RuO_2/TiO_2纳米薄膜的新构建及对CO_2的电催化还原

在旋涂有球状纳米TiO2薄膜的导电玻璃(ITO)基底上采用循环伏安法(CV)电沉积RuO2作为电催化还原CO2的阴极.采用场发射扫描电子显微镜(FE-SEM)表征了RuO2/TiO2纳米薄膜的形貌,并应用近稳态电位扫描法和计时电流法(i～t)研究了薄膜的电催化CO2性能.结果表明所构建的RuO2/TiO2薄膜中纳米粒子大小均匀、排列致密,且较传统热分解法所得催化剂有更好的电催化性能.     

纯相Li2MnO3薄膜的制备及作为锂离子电池正极材料的电化学行为

采用固相烧结法制备了纯相Li₂MnO₃正极材料及靶材,采用脉冲激光沉积（PLD）法在氧气气氛、不同温度下沉积了Li₂MnO₃薄膜. 通过X射线衍射（XRD）和拉曼（Raman）光谱表征了薄膜的晶体结构,采用扫描电镜（SEM）观察薄膜形貌及厚度,利用电化学手段测试了Li₂MnO₃薄膜作为锂离子电池正极材料性能. 结果表明,PLD 方法制备的纯相Li₂MnO₃薄膜随着沉积温度升高薄膜结晶性变好. 25 ℃沉积的薄膜难以可逆充放电,400 ℃沉积的薄膜具有较高的电化学活性和循环稳定性. 相对于粉末材料,400与600 ℃制备的Li₂MnO₃薄膜电极平均放电电位随着循环次数的衰减速率明显低于相应的粉体材料.     

脉冲电沉积法制备Pt-TiO2 纳米管电极及其电催化性能

采用阳极氧化法在高纯钛片上原位组装TiO2纳米管阵列, 然后用脉冲电沉积方法将Pt沉积到TiO2纳米管阵列上, 制备出Pt-TiO2纳米管电极. 利用XRD和SEM对所获电极的微观结构和形貌进行表征, 结果表明, Pt纳米颗粒以花簇状分散在TiO2纳米管上, 晶粒大小约为25.6 nm. 对甲醇的电催化性能的研究结果表明, 脉冲电沉积制得的Pt-TiO2纳米管电极比TiO2纳米管电极和纯Pt片电极具有更高的电催化活性, 是Pt电极的40多倍.     

Ag2S/Ag3PO4/Ni复合薄膜的制备及其光催化性能

采用电化学方法制备Ag_2S/Ag_3PO_4/Ni复合薄膜,以扫描电子显微镜(SEM)、X射线衍射(XRD)、紫外-可见漫反射光谱(UVVis DRS)对薄膜的表面形貌、晶相结构、光谱特性及能带结构进行了表征,以罗丹明B为模拟污染物对薄膜的光催化活性和稳定性进行了测定,采用向溶液中加入活性物种捕获剂的方法对薄膜的光催化机理进行了探索。结果表明:最佳工艺制备的Ag_2S/Ag_3PO_4/Ni是由均匀的球形纳米颗粒构成的薄膜,其光催化活性明显优于纯Ag_3PO_4/Ni薄膜和纯Ag_2S/Ni薄膜,且在保持薄膜光催化活性基本不变的前提下可循环使用6次。提出了可见光下Ag_2S/Ag_3PO_4/Ni复合薄膜光催化降解罗丹明B的反应机理。     

Au/Al2O3纳米复合薄膜的制备和表征

用溶胶-凝胶法制备了Au/Al₂O₃纳米复合薄膜。利用X-射线衍射、X-射线光电子能谱、原子力显微镜以及紫外-可见光谱对薄膜的微观结构、表面形貌及光学性能进行了表征,研究表明:Au/Al₂O₃纳米复合薄膜是由纳米微晶组成的颗粒膜, 复合薄膜均匀、致密、无裂纹,Au以纳米晶核形式镶嵌于Al₂O₃基体中,纳米Au晶核的粒径为23～26nm;复合薄膜在可见光区有较强的吸收,吸收峰位置与烧结温度有关,吸收强度随烧结温度和金添加量增大而增大。     

