NiO@SnO2@Zn2TiO4@TiO2同轴四层纳米电缆的制备、表征及形成机理研究

采用静电纺丝技术, 通过改进实验装置, 在最佳的纺丝条件下制备了[Ni(CH₃COO)₂＋PVP]@[SnCl₄＋PVP]@[Zn(CH₃COO)₂＋PVP]@[Ti(OC₄H₉)₄＋CH₃COOH＋PVP]前驱体复合电缆, 将其进行热处理, 制备出NiO@ SnO₂@Zn₂TiO₄@TiO₂同轴四层纳米电缆. 采用热重-差热(TG-DTA)、X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等分析技术对样品进行了表征. 结果表明, 所得产物为同轴四层纳米电缆, 芯层为NiO, 直径为35～55 nm|第二层为SnO₂, 厚度为30～50 nm|第三层为Zn₂TiO₄, 厚度为25～40 nm|壳层为TiO₂, 厚度为40～90 nm. 对同轴四层纳米电缆的形成机理进行了探讨.     

系列Sm3+配合物的合成、结构及光物理性能

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、 劈裂和加宽的原因.     

醋酸铀酰负离子气相分解反应的密度泛函理论研究

采用密度泛函理论(DFT), 选择杂化密度泛函TPSSh和TZVP基组, 对一个UO₂(CO₃)₃^4-负离子的结构进行优化, 理论计算所得结果(键长等参数)与实验数据一致. 应用TPSSh/TZVP(ECP)方法对醋酸铀酰负离子UO₂(CH₃COO)₃^-的气相分解反应进行了理论计算, 成功地解释了含+5价铀的气相自由基负离子的稳定性, 并对2个负离子(CH₃COO)UO₂CH₃^-和CH₃UO₂OH^-分别与水的复分解反应进行了理论计算, 所得数据与质谱的实验结果较好地吻合.     

抗菌医药左氧氟沙星在有机电致发光二极管中的应用

左氧氟沙星(LOFX)是一种知名的抗菌药物, 它的价格非常便宜, 且有成熟的合成和纯化技术. 本文中首次将LOFX作为一种蓝光发光材料和电子传输材料应用于有机电致发光器件(OLED)中. 通过热重分析、UVVis吸收光谱、发射光谱以及循环伏安曲线详细地表征了LOFX的热学及光物理特性. LOFX有高的分解温度,为327 ℃; HOMO、LUMO能级分别为-6.2 和-3.2 eV, 光学带隙为3.0 eV. 以LOFX作为客体材料, 掺杂在主体材料4,4'-二(9-咔唑)联苯(CBP)中制备了蓝光OLED, 该器件的电致发光(EL)发射峰位于452 nm, 最大亮度为2315 cd·m^-2. 进一步, 选择8-羟基喹啉铝(Alq₃)作为参考材料, 分别以LOFX和Alq₃作为电子传输材料制备了结构相同的单载流子器件和绿色磷光OLED. 在相同的电压下, 以LOFX作为电子传输材料的单载流子器件的电流密度比以Alq₃作为电子传输材料的单载流子器件更高. 同时, 以LOFX作为电子传输材料的绿色磷光OLED获得更高的器件效率. 从这些EL性能可以看出, LOFX同时也是一很好的电子传输材料.     

静电纺丝法制备Mn2O3纳米纤维及其磁性研究

采用溶胶-凝胶过程和静电纺丝技术相结合方法, 以聚丙烯腈和醋酸锰为前驱物, 制得了PAN/Mn(CH₃COO)₂复合纳米纤维. 将该复合纤维高温煅烧, 获得了Mn₂O₃纳米纤维. 采用扫描电镜(SEM)、红外光谱(FTIR)、差热-热重(TG-DTA)和X射线衍射(XRD)分析等对样品进行了表征. 结果表明, Mn₂O₃纳米纤维为规则的一维结构, 直径分布均匀, 具有铁磁性-反铁磁性-顺磁性相互转化的特性.     

