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1.
The perovskite CaCu3Ti4O12 (CCT) has been obtained after calcination of oxalate precursors at 900–1000 °C in air. Those precursors are prepared using a soft chemistry method, the coprecipitation. The oxalate powders consist of disk-like particles of 2–3 μm diameter and 300–400 nm thickness. By varying the ratio of the initial amounts of metal chlorides, additional phases (CaTiO3, TiO2 and CuO) could be obtained besides CCT. The corresponding multiphased ceramics present improved dielectric properties.  相似文献   

2.
采用柠檬酸络合法制备Fe2O3/LaFeO3复合氧化物,将该氧化物作为化学链制氢过程的载氧体,在反应温度为900 ℃、常压下,对Fe2O3/CH4(剂烷比)、进水量、金属负载量进行了考察。结果表明,剂烷比为2:1、进水量为0.1 mL、质量分数15%Fe时载氧体性能最好,甲烷转化率达到60%,单次循环氢气产量为45 mL。将该评价结果与XRD和H2-TPR表征结果进行关联发现,反应过程的活性位不是金属氧化物,而是吸附氧,而且吸附氧越容易还原,甲烷转化率和氢气产量越高。通过连续60次还原-氧化循环发现,该载氧体上甲烷转化率和氢气产量比较稳定,循环后仍然保持钙钛矿结构。  相似文献   

3.
F.R. Sale 《Thermochimica Acta》1979,30(1-2):163-171
The heat capacities of the tungsten oxides WO3, W20O58, W18O49 and WO2 have been measured over the temperature range 340–999 K using differential scanning calorimetry. The lower oxides were prepared by controlled reduction of WO3 in H2/H2O gas atmospheres. Previous calorimetric work on WO3 is confirmed in the temperature range 340–800 K, however, significant increases in heat capacity were observed in the range 800–999 K prior to the orthorhombic—tetragonal phase transition. W20O58 is shown to behave similarly to WO3. A high temperture phase change is evident, however, this appears to be complete by 970–990 K. The measured values of heat capacity for W18O49 are in close agreement with estimated data for W18O49. There is no evidence of any phase transitions for this oxide in the temperature range studied. The heat capacity data for WO2 confirm previous drop calorimetry measurements and give no evidence of any phase changes for WO2 in the temperature range 340–990 K.  相似文献   

4.
The complexes, M[M(C2O4)3xH2 O, where x=4 for M=Cr(III), x=2 for M=Sb(III) and x=9 for M=La(III) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR and electronic spectral data, conductivity measurement and powder X-ray diffraction (XRD) studies. The chromium(III)tris(oxalato)chromate(III)tetrahydrate (COT), Cr[Cr(C2 O4)3]·4H2O, released water in a stepwise fashion. Removal of the last trace of water was accompanied by a partial decomposition of the oxalate group. Thermal investigation using TG, DTG and DTA techniques in air produced Cr2O3 at 858°C through the intermediate formation of Cr2O3 and CrC2O4 at around 460°C. While DSC study in nitrogen up to 670°C produced a mixture of Cr2O3 and CrC2O4. In antimony(III)tris(oxalato)antimonate(III)dihydrate (AOD), Sb[Sb(C2O4)3]·3H2O the dehydration took place during the decomposition of precursor at 170–290°C and finally at ca. 610°C Sb2 O5 along with trace amounts of Sb2O4 were produced. Trace amount of Sb2O3 and Sb along with Sb2O is proposed as the end product at 670°C of AOD in nitrogen. The oxide La2O3 is formed at 838°C from the study with TG, DTG and DTA in air of lanthanum(III)tris(oxalato)lanthanum(III)nonahydrate (LON), La[La(C2O4)3]·9H2O. Intermediate dioxycarbonate, La2O2CO3 was generated at 526°C prior to its decomposition to lanthanum oxide in air; whereas in N2 the formation of La2(CO3)3 at 651°C was proposed. The thermal parameters have been evaluated for each step of the dehydration and decomposition of COT, AOD and LON using five non-mechanistic equations i.e. Flynn and Wall, Freeman and Carroll, Modified Freeman and Carroll, Coats–Redfern and MacCallum–Tanner equations. Kinetic parameters, such as, E*, ko, ΔH*, ΔS* etc. were also supplemented by DSC studies in nitrogen for all the three complexes. Some of the intermediate species have been identified by analytical and powder XRD studies. Tentative schemes has been proposed for the decomposition of all three compounds in air and nitrogen.  相似文献   

