同轴三层纳米电缆NiO@SiO2@TiO2的制备与表征

采用静电纺丝技术, 通过改进实验装置, 成功地制备出了NiO@SiO₂@TiO₂同轴三层纳米电缆. 采用差热-热重(TG-DTA)分析、X射线衍射(XRD)分析、傅立叶变换红外光谱(FTIR)分析、扫描电子显微镜(SEM)分析和透射电子显微镜(TEM)等分析技术对样品进行表征, 结果表明, 所得产物为NiO@SiO₂@TiO₂同轴三层纳米电缆, 内层为NiO, 直径大约为40～50 nm|中间层为SiO₂, 厚度大约为40～45 nm|外层为TiO₂, 厚度大约为45～50 nm. 对NiO@SiO₂@TiO₂同轴三层纳米电缆的形成机理进行了讨论.     

静电纺丝技术制备NiO@Al2O3@TiO2同轴三层亚微米电缆及其形成机理

采用静电纺丝技术,通过改进实验装置,采用同轴三喷嘴实验装置代替传统的单喷嘴实验装置,在最佳的纺丝条件下制备了[Ni(CH3COO)2+PVP]@[Al(NO3)3+PVP]@[Ti(OC4H9)4+CH3COOH+PVP]前驱体复合电缆,将其进行热处理,制备出了NiO@Al2O3@TiO2同轴三层纳米电缆. 采用差热-热重(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NiO@Al2O3@TiO2同轴三层纳米电缆. 纳米电缆芯层为NiO,直径大约为137.83±8.85 nm;中间层为Al2O3,厚度大约为215.11±8.66 nm;壳层为TiO2,厚度大约为156.26±16.50 nm. 对NiO@Al2O3@TiO2同轴三层纳米电缆的形成机理进行了讨论.     

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.     

MgF2改性Alq3纳米复合材料的制备及其对OLED抗老化性能的提高

提高有机电致发光器件(OLED)的稳定性和寿命是其市场化应用中需要解决的关键问题.本文从提高发光材料自身的稳定性出发,以Mg(CF₃COO)_2-x(CH₃COO)_x溶胶为前驱体,将其与8-羟基喹啉铝(Alq₃)混合浓缩成糊状后, 300 ℃真空烧结,经过MgF₂的生成和Alq₃的相变后,形成了一系列Mg含量不同的具有超结构ε相的纳米复合材料Alq₃-MgF₂.研究结果表明,相比于纯Alq₃, Alq₃-MgF₂纳米复合材料制备的OLED可以很好地保持Alq₃的发光特性,同时,其抗老化性能得到显著提高.特别是, Mg(CH₃COO)₂投料量为Alq₃的5% (摩尔分数)时,所得Alq₃-MgF₂纳米复合材料制备的器件抗老化性能最优,在空气中老化72 h,最大发光亮度仍保持在起始值的93.5%;而Alq₃制备的OLED在空气中老化24 h后基本失活.     

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.     

新型金属-双二硫杂戊烯(M-BDT)配合物的合成、表征及X射线的指标化

合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH₃)₄N]₂[Ni(C₅S₉)₂](1),[(C₂H₅)₄N]₂·[Ni(C₅S₉)₂](2),[(C₄H₉)₄N]₂[Ni(C₅S₉)₂](3),[(C₆H₅)(CH₃)₃N]₂[Ni(C₅S₉)₂](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2.     

三苯基膦：转换硫醇保护的纳米粒子成[Au25(PPh3)10(SR)5Cl2]2+

我们在此报道了一种未曾发现的有趣现象：尽管[Au₂₃(SC₆H₁₁)₁₆]⁻、Au₂₄(SC₂H₄Ph)₂₀ (Ph:苯环)、Au₃₆(TBBT)₂₈ (TBBTH:对叔丁基苯硫酚)、Au₃₈(SC₂H₄Ph)₂₄、混合Au_x(SC₂H₄Ph)_y团簇及3 nm的金纳米粒子有不同的组成、结构、尺寸和保护性硫醇配体,但它们在三苯基膦(PPh₃)作用下,均能统一地经由亚稳的[Au₁₁(PPh₃)₈Cl₂]²⁺最终转化为稳定的双二十面体[Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺ (SR:硫醇配体)。换句话说,三苯基膦是这些硫醇保护的纳米粒子的统一转化器。然而,聚乙烯吡咯烷酮(PVP)/柠檬酸盐(Citrate)保护的金纳米粒子和[Ag₂₅(SPhMe₂)₁₈]⁻ (Me:甲基)在同样的条件下,却不能转化为[Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺或[Ag₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺,暗示了硫醇保护的金纳米粒子具有与三苯基膦反应的独特性能。另外,我们考察了配体对双二十面体[Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺团簇荧光性能的影响。     