分子自组装法制备具有可控浸润性的铜表面

通过简单浸泡的方法在铜基底上制备出了具有微纳米复合结构的氧化铜, 再利用混合硫醇溶液[含HS(CH₂)₉CH₃和 HS(CH₂)₁₁OH]对浸泡后的表面进行修饰, 通过控制溶液中HS(CH₂)₁₁OH的浓度, 制备出一系列具有不同浸润性的铜表面, 实现表面从超疏水到超亲水的有效调控. 研究发现, 表面浸润的可控性源于表面复合结构与不同化学组成的协同作用, 微纳米复合结构的存在为表面浸润性的调节提供了必要的条件.     

偏氟乙烯与全卤代烷烃的调聚反应及其产物的研究

偏氟乙烯能够分别与四氯化碳和全氟叔丁基碘进行自由基的调聚反应,得到新型的调聚物CCl₃(CH₂CF₂)_nCl(n=1～6)和(CF₃)₃C(CH₂CF₂)_nI(n=1,2).调聚物的结构由核磁共振谱、红外光谱、元素分析和化学转化所证实.反应中亲电自由基·CCl₃与·C(CF₃)₃主要进攻偏氟乙烯上无氟碳原子,亦即在偏氟乙烯的自由基加成中,极性因素对加成方向起决定性作用.     

纳米Al2O3粒子的制备

以异丙醇铝Al(Oprⁱ)₃(即Al(OCH(CH₃)₂)₃)为原料,用醇盐水解法制备纳米氧化铝粒子,比较系统地研究了制备条件(加水方式、反应物配比、浓度、溶剂等)对产物粒子颗粒大小的影响,采用TEM、X射线衍射等技术对所得产品性能进行了表征.实验结果表明,纳米Al₂O₃粒子分散性好,粒径在20-100nm之间,颗粒的形状和尺寸随反应条件的不同而变化.     

电化学合成系列锡配合物及纳米SnO2的制备

采用锡金属为"牺牲"阳极,首次在无隔膜电解槽中,电化学一步法制备了纳米SnO₂前驱体锡配合物Sn(OEt)₄, Sn(OBu)₄, Sn(OCH₂CH₂OCH₃)₄, Sn(OEt)₂(acac)₂, Sn(OBu)₂(acac)₂, Sn(OCH₂CH₂OCH₃)₂(acac)₂[acac为乙酰丙酮基],产物通过红外光谱(FT-IR)、拉曼光谱和核磁共振进行表征.同时采用含Sn(OR)₂(acac)₂>的电解液直接水解制备纳米SnO₂粉体,纳米SnO₂通过X射线粉末衍射(XRD)和透射电子显微镜(TEM)进行表征.实验表明,电解时防止阳极钝化,控制温度在40～60℃之间,采用有机胺溴化物为导电盐,可以提高电合成效率;电解合成Sn(OCH2CH₂OCH₃)₄, Sn(OEt)₂(acac)₂, Sn(OBu)₂(acac)₂, Sn(OCH₂CH₂OCH₃)₂(acac)₂的电流效率比Sn(OEt)₄, Sn(OBu)₄高,适宜作为溶胶-凝胶(Sol-gel)法制备纳米SnO₂的原料,制备得到的纳米SnO₂经600℃煅烧后呈球形单分散结构,晶型为四方锡石型,平均粒径在(10±0.4) nm左右.     

新型含硅表面活性剂的合成及性能研究

含有双胺基的三硅氧烷中的伯胺基与D-葡萄糖酸-δ-内酯进行酰胺化,仲胺基与低聚乙二醇甲醚缩水甘油醚、二缩水甘油醚进行烷基化,制备了新型含硅表面活性剂Me₃SiOSiMeR¹OSiMe₃ [R¹=(CH₂)₃NR²(CH₂)₂NHCO(CHOH)₄CH₂OH; R²=H, CH₂CH(OH)CH₂O(CH₂CH₂O)_xCH₃, x=1, 2, 3] (1a, 2a～2c)和(CH₂OCH₂)_y(Me₃SiOSiMeR³OSiMe₃)₂ [R³=(CH₂)₃NR⁴～(CH₂)₂NHCO(CHOH)₄CH₂OH; R⁴=CH₂CH(OH)CH₂OCH₂, y=0, 1, 2] (3a～3c).这些化合物的结构用¹H, ¹³C核磁共振仪和元素分析仪进行鉴定.研究了这些新型含硅表面活性剂的界面性能,在浓度分别为10^-4和10^-5 mol·L^-1时可以将水的表面张力降低至约21 mN·m^-1.     