5.
The effects of doping of Co3O4with MgO (0.4–6 mol%) and V2O5 (0.20–0.75 mol%) on its surface and catalytic properties were investigated using nitrogen adsorption at −196°C and decomposition of H2O2 at 30–50°C. Pure and doped samples were prepared by thermal decomposition in air at 500–900°C, of pure basic cobalt carbonate and basic carbonate treated with different proportions of magnesium nitrate and ammonium vanadate. The results revealed that, V2O5 doping followed by precalcination at 500–900°C did not much modify the specific surface area of the treated Co3O4 solid. Treatment of Co3O4 with MgO at 500–900°C resulted in a significant increase in the specific surface area of cobaltic oxide. The catalytic activity in H2O2 decomposition, of Co3O4 was found to suffer a considerable increase by treatment with MgO. The maximum increase in the catalytic reaction rate constant (k) measured at 40°C on Co3O4 due to doping with 3 mol% MgO attained 218, 590 and 275% for the catalysts precalcined at 500, 700 and 900°C, respectively. V2O5-doping of Co3O4 brought about a significant progressive decrease in its catalytic activity. The maximum decrease in the reaction rate constant measured at 40°C over the 0.75 mol% V2O5-doped Co3O4 solid attained 68 and 93% for the catalyst samples precalcined at 500 and 900°C, respectively. The doping process did not modify the activation energy of the catalyzed reaction but much modified the concentration of catalytically active constituents without changing their energetic nature. MgO-doping increased the concentration of CO3+–CO2+ ion pairs and created Mg2+–CO3+ ion pairs increasing thus the number of active constituents involved in the catalytic decomposition of H2O2. V2O5-doping exerted an opposite effect via decreasing the number of CO3+–CO2+ ion pairs besides the possible formation of cobalt vanadate.  相似文献   

6.
Hydrothermal reaction of copper(II) acetate, 2,2′-bipyridine (bipy) and NH4VO3 at 170 °C lead to a new layered polyoxovanadate with organically covalent-bonded copper(II) complex, Cu2(bipy)2V6O17 (1). Cu2(bipy)2V6O17 (1) is a new copper(II) vanadium(V) oxide featuring a new layered architecture, in which the V2O7 dimeric units and the cyclic tetranuclear V4O12 cluster units are interconnected via corner sharing into a unique one-dimensional {V6O17}4− anionic chain, such chains are further bridged by {Cu(bipy)}2+ complex cations into a 010 organic–inorganic hybrid layer.  相似文献   

7.
The solid state formation of lithium manganese oxides has been studied from the thermal decomposition of mixtures Li2CO3–Mn3O4 with XLi (lithium cationic fraction)=0.33 (LiMn2O4), 0.50 (LiMnO2) and 0.66 (Li2MnO3). The analysis of the reactivity has been performed mainly by thermoanalytical (TG/DSC) and diffractometric (XRPD) techniques either on physical mixtures and on mixtures subjected to mechanical activation by high energy milling. At XLi=0.33, the cubic lithium manganese spinel oxide (LiMn2O4) forms in air. TG measurements showed that the reaction starts at a considerably lower temperature in the activated mixture. By variable temperature X-ray diffraction it has been assessed that, upon mechanical activation, LiMn2O4 forms directly and its formation is completed within 700 °C whereas, starting from a physical mixture, the formation goes through Mn2O3 and is complete only at 800 °C. At T>820 °C LiMn2O4 reversibly decomposes to LiMnO2 and Mn3O4 with an enthalpy of 30.05 kJ mol−1 of LiMn2O4. At XLi=0.50, by annealing under nitrogen flow for 6 h at 650 °C the activated mixture, the orthorhombic LiMnO2 is formed. Such a formation goes through a mixture of LiMnO2 and LiMn2O4. The enthalpy of LiMnO2 solid state formation from the activated mixture has been determined to be 57.4 kJ mol−1 of LiMnO2. At XLi=0.66 in air the mechanical activation considerably lowers the temperature within the monoclinic phase Li2MnO3 forms. Besides the reaction enthalpy could be determined as 40.13 kJ mol−1 of Li2MnO3. The reaction, when performed under nitrogen flow, goes through the formation of LiMnO2. Such a first stage of the reaction is affected by the temperature of reaction rather than by mechanical activation. The activation greatly enhances the second stage of the reaction leading from LiMnO2 to Li2MnO3.  相似文献   