基于咔唑羧酸配体构筑铁基金属有机框架及其对CO2/CH4混合气体的分离性质

通过咔唑羧酸配体(H₃L)与三核铁簇[Fe₃(μ₃-O)(CH₃COO)₆]在水热条件下反应, 合成了具有三维骨架结构的铁基金属有机框架(1). 气体吸附实验结果表明, 化合物1具有高的比表面积且对CO₂的吸附量大于对CH₄的吸附量. 理想溶液吸附理论(IAST)计算结果表明, 化合物1在100 kPa及温度分别为273和298 K下对CO₂/CH₄(体积比为0.5∶0.5)混合气体的分离比分别为3.52和3.15, 预示其可以作为一种CO₂/CH₄分离型材料.     

孔隙结构可调的Cu2O球状纳米结构及其NO2气体传感性质

报道在聚乙烯吡咯烷酮(PVP)的协助作用下,通过简单调节OH^-离子的浓度及Cu²⁺的释放速度,将Cu₂O调节为具有不同空腔特征(介孔、空心及实心)结构的纳米球.研究表明, OH^-根离子的扩散动力学是决定产物结构的关键因素.当[OH^-] > 0.05 mol·L^-1时,高的化学势使其迅速扩散到PVP胶团内部,与吸附在PVP链上的Cu²⁺反应形成Cu(OH)₂,在抗坏血酸(Vc)的还原作用下经过重结晶得到Cu₂O实心球纳米结构;当[OH^-] < 0.025 mol·L^-1时,其扩散速度下降,首先与吸附在PVP胶团外部的Cu²⁺反应形成Cu(OH)₂, Cu(OH)₂的形成阻碍了OH^-离子的向内扩散,形成具有较大空腔(~220 nm)的空心球;当0.025 mol·L^-1 < [OH^-] < 0.05 mol·L^-1时,形成较小空腔(30-60 nm)的空心球.以NH₃水为OH^-缓释源时,虽然OH^-浓度较低,但同时Cu²⁺的浓度也低,胶团外部形成的Cu(OH)₂不足以阻碍OH^-离子的向内扩散,反应过程中NH₃的释放及较低的OH^-浓度阻碍了重结晶的发生,从而形成Cu₂O介孔纳米球.对三种典型结构特征的产物进行了NO₂气体传感性质研究,结果表明, Cu₂O介孔纳米球相比空心结构和实心结构具有更为优异的响应性.结合比表面积数据,我们认为介孔纳米球疏散的结构有利于NO₂气体的扩散和O₂的吸附,从而表现出了更灵敏的气体传感性.     

SnO2-SnS2复合纳米粒子的制备及光电性质研究

采用离子交换法制备了SnO₂-SnS₂复合纳米粒子.用XRD、TEM和X-EDAS测定了样品的组成、结构、形貌和尺寸,结果表明,样品为SnS₂部分包覆SnO₂的球形复合纳米粒子,其平均粒径为5nm.研究了该复合纳米粒子的紫外-可见漫反射光谱和光电化学性质,观察到SnO₂-SnS₂复合纳米粒子的光吸收比SnO₂的明显向长波区扩展;制成工作电极后的光电流值和光电转换效率(IPCE)都比相应的纯组分纳米粒子电极显著提高.     

Thioether-functionalized mesoporous fiber membranes: sol-gel combined electrospun fabrication and their applications for Hg2+ removal

Mesoporous polyvinylpyrrolidone (PVP)/SiO(2) composite nanofiber membranes functionalized with thioether groups have been fabricated by a combination method of sol-gel process and electrospinning. The precursor sol was synthesized by one-step co-condensation of tetraethyl orthosilicate (TEOS) and 1,4-bis(triethoxysilyl)propane tetrasulfide (BTESPTS, (CH(3)CH(2)O)(3)Si(CH(2))(3)S-S-S-S(CH(2))(3)Si-(OCH(2)CH(3))(3)), with the triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (P123, EO(20)PO(70)EO(20)) as template. After the addition of PVP, nanofiber membranes were prepared by electrospinning. The membranes were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), N(2) adsorption-desorption isotherms, and an Elementar Vario EL analyzer. The composites were used as highly selective adsorbents for Hg(2+) due to the modification with thioether groups (-S-), and were conveniently separated from the waste water. The composite could be regenerated through acidification.     

