硅藻土负载TODGA分离-电感耦合等离子体质谱法测定氧化铈中氧化钆、氧化铽

建立了硅藻土负载N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)分离柱分离,电感耦合等离子体质谱法(ICP-MS)测定氧化铈中氧化钆、氧化铽含量的方法。试样用50%(体积分数)硝酸溶液和30%过氧化氢溶解,取含氧化铈50 mg的样品溶液导入自制的硅藻土负载TODGA的分离柱(连接一个蠕动泵,用于控制流量),用pH 1.5的硝酸溶液以2.0 mL·min~(-1)流量淋洗分离柱,直至淋洗液中铈的质量浓度小于1 000μg·L~(-1)。用60 mL pH 0.92的盐酸溶液以2.0 mL·min~(-1)流量反洗待测元素钆和铽,弃去前20 mL反洗液,收集后40 mL反洗液并用水稀释至50 mL。在线加入10μg·L~(-1)铯内标溶液,用ICP-MS分析样品溶液中目标物的含量。结果显示,氧化钆、氧化铽的质量浓度均在50.00μg·L~(-1)以内与其对应的待测元素与内标元素强度比值呈线性关系,检出限(3s)分别为0.102,0.049μg·g~(-1)。方法用于实际样品分析,氧化钆和氧化铽的测定值分别为0.73,0.68μg·g~(-1),测定值的相对标准偏差(n=11)为4.8%和5.2%,加标回收率分别为101%和99.0%。     

高热稳定性的铈铝复合氧化物用于柴油机尾气中碳烟的消除

采用柠檬酸络合燃烧法制备了一系列铝铈复合氧化物(铝掺杂的氧化铈),并通过程序升温氧化反应在紧密接触的模式下研究了其催化氧化碳烟的活性.结果表明,氧化铝和氧化铈之间存在强烈的相互作用,部分铝可以进入氧化铈晶格形成铝铈固溶体,大部分铝以γ-Αl2O3形式存在.与纯氧化铈相比,铝铈复合氧化物具有较好的催化燃烧活性,这是由于γ-Αl2O3能作为"扩散阻碍"阻止氧化铈粒子之间的接触而增强其热稳定.晶格氧的活动性决定了铝铈复合氧化物的催化活性,当铝与铈的摩尔比为1:30时,复合氧化物的催化活性最高.     

机械力固相化学反应合成纳米氧化铈

采用氯化铈和草酸在低热条件下进行机械力固相化学反应, 制备出前驱体草酸铈Ce2(C2O4)3*10H2O, 通过热重和差热分析后, 在400 ℃下分解该前驱体2 h; 分解产物经XRD, SEM和TEM分析测试, 确认获得了粒度在80 nm以下、表面形貌为球形、结构为立方晶系的黄色CeO2.研究结果表明, 用该法制备的CeO2纳米粉体, 具有简单、易行、效果好的特点.     

氢氧化铈细粉的解聚与分散过程研究

团聚的控制是以氢氧化铈为前驱体制备纳米氧化铈工艺的关键所在,通过加热来破坏氢氧化铈凝胶的稳定性是进行解聚的基础.对非凝胶态的氢氧化铈,剪切分散仅对微米级的团聚体发生作用,采用球磨工艺可得到良好分散的纳米级氢氧化铈颗粒.     

金属材料分析方法的选择和施行——第六讲金属材料中稀土元素的测定（续）

用20 g·L-1焦磷酸钠溶液也可作为钇组稀土的掩蔽剂,但对铈组稀土(Ⅲ)与CPA-mN试剂的配合物的形成也有一定的抑制作用,约使其吸光度下降约10%.比较而言,用草酸溶液作掩蔽剂效果较好.     

草酸盐沉淀法制备超细氧化铈的研究

研究了草酸盐沉淀法制备超细氧化铈粉体的工艺.通过正交实验,研究了沉淀方式、沉淀剂的浓度、硝酸铈的浓度、反应温度、滴加速度等沉淀条件对氧化铈颗粒粒径的影响,找出了制备纳米氧化铈的最佳沉淀工艺条件.利用DTA/TG对氧化铈样品前驱体的热分解行为进行了分析,研究了培烧和干燥条件对氧化铈粒径和比表面积的影响,由此确立了制备氧化铈合适的焙烧和干燥条件.结果表明采用草酸盐反向沉淀法可以得到超细氧化铈粉体,其体积中心粒径D50为1.011μm、比表面积为42.69m2·g-1,晶体结构为立方晶系,CAF2萤石型结构,形状呈薄片状,分散性较好.     