8.
The primary crystallization field of a perovskite solid solution Bi1−xSrxMnO3−δ was delimited by calculating the respective phase equilibria in the quaternary Bi–Sr–Mn–O system. The calculations are based on the recent assessment involving all three ternary subsystems, a quaternary liquid approximated as a mixture of Mn, MnO, Mn2O3, SrO and Bi2O3 species with binary Redlich–Kister coefficients and the perovskite phase described in terms of a point defect model allowing Sr2+ for Bi3+ substitution, oxygen vacancy formation and the related Mn3+/Mn4+ mixing on Mn-sublattice. The crystallization path and the composition of the crystallized solid solution are compared with single crystal growth experiments performed by self-flux method from a Bi-rich melt. The crystallization path obtained for a selected feed composition for which the largest and high quality single crystal have been grown, turns out to end very close to the global eutectic point.  相似文献   

9.
B. S. Suresh  D. K. Padma 《Polyhedron》1985,4(12):2067-2068
Silane undergoes thermal decomposition on the surface of “phosphorus pentoxide” ( P4O10) into its elements around 200–400°C. The hydrogen formed partially reduces the P4O10 forming lower oxides of phosphorus and water. Elemental silicon is precipitated as reddish-brown solid, which is separated by dissolving out the phosphorus oxides. Silica and disiloxane are not formed in the reaction.  相似文献   

10.
以LaCo1-xGaxO3为前驱体,还原后得到的Co/La2O3-La4Ga2O9复合氧化物催化剂,用于CO2加氢直接制乙醇。通过XRD、XPS、TPD和TEM等技术对催化剂结构进行了表征,采用微型固定床反应器在230-290℃、3 MPa、空速(GHSV)为3000 mL/(gcat·h)和H2/CO2进料物质的量比为3.0的条件下,考察了该Co/La-Ga-O复合氧化物用于CO2加氢制乙醇的催化性能。结果显示,该Co/La-Ga-O复合氧化物催化剂对生成乙醇具有很高的选择性。与LaCoO3相比,Ga的掺杂可抑制甲烷的形成,促进醇类(特别是乙醇)的生成。当Co/Ga比为7:3时,还原后的LaCo1-xGaxO3催化剂体现出最好的催化性能,CO2转化率为9.8%,总醇选择性达到74.7%,其中,液相产物中的乙醇质量分数可达到88.1%。基于实验结果推测,该催化剂上Co0和Coδ+的协同作用促使CO2选择性加氢生成乙醇。  相似文献   

11.
采用溶胶凝胶法制备了不同γ-Al2O3含量的钛铝复合载体,以此为载体采用浸渍法负载V2O5和WO3制备了一系列催化剂。采用X射线衍射(XRD)、比表面积测定(BET)、程序升温还原(H2-TPR)、高分辨率透射电子显微镜(HRTEM)等表征技术对催化剂表面形态进行分析,同时在模拟氨气选择性催化还原NO(NH3-SCR)的反应条件下,对催化剂的脱硝反应活性和SO2抗中毒进行考察。结果发现,TiO2和γ-Al2O3之间的协同作用使得V2O5-WO3/TiO2-γ-Al2O3催化剂的脱硝效率及活性窗口明显优于单一载体制备的催化剂,表现出了良好的热稳定性和抗SO2毒化能力,特别是V2O5-WO3/TiO2-15% γ-Al2O3在310~460 ℃,NO的转化率均在80%以上,反应窗口最宽。各种表征结果表明,TiO2-γ-Al2O3复合载体中γ-Al2O3高度分散在TiO2上,复合载体具有较大的比表面积,同时具有较强的还原能力。  相似文献   

