介孔Ce-M-O(M=La,Pr)的合成及其紫外-可见光吸收性能研究

分别利用P123、正硅酸乙酯(TEOS)为模板剂和硅源,在酸性条件下合成了介孔SBA-15材料。利用SBA-15为硬模板剂,La(NO3)3/Pr(NO3)3和Ce(NO3)3为前驱体,通过煅烧方法制备了La-Pr-O/Ce-Pr-O和SiO2混合物。使用2 mol·L-1的NaOH溶液对混合物中的氧化硅进行溶解,获得La-Pr-O/Ce-Pr-O复合氧化物。采用X射线衍射仪、Raman光谱仪、N2吸-脱附技术、透射电镜及紫外-可见光谱仪对La-Pr-O/CePr-O复合氧化物进行了表征。Raman和X射线衍射结果表明产物具有与CaF2相似的萤石结构;N2吸-脱附结果证明产物为介孔结构。紫外-可见光谱表明,在Ce-Pr-O固溶体中,随着Pr含量提高,产物对光(特别是可见光)的吸收强度急剧增加;而在Ce-La-O固溶体中,随着La含量提高,产物对可见光的吸收强度基本保持不变。     

Ce1-xGdxO2-δ固溶体中缺陷物种的拉曼光谱研究

采用溶胶-凝胶法制备一系列Ce1-xGdxO2-δ固溶体。利用紫外(325 nm)和可见(514 nm)Raman光谱,X射线粉末衍射(XRD),透射电子显微镜(TEM)和紫外可见漫反射光谱(UV-Vis DRS),考察了Ce1-xGdxO2-δ固溶体的缺陷物种的分布以及Gd含量对缺陷浓度的影响。结果表明:Ce1-xGdxO2-δ固溶体中存在氧缺位(～560 cm-1)和GdO8型缺陷结构(～600 cm-1)。根据样品对Raman激发光的吸收,紫外Raman光谱反映样品的表层信息,可见Raman光谱反映样品的整体信息。Ce1-xGdxO2-δ固溶体表层氧缺位(να)和GdO8型缺陷物种的浓度(νβ)均高于固溶体体相,这归因于缺陷物种的表面富集。然而,相比于GdO8型缺陷物种,体相中氧缺位浓度增加较表层中的更显著。     

低温燃烧法制备纳米Ce1-xNdxO2-x/2(0≤x≤0.6) 粉体的研究

采用低温燃烧合成工艺，在甘氨酸-硝酸盐体系下制备出纳米Ce1-xNdxO2-x/2(0≤x≤0．6)系列粉体(NDC)。X射线衍射(XRD)结果表明。Nd^3 取代Ce^4 进入晶格内部，形成具有单相立方萤石型结构的固溶体，其晶格常数随Nd^3 掺杂浓度的增大而线性增加，晶粒尺寸在17～28nm之间。透射电镜(TEM)结果表明，粉体尺寸在30-40nm之间，具有较高的烧结活性。拉曼光谱(Rman spectrum)表明％宽化峰与掺杂后固溶体中产生的氧空位有关。     

纳米晶固溶体Ce0.8Nd0.2O2-δ的合成与表征

利用溶胶 -凝胶法合成纳米晶固溶体 Ce0 .8Nd0 .2 O2 -δ.XRD测试表明 ,胶体经 2 0 0℃烧结处理就可以得到晶粒尺寸为 7.2 nm的纳米晶 ,随烧结温度的升高 ,晶粒尺寸增大 .EPR测试给出固溶体 Ce0 .8Nd0 .2 O2 -δ存在少量的 Ce3 +离子 .在纳米晶固溶体 Ce0 .8Nd0 .2 O2 -δ的 Raman光谱上观察到两个峰 ,低频的强峰为特征F2 g振动谱带 ,高频谱带的出现与样品中存在氧缺位有关 .固溶体晶粒尺寸的减小不但使 F2 g振动谱带红移 ,而且谱带明显宽化 .复阻抗谱的测量表明 ,固溶体 Ce0 .8Nd0 .2 O2 -δ具有氧离子导电特性 .4 0 0和 50 0℃时的电导率分别为 4 .55× 1 0 -4 和 2 .65× 1 0 -3 S· cm-1,活化能为 0 .82 e V     

钐掺杂对CeO2电解质导电性能的影响

采用溶胶-凝胶法合成Ce1-xSmxO2-δ(x=0,0.1,0.2)系列固体电解质.通过XRD,Raman,SEM和交流阻抗技术系统研究掺杂浓度、相对密度、晶粒大小和氧空位浓度对电解质导电性能的影响.XRD结果表明,所有样品均呈现CeO2结构,即形成了 Ce1-xSmxO2-δ固溶体.在掺杂离子相同,电解质的晶粒大小和相对密度十分接近的情况下,较多Sm3+的掺人能促使样品形成较多的氧空位,更有利于O2-的传递,从而使得Ce0.8Sm0.2O2-δ的电导性能高于Ce0.9Sm0.1O2-δ样品.     