顺序注射-化学发光法测定环境水样中痕量乐果

基于在盐酸溶液中,乐果在氢氧化钠介质中的水解产物被铈(Ⅳ)氧化而产生强烈的化学发光,并结合应用顺序注射技术,提出了SI-CL法测定环境水样中痕量乐果的方法。采用三区带进样模式,将试剂按以下方式组合:(a)0.3mol·L-1氢氧化钠溶液与8g·L-1 HPC溶液混合,(b)水样及(c)0.035mol·L-1硫酸铈铵溶液与1.2mol·L-1盐酸溶液混合。其进样体积依次为(a)200μL,(b)200μL和(c)80μL。化学发光强度与乐果的质量浓度在1~100μg·L-1和100~800μg·L-1两个范围内呈线性关系。检出限(3σ)为0.17μg·L-1。回收率在85.7%~119%之间。     

二氧化铈催化剂的氧化还原和酸碱性质的原位光谱表征

二氧化铈作为催化剂、催化剂载体和助剂被广泛应用于各类氧化还原的催化反应中,是多相催化领域中至关重要的金属氧化物.氧化铈因具有丰富的缺陷结构、较强的氧化还原能力以及异常的酸碱功能等独特性质,在催化领域中非常重要.在分子层面上理解氧化铈的储氧能力、氧化还原效应和酸碱性质对建立催化构效关系尤为重要,是有效合理地改善和设计铈基催化材料的关键.在诸多的表征手段中,光谱在氧化铈结构和表面性质的研究中显示出无可争议的优势,可以提供原子和分子层面的化学信息.本文总结了各种光谱方法(包括光学、X射线、中子、电子和核磁谱学)对氧化铈表面性质表征的研究进展.分析了直接光谱表征及其与探针分子耦合两种方法在氧化铈表征中的应用;归纳了预处理条件、氧化铈纳米粒子的形貌和尺寸对其表面位点的性质、强度和密度的影响.最后展望了如何利用反应条件下的原位光谱来更好地理解和揭示铈基材料的催化作用机制的可能性.     

柠檬酸络盐沉淀法制备超细氧化铈

以晶状碳酸铈、柠檬酸或柠檬铵为原料, 采用络合沉淀法制备了氧化铈超细粉体. 对温度、摩尔比、 pH值等影响因素进行了试验, 以柠檬酸络盐法制得的超细粉体其分散性好, 粒径在20～40 nm, 粒度分布均匀. 并适合工业规模生产.     

CeO2-ZrO2包覆石墨粉增强铝基复合材料的制备与耐蚀性能

采用非均匀成核法,在机械搅拌条件下通过硝酸亚铈和氧氯化锆水解生成无定形氧化铈、氧化锆对石墨进行表面包覆,利用扫描电镜、 X射线衍射和XPS对所得样品进行了表征,通过搅拌铸造法制备了氧化铈/锆包覆石墨颗粒增强铝基复合材料,并对复合材料耐蚀性能进行了初步研究. SEM和XPS表明,氧化铈/锆在石墨表面形成了均匀、致密的纳米级包覆层,氧化铈/锆通过与铝液的反应性润湿提高了石墨颗粒与铝液的润湿性,阻止了石墨与铝发生化学反应. 测试结果表明,氧化物的包覆基本抵消了由于石墨的添加而降低复合材料的腐蚀电位,也降低了腐蚀电流(两个数量级).     

