共沉淀法制备的CuGa2O4及其气敏性能

采用共沉淀法制备了CuGa_2O_4粉体,采用X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)等对CuGa_2O_4粉体进行了表征。研究了热处理温度和pH对CuGa_2O_4粉体气敏性能的影响,实验结果表明热处理温度为800℃,pH=6.00(热处理4h)条件下制备出的CuGa_2O_4粉体,在室温下(18±2)℃对三甲胺(TMA)具有较好的气敏选择性和较高灵敏度,对1 000μL·L~(-1)的TMA的灵敏度达到310.1,响应和恢复时间分别约为590和80 s,对1μL·L~(-1)的TMA的灵敏度可达到1.3。     

高电化学活性SnO2/TiO2空心微球的制备及其性能

采用一种简便的无模板溶剂热法合成了尺寸在1μm左右、具有堆叠结构的SnO_2/TiO_2空心微球。合成过程的研究结果表明:SnO_2/TiO_2空心微球在形成过程中经历了空心、被填充、分裂到再次形成空心结构的过程。随后,SnO_2/TiO_2空心微球作为锂离子电池负极材料的电化学性能测试结果表明:SnO_2/TiO_2空心微球在0.1 A·g~(-1)的电流密度下,其首次放电容量达到1 484.9mAh·g~(-1),库伦效率为49.0%。经过600次循环后,其放电容量依然可以达到565.6 mAh·g~(-1),显示了高的容量和循环稳定性。     

水热法合成SnO_2空心球及其对乙醇气敏性能研究

采用水热无模板法合成了SnO_2空心微球,研究了不同溶剂比例对材料形貌的影响。将制备的SnO_2空心球和实心球材料制备旁热式半导体传感器,并对乙醇气体的敏感性能进行研究。结果表明:当乙醇和水的比例达到2:3时,合成了SnO_2空心微球,尺寸约为1-2μm。气敏性能研究表明,在加热温度280℃,SnO_2空心球传感器对50 ppm乙醇的灵敏度达到9,是SnO_2实心球的灵敏度的3倍,且具有较短的响应时间,响应时间为4 s。     

NiFe2O4磁性纳米材料的溶剂热法一步合成

以Fe(NO_3)_3·9H_2O和Ni(NO_3)_2·6H_2O为原料,在未添加任何碱性沉淀剂和高温晶化处理的条件下,通过对实验条件(包括溶剂、溶剂热温度和时间)的优化,利用溶剂热法一步制备了具有良好结晶性和超顺磁性的NiFe_2O_4磁性纳米材料。结果表明:用H_2O和EtOH-H_2O做溶剂都不利于NiFe_2O_4的生成;用EtOH做溶剂,为了获得纯度较高的NiFe_2O_4磁性纳米材料,要保证适当的溶剂热温度和时间;所得材料的磁性能与材料中磁性组分NiFe_2O_4的含量和其结晶程度有关。该制备方法最突出的优点是简单、快速、成本低、从源头消除了污染,且所得的材料磁性能优良。     

溶剂热一锅法合成Ag-TiO2微球及其对过氧化氢的电化学检测

采用溶剂热法,通过调控钛酸四丁酯在醇水浴中的醇解作用和维生素C的烯醇还原性制备了细分散的纳米银修饰TiO_2微球。一锅法的制备过程绿色、程序简单,可获得分布均匀的微球,直径约250 nm,微球表面细分散的银晶格具有(111)晶面特征。构建的Ag-TiO_2微球电极对H_2O_2具有良好的电催化活性,展现出良好的电化学检测性能,当H_2O_2的线性范围为0.1～102μmol·L~(-1)时,传感电极的灵敏度为3.13×10~(-3)μA·L·μmol~(-1)·cm~(-2),最低检测限可达0.04μmol·L~(-1)。所得传感器具有良好的长期稳定性、重现性和重复性,一个月后,性能保持率仍可维持在82.1%。     

