AxMn1-xFe2O4铁氧体(A=Zn,Ni)中阳离子的占位有序化行为研究

基于尖晶石晶体结构信息,本文采用热力学三亚晶格模型,将材料热力学计算和第一性原理计算相结合,研究了Zn_xMn_1-x Fe₂O₄和Ni_xMn_1-xFe₂O₄立方相中的Zn²⁺、Ni²⁺、Mn²⁺以及Fe³⁺在8a和16d亚晶格上的占位有序化行为。结果表明:在锰铁氧体中,室温下Mn²⁺完全占据在8a亚晶格上,Fe³⁺完全占据在16d亚晶格上,属于正尖晶石结构;随着热处理温度升高,在1 273 K达到热处理平衡时的占位构型为(Fe_0.09³⁺Mn_0.91²⁺)[Fe_1.91³⁺Mn_0.09²⁺]O₄,在热处理温度升至1 473 K时,达到热处理平衡时的占位构型为(Fe_0.11³⁺ Mn_0.89²⁺)[Fe_1.89³⁺Mn_0.11²⁺]O₄,均与实验结果符合较好。在锌铁氧体中,室温下Zn²⁺完全占据在8a亚晶格上,Fe³⁺完全占据在16d亚晶格上,属于正尖晶石结构;在热处理温度较高时,Zn²⁺和Fe³⁺发生部分置换,符合实验结果。在镍铁氧体中,半数的Fe³⁺在室温下占据在8a亚晶格上,Ni²⁺与剩下另一半的Fe³⁺共同占据在16d亚晶格上,仅在热处理温度较高的时候发生微弱变化,亦与已有的实验结果吻合。在此基础上,本文进一步通过热力学预测建立了立方相尖晶石结构的Zn_xMn_1-xFe₂O₄、Ni_xMn_1-xFe₂O₄复合体系中阳离子占位行为与热处理温度对占位的影响。     

单一基质白光荧光粉Ca0.955-xAl2Si2O8:0.045Eu2+,xMn2+的晶胞参数变化和光谱特性

利用高温固相反应制备了Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)(x=0,0.05,0.10,0.15,0.20,0.25,0.30,0.325,0.35,0.375,0.40,0.425)一系列试样,系统研究了Mn~(2+)取代基质中Ca~(2+)进入晶格中对其晶胞参数和光谱特性影响。Mn~(2+)以类质同相替代Ca~(2+)进入晶体晶格中,形成了连续固溶体,试样均为三斜晶系,P空间群。随着Mn~(2+)掺杂量增加,晶胞参数(a,b,c,γ)和晶胞体积V均呈线性递减,且a轴减幅最大,b轴最小,晶面夹角(α,β)呈线性递增。在357 nm激发下,获得的Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)发射光谱均有Eu~(2+)的4f→5d跃迁产生的433 nm和Mn~(2+)的~4T_1(~4G)→~6A_1(~6S)跃迁产生的567 nm两个宽带谱组成。在荧光粉Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)中,Eu~(2+)与Mn~(2+)间存在能量传递,Eu~(2+)→Mn~(2+)间能量传递的临界距离R_(Eu-Mn)=0.947 1 nm,Eu~(2+)→Mn~(2+)能量传递过程为电四极-电四极的多极矩相互作用。通过改变Mn~(2+)掺杂量,在紫外芯片的有效激发下,荧光粉的发射光颜色可从蓝光区(0.158 2,0.086 0)逐渐移至近白光区(0.295 3,0.298 9),可获得一种紫外激发适用于白光LED的单一组分白色荧光粉。     

无机离子纸上色层分析(一)——第三组阳离子分析

(1)在氧化铝色层纸上第三组阳离子吸附次序是: Fe~(3+)≥Cr~(3+)>Zn~(2+)>Co~(2+)=Ni~(2+)≥Mn~(2+) (2)可以用四个色层纸条检查出上述六种阳离子。 (3)Zn~(2+)可以在紫外线下,用羧基喹啉查出。     