尿素研磨燃烧法合成Ce_(0.8)Zr_(0.2)O_2固溶体对乙硫醇催化分解的研究

采用尿素研磨燃烧法快速制备Ce_(0.8)Zr_(0.2)O_2固溶体催化剂,考察不同焙烧温度下Ce_(0.8)Zr_(0.2)O_2固溶体常压下催化分解乙硫醇的活性。利用XRD,TEM,BET,H2-TPR,XPS和Raman等方法对催化剂的物化性质、表面结构进行研究。结果表明:Ce_(0.8)Zr_(0.2)O_2固溶体对乙硫醇催化降解有较好活性。在一定范围内升高焙烧温度有利于更多Zr4+进入Ce O2晶格,从而增加氧空位浓度,但过高的温度会使催化剂颗粒团聚,并降低催化剂表面吸附氧的相对含量,导致催化剂比表面积降低。600℃焙烧的Ce0.8Zr0.2O2固溶体表现出对乙硫醇催化分解最佳活性,得益于催化剂表面Ce3+浓度、氧空位浓度与比表面积的协同作用。一方面,这些表面Ce3+浓度与催化剂氧空位浓度,有利于氧迁移,对催化分解反应有促进作用,另一方面催化剂比表面积越大,越有利于反应物吸附、暴露更多活性位点,进而增加催化活性。     

固溶体Ce_(1-x)Eu_xO_(2-δ)的~(151)Eu Mssbauer谱和电性能研究

利用溶胶-凝胶方法在800℃灼烧10h后,合成了固溶体Ce1-xEuxO2-δ(x=0.05~0.5),晶粒平均尺寸为60nm左右,XRD分析表明固溶体的结构为单相立方萤石结构。Mssbauer谱测试表明固溶体Ce1-xEuxO2-δ中Eu离子价态为+3价,同质异能移IS值随掺杂量x增加而增大。Eu3+的四极劈裂QS值小于零,表明Eu3+周围的晶体场是非对称的,QS的绝对值随掺杂量x增加而增大,说明随掺杂量x增加,晶体场对称性越差。阻抗谱测试表明通过掺杂使固溶体Ce1-xEuxO2-δ的导电率得到很大提高,电导率在x=0.2时达到最大值σ800℃=1.28×10-2S·cm-1,电导活化能达到最小值为Ea=0.72eV。     

金属铈表面氧化还原过程的原位拉曼光谱研究

采用显微拉曼光谱仪原位监测了金属铈表面的氧化和还原过程。2132和2239 cm-1处尖锐Ce3+电子散射峰的出现及462 cm-1处CeO2特征振动峰的消失表明,在高温、高真空条件下金属铈表层的CeO2已转变为Ce2O3。根据1503,1796和2113 cm-1处多个Ce3+电子散射峰及CeO2特征振动峰强度随时间的变化关系,可将金属Ce在空气中的氧化过程分为3个阶段,首先不同价态铈氧物层均快速增长,随后外层的CeO2陷入停顿,含Ce3+的铈氧物层继续增长,最后随着3603 cm-1处OH-的出现,CeO2再次快速增长。     

Ce1-xEuxO2-δ(x=0.05～0.50)固溶体的溶胶-凝胶法合成与性质研究

利用溶胶-凝胶方法合成了固溶体Ce1-xEuxO2-δ,通过XRD, Raman, XPS和交流阻抗谱系统研究了固溶体Ce1-x-EuxO2-δ的结构,确定了稀土离子价态及掺杂对CeO2基电解质电性能的影响.XPS分析表明固溶体Ce1-xEuxO2-δ中,Eu离子价态为+3价,Ce离子主要以Ce4+离子形式存在,阻抗谱测试表明低价离子掺杂使固溶体Ce1-xEuxO2-δ的导电率得到很大提高,导电率x=0.2时达到最大值σ600 ℃=2.87×10-3 S·com-1.导电活化能为Ea=0.72eV.     

