基于SnO2-In2O3复合纳米纤维的薄膜型甲醛传感器研究

采用双喷嘴静电纺丝技术制备了SnO2/In2O3复合纳米纤维,涂敷于带有金电极的氧化铝陶瓷管表面形成敏感薄膜,设计了一种新型薄膜型甲醛传感器。采用X射线衍射仪、热场发射扫描电子显微镜、O2-程序升温脱附仪和X-射线光电子能谱(XPS)仪,表征了SnO2/In2O3纳米纤维的相组成和微观形貌,分析了敏感薄膜成分配比对甲醛吸附强度与电化学的影响机理。在气体传感器静态测试系统上,采用XEDWS-60A型气敏元件分析仪测试了甲醛传感器敏感特性、温度特性、湿度特性、动态响应、抗干扰和稳定性。结果表明,以S50纳米纤维为敏感薄膜(膜厚为240 nm)的甲醛传感器,在温度为500℃,甲醛浓度为0.5~50 mg/L时,传感器线性度和灵敏度最大值分别为96.8%和97.5%,承受的温度上限为1000℃,动态响应和恢复时间分别为23和12 s。此传感器对CO、NO x、甲苯、菲、丙酮和甲醇等气体具有良好的抗干扰性能。在汽车上连续使用12个月后,响应衰减了5.5%,响应正常时间为6.4个月。     

Mb/AuNPs/MWCNTs/GC电极对H2O2电催化性能的研究

采用还原法制备了AuNPs/MWCNTs复合材料,并构建了氧化还原蛋白质的固定化和生物传感界面AuNPs/MWCNTs/GC电极.以肌红蛋白(Myoglobin,Mb)为例,研究了固定化蛋白质在AuNPs/MWCNTs/GC电极上的直接电化学.结果表明,AuNPs/MWCNTs复合材料不仅能有效地促进Mb与电极表面的直接电子转移,而且能很好地保持固定化Mb的生物催化活性.Mb/AuNPs/MWCNTs/GC电极对H2O2具有良好的电催化还原性能,其线性响应范围为1～138μmol·L-1,检测限为0.32μmol·L-1(S/N=3),并具有较低的米氏常数(0.143 mmol·L-1).该电极操作简单,响应迅速,稳定性和重现性好,有望用于蛋白质的固定化及第三代生物传感器的制备.     

水热法制备MoO3-GQDs的三甲胺气敏性能

采用水热法制备了一系列具有不同碳量子点(GQDs)含量的MoO3?GQDs纳米复合材料,利用X射线衍射、扫描电子显微镜、透射电子显微镜、FTIR等对MoO3?GQDs复合材料进行了表征,研究了其气敏性能。结果表明,复合材料中GQDs的含量对MoO3?GQDs复合材料的气敏响应和选择性有显著影响。MoO3?GQDs纳米复合材料(S?6,GQDs悬浮液的含量为6 mL)传感器在230℃时对三甲胺(TMA)表现出高的气敏响应和好的气敏选择性;该传感器对1000μL·L^-1 TMA的响应为74.08;对1000μL·L^-1 TMA的响应时间和恢复时间分别为73和34 s;S?6复合材料气敏传感器在230℃时可以检测到1μL·L^-1的TMA。     

基于负温度系数热敏电阻的催化燃烧型一氧化碳传感器

介绍一种能检测0.0232 g/m3CO的新型催化燃烧型传感器。这种传感器使用电阻温度系数高的负温度系数热敏电阻(NTCT)代替传统的铂丝线圈。传统的催化燃烧型传感器只能检测百分浓度的可燃气体,而基于NTCT的催化燃烧型CO传感器可以检测到0.0232 g/m3CO气体。当桥电压为9 V时,传感器输出信号与CO浓度在0.0232~0.58 g/m3之间具有良好的线性关系。传感器对0.58 g/m3CO的响应和恢复时间分别为50和120 s。考察了传感器的选择性和长期稳定性,结果表明:传感器对甲烷等气体具有较好的选择性,老化处理后的传感器,连续观察100 d,对CO的响应强度未发生明显下降。     