单分散NixZn1-xFe2O4纳米颗粒的制备及其磁热效应

以乙酰丙酮金属盐为前驱体,三乙二醇为溶剂,采用多元醇法制备了镍锌不同配比的Ni_xZn_(1-x)Fe_2O_4(x=0,0.3,0.5,0.7和1.0)铁氧体,并通过X射线衍射仪(XRD),透射电子显微镜(TEM)和振动样品磁强计(VSM)等对样品的结构、形貌、磁性能和磁热性能进行了表征。结果表明:Ni_xZn_(1-x)Fe_2O_4铁氧体分散性较好,尺寸均一,形状近似球形,平均粒径为4~5 nm。Ni_xZn_(1-x)Fe_2O_4纳米颗粒在室温下表现出亚铁磁性,饱和磁化强度随着镍含量的增加先增大后减小,当x=0.5时达到最大值29.38 emu·g~(-1)。在382k Hz交变磁场作用下,Ni_(0.5)Zn_(0.5)Fe_2O_4铁氧体温度可升温至313 K,表现出较好的磁热性能。     

CoxFe3—xO4纳米晶的合成与性能研究

Co_xFe_(3-x)O_4晶体属尖晶石型结构,具有良好的磁光效应及化学稳定性。在尖晶石型铁氧体中,金属离子存在着A-A、B-B和A-B晶位间超交换作用,其中以A-B间的超交换作用最强。超交换作用引起不同次晶格的磁矩反向排列,而铁氧体的亚铁磁性则来源于晶格中A、B位上未抵消的反向磁矩。尖晶石型单一铁氧体MFe_2O_4晶格中离子分布通常为Fe_xM_(1-x)[M_xFe_(2-x)]O_4。在三价铁盐和二价钴盐混合水溶液中滴加碱液可制备CoFe_2O纳米晶。本文用改进的化学共沉淀法,以不同摩尔浓度的Co(Ⅱ)和Fe(Ⅱ)合成Co_xFe_(3-x)O_4纳米晶系列样品,考察了样品组成与其磁性的关系。     

丙醇-溴化十六烷基三甲胺-硫酸按-水体系萃取分离汞(Ⅱ)

研究了丙醇-溴化十六烷基三甲胺(CTMAB)-(NH_4)_2SO_4-水体系萃取分离汞的行为及与常见离子分离条件.试验表明:调节pH1.0或3.0,能使Hg(Ⅱ)从Fe~(3+)、Co~(2+)、Ni~(2+)、Zn~(2+)、Mn~(2+)、Cu~(2+)、Al~(3+)等离子混合液中分离出来.     

热力学基本原理在Fe/Fe_3O_4纳米磁性材料合成中的应用

探讨了热力学基本原理及判据,以及如何利用吉布斯自由能判断变化的方向和限度;并对Fe/Fe_3O_4纳米磁性材料合成过程中的热力学行为进行了较详细的研究。通过热力学分析,认为可以利用歧化反应及以Fe~(2+)离子作为起始物合成Fe/Fe_3O_4磁性材料。     

影响Fe3O4超微粒子性能因素的研究

超微Fe_3O_4粒子正在广泛地应用到磁流体和催化等领域。化学共沉淀法制备Fe_3O_4是将碱液滴入一定温度的Fe~(2+)、Fe~(3+)混合液中。反应式为Fe~(2+)+2Fe~(3+)+8OH~-=Fe_3O_4+4H_2O。本文研究了Fe_3O_4超微粒子的磁性、粒度与工艺条件的关系。 1 实验 配制一定浓度的FeCl_2和FeCl_3溶液,按一定比例混合并置于三颈瓶中恒温。搅拌后,缓     

锰矿中铁、锌、铅的连续示波极谱快速测定

本文解决了长期以来存在的氨性底液中Zn~(2+)与Co~(2+)、Bi~(3+)与Pb~(2+)的两种干扰问题,提出了加入氨三乙酸的氨溶液(NTA-NH_3)和抗坏血酸(VC)使矿样不经任何分离即可直接在CU~(2+)、Bi~(3+)、Ni~(2+)、Co~(2+)、Cd~(2+)、Sb~(2+)和大量Mn~(2+)存在下,在(NH_4)_2CO_3-NH_3底液中连续快速测定Fe~(3+)、Zn~(2+)、Pb~(2+)的新方法。即使Fe~(3+)含量比Pb~(2+)大200倍也能顺利测Pb~(2+)。如Sb~(3+)不存在可连续测Cd~(2+)。若Zn~(2+)、Co~(2+)含量相差不大,则溶解一个矿样后同时可用文献[1]的方法测Zn~(2+)和Co~(2+)的重合波作为Zn~(2+)、Co~(2+)总量,然后减去本法测定的Zn~(2+)含量,半定量估计Co~(2+)含量,并定量测定Cu~(2+)和Ni~(2+)。本法溶矿手续简便,用固体Na_2SO_3除氧,不需加极大抑制剂,测定手续几分钟内即完成,误差在允许范围以内。     

