Adhesion of Colloidal ZnO Particles on ZnS-Type Phosphor Surfaces

Chemical and physical aspects of the adhesion of colloidal ZnO particles (d(50)=81 nm) on the surface of ZnS-type phosphors have been studied. Here, the green-emitting phosphor ZnS:Cu,Al,Cu (d(50)=5.0 μm) applied in TV screens was chosen as model compound. The ZnS material was pretreated in various ways (H(2)O, HCl, H(2)O(2)) and reacted thereafter with a suspension containing colloidal ZnO particles. Analytical investigations (SEM, ESCA) have shown that the adhesion of colloidal ZnO particles is strongly affected by the degree of hydrolysis of the ZnS surface. Electroacoustic investigations (ESA) prove that both types of surfaces, hydrolyzed ZnS as well as colloidal ZnO, are positively charged. Even so, adhesion of ZnO particles is encouraged very much under these conditions, indicating that secondary attractive forces (electrostatic interaction, chemical bonding) determine the amount of colloidal ZnO adhered on a ZnS-type phosphor. Copyright 2000 Academic Press.     

Complex Langmuir-Blodgett films of SiO2 and ZnO nanoparticles with advantageous optical and photocatalytical properties

Multifunctional Langmuir-Blodgett (LB) films were fabricated on the surface of glass substrates using sol-gel derived ZnO and SiO2 particles. ZnO particles of 6 and 110 nm diameter were synthesized according to the methods of Meulenkamp and Seelig et al. (Meulenkamp, E. A. J. Phys. Chem. B 1998, 102, 5566; Seelig, E. W.; Tang, B.; Yamilov, A.; Cao, H.; Chang, R. P. H. Mater. Chem. Phys. 2003, 80, 257). Silica particles of 37 and 96 nm were prepared by the Stober method (Stober, W.; Fink, A.; Bohn, E. J. Colloid Interface Sci. 1968, 26, 62). Alternate deposition of monoparticulate Langmuir films of SiO2 and ZnO nanoparticles provided complex (six- and nine-layered) LB films with both antireflective and photocatalytic properties. The LB films were investigated with scanning electron microscopy (morphology and structure) and UV-vis spectroscopy (optical properties and stability). The photocatalytic activity was measured by immersing the UV-irradiated films into an aqueous solution of Methyl Orange and following the photodegradation of the dye by optical spectroscopy. Adding ZnO particles to the silica films slightly lowered the antireflection property but ensured strong photocatalytic activity. Both the photocatalytic activity and antireflection properties were proved to be sensitive to the sequence of the silica and ZnO layers, with optimum properties in the case of nine-layered films with a repeated (SiO2-ZnO-ZnO) structure.     

Regenerable Fe-Mn-ZnO/SiO2 sorbents for room temperature removal of H2S from fuel reformates: performance, active sites, Operando studies

Fe- and Mn-promoted H(2)S sorbents Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) (x, y = 0, 0.025) for desulfurization of model fuel reformates at room temperature were prepared, tested and characterized. Sulfur uptake capacity at 25 °C significantly exceeds that of both commercial unsupported ZnO sorbents and un-promoted supported ZnO/SiO(2) sorbents. Sulfur capacity and breakthrough characteristics remain satisfactory after multiple (～10) cycles of adsorption/regeneration, with regeneration performed by a simple and robust heating in air. XRD shows that both "calcined" and "spent" sorbents contain nano-dispersed ZnO, and XPS confirms conversion of ZnO to ZnS. "Calcined" sorbent contains Fe(3+) and Mn(3+) that are reduced to Mn(2+) upon reaction with H(2)S, but not with H(2). Operando ESR is used for the first time to study dynamics of reduction of Mn(3+) promoter sites simultaneously with measuring sulfidation dynamics of the Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) sorbent. Fe cations are believed to occupy the surface of supported ZnO nanocrystallites, while Mn cations are distributed within ZnO.     

TiO2对ZnO/ZnS:Eu3+荧光粉发光性能的影响

采用溶胶-凝胶-沉淀法制备ZnO/ZnS/2TiO2:Eu3+荧光粉,并采用X射线衍射(XRD)、红外光谱(IR)、透射电镜(TEM)以及荧光光谱技术对其结构、组成、形貌和发光性能进行表征,探讨其发光机理。结果显示,ZnO/ZnS/2TiO2:Eu3+荧光粉的结构在温度高于600℃时趋于稳定状态,呈不规则结构,由ZnO、TiO2和ZnS构成。IR谱图表明,Ti-O-Ti桥氧键网络结构有利于Eu3+之间的能量传递。荧光光谱分析表明,引入TiO2使Eu3+光谱选律禁阻解除,提高了ZnO/ZnS/2TiO2:Eu3+荧光粉的发光性能,且当nZn(NO3)2:nTiO2=1:2时荧光粉的发光性能最好,612 nm处的5D0→7F2电偶极跃迁为最强发射峰,最佳退火温度为600℃。     