基于纳米CuO敏感材料的电流型NO2传感器研究

采用浸渍技术在多孔的氧化钇稳定的氧化锆(YSZ)中制备了纳米CuO敏感材料,并以其为敏感电极,YSZ为固体电解质,制备了一种新型的电流型NO2传感器。采用X射线衍射仪和扫描电子显微镜表征了NO2传感器的相组成和微观形貌,应用IM6e型电化学工作站测试了其气敏性能。结果表明,CuO颗粒粒径约为100 nm,且与基体结合紧密。在500～600℃时,传感器对NO2表现出良好的敏感性。在极化电压为-300 mV,NO2体积分数为0～5.0×10-4时,传感器的响应电流值与NO2浓度之间呈良好的线性关系。在被测气体总流量为400 cm3/min时,传感器信号90%的响应和恢复时间均为50 s。传感器响应信号在测试时间内具有良好的稳定性。共存气体O2和CO2对传感器的敏感性几乎没有影响。     

基于La1-xSrxMnO3敏感材料的电流型NOx传感器研究

采用喷雾热分解技术制备了NO x传感器敏感材料La1-x Sr x MnO3,以多孔的氧化钇稳定的氧化锆(YSZ)为固体电解质,设计了一种新型的电流型NO x传感器。采用X射线衍射仪、扫描电子显微镜、程序升温脱附仪和X-射线光电子能谱(XPS)仪,表征了La1-x Sr x MnO3粉体的相组成和微观形貌,分析了敏感材料La1-x Sr x MnO3对NO x吸附强度与Mn氧化价态变化机理。在NO x传感器气敏性能测试装置上,利用DJS-292型恒电位仪测试了传感器敏感特性、温度特性、动态响应、抗干扰和稳定性。结果表明,以La0.5Sr0.5MnO3为敏感材料的NO x传感器,在极化电压为#300 mV,NO x浓度为0~1000μL/L时,NO x传感器线性度和灵敏度最大值分别为96.6%和97.1%,承受的温度上限为1200℃。在650℃,浓度从200μL/L转换到500μL/L时,NO x传感器动态响应和恢复时间分别为25 s和15 s。此传感器对CO、SO2、甲醛、乙醛、菲、丙酮和丙烯醛等气体具有良好的抗干扰性能。在汽车上连续使用12个月后,响应电流衰减了8.6%,响应电流正常时间为5个月。     

GO/Fe3O4/有机胺复合材料的制备及对结晶紫染料的吸附性能

用改进的Hummers法制备了氧化石墨烯,用乙二胺、乙二胺与丁二胺/己二胺混溶来改性氧化石墨烯。用水热法制备了Fe3O4,并用物理混合法制备了GO/Fe3O4/有机胺的三元复合体系。用透射电镜、扫描电镜、红外光谱、热重分析、X射线衍射、VSM和XPS等对所制得的样品进行了结构表征和性能测试,研究了三元复合粒子对结晶紫染料的吸附性能及影响结晶紫染料吸附效果的因素。结果表明:所制备的Fe3O4的平均粒径约为200 nm,粒径分布均匀;复合物中GO为典型的片状结构,GO及有机胺的掺杂没有影响Fe3O4的尖晶石结构;复合物为超顺磁性,Ms为53.0 emu·g~(-1)。吸附结果表明:石墨烯/Fe3O4/有机胺的三元复合材料对结晶紫染料的最大吸附量随浓度增大而增大,而吸附结晶紫染料的移除率却随结晶紫染料浓度增大而减小,并趋向一定值;乙二胺和己二胺混溶比例为5∶1的GO/Fe3O4复合材料吸附性能最佳:结晶紫浓度为400 mg·L~(-1),最大吸附量为164.3 mg·L~(-1)。     

