-DSC、TPR、FTIR、微量量热吸附和异丙醇催化反应等测试方法,对以共沉淀法合成的水滑石(HT)和类水滑石(HTLcs)为前体制备的4Mg/Al、3Ni/Mg/Al、3.5Ni/0.5Mg/Al和4Ni/Al混合氧化物和前体进行了研究。测定表明:制备的混合氧化物的比表面积较大、随着镍含量的增大而降低。由于Ni2+离子的氧化还原属性,Ni2+离子进入后,削弱了HT层对阴离子的键合能力,从而使得样品的热分解温度及热稳定性降低,导致焙烧后  相似文献   

4.
以共沉淀法合成的水滑石(HT)和类水滑石(HTLc)为前体制备了镁铝、钴铝、钴镁铝混合氧化物,采用了BET、XRD、TG-DTA、TPR、FTIR和微量量热吸附及异丙醇催化反应进行了研究。结果表明:以HT和HTLc为前体制备的混合氧化物,其比表面积较大、并随着钴含量的增加而降低。在HT中引入Co2+离子后,由于Co2+离子的氧化还原属性,削弱了水滑石层对阴离子的键合能力,从而使其热分解温度及热稳定性降低,导至焙烧后生成的混合氧化物的比表面积比不含钴的2Mg/Al混合氧化物的低。在TPR过程中,镁铝混合氧化物不被还原,而含钴的混合氧化物的还原是经由Co3+ → Co2+ → Co0的过程。混合氧化物表面含有酸性位和碱性位,并随着钴含量的变化而得到调变。含钴氧化物样品的表面以L酸为主和含有很少量的B酸。异丙醇催化反应生成丙酮的选择性最高,表明样品表面的氧化还原位是主要的,随着钴的加入及含量的增大,异丙醇催化反应的转化率也是增大的。  相似文献   

5.
The reaction of the chloride form of lithium aluminum layered double hydroxide (Li-Al LDH) with an aqueous solution of NaFeEdta · 2H2O (pH 3.7) was studied. Anion exchange of chloride ions for [FeEdta]? anions almost does not occur under the conditions of our experiment. Increasing pH to 8.0 initiates anion exchange of chloride ions for [Fe(OH)Edta]2? anions, generating Li-Al LDH, whose structure is built of metal-hydroxide layers [LiAl2(OH)6]+ and layers containing [Fe(OH)Edta]2? anions and water molecules. Thermolysis of Li-Al-[Fe(OH)Edta] was studied in an inert atmosphere and in vacuo. Heating to 220°C mainly eliminates interlayer water molecules. A further rise in temperature induces the dehydration of metal-hydroxide layers and OH groups of [Fe(OH)Edta]2? anions and the destruction of the organic component of the anionic complex. At 375°C, an X-ray amorphous product is formed, in which most iron is in the form of Fe2+ cations. With increasing thermolysis temperature to 450°C, a magnetically ordered solid phase containing Fe2+ cations appears. Further temperature elevation to 550°C generates an α-Fe phase.  相似文献   

6.
Influence of the nature of a doubly charged cation in the layered double hydroxides (LDH) on the conditions of formation and properties of mixed oxide phase MAlO x (M = Mg2+, Zn2+ and Ni2+), its ability to reconstruct the structure of the original precursor under contact with water has been studied. Hydrotalcite-like compounds and corresponding oxides with different M2+: M3+ ratio were investigated by XRD, TEM, TG-DTG-DTA, 27Al NMR, N2 adsorption, and differentiating dissolution. It has been found that the nature of the cation M2+ influences the conditions of LDH thermal decomposition, structural and textural characteristics of the formed mixed oxides. The obtained data can be used to synthesize the oxide supports with desired acid-base and adsorption properties.  相似文献   