Effect of ZnO on the performance of Ag/SiO2 catalyst for the vapor-phase synthesis of 3-methylindole

The vapor-phase synthesis of 3-methylindole over Ag/SiO2 doped with ZnO was investigated. The catalysts were characterized by XRD, H2- TPR, NH3-TPD and TG techniques. The results indicated that ZnO promoter greatly enhanced the initial activity of the catalyst but disfavored its stability. H2-TPR and XRD results showed that the reduction peak of Ag2O shifted to higher temperature and the intensity of silver diffraction peaks was much weaker after the addition of ZnO promoter to Ag/SiO2. This indicated that there existed the interaction between Ag2O and SiO2-ZnO which promoted the silver particles dispersing on the support and inhibited the sintering of silver during the reaction. NH3-TPD and TG results revealed that the acid amounts of the catalyst and coking increased after adding ZnO to Ag/SiO2, which resulted in the deactivation of Ag/SiO2-ZnO catalyst rapidly.     

ZnO或K_2O助剂对Cu/SiO_2-Al_2O_3催化剂上丙三醇和苯胺气相催化合成3-甲基吲哚反应的促进作用

研究了ZnO或K2O助剂对Cu/SiO2-Al2O3上丙三醇和苯胺气相催化合成3-甲基吲哚反应的促进作用,采用X射线衍射、透射电子显微镜、H2程序升温还原、NH3程序升温脱附以及热重-差热分析等技术对催化剂进行了表征.结果表明,适量ZnO或K2O的加入可明显提高催化剂的活性、选择性和稳定性,其中以ZnO的促进作用更强.ZnO不仅能增强活性组分Cu与SiO2-Al2O3载体之间的相互作用、提高Cu在载体表面的分散度,而且可有效抑制反应过程中Cu粒子的烧结;而K2O的加入却降低了Cu分散度,但也对反应过程中Cu粒子的烧结有所抑制.ZnO或K2O的加入均不同程度地增加了Cu/SiO2-Al2O3催化剂的弱酸中心数量,从而促进3-甲基吲哚的生成.     

Size distribution of colloidal silica in sodium silicate solutions investigated by dynamic light scattering and viscosity measurements

Three types of aqueous sodium silicate solutions characterized by molar SiO(2):Na(2)O ratios of 2.2, 3.3, and 3.9 were investigated by dynamic light scattering and viscosity measurements. The solutions were prepared by diluting concentrated commercial products to SiO(2) content between 0.5 and 15 wt%. Dynamic light scattering (DLS) was used for the investigation of size distributions of colloids immediately after dilution. At least three size classes of colloidal particles were detected, which exist in parallel in the solutions. The respective radii are 0.4 to 0.6 nm, 2.5 to 13 nm, and 75 to 85 nm. The larger colloids dominate the mass distribution, whereas the smaller colloids control the surface area of the colloidal fraction. Material properties such as pH, viscosity, refractive index, and density were measured as a function of dilution. The evaluation of the viscosity data indicated that the colloids have a lower density than dense amorphous silica. Aging effects could be suppressed by measuring within 1 h after dilution.     

Release and formation of surface-localized ionic clusters (SLICs) into phospholipid rafts from colloidal solutions during coalescence

Stimuli-responsive behavior of phospholipids in the presence of ionic surfactants utilized in synthesis of MMA/nBA colloidal particles was investigated. Utilizing 1-myristoyl-2-hydroxy-sn-glycero-phosphocholine (MHPC) phospholipid, and sodium dioctyl sulfosuccinate (SDOSS) surfactant as dispersing media in H(2)O, narrow unimodal particle size distributions of methyl methacrylate (MMA)/n-butyl acrylate (nBA) copolymers were synthesized. The particle diameters were 154 nm when a SDOSS/MHPC mixture was used and 161 nm using MHPC as the only surface-stabilizing species. When such colloidal dispersions are exposed to 1.7, 3.3, and 6.7 mM aqueous CaCl(2) and KCl electrolyte solutions, surface-localized ionic clusters are generated at the film-air interface that may serve as lipid rafts composed of crystalline phases of MHPC deposited on poly(MMA)/nBA films. These studies illustrate that it is possible to control release and morphology developments of surface phospholipid rafts on artificial surfaces.     