基于Nafion共固定Pt/PEDOT/MWCNTs复合材料和辣根过氧化物酶电化学H2O2生物传感器

以多壁碳纳米管(MWCNTs)为载体,采用改进的一步化学合成法制备了Pt/聚3,4-乙烯二氧噻吩(PEDOT)/MWCNTs复合材料,以Nafion共固定此复合材料和辣根过氧化物酶(HRP)从而研制出性能优良的生物传感器。利用扫描电子显微镜(SEM)、傅立叶变换红外(FTIR)光谱和紫外-可见(UV-Vis)吸收光谱对制得的复合材料进行表征,同时通过循环伏安法详细探讨了该传感器对H2O2的响应性能。结果表明,固定的HRP仍能维持其结构和生物活性,并进行有效和稳定的直接电子转移。该方法由于使用了载体MWCNTs及NaBH4的进一步还原过程,明显增强了传感器对H2O2的电催化活性。在优化条件下,该传感器对H2O2在0.008～1.8mmol/L浓度范围内成线性相关,检出限为0.4μmol/L,且具有良好的重现性、稳定性和选择性。     

葡萄糖氧化酶在纳米金/壳聚糖/离子液体BMIMPF6修饰电极上的直接电化学及其应用

用滴涂法将葡萄糖氧化酶(GOD)修饰到纳米金(Nano-Au)/壳聚糖(CS)/1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)复合材料修饰的金电极表面,制备了GODNano-Au/CS/BMIMPF6/Au生物传感器。采用循环伏安法(CV)和扫描电子显微镜(SEM)对该生物传感器进行表征,并对其制备条件、电化学性质进行了较为详细的研究。结果表明,复合材料不仅为GOD提供了良好的微环境,而且通过纳米尺寸效应和离子液体的高导电性,促进电子转移,使GOD具有更高的活性。该修饰电极可作为葡萄糖生物传感器,在最优条件下,葡萄糖浓度在1.0×10-4~1.0×10-6 mol·L-1范围内呈良好的线性关系,其线性相关系数r=0.9995,检出限为3.85×10-8 mol·L-1。     

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%。     

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.     

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…     

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.     

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.     

Ion-beam irradiation of lanthanum compounds in the systems La2O3-Al2O3 and La2O3-TiO2

Thin crystals of La₂O₃, LaAlO₃, La_2/3TiO₃, La₂TiO₅, and La₂Ti₂O₇ have been irradiated in situ using 1 MeV Kr²⁺ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La₂O₃ remained crystalline to a fluence greater than 3.1×10¹⁶ ions cm⁻² at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (T_c) of 647 K for LaAlO₃, 840 K for La₂Ti₂O₇, 865 K for La_2/3TiO₃, and 1027 K for La₂TiO₅. The T_c values observed in this study, together with previous data for Al₂O₃ and TiO₂, are discussed with reference to the melting points for the La₂O₃-Al₂O₃ and La₂O₃-TiO₂ systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T_c and melting temperature (T_m) in the two systems. More complex relationships exist between T_c and crystal structure, with the stoichiometric perovskite LaAlO₃ being the most resistant to amorphisation.     

Synthesis, crystal structure, infrared and Raman spectra of Sr4Cu3(AsO4)2(AsO3OH)4·3H2O and Ba2Cu4(AsO4)2(AsO3OH)3

The two new compounds, Sr₄Cu₃(AsO₄)₂(AsO₃OH)₄·3H₂O (1) and Ba₂Cu₄(AsO₄)₂(AsO₃OH)₃(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As₂O₅-H₂O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å³, Z=4 for 1; space group P4₂/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å³, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu²⁺-(XO₄)³⁻ layers (X=P⁵⁺, As⁵⁺) linked by M cations (M=alkali, alkaline earth, Pb²⁺, or Ag⁺) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu₂O₈ centrosymmetric dimers crosslinked by As1φ₄ tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu₂O₈ centrosymmetric dimers of CuO₅ edge-sharing polyhedra, crosslinked by As1O₄ tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.     

Raman scattering investigations on lanthanum-doped Bi4Ti3O12-SrBi4Ti4O15 intergrowth ferroelectrics

The ferroelectric ceramics of Bi₄Ti₃O₁₂, SrBi₄Ti₄O₁₅, and lanthanum-doped Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅ were synthesized, and their Raman spectra were investigated. La-doping resulted in the enlargement of remnant polarization of Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅. The structure of the Bi₂O₂ layers and TiO₆ octahedra of the intergrowth was found to be different from those of Bi₄Ti₃O₁₂ and SrBi₄Ti₄O₁₅. La³⁺ ions exhibit pronounced selectivity for the occupation of A site as La content is lower than 0.50, and tend to be incorporated into Bi₂O₂ layers when the La content is higher than 0.50. Lanthanum substitution brings about the structural phase transition in Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅. The variation of ferroelectric property may be attributed to combined contribution from the decreasing of the oxygen vacancies, the relaxation of the lattice distortion, the destroying of the insulation and the space charge compensation effects of the Bi₂O₂ slabs.     

