钨酸铋/还原氧化石墨烯二氧化氮传感器的研制EI北大核心CSCD

通过一步水热法合成了钨酸铋/还原氧化石墨烯(Bi_(2)WO_(6)/rGO)复合材料,并基于此材料制备了NO_(2)气体传感器。用X射线衍射光谱、拉曼光谱、扫描电镜和透射电镜对复合材料的晶相、形貌和微观结构进行的表征表明,Bi_(2)WO_(6)和rGO成功复合,且获得了具有花状超结构的Bi_(2)WO_(6)/rGO复合材料。将复合材料负载到叉指电极上制备了NO_(2)气体传感器,利用自制的气敏测试装置对气体传感器的气敏性能进行了系统测试。结果表明,Bi_(2)WO_(6)/rGO复合气体传感器在室温下对NO_(2)气体具有较高选择性、较高响应值和较好长期稳定性,对质量浓度为47.03 mg/m^(3)NO_(2)的响应值为28.35%,是纯rGO气体传感器的3.5倍,响应时间为55 s,恢复时间为549 s,对NO_(2)的检出限为62μg/m^(3)。     

基于氧化锌/聚苯胺复合材料的薄膜型甲醇传感器研究

采用低温水热法制备了纳米氧化锌(ZnO),并利用原位聚合法制备了ZnO/聚苯铵复合材料。将制备的ZnO/PANI纳米晶粒均匀涂覆于刻有叉指Pt电极玻璃基底表面形成敏感薄膜,设计了一种薄膜型甲醇传感器。采用X射线衍射仪、扫描电子显微镜和X-射线光电子能谱(XPS)仪表征了ZnO/PANI纳米晶粒的相组成和微观形貌,分析了敏感薄膜成分配比对甲醇气敏机理和电化学特性,测试了甲醇传感器敏感特性、温度特性、湿度特性、动态响应和选择稳定性。结果表明,以PZ50纳米晶粒为敏感薄膜的甲醇传感器,在温度为30℃、甲醇气体浓度为25 mg/m~3时,传感器响应最大值为1795.6,相对湿度限值为90%,动态响应和恢复时间分别为6.9和19.6 s。此传感器对N_2O、甲醛、乙醇、丙酮和1,3-丁二烯等气体无明显响应,在汽车上连续使用12周后,响应衰减了2.3%。     

纳米复合材料ZnO/TiO_2-ZrO_2的制备及其微波辅助光催化降解甲基橙

采用EO20PO70EO20（P123）作为模板剂,通过溶胶-凝胶-程序升温溶剂热一步法将金属氧化物ZnO掺杂到TiO2-ZrO2二元体系中,经过450℃煅烧,制备了三元纳米半导体复合材料ZnO/TiO2-ZrO2。通过X-射线衍射、氮气吸附-脱附测定、透射电子显微镜以及扫描电镜配合X-射线能量色散谱仪等测试手段对合成...     

Y掺杂的ZnO纳米纤维材料的制备及其气敏传感器作用机理

采用静电纺丝法成功制备了Y掺杂的ZnO纳米纤维.并通过X射线衍射(XRD),扫描电子显微镜(SEM),能量色散X射线(EDX),透射电子显微镜(TEM)以及热重差热分析(TG-DTA)等手段对样品的结构和形貌进行了表征分析.同时用纯的ZnO和Y掺杂的ZnO纳米纤维制备了传感器,对浓度为(1-200)×10^-6 (体积分数)丙酮的气敏特性进行了测试分析.测试结果表明,可以通过简单控制纳米纤维中Y的含量,来微调该传感器的气敏特性.同时也发现通过Y掺杂, ZnO纳米纤维对丙酮的气敏特性有所改善,表现出很高的响应.纯ZnO和Y掺杂ZnO制成的传感器对几种潜在干扰气体表现出良好的选择性,比如氨气、苯、甲醛、甲苯以及甲醇.本文最后也讨论了该传感器的气敏作用机理.     