Epitaxial heterostructures: side-to-side Si-ZnS, Si-ZnSe biaxial nanowires, and sandwichlike ZnS-Si-ZnS triaxial nanowires

Epitaxial semiconducting heterostructures: side-to-side Si-ZnS, Si-ZnSe biaxial nanowires, and sandwichlike ZnS-Si-ZnS triaxial nanowires were grown via a simple two-stage thermal evaporation of mixed SiO and ZnS or SiO and ZnSe powders under a precise temperature control. Each nanowire had a uniform diameter of 40-120 nm and length ranging from several to several tens of micrometers. Subnanowires of Si, ZnS, and ZnSe within them had a diameter of 20-50, 40-60, and 20-50 nm, respectively. The optical property (nanoscale cathodoluminescence) was also investigated from these new structures. It is proposed that the Si nanowires formed through disproportionation of SiO to Si in the first evaporation stage and then served as one-dimensional nanoscale substrates (or templates) for an epitaxial growth of ZnS or ZnSe nanowires in the following thermal evaporation of ZnS or ZnSe powders. The present results suggest that the simple method might be useful for the synthesis of many other heterostructures containing Si and II-VI or III-V semiconducting composite nanowires to meet the growing demands of nanoscale science and technology.     

Novel ZnO-Al2O3 composite particles as sorbent for low temperature H2S removal

ZnO-Al₂O₃ composite particles composed of ZnO nanosheets（thickness of 40-80 nm） on alumina particles were prepared by heterogeneous precipitation method using bayerite seed particles.The asprepared composite particles were characterized in terms of crystal structure,morphology,surface area and pore volume.The composite particles were used as sorbent for H₂S adsorption at low temperature, and were compared with pure ZnO sorbent.The composite sorbent showed a greater sulfur adsorption capacity（0.052 g/g） than pure form of ZnO（0.028 g/g）.This significant improvement was mainly attributed to higher surface area,more pore volume and unique morphology in nanoscale,which were also obtained by low cost presented method in this work for synthesis of ZnO sorbent supported on alumina particles.     

种子表面改性法制备核壳结构PSt/SiO_2复合微球

首先采用无皂乳液聚合法合成了表面带负电荷、粒径为360nm的单分散聚苯乙烯(PSt)种子乳液,并以EtOH/H2O混合物为分散介质,利用γ-氨丙基三乙氧基硅烷(KH-550)在25℃下对PSt微球表面进行改性,得到了表面硅烷化并带有正电荷的改性PSt种子乳液,然后在碱性条件下加入原硅酸乙酯(TEOS)使其和微球进行共水解与共缩聚,制备出了核壳结构PSt/SiO2复合微球,并利用电镜对复合微球的结构形态进行了表征.研究表明,PSt种子乳液改性时体系的zeta电位随着KH-550用量的增加而升高,当KH-550用量为PSt种子重量的1/3时,体系的zeta电位从原来的-34.5mV升高到了38mV,达到对PSt微球表面改性的最佳值;在制备PSt/SiO2复合微球时,TEOS水解缩聚形成的SiO2包覆到改性微球上的量随着反应时间的延长而增加,反应24h时达到97.9%的最大值;随介质中水含量的增加,吸附到复合微球表面上的SiO2纳米颗粒逐渐减少,复合微球表面逐渐变得光滑,当EtOH/H2O质量比降低到60/28.5时,得到结构均一、壳层厚度为35nm的核壳结构PSt/SiO2复合微球。     

MAA修饰ZnO量子点及其发光特性

以ZnAc2·2H2O为原料,在乙醇中通过70℃回流4h,得到ZnO前驱物,与LiOH·H2O反应,制备出ZnO.采用巯基乙酸(mercaptoacetic acid,MAA)对所合成的ZnO进行表面修饰,修饰后的产物经SEM和XRD表征,证明获得了物相单一、近似球状、粒径为4.6nm的ZnO量子点.借助紫外-可见和荧光分析,研究了MAA对该量子点的修饰效果,探讨了设置条件下ZnO的发光机理和性质.发现该实验体系之所以产生荧光表面缺陷发射峰消失和激子发射峰明显增加的光学现象,是因为MAA有效地覆盖了ZnO的表面缺陷,并稳定包裹住ZnO粒子.同时还研究了MAA加量、温度、电解质对修饰产物发光性能的影响,发现经MAA修饰后的ZnO量子点具有较强的荧光发光性能、良好的长期陈放稳定性,以及一定的抗电解质影响能力.研究结果对ZnO量子点应用于生物分析具有重要参考价值.     

Preparation of Gd(2)O(3) : Eu(3+) and Gd(2)O(2)S : Eu(3+) phosphor fine particles using an emulsion liquid membrane system

Size- (submicrometer-sized) and morphology- (spherical) controlled composite Gd-Eu oxalate particles were prepared in an emulsion liquid membrane (water-in-oil-in-water emulsion) system. The oxalate particles thus prepared were calcined in air to obtain Gd(2)O(3) : Eu(3+) phosphor particles and in sulfur atmosphere to obtain Gd(2)O(2)S : Eu(3+) phosphor particles. These submicrometer-sized spherical phosphor particles showed photoluminescence properties with emission peak at 614 nm for Gd(2)O(3) : Eu(3+) and 628 nm for Gd(2)O(2)S : Eu(3+).     