一种通过纳米粒子的组装制备基于二氧化铈中孔材料的简易方法

用HF或者HCl作联合剂,三嵌段共聚物表面活性剂作模板剂,通过二氧化铈纳米粒子(或者过渡金属掺杂的二氧化铈纳米粒子)组装形成具有热稳定和晶化孔壁的基于二氧化铈的中孔材料。焙烧该合成的超分子模板中孔结构的材料可以形成具有高比表面的基于二氧化铈的中孔材料,这些中孔材料用不同的光谱技术表征。通过D₂-OH交换测得的二氧化铈表面的羟基在组装过程和中孔材料的稳定性方面至关重要。联结剂中的卤素离子(F和Cl离子)可以替代中孔材料的表面羟基,从而影响这些中孔材料的结构稳定性和光学活性,而用具有3 d的过渡金属在组装前掺杂二氧化铈纳米粒子可以显著地提高中孔材料的光学活性,这种提高主要归结为通过掺杂可以促使能量转移的提高。     

规则中孔氧化铈的纳米铸型合成及作为高CO氧化活性金催化载体的应用(英文)

以有序的中孔炭材料CMK-3为模板,以硝酸铈为前体,利用纳米铸型法合成了具有规则结构的中孔氧化铈,考察了模板脱除温度对中孔氧化铈微结构的影响.热重、元素分析、X射线衍射、透射电镜和氮气物理吸附结果表明,炭模板的脱除温度可低至350℃,所得氧化铈具有二维六方规则结构,比表面积高达167 m~2/g,孔径分布集中在3～5nm.采用胶体沉积法将2-5nm的金溶胶粒子沉积到所得氧化铈表面制得了Au/CeO_2催化剂,考察了Au/CeO_2在CO氧化反应中的活性.结果表明,该催化剂的活性较常规氧化铈制备的金催化利有明显提高,这可能与载体的规则结构有关.     

颗粒可控分散技术在CeO2抛光粉生产中的应用研究

通过高能湿法球磨与低温喷雾干燥联用技术对传统沉淀法氧化铈抛光粉后处理工艺进行改进,从而实现生产过程中颗粒的可控分散.通过XRD确定产品晶型,采用SEM,BET和激光粒度仪对改进前后颗粒度变化进行了分析.将该产品与进口产品在ZF7和K9玻片抛光生产线上比较使用,良品率高于进口产品.结果表明该颗粒可控分散技术有效降低了颗粒的团聚程度,提高了颗粒均匀性,改善了抛光性能.     

Special quasirandom structures for gadolinia-doped ceria and related materials

Gadolinia doped ceria in its doped or strained form is considered to be an electrolyte for solid oxide fuel cell applications. The simulation of the defect processes in these materials is complicated by the random distribution of the constituent atoms. We propose the use of the special quasirandom structure (SQS) approach as a computationally efficient way to describe the random nature of the local cation environment and the distribution of the oxygen vacancies. We have generated two 96-atom SQS cells describing 9% and 12% gadolinia doped ceria. These SQS cells are transferable and can be used to model related materials such as yttria stabilized zirconia. To demonstrate the applicability of the method we use density functional theory to investigate the influence of the local environment around a Y dopant in Y-codoped gadolinia doped ceria. It is energetically favourable if Y is not close to Gd or an oxygen vacancy. Moreover, Y-O bonds are found to be weaker than Gd-O bonds so that the conductivity of O ions is improved.     

Innovative Precipitation in Emulsion Process: Toward a Non-nuclear Industrial Application

A precipitation in emulsion process has been proposed by Borda et al. in 2008 for the continuous precipitation of lanthanides or actinides as oxalate, in order to either increase the production capacity or allow the precipitation of long-life radioactive elements under optimum safety conditions. During R&D tests, a strong correlation between the emulsion's properties and those of the particles produced have been evidenced, thus enabling the size and morphology of the powder to be tuned by varying the droplets properties, the latter being controlled by the column operating conditions. This process thus appears as an attractive alternative to conventional processes for the synthesis of high-value precipitates; as it offers interesting intensification capabilities.In this context, the feasibility of the precipitation of bismuth subnitrate (BSN), for which the emulsion route for precipitation seems to be particularly attractive, has been studied. Indeed, the division of the reacting volume into droplets may allow efficient temperature regulation of the exothermic reaction. In addition, an improvement of the product appearance is expected.This first phase of the feasibility study focused on the choice of the organic phase and the sensitivity of the droplets and solid particles properties to the operating conditions. Following the encouraging results observed in stirred-tank reactor, we successfully tested the implementation in a pulsed column, at lab-scale.     