旋涂水溶液前驱体制备氧化锌薄膜及其性质

通过旋涂法, 采用Zn(OAc)2·2H2O和聚环氧乙烷(PEO)的水溶液为前驱体在不同的热处理温度下制备了ZnO薄膜. PEO的加入增加了溶液的成膜性, 其较低的热分解温度有利于制得纯净的ZnO薄膜. 文中考察了在不同热处理温度下制备的ZnO薄膜的形貌、结晶性、带隙(Eg)以及电导性. 原子力显微镜(AFM)测试表明在热处理温度为400、450和500 ℃制备的ZnO薄膜的粗糙度均方根值分别为3.3、2.7和3.6 nm. 采用透射电子显微镜(TEM)测试发现ZnO薄膜中含有大量纳晶粒子. 通过测试ZnO薄膜的UV-Vis吸收光谱, 根据薄膜位于373 nm处的吸收带边计算得到ZnO的带隙为3.3 eV. 通过对薄膜的电流-电压(I-V)曲线的测试计算得到在热处理温度为400、450和500 ℃制备的ZnO薄膜的电阻率分别为3.3×109、2.7×109和6.6×109 Ω·cm. 450 ℃时制备的ZnO薄膜的电阻率最小, 主要是由于较高的热处理温度有利于提高薄膜的纯度、密度和吸附氧. 而纯度较高、密度较大的薄膜电阻率比较小; 吸附氧含量增加, 晶界势垒增大, 电阻率增大. 因此在纯度和吸附氧的双重作用下450 ℃时制备的ZnO薄膜的电阻率最小, 而500 ℃时制备的ZnO薄膜的电阻率最大.     

溶剂热法制备石墨烯/SnO2及其气敏性

采用溶剂热法制备了石墨烯/SnO_2(G/SnO_2)纳米材料,利用扫描电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱(Raman)等对G/SnO_2进行了表征,研究了石墨烯的量和溶剂热温度对该纳米材料气敏性能的影响。实验结果表明,石墨烯可以调节SnO_2晶体的生长:当石墨烯上清液的量为1 mL、热处理温度为160℃时,制备的G/SnO_2纳米材料在室温下对氨气具有较好的气敏选择性和较高的灵敏度;且当气体体积浓度为1 000μL·L~(-1)时,对NH3的灵敏度为266.4,检出限达到了0.01μL·L~(-1)。     

ZnO掺杂的SnO_2纳米纤维的制备、表征及气敏机理(英文)

以二水氯化亚锡(SnCl2·2H2O)为盐原料,采用静电纺丝的方法制备了SnO2纳米纤维.为了研究ZnO掺杂对SnO2形貌、结构及化学成分的影响,分别制备了不同含量ZnO掺杂的SnO2/ZnO复合材料.利用热重-差热分析(TG-DTA)、X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱仪、扫描电镜(SEM)及能量色散X射线(EDX)光谱对材料的结晶学特性及微结构进行了表征.制备的SnO2/ZnO复合材料是由纳米量级的小颗粒构成的分级结构材料.ZnO含量不同,对应的SnO2/ZnO复合材料结构不同.表征结果表明ZnO的掺杂量对SnO2材料的形貌及结构均起着重要作用.将制备的不同ZnO含量的SnO2/ZnO复合材料进行气敏测试,测试结果表明,Sn:Zn摩尔比为1:1制作的气敏元件对甲醇的灵敏度优于其它摩尔比的气敏元件.讨论了SnO2/ZnO复合材料气敏元件的敏感机理.同时针对Sn:Zn摩尔比为1:1时表现出最好的气敏响应,分析了其原因,包括Zn的替位式掺杂行为、ZnO的催化作用、过量ZnO对SnO2生长的抑制作用以及SnO2与ZnO晶粒界面处的异质结.     

片状Co9S8/ZnS/C复合材料的制备及电催化产氧性能

以六水合硝酸钴[Co(NO_3)_2·6H_2O]为钴源、六水合硝酸锌[Zn(NO_3)_2·6H_2O]为锌源、2,2′-硫代二乙酸(C4H6O4S)为硫源,采用溶剂热法制备出了片状的Co_9S_8/ZnS/C复合材料。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和N_2吸附/脱附测试等手段对于片状Co_9S_8/ZnS/C复合材料结构和形貌等进行表征,同时对片状Co_9S_8/ZnS/C复合材料进行了电催化产氧性能测试。结果表明:片状Co_9S_8/ZnS/C复合材料的起始过电位为390 mV,塔菲尔斜率为144 mV·dec~(-1),具有高的电催化产氧性能。     

分级多孔结构ZnO的秸秆生物模板法制备及光催化性能

以玉米秸秆为生物模板,经过焙烧工艺制备了具有秸秆分级多孔结构的ZnO纳米材料.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、热重分析、氮气吸附-脱附分析(BET)、紫外-可见温反射光谱(UV-Vis-DRS)、X射线光电子能谱(XPS)等对样品的组成和微观结构进行表征.结果表明,通过模板法制备的ZnO为纤锌矿型,具有分级多孔结构,晶体粒径为46.2 nm,材料比表面积为32.8m~2/g.以亚甲基蓝为目标污染物,氙灯光照3.0 h后,采用模板法制备的ZnO对亚甲基蓝的降解率明显高于无模板ZnO,分别为98%和74%.研究了污染物浓度、催化剂投加量及重复使用对降解率的影响,结果表明,模板法制备的ZnO光催化性能稳定,可多次回收利用,重复使用5次后其降解率维持在95%.     