MOFs自牺牲模板法制备ZnO及其对NO2的气敏性能

以硝酸锌和2,5-二羟基对苯二甲酸为原料,采用溶剂热法制备了Zn-MOF-74,并利用MOFs自牺牲模板法制备了ZnO纳米材料。利用热重-差示扫描量热法(TG-DSC)、X射线衍射(XRD)、红外光谱测试(FT-IR)、X射线光电子能谱测试(XPS)、氮气吸附-脱附、扫描电镜(SEM)和高倍透射电镜(HRTEM)等方法对合成的样品进行了结构表征。研究了煅烧温度对产物结构、形貌和组成的影响,以及材料的气敏传感性能。结果表明,450℃煅烧Zn-MOF-74制备的六方柱状介孔氧化锌(ZnO450)是由直径约为20 nm的粒子组成的纳米片堆叠形成的,表面残留部分有机官能团,且吸附氧含量明显高于350和550℃处理的样品。基于ZnO450的气敏传感器选择性响应NO_2气体,对100 mL·m~(-3)的NO_2气体响应值达到了77.40,是所测试的其他气体响应值的6～105倍,检出限为0.1 mL·m~(-3);并且在有SO_2等气体共存时,对NO_2的响应值基本不变,抗干扰能力强。该传感器对NO_2优异的响应能力是由于材料表面吸附氧含量高、比表面积及孔径较大,这些有利于NO_2的吸附、表面反应和扩散。     

热处理温度对溶剂热合成Co3O4纳米片气敏和吸附性能之影响

以Co(Ac)2·4H_2O和六次甲基四胺(HMTA)为起始反应物,聚氧乙烯-聚氧丙烯-聚氧乙烯(P123)为表面活性剂,在乙二醇(EG)和水混合溶剂中用溶剂热法得到中间产物,通过煅烧热处理制备了Co_3O_4纳米片。利用XRD、SEM和N_2吸附-脱附等方法进行了样品表征,研究了不同热处理温度对产物形貌和结晶度的影响,以及所制备纳米片的气敏性能。根据气敏测试和吸附性能结果,分析了气敏机理和吸附动力学。结果表明:热处理温度是影响产物形貌的关键因素,350℃是最佳的热处理温度,此时得到的纳米片最薄也最均匀。由于产物形貌变化改变了材料的比表面积,进而影响到产物的气敏性能和吸附性能。总体而言,纳米片厚度越小,比表面积越大,材料的气敏灵敏度和吸附效率越高。     

WS2/CuGa2O4复合材料的制备及其气敏性

采用共沉淀法制备了CuGa₂O₄纳米材料,并利用水热法制备了一系列WS₂/CuGa₂O₄复合材料。结合X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等对制备的材料进行了物相组成、表面形貌以及元素价态的分析。研究了WS₂的复合量对CuGa₂O₄材料检测乙醇气体敏感性能的影响。实验结果表明,当WS₂与CuGa₂O₄质量比为1%时,该复合材料制备的传感器在室温下对100μL·L^-1乙醇气体表现出345.3的灵敏度,响应时间和恢复时间分别为184和69 s,且最低检测限为0.1μL·L^-1。     

石墨烯修饰电极电化学发光分析法测定甲巯咪唑

基于碱性介质中鲁米诺在石墨烯修饰玻碳电极(GCE)表面的弱电化学发光信号可被少量甲巯咪唑显著增敏的原理建立了一种灵敏测定甲巯咪唑的电化学发光新方法。实验考察了反应介质、石墨烯用量、鲁米诺浓度及电化学扫描速率对体系电化学发光信号的影响。结果发现:在8. 0μL的石墨烯用量、0. 01 mol·L~(-1)NaOH、0. 7μmol·L~(-1)鲁米诺及100 mV/s的扫描速率的优化条件下,甲巯咪唑浓度在6. 0×10~(-8)～1. 0×10~(-5)mol·L~(-1)范围内与其增敏的电化学发光强度呈良好的线性关系,检出限为2. 0×10~(-8)mol·L~(-1),其相对标准偏差(RSD)为3. 5%(c=0. 5μmol·L~(-1),n=11)。该方法可用于甲巯咪唑含量的临床测定,结果较为满意。     