氮川三甲撑膦酸(NTMP)螯合滴定铜

本文计算了cu~(2+)、Zn~(2+)、Co~(2+)、Ni~(2+)、Cd~(2+)及Mn~(2+)与氮川三甲撑膦酸(NTMP)螯合物的表观稳定常数,发现Cu~(2+)-NTMP螯合物在pH5.3—9.1、Zn~(2+)—NTMP螯合物在pH5.8—9.7及Co~(2+)-NTMP螯合物在pH6.4—10.9,其表观稳定常数logK_(ML)>8,理论和实验都表明,NTMP螯合滴定Cu~(2+)的选择性比EDTA或NTA都好。在pH5.3,用铬天青S作指示剂,NTMP螯合滴定10毫克Cu~(2+)时,能允许Ni~(2+)(40),Mn~(2+)(30),Cd~(2+)和Pb~(2+)(25)、Co~(2+)(2.5)、Bi~(3+)(8)以及用NH_4F掩蔽时,允许Sn~(4+)(30)、Al~(3+)(5.4)、Fe~(3+)(2.1)、Ti~(4+)(4.0)及Zn~(2+)(4.0)及Zn~(2+)(0.33)(括号内为毫克数)等离子存在。拟订的方法用于一些铜合金中铜的测定,操作简便、结果满意。     

Nanocrystalline ferrites NixZn1−xFe2O4: Influence of cation distribution on acidic and gas sensing properties

This work is devoted to a detailed analysis of the interconnection between composition, cation distribution and acidic properties of the surface of nanocrystalline ferrites Ni_xZn_1−xFe₂O₄ obtained by aerosol pyrolysis. The detailed analysis of the Mössbauer spectra allows us to determine the distribution of cations between tetrahedral and octahedral positions in spinel structure. Depending on samples composition, the tetrahedral positions can be occupied by only Fe³⁺ cations (inverse spinel, x≥0.4) or by Fe³⁺ and Zn²⁺ cations (mixed spinel, x=0, 0.2). Increasing the nickel concentration in the ferrite leads to decrease in the number of strong acid centers on the surface. It was found that the decrease in the contribution of strong surface acid sites leads to an increase in sensory sensitivity of the ferrite towards ammonia. For ethanol detection an inverse relationship between sensor signal and surface acidity was observed.     

Preparation of MnxNi0.5-xZn0.5Fe2O4 Nanorods by the Co-precipitation Method

Mn_xNi_0:5-xZn_0:5Fe₂O₄ nanorods were successfully synthesized by the thermal treatment of rod-like precursors that were fabricated by the co-precipitation of Mn²⁺, Ni²⁺, and Fe²⁺ in the lye. The phase, morphology, and particle diameter were examined by the X-ray diffrac-tion and transmission electron microscopy. The magnetic properties of the samples were stud-ied using a vibrating sample magnetometer. The results indicated that pure Ni_0:5Zn_0:5Fe₂O₄ nanorods with a diameter of 35 nm and an aspect ratio of 15 were prepared. It was found that the diameter of the Mn_xNi_0:5-xZn_0:5Fe₂O₄ (0≤x≤0.5) samples increased, the length and the aspect ratio decreased, with an increase in x value. When x=0.5, the diameter and the aspect ratio of the sample reached up to 50 nm and 7～8, respectively. The coercivity of the samples first increased and then decreased with the increase in the x value. The coer-civity of the samples again increased when the x value was higher than 0.4. When x=0.5,the coercivity of the Mn_xNi_0:5-xZn_0:5Fe₂O₄ sample reached the maximal value (134.3 Oe)at the calcination temperature of 600 oC. The saturation magnetization of the samples first increased and then decreased with the increase in the x value. When x=0.2, the satura-tion magnetization of the sample reached the maximal value (68.5 emu/g) at the calcination temperature of 800 oC.     