7.
The present study deals with preparation and characterization of spinel mixed oxide systems NiM 2 III O4, where MIII?=?FeIII, CrIII. In order to obtain 50% NiFe2O4/50% SiO2 and 50% NiCr2O4/50% SiO2 nanocomposite, we have used a versatile route based on the thermal decomposition inside the SiO2 matrix, of some particular precursors, coordination compounds of the involved MII and MIII cations with dicarboxylate ligands. The ligands form in the redox reaction between metal nitrates mixture and 1,3-propanediol at the heating around 140?°C of the gels (tetraethylorthosilicate?Cmetal nitrates?C1,3-propanediol?Cwater). The as-obtained precursors, embedded in silica gels, have been characterized by FT-IR spectrometry and thermal analysis. Both precursors thermally decompose up to 350?°C leading to the formation of the corresponding metal oxides inside the silica matrix. X-ray diffraction of the annealed powders have evidenced the formation of NiFe2O4 starting with 600?°C, and NiCr2O4 starting with 400?°C. This behavior can be explained by the fact that, by thermal decomposition of the Fe(III) carboxylate at 300?°C, the spinelic phase ??-Fe2O3 is formed, which interacts with the NiO, forming the ferrite nuclei. By thermal decomposition of chromium carboxylate, a nonstoichiometric chromium oxide (Cr2O3+x ) is formed. In the range 380?C400?°C, Cr2O3+x turns into Cr2O3 which immediately interacts with NiO leading to the formation of nickel chromites nuclei inside the pores of silica matrix. Both spinels have been obtained as nanocrystalites homogenously dispersed as resulted from XRD and TEM data.  相似文献   

8.
The synthesis of upconverting hydrogel nanocomposites by base‐catalyzed thiol‐ene click reaction between 10‐undecenoic acid capped Yb3+/Er3+‐doped NaYF4 nanoparticles and pentaerythritol tetrakis(3‐mercaptopropionate) (PETMP) as tetrathiol monomer is reported. This synthetic strategy for nanocomposite gels is quite different from works where usually the preformed gels are mixed with the nanoparticles. Developing nanocomposites by surface modification of capping ligands would allow tuning and controlling of the separation of the nanoparticles inside the gel network. The hydrogel nanocomposites prepared by thiol‐ene click reaction show strong enhancement in luminescence intensity compared to 10‐undecenoic acid‐capped Yb3+/Er3+‐doped NaYF4 nanoparticles through the upconversion process (under 980 nm laser excitation). The hydrogel nanocomposites display strong swelling characteristics in water resulting in porous structures. Interestingly, the resulting nanocomposite gels act as templates for the synthesis of dendrimer‐like Au nanostructures when HAuCl4 is reduced in the presence of the nanocomposite gels.  相似文献   

9.
Low cost adsorption technology offers high potential to clean up laundry rinsing water. From an earlier selection of adsorbents (Schouten et al. 2007), layered double hydroxide (LDH) proved to be an interesting material for the removal of anionic surfactant, linear alkyl benzene sulfonate (LAS) which is the main contaminant in rinsing water. The main research question was to identify the effect of process parameters of the LDH synthesis on the stability of the LDH structure and the adsorption capacity of LAS. LDH was synthesized with the co-precipitation method of Reichle (1986); a solution of M2+(NO3)2 and M3+(NO3)3 and a second solution of NaOH and Na2CO3 were pumped in a beaker and mixed. The precipitate that was formed was allowed to age and was subsequently washed, dried and calcined. The process parameters that were investigated are the concentration of the initial solutions, M2+/M3+ ratio and type of cations. The crystallinity can be improved by decreasing the concentration of the initial solutions; this also decreases the leaching of M3+ from the brucite-like structure into the water. The highest adsorption capacity is obtained for Mg2+/Al3+ with a ratio 1 and 2 because of the higher charge density compared to ratio 3. Storing the LDH samples in water resulted in a reduction of adsorption capacity and a decrease in surface area and pore volume. Therefore, LDH is not applicable in a small device for long term use in aqueous surroundings. The adsorption capacity can be maintained during storage in a dry N2 atmosphere.  相似文献   