固溶体Ce0.8Pr0.2O2-δ的合成及性质研究

利用溶胶-凝胶方法合成了Ce0.8Pr0.2O2-δ固溶体, XRD结果表明,经200 ℃焙烧就已经形成立方萤石结构固溶体,晶粒尺寸为8.1 nm, 随焙烧温度的升高,晶粒尺寸增大. X射线光电子能谱(XPS)结果表明,样品中存在氧离子缺位,铈离子主要为Ce4 离子,镨离子以混合价态Pr3 和Pr4 存在. 固溶体Ce0.8Pr0.2O2-δ的拉曼谱(Raman)观察到4个峰,458和1140 cm-1峰为特征F2g振动谱带,较宽的570和187 cm-1峰对应氧离子缺位及引起的不对称振动. 交流阻抗谱表明固溶体Ce0.8Pr0.2O2-δ在600 ℃时的电导率为1.44×10-3 S·cm-1, 活化能为Ea=0.67 eV (650～800 ℃), Ea=0.91 eV (400～600 ℃).     

多孔纳米Ce-M-O(M=Pr,La)粉末的微波诱导燃烧合成及其表征

使用Ce(NO₃)₃•6H₂O, Pr(NO₃)₃•6H₂O, La(NO₃)₃•6H₂O, 尿素为原料, 利用微波引诱燃烧法合成了多孔纳米Ce-M-O (M＝Pr, La)固溶体. 使用XRD, X光电子能谱仪(XPS), Raman光谱仪, 红外光谱仪(FT-IR), 透射电镜(TEM), 场发射扫描电镜(FE-SEM)等仪器对纳米粉体进行了表征. XRD分析显示Ce-M-O粉体的粒径在20～50 nm之间, 且所有样品均具有萤石结构. XPS证明在Ce-Pr-O固溶体中Pr以＋3和＋4两种形式存在. Raman光谱表明随着M^3＋的掺杂, 在CeO₂晶格中产生氧缺陷, 且缺陷浓度随掺杂量增加不断提高. 红外光谱证明Ce—O键的吸收峰在1400 cm^－1左右, 且由于M^3＋的掺杂在2346 cm^－1的吸收峰消失. TEM照片说明样品具有类盘状的网络纳米微晶结构. 扫描图像说明产物具有多孔的外貌特征, 且孔径分布在2～40 nm之间.     

Mo掺杂对高纯Ce1-xNdxO2-x/2(x=0.10, 0.15)体系烧结温度及晶界电性能的影响

用柠檬酸硝酸盐法制备高纯Ce1-xNdxO2-x/2(x=0.10, 0.15)固溶体, 加入摩尔分数为5%的Mo, 研究了Mo掺杂对烧结温度、结构及电性能的影响. 通过X射线衍射、电感偶合等离子体和场发射扫描电镜等手段对氧化物进行了结构表征, 采用交流阻抗谱测试其电性能. 柠檬酸硝酸盐法制备的前驱体经1450 ℃烧结24 h得到致密度大于96%的陶瓷材料; 加入5%Mo, 在1250 ℃下烧结8 h即可达到理想的致密度(>95%). 加入Mo在烧结过程中可加快晶界迁移, 促进晶粒生长, 显著提高了晶界电导率. 在600 ℃时Ce0.85Nd0.15O1.925的晶界电导率为2.56 S/m, 加入Mo后材料的电导率增加到5.62 S/m.     

Nanostructured Cu(x)Ce1-xO2-y mixed oxide catalysts: characterization and WGS activity tests

Cu(x)Ce(1-x)O(2-y) mixed oxide catalysts were prepared by different preparation procedures: co-precipitation, the sol-gel peroxide route, and the sol-gel citric acid-assisted route. The resulting solids were investigated by means of XRD, BET, H(2) and CO temperature-programmed reduction (TPR), oxidation (TPO) and desorption (TPD) analyses, and N(2)O pulse selective reaction. It was confirmed that H(2) (CO) consumed for complete reduction of well-dispersed and bulk-like CuO phases to Cu(0), reduction of surface ceria and H(2) (CO) adsorption on the catalyst surface contribute to the total H(2) (CO) consumption. Among catalysts examined, the Cu(0.15)Ce(0.85)O(2-y) mixed oxide sample prepared by means of co-precipitation method exhibits the highest activity and stability for water-gas shift (WGS) pulse reaction in the range of employed operating conditions. WGS activity of copper-ceria mixed oxide catalysts is determined by the extent of surface ceria reduction and dispersion of copper species.     