ZnAl2O4:Mn材料的制备及发光性能

以共沉淀法与煅烧法联用,成功制备了一系列ZnAl₂O₄:xMn样品。通过扫描电镜和X射线粉末衍射测试研究了样品的形貌和物相特征,结果表明尖晶石结构的ZnAl₂O₄中[AlO₆]的八面体位可以有效被Mn⁴⁺替代。通过荧光激发和发射光谱研究了样品的发光性能,发现Mn⁴⁺在ZnAl₂O₄体系中掺杂可以显示出明亮的红色发光(发射峰值位于680 nm处)。比较不同Mn⁴⁺浓度(Mn与Al的物质的量之比)掺杂样品的发光强度时发现,Mn⁴⁺最佳掺杂浓度为0.06%。通过德克斯特公式分析了发光强度与浓度关系,探究浓度猝灭机制,结果表明最邻近离子之间能量传递造成Mn⁴⁺浓度猝灭的发生。为了提高Mn⁴⁺的发光强度,选择了7种金属离子(Li⁺、Na⁺、K⁺、Ca²⁺、Sr²⁺、Sn²⁺和Ga³⁺)与Mn⁴⁺共掺杂进入ZnAl₂O₄基质中,其中效果较突出的为Li⁺和Ga³⁺,其共掺杂使Mn⁴⁺发光强度分别增强0.6倍和1倍。     

Nanocrystalline Ni0.6Zn0.4Fe2O4: A novel semiconducting material for ethanol detection

The structure and crystal phase of the nanocrystalline powders of Ni_1−xZn_xFe₂O₄ (0 ≤ x ≤ 0.5) mixed ferrite, synthesized by ethylene glycol mediated citrate sol-gel method, were characterized by X-ray diffraction and microstructure by transmission electron microscopy. Further studies by Fourier transform infrared spectroscopy were also conducted. Moreover, DC electrical properties of the prepared nanoparticles were studied by DC conductivity measurements. The response of prepared Ni_1−xZn_xFe₂O₄ mixed ferrites to different reducing gases (ethanol, hydrogen sulfide, ammonia, hydrogen and liquefied petroleum gas) was investigated. In particular, Ni_0.6Zn_0.4Fe₂O₄ composition exhibited high response to 100 ppm ethanol gas at 300 °C. Incorporation of palladium further improved the response, selectivity and response time of Ni_0.6Zn_0.4Fe₂O₄ to ethanol gas with the blue shift in the operating temperature by 25 °C.     

The influence of Ni2+ lons on the distribution of Mg2+ and Cu2+ lons in spinel ferrites

Cation distribution in quenched and furnace-cooled samples of composition Ni_xM_1?xFe₂O₄ (where M is either Mg²⁺ or Cu²⁺) has been studied through magnetization measurements. It has been found that cation distribution in these mixed ferrites cannot be predicted by site preference energies. In magnesium-nickel ferrites, cation distribution is controlled by heat treatment up to x = 0.5, beyond which the effect of heat treatment diminishes. Addition of Ni²⁺ ions in copper ferrite reduces the diffusibility of Cu²⁺ ions and the distribution tends toward inverse spinel in the high-nickel region.     

基于苯并噻唑Zn2+荧光探针及其细胞造影应用

设计合成基于苯并噻唑Zn²⁺荧光增强型探针BHP,在HEPES缓冲液中测其对Zn²⁺识别性能。实验结果表明,BHP对Zn²⁺有较高的选择性,对其他金属离子如Cd²⁺,Fe²⁺,Ni²⁺,Pb²⁺,Hg²⁺,Al³⁺,Mn²⁺,Ag⁺,Cu²⁺,Co²⁺,Na⁺,K⁺,Mg²⁺和Ca²⁺无明显荧光增强响应。BHP与Zn²⁺按1：1计量比配位,在生理条件下荧光强度不受pH值影响。在HeLa细胞中对Zn²⁺的造影表明BHP可用于生物体Zn²⁺检测。     

正极材料Li(Ni0.5Mn0.5)1-xMxO2 (M=Ti，Al；x=0，0.02)电化学行为的比较研究

0IntroductionMany efforts have been made to develop newmaterials as an alternative to LiCoO2due to the rela-tively high cost and toxicity of Co.Much attention hasbeen paid to layered structure cathode materials suchas LiMnO2and LiNiO2due to their lower co…