10.
The reactions of Fe(CN)5dpa3? and Ru(NH3)5dpa2+ (dpa = 4,4′-dipyridylamine) with Co(edta)? have been investigated kinetically. For Fe(CN)5dpa3? complex, a linear relationship was observed between the pseudo-First-order rate constants and the concentrations of Co(edta) which leads to a specific rate 0.876 ± 0.006 M?1S?1 at T = 25°C., μ = 0.10 M and pH = 8.0. For the Ru(NH3)5dpa2+ system, the plots kobs vs [Co(edta)?] become nonlinear at concentrations of Co(edta) greater than 0.01 M and the reaction is interpreted on the basis of a mechanism involving the formation of an ion pair between Ru(NH3)5dpa2+ and Co(edta)? followed by electron transfer from Ru(II) to Co(III). The nonlinear least squares fit of the kinetic results shows that Qip = 10.6 ± 0.7 M?1 and ket = 93.9 ± 0.7 s?1 at pH = 8.0,μ = 0.10 M and T = 25°C.  相似文献   

11.
Hydrogen‐bond assembly of tripod‐like organic cations [H3‐MeTrip]3+ (1,2,3‐tri(4′‐pyridinium‐oxyl)‐2‐methylpropane) and the hexa‐anionic complex [Zr2(oxalate)7]6? leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the material at the single‐crystal level during a sorption cycle. The framework crystal structure was found to remain the same for the native compound, its activated phase, and after guest resorption. The channels exhibit affinities for polar organic molecules ranging from simple alcohols to aniline. Halogenated molecules and I2 are also taken up from hexane solutions by this unique supramolecular framework.  相似文献   

12.
Composition‐tailored Mn1?xRuxO2 2 D nanosheets and their reassembled nanocomposites with mesoporous stacking structure are synthesized by a soft‐chemical exfoliation reaction and the subsequent reassembling of the exfoliated nanosheets with Li+ cations, respectively. The tailoring of the chemical compositions of the exfoliated Mn1?xRuxO2 2 D nanosheets and their lithiated nanocomposites can be achieved by adopting the Ru‐substituted layered manganese oxides as host materials for exfoliation reaction. Upon the exfoliation–reassembling process, the substituted ruthenium ions remain stabilized in the layered Mn1?xRuxO2 lattice with mixed Ru3+/Ru4+ oxidation state. The reassembled Li–Mn1?xRuxO2 nanocomposites show promising pseudocapacitance performance with large specific capacitances of approximately 330 F g?1 for the second cycle and approximately 360 F g?1 for the 500th cycle and excellent cyclability, which are superior to those of the unsubstituted Li–MnO2 homologue and many other MnO2‐based materials. Electrochemical impedance spectroscopy analysis provides strong evidence for the enhancement of the electrical conductivity of 2 D nanostructured manganese oxide upon Ru substitution, which is mainly responsible for the excellent electrode performance of Li–Mn1?xRuxO2 nanocomposites. The results underscore the powerful role of the composition‐controllable metal oxide 2 D nanosheets as building blocks for exploring efficient electrode materials.  相似文献   

13.
The nanocomposites based on cobalt oxide and nitrogen-doped carbon nanofibers (N-CNFs) with cobalt oxide contents of 10–90 wt% were examined as catalysts in the CO oxidation and supercapacity electrodes. Depending on Со3О4 content, such nanocomposites have different morphologies of cobalt oxide nanoparticles, distributions over the bulk, and ratios of Со3+/Co2+ cations. The 90%Со3О4-N-CNFs nanocomposite showed the best activity because of the increased concentration of defects in N-CNFs. The capacitance of electrodes containing 10%Со3О4-N-CNFs was 95 F/g, which is 1.7 times higher than electrodes made from N-CNFs.  相似文献   