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.     

Structural characterization of nano-crystalline Co3O4 ultra-fine fibers obtained by sol–gel electrospinning

In this paper, we report the obtention of ultrafine fibers of cobalt oxide (Co₃O₄) by combining electrospinning method with high-temperature calcinations from the precursor sol of poly(2-ethyl-2-oxazoline) (PEtOx)/cobalt acetate tetrahydrate [Co(CH₃COO)₂·4H₂O] in water. The optimum electrospinning conditions for obtaining precursor composite nanofibers from PEtOx/Co(CH₃COO)₂·4H₂O solution in water, to produce ceramic nanofibers, were studied. The average fiber diameter of the precursor composite fibers measured by scanning electron microscopy (SEM) was approximately 200 nm. Thermogravimetric analysis of PEtOx was performed to estimate the suitable calcination temperature of the precursor fibers. SEM images of the ceramic fibers obtained after calcination revealed the shrinkage in diameter due to complete degradation of the polymer and Co(CH₃COO)₂·4H₂O. Fourier transform infrared spectroscopy was used to ensure the complete pyrolysis of polymer during calcinations of the composite fibers. Crystalline properties of the ceramic fibers were studied by X-ray diffraction and high resolution transmission electron microscopy. The ceramic fibers are polycrystalline with an average grain size of ≈40 nm obtained at a calcination temperature of 773 K. It was observed that the grain sizes increased as the calcination temperature was increased, due to self assembly mechanism.     

First hexadecavanadate compound: hydrothermal synthesis and characterization of a three-dimensional framework [(Cu(1,2-pn)2)7(V16O38(H2O))2].4H2O

The hydrothermal reaction of V2O5, Cu(CH3COO)2.H2O, 1,2-diaminopropane and [N(CH3)4]OH yields the novel three-dimensional open-framework solid [(Cu(1,2-pn)2)7-(V16O38(H2O))2].4H2O constructed from the new mixed-valence [V16O38(H2O)]7- clusters interconnected through mu 2-[Cu(1,2-pn)2]2+ groups.     

Comproportionation reaction and hindered rotation of coordinated pyridine rings in an acetate-bridged tetraplatinum(II) cluster with pyridine-based ligands in the cluster plane

A series of pyridine-substituted derivatives of octaacetatotetraplatinum(II), [Pt4(CH3COO)8-n(L)2n]n+ (L= 4-dimethylaminopyridine (dmap), pyridine (py), 4-cyanopyridine (cpy); n = 1-4) were prepared, and the tetra- and octasubstituted forms (n = 2 and 4) were isolated. 1HNMR spectra showed that this type of cluster undergoes a comproportionation reaction. Reactions between clusters in which n = 0 and 2, n = 0 and 4, and n = 2 and 4 afforded Pt4 clusters with n = 1, 2, and 3, respectively, as a main product in acetonitrile. The dmap-substituted clusters, trans-[Pt4(CH3COO)6(dmap)4](ClO4)2 x 3CH3NO2 (3a(ClO4)2 x 3CH3NO2) and [Pt4(CH3COO)4(dmap)8](ClO4)4 x 4 H2O (5a(ClO4)4-4H2O), have been structurally characterized. Both 3a and 5a have a square-planar cluster core comprised of four PtII ions, and all eight out-of-plane coordination sites are occupied by acetate ligands in a bridging mode. In 5a, all of the in-plane sites are occupied by dmap ligands. In 3a, four dmap ligands occupy the coordination sites at the two mutually opposite edges of the square planar cluster skeleton, giving a trans tetrasubstituted form of [Pt4(CH3COO)8-] (1). In octasubstituted 5a, adjacent dmap ligands are so closely arranged that the Pt-N distances (2.20(3), 2.30(3) A) are longer than those in tetrasubstituted 3a (2.13(1), 2.15(1) A) and related Pt4 clusters. Furthermore, rotation of the dmap ligand about the Pt-N bond in 5a was restricted, and the rate constant of the rotation was 4.5s(-1) at 20 degrees C from dynamic NMR study. Cluster [Pt4(CH3COO)5(dmap)6]3+ (4a) also exhibited similar hindered rotation with the rate constants of 2.0s(-1), 12s(-1) and approximately 10(4)s(-1) at 20 degrees C depending on the coordination sites of the dmap ligands in 4a.     