Solid-liquid equilibrium diagrams of common ion binary salt hydrate mixtures involving nitrates and chlorides of magnesium, cobalt, nickel, manganese, and iron(III)

The solid-liquid equilibrium diagrams of binary mixtures involving magnesium nitrate hexahydrate with cobalt nitrate hexahydrate, nickel nitrate hexahydrate (partly), manganese nitrate tetrahydrate, and iron(III) nitrate nonahydrate and of magnesium chloride hexahydrate with cobalt and nickel chlorides hexahydrates and manganese chloride tetrahydrate, and the of two manganese salts were determined. Those diagrams that showed a simple eutectic were fitted by the Ott equation and where the required BET parameters were available, the magnesium salt rich parts of the liquidus were modeled by means of this method.     

Crucial role of the reaction conditions in isolating several metastable phases in a Gd-Ce-Zr-O system

A series of samples with composition Gd(2-y)Ce(y)Zr(2)O(7) (0.0 ≤ y ≤ 2.0) were prepared by the gel combustion method followed by high-temperature reduction. The details of the structural variations as a function of the composition, temperature, and oxygen stoichiometry have been investigated by X-ray diffraction (XRD), high-temperature XRD (HT-XRD), and thermogravimetry. A complete solubility of Gd(3+) in Ce(2)Zr(2)O(7) and Ce(2)Zr(2)O(8) could be achieved by this adaptive preparative method. Analysis of the XRD data revealed a sequential variation of the structural features with oxygen stoichiometry as well as Gd(3+) contents in these compositions. The variation in the unit cell parameter along the compositions has a strong influence on the oxygen uptake behavior in the Gd(2-y)Ce(y)Zr(2)O(7) system, as observed from the thermogravimetric and HT-XRD studies. The preparation and stability of various metastable phases in Gd-Ce-Zr-O have been addressed in detail. The details of the study will be useful for the design and application of a potential redox catalyst and an oxygen storage capacitor.     

Synthesis and characterization of single-crystal Ce(OH)CO3 and CeO2 triangular microplates

Single-crystal cerium hydroxide carbonate (Ce(OH)CO3) triangular microplates with the hexagonal phase have been successfully synthesized by a hydrothermal method at 150 degrees C using cerium nitrate (Ce(NO3)3.6H2O) as the cerium source, aqueous carbamide as both an alkaline and carbon source, and cetyltrimethylammonium bromide (CTAB) as a surfactant. Single-crystal ceria (CeO2) triangular microplates have been fabricated by a thermal decomposition-oxidation process at 650 degrees C for 7 h using single-crystal Ce(OH)CO3 microplates as the precursor. The shape of the Ce(OH)CO3 microplate was sustained after thermal decomposition-oxidation to CeO2. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), differential scanning calorimetric analysis (DSC), and thermogravimetric analysis (TG).     

Role of Zr4+ cations in NO2 adsorption on Ce(1-x)Zr(x)O2 mixed oxides at ambient conditions

Mixed oxides Ce(1-x)Zr(x)O(2) prepared by slow coprecipitation in NaOH were tested for NO(2) adsorption in dynamic conditions at room temperature. The samples were characterized before and after exposure to NO(2) by XRD, N(2)-adsorption, thermal analysis, potentiometric titration, and FT-IR. Mixed oxides show a better NO(2) adsorption capacity than the parent materials (CeO(2) and Zr(OH)(4)). This effect is linked to the presence of reduced cerium and oxygen vacancies induced by the addition of Zr(4+) cations to the structure. The results indicate that NO(2) reacts with Ce(3+) to form nitrite and nitrate species on the surface. The NO retention increases with an increase in the Zr(OH)(4) content. A decrease in the density of -OH groups on the surface after the exposure to NO(2), suggests their involvement in reactive adsorption of NO and/or NO(2). From the structural point of view, no real difference was observed on the Ce(1-x)Zr(x)O(2) materials before and after exposure to NO(2).     