14.
Thiosilicates of the Rare‐Earth Elements: III. KLa[SiS4] and RbLa[SiS4] – A Structural Comparison Pale yellow, platelet shaped, air‐ and water resistant single crystals of KLa[SiS4] derived from the reaction of lanthanum (La) and sulfur (S) with silicon disulfide (SiS2) in a molar ratio of 2 : 3 : 1 with an excess of potassium chloride (KCl) as flux and source of potassium ions in evacuated silica ampoules at 850 °C within seven days. The analogous reaction utilizing a melt of rubidium chloride (RbCl) instead also leads to yellow comparable single crystals of RbLa[SiS4]. The potassium lanthanum thiosilicate crystallizes monoclinically with the space group P21/m (a = 653.34(6), b = 657.23(6), c = 867.02(8) pm, β = 107.496(9)°) and two formula units per unit cell, while the rubidium lanthanum thiosilicate has to be assigned orthorhombically with the space group Pnma (a = 1728.4(2), b = 667.23(6), c = 652.89(6) pm) and four formula units in its unit cell. In both compounds the La3+ cations are surrounded by 8+1 sulfide anions in the shape of tricapped trigonal prisms. The Rb+ cations in RbLa[SiS4] show a coordination number of 9+2 relative to the S2? anions, which form pentacapped trigonal prisms about Rb+. This coordination number, however, is apparently too high for the K+ cations in KLa[SiS4], so that they only exhibit a bicapped trigonal prismatic environment built up by eight S2? anions. The isolated thiosilicate tetrahedra [SiS4]4? of the rubidium compound are surrounded by La3+ both edge‐ and face‐capping, but terminal as well as edge‐ and face‐spanning by Rb+. In the potassium compound there is no change for the La3+ environment about the [SiS4]4? tetrahedra, but the K+ cations are only able to attach terminal and via edges. The whole structure is built up by anionic equation/tex2gif-stack-1.gif{La[SiS4]}? layers that are separated by the alkali metal cations. In direct comparison the two thiosilicate structures can be regarded as stacking variants.  相似文献   

15.
Complex vanadium and titanium oxides modified by copper ions are studied by the electrochemical and ESR methods. Oxides Cu x V2?y Ti y O5?δ·nH2O (0<y<1.33) have a layered structure and oxides Cu x Ti1?y V y O5+δ·nH2O (0<y<0.25), an anatase structure. The intercalation of cations Cu2+ into the hydrates leads to oxidation of V4+. According to ESR data, V4+ exists in the oxides in the form of VO2+ and an octahedral surround of oxygen (V4+?O6), respectively. The electroreduction of ions of d-elements and chemisorbed oxygen in the oxides is analyzed. The intercalation of cations Cu2+ alters the content of V4+ and the chemisorption ability of the oxides. Possible reasons for this phenomenon are discussed.  相似文献   

16.
In the present study, a novel environment-friendly hybrid nanocomposite of Banana Peel Cellulose-g-poly(acrylic acid)/PVA (BPC-g-PAA/PVA) hydrogel and Layered double hydroxides (LDH) nanosheets was developed using in situ graft polymerization for slow release of NP (nitrogen, phosphorous) fertilizers and water retention. The hybrid nanocomposite hydrogel containing NP fertilizers was characterized using FTIR, and SEM. The effects of pH changes and different saline solutions on the swelling behavior, fertilizer release and water retention properties of the nanocomposite were investigated.The nanocomposite hydrogel showed a pH dependent swelling, as in the pH range of 7–10, the hydrogel had higher water absorbency. However, pH had opposite effects on the release of fertilizers. Phosphorus release had an increasing trend from pH 2 to 7 and it reached its maximum value at normal pH while nitrogen had a higher release rate at acidic pH and by increasing pH from 2 to 7, the release of nitrogen decreased gradually. Water absorption and fertilizer release of hydrogel was influenced by different cations in the order of Ca2+ < K+ < Na+. Water retention study in loamy sand soil showed that the nanocomposite hydrogel significantly improved the water retention of the soil for a longer period of time, compared to neat BPC-gPAA. This result indicated that incorporation of LDH nanosheets in hydrogel matrix improved its water retention property. The obtained results revealed that the nanocomposite of BPC-g-PAA/PVA hydrogel and LDH nanosheets can be a promising controlled release fertilizer formulation with enhanced water retention properties for agricultural applications.  相似文献   