纳米复合材料Ag/ZnO的制备与微波增强光催化二甲酚橙

采用溶胶凝胶再结合程序升温溶剂热法制备了纳米复合材料Ag/ZnO,通过X射线衍射(XRD)、N2吸附-脱附、透射电子显微镜(TEM)以及扫描电子显微镜配合X射线能量色散谱仪(SEM-EDS)等测试手段对其结构、形貌等进行了表征.结果表明,复合材料中Ag以单质形式存在且掺杂于ZnO表面,产物具有六方晶系纤锌矿结构,其颗粒...     

Li_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3,Na_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3的离子交换研究

研究了在不同温度下的NaNO3和AgNO3水溶液中Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3离子交换行为.实验表明Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3均显示出了高选择性与Na+和Ag+进行离子交换的特征,且对Ag+的选择性高于Na+.升高温度可显著提高Ag/Li和Ag/Na的交换反应速度.     

Crystal growth, structure determination, and optical properties of new potassium-rare-earth silicates K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Single crystals of K₃RESi₂O₇ (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K₃RESi₂O₇ that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K₃LuSi₂O₇, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K₃LuSi₂O₇ crystallizes in space group P6₃/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P6₃/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K₃GdSi₂O₇); a=9.88730(10) Å, c=14.3856(3) Å, (K₃TbSi₂O₇); a=9.8673(2) Å, c=14.3572(4) Å, (K₃DySi₂O₇); a=9.8408(3) Å, c=14.3206(6) Å, (K₃HoSi₂O₇); a=9.82120(10) Å, c=14.2986(2) Å, (K₃ErSi₂O₇); a=9.80200(10) Å, c=14.2863(4) Å, (K₃TmSi₂O₇); a=9.78190(10) Å, c=14.2401(3) Å, (K₃YbSi₂O₇). The optical properties of the silicates were investigated and K₃TbSi₂O₇ was found to fluoresce in the visible.     

Near infrared study of aqueous rare-earth ethylsulfates

The near infrared spectra of aqueous solutions of the ethylsulfates of La, Nd, Gd, Tb, Er, Yb, Lu, Y, and Na have been determined from about 0.2 mol-dm^–3 to nearly saturation. The extinction coefficients of water have been calculated taking into account the absorption of ethylslfate anions determined in separate experiments. Their values appeared to be nearly the same as that of pure water. The relative contents of free OH groups in 0.5 and 0.7M solutions have been estimated from the absorbances at 1160 nm. They were lower in solutions of the heavy rare-earth ethylsulfates (Tb, Er, Yb, Lu) than in equimolar solutions of the lighter ones (La, Nd), confirming our previous view that secondary hydration of the heavy trivalent rare-earth cations is distinctly stronger than that of the lighter ones. A comparison of the spectra of these aqueous ethylsulfates with those of perchlorates shows that the structure-breaking ability of the C₂H₅SO ₄ ^– ion is much smaller than that of perchlorate anion.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃-Bi₂O₃-ZnO-Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1 350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1 364,介电损耗低至1.2%。     

电感耦合等离子体光谱法(ICP-AES)测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量

针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限：Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限：Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。     

Structural studies of five layer Aurivillius oxides: A2Bi4Ti5O18 (A=Ca, Sr, Ba and Pb)

The room temperature structures of the five layer Aurivillius phases A₂Bi₄Ti₅O₁₈ (A=Ca, Sr, Ba and Pb) have been refined from powder neutron diffraction data using the Rietveld method. The structures consist of [Bi₂O₂]²⁺ layers interleaved with perovskite-like [A₂Bi₂Ti₅O₁₆]²⁻ blocks. The structures were refined in the orthorhombic space group B2eb (SG. No. 41), Z=4, and the unit cell parameters of the oxides are a=5.4251(2), b=5.4034(1), c=48.486(1); a=5.4650(2), b=5.4625(3), c=48.852(1); a=5.4988(3), b=5.4980(4), c=50.352(1); a=5.4701(2), b=5.4577(2), c=49.643(1) for A=Ca, Sr, Ba and Pb, respectively. The structural features of the compounds were found similar to n=2-4 layers bismuth oxides. The strain caused by mismatch of cell parameter requirements for the [Bi₂O₂]²⁺ layers and perovskite-like [A₂Bi₂Ti₅O₁₆]²⁻ blocks were relieved by tilting of the TiO₆ octahedra. Variable temperature synchrotron X-ray studies for Ca and Pb compounds showed that the orthorhombic structure persisted up to 675 and 475 K, respectively. Raman spectra of the compounds are also presented.     

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.     

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.     

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.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃‐Bi₂O₃‐ZnO‐Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1364,介电损耗低至1.2%。