抗坏血酸对等离子体质谱法测定汞的增敏作用研究

研究了将抗坏血酸加入到样品中作为增敏剂,以电感耦合等离子体质谱测定汞的增敏效应。考察了硝酸浓度、抗坏血酸浓度、水浴温度和时间等实验条件对增敏作用的影响。结果表明,在5%硝酸,500 mg·L~(-1)的抗坏血酸,水浴温度50℃,时间为20 min的条件下,汞的灵敏度最高,此时,汞的灵敏度增强近30倍,其检出限低至1 ng·L~(-1)。在汞浓度为0.005~10.0μg·L~(-1)范围内线性关系良好,相关系数为0.999,相对标准偏差为5.6%(0.1μg·L~(-1),n=7)。该文还进一步探讨了抗坏血酸产生增敏作用的机理。     

Sol-gel synthesis of K3InF6 and structural characterization of K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18

K₃InF₆ is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K₂InC₁₀O₁₀H₆F₉, K₃InC₁₂O₁₄H₄F₁₈ and K₃InC₁₂O₁₂F₁₈. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K₃InF₆ by decomposition at high temperature. The crystal structure of K₃InC₁₂O₁₄H₄F₁₈ is characterized by complex anions [In(CF₃COO)₄(OH_x)₂]^(5−2x)− and isolated [CF₃COOH_2−x]^(x−1)− molecules with x=2 or 1, surrounded by K⁺ cations. The crystal structure of K₃InC₁₂O₁₂F₁₈ is only constituted by complex anions [In(CF₃COO)₆]³⁻ and K⁺ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K₂InC₁₀O₁₀H₆F₉ and K₃InC₁₂O₁₂F₁₈ were also performed at room temperature on pulverized crystals.     

Structure Study of Bi2.5Na0.5Ta2O9 and Bi2.5Nam−1.5NbmO3m+3 (m=2-4) by Neutron Powder Diffraction and Electron Microscopy

The crystal structures of Bi_2.5Na_0.5Ta₂O₉ and Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=3,4) have been investigated by the Rietveld analysis of their neutron powder diffraction patterns (λ=1.470 Å). These compounds belong to the Aurivillius phase family and are built up by (Bi₂O₂)²⁺ fluorite layers and (A_m-1B_mO_3m+1)^2- (m=2-4) pseudo-perovskite slabs. Bi_2.5Na_0.5Ta₂O₉ (m=2) and Bi_2.5Na_2.5Nb₄O₁₅ (m=4) crystallize in the orthorhombic space group A2₁am, Z=4, with lattice constants of a=5.4763(4), b=5.4478(4), c=24.9710 (15) and a=5.5095(5), b=5.4783(5), c=40.553(3) Å, respectively. Bi_2.5Na_1.5Nb₃O₁₂ (m=3) has been refined in the orthorhombic space group B2cb, Z=4, with the unit-cell parameters a=5.5024(7), b=5.4622(7), and c=32.735(4) Å. In comparison with its isostructural Nb analogue, the structure of Bi_2.5Na_0.5Ta₂O₉ is less distorted and bond valence sum calculations indicate that the Ta-O bonds are somewhat stronger than the Nb-O bonds. The cell parameters a and b increase with increasing m for the compounds Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=2-4), causing a greater strain in the structure. Electron microscopy studies verify that the intergrowth of mixed perovskite layers, caused by stacking faults, also increases with increasing m.     

Composition-induced phase transition in Ca14Zn6−xGa10+xO35+x/2 (x=0.0 and 0.5)