17.
We report the binding of chromate, a toxic heavy metal ion to the macrocyclic host molecule, cucurbituril using density functional theory. Due to the anionic nature of the guest molecule and the portals of the host molecule, we propose that the binding mechanism should be assisted by cations. The calculated barrier for chromate binding to cucurbituril is found to be?~17?kcal?mol?1. The large barrier can be attributed to portal opening of the host molecule, electrostatic repulsion between the guest molecule and the portals of the host molecule and the solvent re-organization around guest molecule.  相似文献   

18.
Fluoroalkyl end‐capped vinyltrimethoxysilane oligomer [RF‐(VM)nRF] reacted with boric acid to afford the corresponding fluorinated oligomeric silica/boric acid nanocomposite [RF‐(VM? SiO2)nRF/B(OH)3] fine particles with mean diameter: 36–105 nm. The obtained RF‐(VM? SiO2)nRF/B(OH)3 nanocomposites were applied to the encapsulation of low molecular weight organic compounds such as diphenylsilanediol, 1,1′‐bi‐2‐naphthol, 4,4′‐biphenol, bisphenol A, bisphenol F, bisphenol AF, biphenyl, dibenzyl, and pentaerythritol into these nanocomposite cores to provide the corresponding fluorinated oligomeric silica/boric acid nanocomposites—encapsulated these organic molecules. Interestingly, the obtained nanocomposites were found to exhibit no weight loss behavior corresponding to the contents of these guest molecules even after calcination at 800 °C, although these nanocomposites were isolated through no purification process. The RF‐(VM? SiO2)nRF nanocomposites—encapsulated these organic guest molecules were prepared under similar conditions. However, it was demonstrated that these nanocomposites can provide the clear weight loss corresponding to the contents of these guest molecules in the nanocomposites after calcination at 800 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3835–3845  相似文献   

19.
Perovskite-structure oxides La1?x Sr x FeO3?y (x = 0, 0.2, 0.6, 1) were synthesized by the mechanochemical method. In order to refine the stoichiometric composition and the charge state of ions, these samples were studied by X-ray photoelectron spectroscopy (XPS). An investigation of perovskites with x = 0, 0.2, and 0.6 in air at room temperature showed that these samples do not contain oxygen vacancies (y = 0), i.e., they are fully oxidized. Hence, to produce electrical neutrality, these samples should contain iron(4+) cations in an amount proportional to the degree of substitution (x) of strontium(2+) for lanthanum(3+). However, no Fe4+ cations were found in the oxides. All perovskites contain only Fe3+ cations, oxygen ions O2? along with oxygen ions with reduced electron density (O?). These data provid evidence of the possible electron density redistribution from oxygen ions to iron cations. The fact that the oxides contain oxygen ions with reduced electron density suggests that weakly bound lattice oxygen in substituted perovskites is represented by O? ions.  相似文献   

20.
The crystal structure of complex [Mg(H2O)6][VO(edta)] · 3.5H2O (I) was determined by X-ray diffraction study. The crystals are monoclinic, a = 6.779 Å, b = 13.373(6) Å, c = 25.054 Å, β = 96.55°, Z = 4, space group P21. The unit cell contains two independent [VO(edta)]2? anions, two independent [Mg(H2O)6]2+ cations, and seven crystal-water molecules. The coordination polyhedron of each vanadium atom is formed by five donor atoms of the edta ligand (2N + 3O) (V(1)-N(1), 2.278 Å; V(1)-N(2), 2.149 Å; V(2)-N(3), 2.301 Å; V(2)-N(4), 2.165 Å; V-O(acet), 2.00 ± 0.02 Å) and the oxygen atom of the oxo group (V-O, 1.60 ± 0.01 Å). The edta ligands and the vanadium atom form three glycinate rings: two R-type rings and one G-type ring (one acetate branch remains free), as well as an E-type ring with an asymmetric gauche configuration. The [Mg(H2O)6] cations are slightly distorted octahedra (Mg-O, 2.013–2.132 Å, the OMgO angles are 86.6°–94.2°). The H2O molecules form a bifurcate system of H-bonds. The crystals of compound I belong to OD-type structures with an incomplete ordering of layers.  相似文献   

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