Physicochemical and catalytic properties of micro-mesoporous zeolite materials

Micro-mesoporous zeolite materials differing in their content of micro- and mesopores are obtained by the recrystallization of modernite zeolite. Using physicochemical methods such as scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction analysis, small-angle X-ray scattering analysis, low-temperature adsorption of nitrogen, temperature-programmed desorption of NH3, and IR spectroscopy, it is shown that recrystallization leads first to the formation of mesopores with sizes of 20–30 Å in zeolite crystals, then to the appearance of zeolite/MCM-41 nanocomposite, and finally to the complete conversion of zeolite into mesoporous MCM-41. During this process, the concentration of strong Brønsted acid sites accessible to pyridine bases first increases then drops. The catalytic properties of the synthesized materials are studied in the reaction of alkylation of benzene by dodecene-1. It is shown that the creation of transport pores and the increase in the accessibility of acid sites due to recrystallization under soft conditions facilitate the alkylation reaction.     

A concerted migration mechanism of mixed oxide ion and electron conduction in reduced ceria studied by first-principles density functional theory

Ceria based oxides are regarded as key oxide materials for energy and environmental applications, such as solid oxide fuel cells, oxygen permeation membranes, fuel cell electrodes, oxygen storage, or heterogeneous catalysis. This great versatility in applications is rendered possible by the fact that rare earth-doped ceria is a pure oxygen ion conductor while undoped ceria, CeO(2-δ), is a mixed oxygen ion-electron conductor. To get deeper insight into the mixed conduction mechanism of oxygen ions and electrons from atomistic and electronic level viewpoints we have applied first-principles density functional theory (DFT + U method). The calculation results show that oxygen vacancies strongly attract localized electrons, forming associates between them. The migration energy of an oxygen vacancy in such an associate is substantially lowered compared to the unassociated case due to the simultaneous positional rearrangement of localized electrons during the ionic jump process. Accordingly, we propose a concerted migration mechanism of oxygen vacancies and localized electrons in reduced ceria; this mechanism results in an increased diffusivity of oxygen vacancies supported by localized electrons compared with that in pure oxide ion conductors.     

Effect of acid on morphology of calcite during acid enhanced defluoridation

Fluoride removal from water by lime materials is a promising defluoridation process. Acid enhanced limestone defluoridation (AELD) technique involves precipitation of CaF₂ as well as adsorption of fluoride on the surface of limestone which is capable of reducing fluoride concentration to below the WHO guideline value of 1.5 mg/L. Acids such as acetic acid and citric acid are added to the fluoride water before filtration through limestone column to enhance the Ca²⁺ activity in solution for precipitation of fluoride as CaF₂. This paper describes the effects of these acids on the quality of the limestone during the AELD process, which has been studied to evaluate the reusability of the limestone. The reaction products that formed during the AELD process have also been analyzed. The detail study of the morphology of the limestone before and after use have been done using various analytical techniques, viz., X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The study reveals that the limestone degrades to some extent in the process due to dissolution of calcium carbonate by the acids and adsorption of fluoride by the limestone. While appreciable quantity of the citrate salt of calcium was formed in the column, the acetate salt mostly remained dissolved in the water. Since mainly the surface of the limestone particles take part in the reaction, the limestone particles can be reused for the defluoridation process after cleaning the outer surface. The limestone after use remains also suitable as raw material for cement.     

超临界流体沉淀技术制备超细粒子研究

超临界流体沉淀(简称SFP)技术以其特有的优点成为引人注目的在无机化学、有机化学、医药等领域具有广阔应用前景的超细微粒制备方法.为充分发挥SFP技术的优势,科研工作者以RESS与SAS为基础提出了ASES、SEDS、SAS-EM等各种新技术.本文着重综述了以RESS及SAS为基础发展起来的SFP新技术的原理、特点及相关的应用,指出了目前SFP技术存在的问题及今后的研究方向.     

Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes

The vanadium(III) cation structure in mixed acid based electrolyte solution from vanadium redox flow batteries is studied by (17)O and (35/37)Cl nuclear magnetic resonance (NMR) spectroscopy, electronic spectroscopy and density functional theory (DFT) based computational modelling. Both computational and experimental results reveal that the V(III) species can complex with counter anions (sulfate/chlorine) depending on the composition of its solvation sphere. By analyzing the powder precipitate it was found that the formation of sulfate complexed V(III) species is the crucial process in the precipitation reaction. The precipitation occurs through nucleation of neutral species formed through deprotonation and ion-pair formation process. However, the powder precipitate shows a multiphase nature which warrants multiple reaction pathways for precipitation reaction.