Crystal Structure of catena-[(Tetrakis-μ2-acetato-μ2-4,4'-bipyridine) dicopper(Ⅱ)] Acetonitrile Solvate

The title compound,[Cu2(CH3COO)4(C8H10N2)]n·nCH3CN1 (C8H10N2,4,4'-bipy = 4,4'-bipyridine),has been solvothermally synthesized in CH3CN and characterized by X-ray diffraction.The crystal is of monoclinic,space group Cc with a = 22.626(6),b = 14.012(4),c =15.106(4) (A),β = 107.610(3)°,V = 4565(2) (A)3,C20H23Cu2N3O8,Mr = 560.49,Z = 8,Dc = 1.631 g/cm3,μ = 1.914 mm-1,Flack parameter = 0.48(1),F(000) = 2288,R = 0.042 and wR = 0.)98 for 8887 observed reflections (I ＞ 2σ(I)).It consists of nearly linear one-dimensional chains [Cu2(CH3COO)4(C8H10N2)]n derived from paddle-wheel [Cu2(CH3COO)4] unit linked by 4,4'-bipy,and CH3CN as guest molecule regularly decorates between the chains.     

One-dimensional coordination polymers of antiferromagnetically-coupled [Mn4] single-molecule magnets

Reactions of the rhombic [MnII2 MnIII2 (hmp)6]4+ complex in acetonitrile with simple carboxylate ligands yield (i) three new isolated [Mn4] complexes, namely [Mn4(hmp)6(CH3COO)2(H2O)2](ClO4)2.4H2O (1), [Mn4(hmp)6(CCl3COO)2(H2O)2](ClO4)2 (2) and [Mn4(hmp)6(C6H5COO)2(H2O)2](ClO4)2.4CH3CN.2H2O (3) in the presence of either bulky carboxylate or of an excess of Mn(II) source; and (ii) two 1D arrangements of [Mn4] complexes connected through double syn-syn carboxylate bridges when using acetate and chloroacetate, namely {[Mn4(hmp)6(CH3COO)2](ClO4)2.H2O}n (4) and {[Mn4(hmp)6(ClCH2COO)2](ClO4)2.2H2O}n (5). The assembly of such building blocks can thus be controlled by an adequate choice of the bridging anion. As expected, the isolated [Mn4] complexes behave as Single-Molecule Magnets as shown by the study of their static and dynamic magnetic properties. Detailed magnetic studies both on polycrystalline samples and single crystals show that the chain compounds are isolated antiferromagnetic chains. The slow relaxation of their staggered magnetization has been studied thanks to finite-size effects induced by the intrinsic defects of the material     

Photochemical [2 + 2] cycloaddition as a tool to study a solid-state structural transformation

The solid-state structural transformation of the hydrogen-bonded 1D coordination polymer [Cd(bpe)(CH(3)COO)(2)(H(2)O)](n), to a ladder-type structure is evident from a photochemical [2 + 2] cycloaddition reaction forming 100% rctt-cyclobutane isomer.     

Synthesis,Characteristic Spectral Studies and in Vitro Antimicrobial Activity of Organosilicon(IV) Complexes of N-(2-Hydroxynaphthalidene)-Amino Acid Schiff Bases

Fifteen new organosilicon(IV) complexes formulated as R 3 Si[2-HOC 10 H 6 CH=NCH(X)COO] and Me 2 Si[2-OC 10 H 6 CH=NCH(X)COO] (where X = H[H 2 L 1 ], --CH 2 CH(CH 3 ) 2 [H 2 L 2 ], --CH 2 CH 2 -SCH 3 [H 2 L 3 ], --CH 3 [H 2 L 4 ] and --CH(CH 3 ) 2 [H 2 L 5 ] were prepared and characterized by 1 H and 13 C NMR, IR, electronic spectral studies, and elemental analysis. All of the complexes are nonelectrolytes. The spectral studies suggested a distroted trigonal-bipyramidal geometry around the silicon atom. Antimicrobial activity screening for all of the complexes was carried out against various bacteria [ Escherichia coli, Aeromonas formicans, Pseudomonas putida-2252, and Staphylococcus aureus-740 ] and fungi [ Aureobasidium pullulans-1991, Penicillium chrysogenum-1348, Verticillium dahliae-2063, and Aspergillus niger ORS-4 ]. The complexes showed good activity.