Surface stabilized nanosized Ce(x)Zr(1-x)O(2) solid solutions over SiO(2): characterization by XRD, Raman, and HREM techniques

Ce(x)Zr(1)(-)(x)O(2) solid solutions deposited over silica surface were investigated by X-ray diffraction (XRD), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques in order to understand the role of silica support and the temperature stability of these composite oxides. For the purpose of comparison, an unsupported Ce(x)Zr(1)(-)(x)O(2) was also synthesized and subjected to characterization by various techniques. The Ce(x)Zr(1)(-)(x)O(2)/SiO(2) (CZ/S) (1:1:2 mole ratio based on oxides) was synthesized by depositing Ce(x)Zr(1)(-)(x)O(2) solid solution over a colloidal SiO(2) support by a deposition precipitation method and unsupported Ce(x)Zr(1)(-)(x)O(2) (CZ) (1:1 mole ratio based on oxides) was prepared by a coprecipitation procedure, and the obtained catalysts were subjected to thermal treatments from 773 to 1073 K. The XRD measurements disclose the presence of cubic phases with the composition Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) in CZ samples, while CZ/S samples possess Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), and Ce(0.5)Zr(0.5)O(2) in different proportions. The crystallinity of these phases increased with increasing calcination temperature. The cell a parameter estimations indicate contraction of ceria lattice due to the incorporation of zirconium cations into the CeO(2) unit cell. Raman measurements indicate the presence of oxygen vacancies, lattice defects, and displacement of oxygen ions from their normal lattice positions in both the series of samples. The HREM results reveal, in the case of CZ/S samples, a well-dispersed nanosized Ce-Zr-oxides over the surface of amorphous SiO(2). The structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic geometry and exhibit high thermal stability. Oxygen storage capacity measurements by a thermogravimetric method reveal a substantial enhancement in the oxygen vacancy concentration of CZ/S sample over the unsupported CZ sample.     

The ternary system H2O–Fe(NO3)3–Co(NO3)2 isotherms 0 and 15 °C

The solid–liquid equilibria of the ternary system H₂O–Fe(NO₃)₃–Co(NO₃)₂ were studied by using a synthetic method based on conductivity measurements.

Two isotherms were established at 0 and 15 °C, and the stable solid phases which appear are the iron nitrate nonahydrate (Fe(NO₃)₃·9H₂O), the iron nitrate hexahydrate (Fe(NO₃)₃·6H₂O), the cobalt nitrate hexahydrate (Co(NO₃)₂·6H₂O) and the cobalt nitrate trihydrate (Co(NO₃)₂·3H₂O).     

Structural characterization of CeO(2)-ZrO(2)/TiO(2) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) mixed oxide catalysts by XRD, Raman spectroscopy, HREM, and other techniques

Structural characteristics of CeO(2)-ZrO(2)/TiO(2) (CZ/T) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) (V/CZ/T) mixed oxide catalysts have been investigated using X-ray diffraction (XRD), BET surface area, Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques. The CeO(2)-ZrO(2) (1:1 mole ratio) solid solution was deposited over a finely powdered TiO(2) support by a deposition precipitation method. A nominal 5 wt % V(2)O(5) was impregnated over the calcined (773 K) CZ/T mixed oxide carrier by a wet impregnation technique. The obtained CZ/T and V/CZ/T samples were further subjected to thermal treatments from 773 to 1073 K to understand the dispersion and temperature stability of these materials. In the case of CZ/T samples, the XRD results suggest the formation of different cubic and tetragonal Ce-Zr-oxide phases, Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), Ce(0.5)Zr(0.5)O(2), and Ce(0.16)Zr(0.84)O(2) in varying proportions depending on the treatment temperature. With increasing calcination temperature from 773 to 1073 K, the intensity of the lines pertaining to cubic Ce(0.6)Zr(0.4)O(2) and Ce(0.5)Zr(0.5)O(2) phases increased at the expense of cubic Ce(0.75)Zr(0.25)O(2), indicating more incorporation of zirconia into the ceria lattice. The TiO(2) was mainly in the anatase form whose crystallite size also increased with increasing treatment temperature. A better crystallization and more incorporation of zirconia into the ceria lattice was noted when CZ/T was impregnated with V(2)O(5). However, no crystalline V(2)O(5) could be seen from both XRD and RS measurements. In particular, a preferential formation of CeVO(4) compound and an intense tetragonal Ce(0.16)Zr(0.84)O(2) phase were noted beyond 873 K. The HREM results indicate, in the case of CZ/T samples, a well-dispersed Ce-Zr-oxide of the size approximately 5 nm over the bigger crystals ( approximately 40 nm) of TiO(2) when treated at 873 K. The exact structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic fluorite geometry and the TiO(2) is in anatase form. A better crystallization of Ce-Zr-oxides ( approximately 8 nm) over the surface of bigger crystals of TiO(2) was noted at 1073 K. A further enhancement in the crystallite size and zirconia-rich tetragonal phase was noted in the case of V/CZ/T samples. Further, the structure of CeVO(4) formed was also clearly identified in conformity with XRD and RS results.