g-C_3N_4/CaTi_2O_5复合材料制备及其光催化性能

利用类石墨氮化碳(g-C_3N_4)和亚稳相钙钛氧化物(CaTi_2O_5)固相法制备C_3N_4/CaTi_2O_5复合材料。利用X射线衍射(XRD)、金相显微镜、扫描电子显微镜(SEM)及附带能谱分析仪(EDS)和N2吸附-脱附对样品的显微结构和比表面积进行检测分析,并用紫外-可见吸收光度计(UV-Vis)测试了样品的光吸收性能,研究C_3N_4与CaTi_2O_5物质的量之比(nC_3N_4/nCaTi_2O_5)对C_3N_4/CaTi_2O_5复合样品的物相结构和微观形貌的影响,同时考察C_3N_4/CaTi_2O_5复合样品在可见光照射下光催化降解罗丹明染料效果。实验结果表明:相比纯C_3N_4和CaTi_2O_5样品,C_3N_4/CaTi_2O_5复合样品在可见光下具有较高的光催化性能,随着nC_3N_4/nCaTi_2O_5增加,样品的光催化降解率随之增加而后降低,当nC_3N_4/nCaTi_2O_5=1∶1时,样品的光催化降解率达到最大值99.5%,并且循环重复利用5次后,样品的光催化剂降解率仍几乎保持不变。复合样品光催化性能提高主要归因于复合能级结构有效地抑制了电子和空穴复合所致。     

Magnetic diphase nanostructure of ZnFe2O4/γ-Fe2O3

Magnetic diphase nanostructures of ZnFe₂O₄/γ-Fe₂O₃ were synthesized by a solvothermal method. The formation reactions were optimized by tuning the initial molar ratios of Fe/Zn. All samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and Raman spectra. It is found that when the initial molar ratio of Fe/Zn is larger than 2, a diphase magnetic nanostructure of ZnFe₂O₄/γ-Fe₂O₃ was formed, in which the presence of ZnFe₂O₄ enhanced the thermal stability of γ-Fe₂O₃. Further increasing the initial molar ratio of Fe/Zn larger than 6 destabilized the diphase nanostructure and yielded traces of secondary phase α-Fe₂O₃. The grain surfaces of diphase nanostructure exhibited a spin-glass-like structure. At room temperature, all diphase nanostructures are superparamagnetic with saturation magnetization being increased with γ-Fe₂O₃ content.     

g-C3N4/CaTi2O5复合材料制备及其光催化性能

利用类石墨氮化碳（g-C₃N₄）和亚稳相钙钛氧化物（CaTi₂O₅）固相法制备C₃N₄/CaTi₂O₅复合材料。利用X射线衍射（XRD）、金相显微镜、扫描电子显微镜（SEM）及附带能谱分析仪（EDS）和N₂吸附-脱附对样品的显微结构和比表面积进行检测分析,并用紫外-可见吸收光度计（UV-Vis）测试了样品的光吸收性能,研究C₃N₄与CaTi₂O₅物质的量之比（n_C3N4/nCaTi₂O₅）对C₃N₄/CaTi₂O₅复合样品的物相结构和微观形貌的影响,同时考察C₃N₄/CaTi₂O₅复合样品在可见光照射下光催化降解罗丹明染料效果。实验结果表明：相比纯C₃N₄和CaTi₂O₅样品,C₃N₄/CaTi₂O₅复合样品在可见光下具有较高的光催化性能,随着n_C3N4/nCaTi₂O₅增加,样品的光催化降解率随之增加而后降低,当n_C3N4/nCaTi₂O₅=1：1时,样品的光催化降解率达到最大值99.5%,并且循环重复利用5次后,样品的光催化剂降解率仍几乎保持不变。复合样品光催化性能提高主要归因于复合能级结构有效地抑制了电子和空穴复合所致。