Surfactants having polyfluoroalkyl chains. II. Syntheses of anionic surfactants having two polyfluoroalkyl chains including a trifluoromethyl group at each tail and their flocculation-redispersion ability for dispersed magnetite particles in water

Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF₃(CF₂)₇(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₇CF₃, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF₃(CF₂)₅(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₅CF₃, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF₃(CF₂)₃(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₃CF₃, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured.     

Judd-Ofelt Analysis on Trifluoroacetate Europium Complexes for Liquid Laser Media

Four europium trifluoroacetate complexes, Eu(CF₃COO)₃·bpy(bpy=2,2′-bipyridine)(1), Eu(CF₃COO)₃· phen(phen=1,10-phenanthroline)(2), Eu(CF₃COO)₃·2bp(bp=benzophenone)(3) and Eu(CF₃COO)₃·2tppo(tppo=triphenyl-phosphine oxide)(4) were synthesized and characterized by elemental analysis, Fourier transform infrared(FTIR) spectroscopy, photoluminescence(PL) spectroscopy and thermogravimetric analysis(TGA). The PL spectra of the complexes at room temperature show the strong typical Eu³⁺ ion red emission, due to the efficient energy “antenna absorption” of ligands and transitions of Eu³⁺ ion between ⁵D₀→⁷F_J(J=0―4). The long lifetime and high quantum yield reflect that the multiphonon relaxations by coupling to O―H and C―H vibrations were reduced. According to the photoluminescent spectra, the Judd-Ofelt parameters Ω₂ and Ω₄ of the complexes were calculated and the radiative properties were also presented. The ⁵D₀ radiative lifetime, quantum yield and the stimulated emission cross-section of the complexes are excellent, which prove that they have promising optical properties for liquid laser. The thermal analyses indicate that they are quite stable to heat.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption     

Filling of antibonding orbitals—II Chemical bond properties

Antibonding effects, which accompany double-bonding in saturated compounds, account for many chemical bond lengths which are anomalous on the basis of electronegativity. Double-bonding influences the Pauling Electronegativity values of N, O, F, Al and Si and also widens the interbond angles in molecules such as (CH₃)₃N, (CF₃)₃N, (CH₃)₂O and (CF₃)₂O.     

两步沉积法制备Br或Cl掺杂的有机-无机杂化钙钛矿太阳电池

采用控制前驱体浓度的两步沉积法和插入PbI₂层的DMSO分子（PbI₂（DMSO）复合体）分别与MAX（MA=CH₃NH₃,X=I,Br）或MAX（X=I,Cl）进行的分子内交换法,实现了Br或Cl的掺杂并合成了厚度为300nm左右的混合卤化物钙钛矿MAPbI_3-xBr_x和MAPbI_3-xCl_x膜。MAX前驱体溶液中含5%（摩尔分数,下同）MABr或15% MACl所生成的Br或Cl掺杂钙钛矿膜能提高钙钛矿太阳电池的光伏性能,进一步提高MABr或MACl的含量并不会明显改变掺杂量,但会形成小的白色颗粒或者针孔,这些将对电池的性能产生不利影响。前驱体溶液含5% MABr的MAPbI_3-xBr_x钙钛矿太阳电池所获得的能量转换效率（PCE）为13.2%,含15% MACl的MAPbI_3-xCl_x钙钛矿太阳电池获得了最高13.5%的PCE。     

[(Me3Sn)2(Me3Sb)M(CN)6]∞ (M = Fe, Ru): Neuartige Organo-Sn/Sb-Polymere von besonderer chemischer und thermischer stabilität