Fe3O4@SiO2@mTiO2介孔多功能纳米复合颗粒的制备及载药能力

以溶剂热法制备氨基功能化的Fe_3O_4纳米颗粒为磁核,结合溶胶-凝胶法和模板法在其表面先后包覆上致密的SiO_2层和介孔TiO_2层,制备了磁性-发光-微波热转换性-介孔结构为一体的多功能核-壳结构纳米复合颗粒,并对其结构、性能及载药能力进行了研究。XRD分析表明:Fe_3O_4表面包覆上了无定形结构的SiO_2和TiO_2。TEM照片表明:所得的纳米复合颗粒具有明显的核壳结构和完美的球形,构成核的Fe_3O_4颗粒的尺寸在40~50 nm之间,Fe_3O_4@SiO_2@mTiO_2核壳结构纳米复合颗粒的尺寸为60~70 nm,壳层厚度约10 nm,并可观察到壳层中清晰的孔状结构。磁性、荧光光谱和微波热转换特性分析表明:该复合颗粒同时具有良好的发光性、磁性和微波热转换特性。N_2气吸附及药物负载率分析表明,该复合颗粒具有较高的比表面积(640 m~2·g~(-1))和介孔结构(孔径约2.8 nm)并且具有较高的药物负载率。     

Gd-N共掺杂SrTiO3/TiO2复合纳米纤维制备及光催化性能

以静电纺丝技术制备的TiO_2纳米纤维为基质和反应物,结合一步水热法制得Gd-N共掺杂SrTiO_3/TiO_2复合纳米纤维光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射(UV-Vis DRS)和荧光光谱(PL)等方法对其微观结构、形貌和光学性能进行表征。结果表明:SrTiO_3和TiO_2形成异质结能够使光生电子和空穴得到很好的分离,而Gd-N共掺杂产生新带隙,可以拓宽光谱响应范围至可见光区,并引起晶格缺陷,成为光生电子-空穴对的浅势捕获阱。Gd-N共掺杂与异质结的协同作用有效提高了SrTiO_3/TiO_2复合纳米纤维的可见光催化活性。     

Cu2ZnSnS4(CZTS)纳米微球的制备及表征

为研究PVP含量对CZTS颗粒形貌以及分散性的影响,本文采用溶剂热法,以CuCl₂·2H₂O、Zn(Ac)₂·2H₂O、SnCl₄·5H₂O作金属源,硫脲作硫源,乙二醇为溶剂,在体系中加入不同含量的PVP,成功制备了CZTS微球。通过XRD、Raman、SEM、TEM、UV-Vis等方法检测分析CZTS纳米微球的物相、结构、形貌以及光学性能。结果表明:所得CZTS纳米颗粒具有锌黄锡矿结构;当体系中PVP含量为0.2g时,颗粒分散性较好,制备的颗粒形貌为表面嵌有纳米薄片的微球,纳米片较在体系中加入0.1gPVP更致密;光学带隙约为1.47eV,与太阳能电池所需的最佳带隙接近。最后,对表面嵌有纳米薄片的CZTS微球可能的形成机理进行了推测。     

Bi/Yb3+,Er3+:TiO2复合纳米纤维的合成及光催化产氢性能

以静电纺丝技术制备的稀土Yb~(3+)和Er~(3+)共掺杂TiO_2纳米纤维为基质,结合水热法合成了Bi复合Yb~(3+),Er~(3+)∶TiO_2纳米纤维光催化剂。以三乙醇胺为牺牲剂,研究了Bi/Yb~(3+),Er~(3+)∶TiO_2的紫外、可见、近红外和全谱光催化产氢性能。结果表明:全谱光照5 h,产氢速率达到1 650.3μmol·g~(-1)·h~(-1)。Bi作为一种新兴的非贵金属具有独特的等离子体光催化或辅助光催化性能,能与稀土元素丰富的能级结构和特殊的上转换发光特性相结合。对TiO_2进行双重协同修饰改性,可以有效提高TiO_2纳米纤维的光催化活性。     

溶剂热法制备BiFeO_3基纳米颗粒光催化剂及其性能

以聚酰胺-胺(PAMAM)树形分子为稳定剂,采用溶剂热法制得了纯相BiFeO_3纳米颗粒(A)和BiFeO_3/Bi_(25)FeO_(40)/Fe_2O_3复合纳米颗粒(B),并采用HRTEM、XRD、UV-Vis、SQUID对其结构和性能进行了表征。2种颗粒结晶良好,粒径小于10 nm,能有效光催化降解亚甲基蓝,磁性回收率分别为74.6%(A)和90.2%(B)。BiFeO_3/Bi_(25)FeO_(40)/Fe_2O_3复合纳米颗粒的光催化与磁性能均优于纯相BiFeO_3纳米颗粒,是因为复合纳米颗粒含有多种相,相界面存在异质结构有利于光生载流子的分离和迁移,并且对可见光的吸收能力更强。     

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.     

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.     

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, 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。