Novel complex oxides Ca₁₄Zn₆Ga₁₀O₃₅ and Ca₁₄Zn_5.5Ga_10.5O_35.25 were prepared in air at 1200 °C, 72 h. Refinements of their crystal structures using X-ray powder diffraction data showed that Ca₁₄Zn₆Ga₁₀O₃₅ is ordered (S.G. F23, =0.0458, R_p=0.0485, R_wp=0.0659, χ²=1.88) and Ca₁₄Zn_5.5Ga_10.5O_35.25 disordered (S.G. F432, =0.0346, R_p=0.0601, R_wp=0.0794, χ²=2.82) variants of the crystal structure of Ca₁₄Zn₆Al₁₀O₃₅. In the crystal structure of Ca₁₄Zn₆Ga₁₀O₃₅, there are large empty voids, which could be partially occupied by additional oxygen atoms upon substitution of Zn²⁺ by Ga³⁺ as in Ca₁₄Zn_5.5Ga_10.5O_35.25. These oxygen atoms are introduced into the crystal structure of Ca₁₄Zn_5.5Ga_10.5O_35.25 only as a part of four tetrahedra (Zn, Ga)O₄ groups sharing common vertex. This creates a situation where even a minor change in the chemical composition leads to considerable anion and cation disordering resulting in a change of space group from F23 (no. 196) to F432 (no. 209).     

La3Ru8B6 and Y3Os8B6, new members of a homologous series R(A)nM3n−1B2n

Two new compounds, La₃Ru₈B₆ and Y₃Os₈B₆, were synthesized by arc melting the elements. Their structural characterization was carried out at room temperature on as-cast samples by using X-ray diffractometry. According to X-ray single-crystal diffraction results these borides crystallize in Fmmm space group (no. 69), Z=4, a=5.5607(1) Å, b=9.8035(3) Å, c=17.5524(4) Å, ρ=8.956 Mg/m³, μ=25.23 mm⁻¹ for La₃Ru₈B₆ and a=5.4792(2) Å, b=9.5139(4) Å, c=17.6972(8) Å, ρ=13.343 Mg/m³, μ=128.23 mm⁻¹ for Y₃Os₈B₆. The crystal structure of La₃Ru₈B₆ was confirmed from Rietveld refinement of X-ray powder diffraction data. Both La₃Ru₈B₆ and Y₃Os₈B₆ compounds are isotypic with the Ca₃Rh₈B₆ compound and their structures are built up from CeCo₃B₂-type and CeAl₂Ga₂-type structural fragments taken in ratio 2:1. They are the members of structural series R(A)_nM_3n−1B_2n with n=3 (R is the rare earth metal, A the alkaline earth metal, and M the transition metal). Structural and atomic parameters were also obtained for La_0.94Ru₃B₂ compound from Rietveld refinement (CeCo₃B₂-type structure, P6/mmm space group (no. 191), a=5.5835(9) Å, c=3.0278(6) Å).     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

The crystal chemistry of Bi6TP2O15+x, T=Fe, Ni, Zn: Isomorphism and polymorphism, structural relationship to Bi6TiP2O16

The crystal structures of compounds with nominal compositions Bi₆FeP₂O_15+x (I), Bi₆NiP₂O_15+x (II) and Bi₆ZnP₂O_15+x (III) were determined from single-crystal X-ray diffraction data. They are monoclinic, space group I2, Z=2. The lattice parameters for (I) are a=11.2644(7), b=5.4380(3), c=11.1440(5) Å, β=96.154(4)°; for (II) a=11.259(7), b=5.461(4), c=11.109(7) Å, β=96.65(1)°; for (III) a=19.7271(5), b=5.4376(2), c=16.9730(6) Å, β=131.932(1)°. Least squares refinements on F² converged for (I) to R1=0.0554, wR₂=0.1408; for (II) R₁=0.0647, wR₂=0.1697; for (III) R₁=0.0385, wR₂=0.1023. The crystals are complexly twinned by 2-fold rotation about , by inversion and by mirror reflection. The structures consist of edge-sharing articulations of OBi₄ tetrahedra forming layers in the a-c plane that then continue by edge-sharing parallel to the b-axis. The three-dimensional networks are bridged by Fe and Ni octahedra in (I) and (II) and by Zn trigonal bipyramids in (III) as well as by oxygen atoms of the PO₄ moieties. Bi also randomly occupies the octahedral sites. Oxygen vacancies exist in the structures of the three compounds due to required charge balances and they occur in the octahedral coordination polyhedron of the transition metal. In compound (III), no positional disorder in atomic sites is present. The Bi-O coordination polyhedra are trigonal prisms with one, two or three faces capped. Magnetic susceptibility data for compound (I) were obtained between 4.2 and 350 K. Between 4.2 and 250 K it is paramagnetic, μ_eff=6.1 μ_B; a magnetic transition occurs above 250 K.     