The thermally (decomp. temp. 300°C) and completely air stable, novel coordination polymers [(Me₃Sn^IV)₂(Me₃Sb^V)M^II(CN)₆]_∞ with M = Fe and Ru can be prepared by co-precipitation from aqueous solutions of Me₃SnCl, Me₃SbBr₂ and K₄[(M(CN)₆], or, alternatively, by the ion-exchange-like reaction of the polymers [A(Me₃Sn)₃M(CN)₆]_∞ (A⁺ = Et₄N⁺, Cp₂Co⁺, Me₃Sn⁺ etc.) with Me₃SbBr₂. IR-spectroscopic findings suggest a statistical distribution of quasi-octahedral M(CN-Sn··)_6-x(CNSb ··)_x building blocks (with x = 0–6) within a three-dimensional network.     

The structural basis of transitions between highly ordered smectic phases in semifluorinated alkanes

The semifluorinated alkanes F(CF₂)₁₀(CH₂)₉H and F(CF₂)₁₀(CH₂)₁₁H both undergo a reversible transition between tilted smectic phases above room temperature as demonstrated previously for F(CF₂)₁₀(CH₂)₁₀H. The transformation on cooling is achieved in two stages: an increase in molecular tilt relative to the layer normal, followed by a change in the molecular interdigitation within each layer. The extent of complete transformation is sensitive to temperature and time, due to strains occasioned by the accompanying volume change, and because the second stage requires significant molecular translations. Characterization of the transformation is possible by transmitted light microscopy, supplemented by X-ray diffraction.     

Ergebnisse aus versuchen zur darstellung von bis(trifluormethylsulphanyl)thioketen (CF3S)2C=C=S

The attempted preparation of bis(trifluoromethylsulphanyl)thioketene is described. Mono-and di-(trifluoromethylsulphanyl)-substituted orthothioesters may be prepared fromCH₃C(SC₂H₅)₃ and CF₃SCl in the presence of anhydrous ZnCl₂. The unstable compoundshave been isolated and characterized. The corresponding CF₃Se and CF₃SO₂ derivativesare only formed as intermediates which decompose to ketene diethylmercaptal. Suchmono- and di-substituted products are obtained in good yield from H₂C=C(SC₂H₅)₂ andCF₃ECl (E=S, Se). The reaction of H₂C=C(SC₂H₅)₂ with CF₃SO₂F gave only poor yieldsof (CF₃SO₂)_nCH_2−n=C(SC₂H₅)₂ (n=1, 2) which were only capable of characterizationin etheral solution by spectral means. Attempts to prepare (CF₃S)₂C=C=S by refluxing(CF₃S)₂CHC(O)Cl, (CF₃S)₂CHC(O)OH or (CF₃S)₂C=C=O with P₄S₁₀ in toluene yieldedonly the cyclic dimer and the corresponding 1,3,4-trithiolan.     

Perfluoromethyl—element-liganden : XX. Bildung von heteronuclearen zweikernkomplexen des typs mm′(CO)nXY (M = Mn; M′ = Re, Co)

The reactions of MnRe(CO)₁₀ with As₂(CF₃)₄ and MnCo(CO)₉ with P₂(CF₃)₄, As₂(CF₃)₄, S₂(CF₃)₂, Se₂(CF₃)₂, (CF₃)₂EI (E = P, As), (CF₃)₂AsH, (CF₃)₂AsE′CF₃ (E′ = S, Se), (CF₃)₂PSeCF₃, Me₂AsI and (CF₃)₂PPMe₂, respectively, have been studied under various conditions. Besides already known mono- and binuclear compounds the heteronuclear complexes MnRe(CO)₈[As(CF₃)₂]₂ and MnCo(CO)₇[E(CF₃)₂]₂ (E = P, As) are formed. The reactions proceed via cleavage of the M---M′ bond and formation of the mononuclear species Mn(CO)₅X and M′(CO)_nY (M′ = Re, n = 5; M′ = Co, n = 4).