12.
以十二磷钨杂多酸(Tungstophosphoric acid,H_3PW_(12)O_(40))为基体,分别通过普通浸渍法、溶胶凝胶法和超声浸渍法进行了La3+改性作用,合成了三种固体酸催化剂A-LaPW_(12)O_(40)、B-LaPW_(12)O_(40)/Si O2和C-LaPW_(12)O_(40)。采用X射线荧光光谱(XRF)、孔径比表面积测定、X射线粉末衍射(XRD)、透射电镜(TEM)、红外光谱(FT-IR)、热重(TG)、N2吸附-脱附、NH3程序升温脱附(NH3-TPD)、吡啶吸附红外光谱(Py-FTIR)、X射线光电子能谱(XPS)等方法对合成的催化剂进行了表征,并比较了以上催化剂在用于催化以油酸和甲醇为反应物经酯化反应合成生物柴油时的活性和稳定性。结果表明,B-LaPW_(12)O_(40)/Si O2具有最高催化活性,当甲醇与油酸的物质的量比为8∶1,催化剂用量为反应物总质量的2%,反应温度为65℃,反应1 h后,油酸的转化率即高达93%。循环使用B-LaPW_(12)O_(40)/Si O2催化剂六次后,油酸的转化率仍高达86.4%。B-LaPW_(12)O_(40)/Si O2的高催化活性和稳定性可归因于在溶胶凝胶的转化过程中,作为硅源材料的四乙氧基硅(TEOS)易在酸性条件下发生水解反应形成Si O2网络,进而Si O2网络中的硅醇键与H_3PW_(12)O_(40)中的H+发生配位作用,生成具有强静电吸附力的(≡Si-OH2+)(H2PW12O-40)络合物。随着该络合物的形成,促进了La3+在Si O2表面的吸附而堵塞了H_3PW_(12)O_(40)的孔道结构,抑制了H_3PW_(12)O_(40)颗粒在焙烧过程中进一步聚集长大。Si O2将作为载体并以干凝胶状态存在于B-LaPW_(12)O_(40)/Si O2催化剂中,由于Si O2凝胶的高比表面积而使B-LaPW_(12)O_(40)/Si O2具有了较大的比表面积,从H_3PW_(12)O_(40)的1.4 m2/g增加至31.3 m2/g。并且,通过吡啶吸附红外光谱确定B-LaPW_(12)O_(40)/Si O2为Br9nsted-Lewis酸型固体酸,由于Br9nsted酸位易与酯化反应过程中生成的水发生水合反应而失活,因而Lewis酸位的形成有助于减少催化剂的失活现象发生。Lewis酸位的出现可归因于(≡Si-OH2+)(H2PW12O-40)与吸附在其表面的具有强吸电子作用的La3+发生键合作用后生成了LaPW_(12)O_(40)/Si O2。  相似文献   

13.
The arsenic oxide pressure of As2O5 has been studied using mass spectrometry and a transportation method. Mass spectrometry revealed the presence of the species As4O+6, As4O+7, and As4O+8 in the vapour. The existence of volatile species up to As4O10(g) as a result of the reaction As4O10(g) As4O(10−y) (g) +1/2yO2(g) has been assumed.

The oxygen pressure of this equilibrium builds up very slowly. The equilibrium pressure can be expressed by log(pO2/atm) (880−952 K) = −(13940±930)/T + (14.53 ± 1.01)

A stationary arsenic oxide pressure has been measured using the transportation method. Since the oxygen pressure in the transportation gas did not influence the arsenic oxide pressure, it is assumed that only the As4O10(g) pressure has been measured. The results can be expressed by the linear function log(pAs4O10/atm) (865−1009 K) = −(15741 ± 410)/T + (13.87 ± 0.42).  相似文献   


14.
ZrO2-supported La, Co oxide catalysts with different La, Co loading (2, 6, 8, 12 and 16 wt.% as LaCoO3) were prepared by impregnation of tetragonal ZrO2 with equimolar amounts of La and Co citrate precursors and calcination at 1073 K. The catalysts were characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and BET specific surface area determination. Catalytic CO oxidation was performed at 298–800 K. XRD revealed the presence of tetragonal zirconia with traces of the monoclinic phase. LaCoO3 perovskite was also detected for loading higher than 6%. XAS experiments suggested that at high loading LaCoO3 and Co3O4 were formed, while at low loading, La, Co oxide species interacting with support, and hard to be structurally defined, prevailed. The catalysis study evidenced that the catalytic activity was due to segregated and highly dispersed cobalt oxide species.  相似文献   

15.
Gaseous nitryl azide N4O2 is generated by the heterogeneous reaction of gaseous ClNO2 with freshly prepared AgN3 at −50 °C. The geometric and electronic structure of the molecule in the gas phase has been characterized by in situ photoelectron spectroscopy (PES) and quantum chemical calculations. The experimental first vertical ionization energy of N4O2 is 11.39 eV, corresponding to the ionization of an electron on the highest occupied molecular orbital (HOMO) {4a″(πnb(N4–N5–N6))}−1. An apparent vibrational spacing of 1600 ± 60 cm−1asO1N2O3) on the second band at 12.52 eV (πnb(O1–N2–O3)) further confirms the preference of energetically stable chain structure in the gas phase. To complement the experimental results, the potential-energy surface of this structurally novel transient molecule is discussed. Both calculations and spectroscopic results suggest that the molecule adopts a trans-planar chain structure, and a five-membered ring decomposition pathway is more favorable.  相似文献   