A new 2212-type stair like structure: Bi14Sr21Fe12O61, m=5 member of the generic [Bi2Sr3Fe2O9]m[Bi4Sr6Fe2O16] family

A new oxide, Bi₁₄Sr₂₁Fe₁₂O_61, with a layered structure derived from the 2212 modulated type structure Bi₂Sr₃Fe₂O₉, was isolated. It crystallizes in the I2 space group, with the following parameters: a=16.58(3) Å, b=5.496(1) Å, c=35.27(2) Å and β=90.62°. The single crystal X-ray structure determination, coupled with electron microscopy, shows that this ferrite is the m=5 member of the [Bi₂Sr₃Fe₂O₉]_m[Bi₄Sr₆Fe₂O₁₆] collapsed family. This new collapsed structure can be described as slices of 2212 structure of five bismuth polyhedra thick along , shifted with respect to each other and interconnected by means of [Bi₄Sr₆Fe₂O₁₆] slices. The latter are the place of numerous defects like iron or strontium for bismuth substitution; they can be correlated to intergrowth defects with other members of the family.     

Synthesis and structural characterization of Al7C3N3-homeotypic aluminum silicon oxycarbonitride, (Al7−xSix)(OyCzN6−y−z) (x∼1.2, y∼1.0 and z∼3.5)

A new aluminum silicon oxycarbonitride, (Al_5.8Si_1.2)(O_1.0C_3.5N_1.5), has been synthesized and characterized by X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS). The title compound is hexagonal with space group P6₃/mmc and unit-cell dimensions a=0.322508(4) nm, c=3.17193(4) nm and V=0.285717(6) nm³. The atom ratios of Al:Si and those of O:C:N were, respectively, determined by EDX and EELS. The initial structural model was successfully derived from the XRPD data by the direct methods and further refined by the Rietveld method. The crystal is most probably composed of four types of domains with nearly the same fraction, each of which is isotypic to Al₇C₃N₃ with space group P6₃mc. The existence of another new oxycarbonitride (Al_6.6Si_1.4)(O_0.7C_4.3N_2.0), which must be homeotypic to Al₈C₃N₄, has been also demonstrated by XRPD and TEM.     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

Synthesis and crystal structure of Bi6.4Pb0.6P2O15.2: A new polymorph in the series Bi6+xM1−xP2O15+y

Bi_6.4Pb_0.6P₂O_15.2 is a polymorph of structures with the general stoichiometry Bi_6+xM_1−xP₂O_15+y. However, unlike previously published structures that consist of layers formed by edge sharing OBi₄ tetrahedra bridged by PO₄ and TO₆ (T=transition metal) tetrahedra and octahedra the title compound's structure is more complex. It is monoclinic, C2, a=19.4698(4) Å, b=11.3692(3) Å, c=16.3809(5) Å, β=101.167(1)°, Z=10. Single-crystal X-ray diffraction data were refined by least squares on F² converging to R₁=0.0387, wR₂=0.0836 for 7023 intensities. The crystal twins by mirror reflection across (001) as the twin plane and twin component 1 equals 0.74(1). Oxygen ions are in tetrahedral coordination to four metal ions and the O(BiPb)₄ units share corners to form layers that are part of the three-dimensional framework. Eight oxygen ions form a cube around the two crystallographically independent Pb ions. Pb-O bond lengths vary from 2.265(14) to 2.869(14) Å. Pairs of such cubes share an edge to form a Pb₃O₂₀ unit. The two oxygen ions from the unshared edges are part of irregular Bi polyhedra. Other oxygen ions of Bi polyhedra are part only of O(BiPb)₄ units, and some oxygen ions of the polyhedra are also part of PO₄ tetrahedra. One, two, three and or four PO₄ moieties are connected to the Bi polyhedra. Bi-O bond lengths ?3.1 Å vary from 2.090(12) to 3.07(3) Å. The articulations of Pb cubes, Bi polyhedra and PO₄ tetrahedra link into the three-dimensional structure.