16.
The thermal decomposition of CaOsO3 by differential thermal analyses, thermogravimetry and X-ray powder diffraction has been studied. In nitrogen CaOsO3 decomposes at 880 ± 10°C into CaO, osmium metal and oxygen due to the reaction CaOsO3 → CaO + Os + O2. In static air the decomposition occurs in three stages: 2CaOsO3 + 1/2O2 → Ca2Os2O7 (in region 775–808°C), Ca2Os2O7 → Ca2Os2O6,5 + 1/4O2 (at a temperature interval of 850–1000°C) and in the third stage Ca2Os2O6,5 → 2CaO + OsO4 ÷ 1/4 O2 (at 1005 ± 5°C). The first intermediate Ca2Os2O7 is isostructural with orthorhombic Ca2Nb2O7 and its cell parameters are: a0 = 3.745 Å, b0 = 25.1 Å, c0 = 5.492 Å, Z = 4, space group Cmcm or Cmc2. Ca2Os2O7 exhibits metallic conductivity and its electrical resistivity is 4.6 × 10−2 ohm-cm at 296K.  相似文献   

17.
The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen2)2V4O12]·5H2O (1) and [Ni(phen)3]2[V4O12]·17.5H2O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C72H131N12Ni2O29.5V4 (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V4O12]4− cluster covalently attached to two {Cd(phen)2}2+ fragments, in which the [V4O12]4− cluster adopts a chair-like configuration. In the structure of 2, the [V4O12]4− cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V4O12]4− unit and crystallization water molecules.  相似文献   

18.
将原料Ni(NO3)2·6H2O、Mn3O4粉末和拟薄水铝石用球磨机球磨,以所得的浆料浸渍堇青石,经过焙烧,得到不同比例的NiO/Mn3O4催化剂。 通过催化分解臭氧活性测试发现,在空速为20000 h-1时, 30NiO/Mn3O4(NiO占总质量的30%)催化剂的活性最高,臭氧分解率达到98%,催化剂活性稳定。 当提高空速为40000 h-1,50NiO/Mn3O4(NiO占总质量的50%)催化剂的活性最高,臭氧分解率在90%左右,并且出现失活现象。 通过X射线衍射(XRD)、程序升温(TPR)、X射线光电子能谱分析(XPS)、BET比表面积法等表征,发现Mn3O4和NiO复合催化剂的比表面积大于单一金属氧化物催化剂的比表面积并且在Mn3O4和NiO复合催化剂中Mn3O4与NiO发生电子相互作用。 催化剂中的Mn3O4与NiO的协同催化作用。 使得Mn3O4与NiO混合物催化剂的还原温度降低,分解臭氧(O3)活性提高。  相似文献   

19.
Nanometer-sized Bi4Ti3O12 particles have been prepared by chemical reaction of bismuth nitrate pentahydrate, titanium sulfate and ammonia solution in a reverse microemulsion system consisting of water, OP (P-octyl polyethylene glycol phenylether, non-ionic surfactant), n-butanol (co-surfactant), and cyclohexane (oil). Precursor hydroxides precipitated in the droplets of water-in-oil (w/o) microemulsion were calcined at 800 °C for 4 h to form Bi4Ti3O12 nanoparticles. The samples were investigated with X-ray diffraction (XRD), transmission electron microscopy (TEM), fourier transform infrared spectrophotometer (FT-IR) and ultraviolet visible spectrophotometer (UV–vis). It was found that the as-prepared Bi4Ti3O12 nanoparticles had small particle sizes (35 nm), high crystallinity, narrow size distributions and strong light absorption properties not only in the ultraviolet light but also in the visible light region.  相似文献   

20.
The reaction between transition metal alkoxides and benzyl alcohol provides a novel soft chemistry route to metal oxide nanoparticles. The method allows the preparation of nanocrystals of two important transition metal oxides, namely V2O3 and Nb2O5. Although the reaction temperatures of 200–220 °C are comparably low, the obtained particles are highly crystalline. According to TEM investigations, the V2O3 crystals exhibit particle sizes between 20 and 50 nm, and the Nb2O5 crystals display platelet-like particle shapes with sizes of 50–80 nm, without any indications of amorphous character.  相似文献   

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