微波加热在高岭石表面制备ZnO纳米微晶及其机理分析

报道了一种新的制备纳米氧化锌的方法, 即在微波辐射条件下, 将熔融态聚乙二醇(PEG)直接插入到高岭石层间, 继续延长辐射时间使高岭石发生剥片. 以剥片的高岭石片晶为模板, 经微波加热水解, 在其表面合成了簇状纳米氧化锌晶须.     

光促甲烷和水合成甲醇和氢催化剂的研究

用表面改性法制备TiO2/SiO2，以等体积浸渍法制备负载型复合半导体催化剂(MoO3,ZnO)-TiO2/SiO2，通过XRD、BET、TPR、IR、UV-Vis DRS和TPD等技术对材料的表面形态结构、吸光特性、化学吸附性能及光催化甲烷和水的反应性能进行了表征和分析。结果表明，MoO3-TiO2/SiO2和ZnO-TiO2/SiO2的表面物种均具有显著的量子尺寸效应，在表面分别形成Mo—O—Ti和Zn—O—Ti复合结构；MoO3和TiO2在载体表面的复合可提高对光能的利用率并可增强对甲烷的化学吸附性能， 结果使得MoO3-TiO2/SiO2的光催化反应性能明显优于ZnO-TiO2/SiO2；在固定床环隙反应器中，150℃MoO3-TiO2/SiO2光催化气相甲烷和水合成了目的产物甲醇和氢，甲醇的选择性达到87.3％。     

SiO2 溶胶及其静电自组装薄膜的制备

Silica sols were prepared by hydrolysis of Si（OC2H5）4（TEOS）using HCl,NH3·H2O,HCl/NH3·H2O as catalyzers,and the different granularities of SiO2 sols which catalyzed by HCl first and then NH3·H2O have the same terminal pH value were prepared. The silica colloidal particles were investigated with Transmission Electron Microscope（TEM）. The results showed sol catalyzed by HCl possesses very little particle,catalyzed by NH3·H2O has particle configuration,catalyzed by HCl/NH3·H2O possesses consecutive configuration. Poly（diallyldimethylammonium chloride）（PDDA）and SiO2 nanoparticulate complex thin films were prepared by electrostatic self-assembly multiplayer（ESAM）method. After assembling films,thin films surface conformation was observed with Electron Microscope and their transmittance was tested with 721 Spectrophotometer. The results showed that the silica sol catalyzed with HCl is not good for the fabrication of ESAM films and the silica sol catalyzed with HCl first and then NH3·H2O or by NH3·H2O only are very suitable for ESAM film fabrication. TEM data indicate that the microstructure of PDDA/ SiO2 prepared from silica sol catalyzed with HCl first and then NH3·H2O is consecutive and that the microstructure of PDDA/ SiO2 prepared from silica sol catalyzed by NH3·H2O only is particulate-parking like. The dependence of the transmittance of assembled films on the bilayer number of the films and the anti-scratching properties of the films were investigated. The results show that PDDA/ SiO2 films prepared from silica sol catalyzed by NH3·H2O only possess higher transmittance but lower anti-scratching properties. The effect of granularity of sols on optical performances of the thin films was studied,results showed the less the granularity of sol,the better the optical performances. For the sake of improving the light transmittance of films,we can reduce the granularity of sol,but it may play down its mechanical damage resist intensity.     

A Model for Simultaneous Homogeneous and Heterogeneous Nucleation in the Case of Slow Reaction Rate

(Gd(x)Y(1-x))(2)O(3):Eu [x=0, 0.25, 0.5, 0.75, 1.0] phosphor particles with 6 at.% Eu dopant of total concentration were prepared using spray pyrolysis. The effects of composition on the morphology, crystallinity, and photoluminescence characteristics of composite particles were investigated. The morphological control of (Gd(x)Y(1-x))(2)O(3):Eu particles in spray pyrolysis was also attempted by using colloidal and aqueous solutions. The particles prepared from colloidal solutions containing small amounts of Gd or Y hydroxy carbonate sol as seed material had spherical and filled morphology after the post-treatment at high temperature. On the other hand, the (Gd(x)Y(1-x))(2)O(3):Eu particles prepared from aqueous solutions were hollow and porous after post-treatment in all compositions. Particles prepared from colloidal solutions had photoluminescence emission intensities higher than those of particles prepared from aqueous solutions. Copyright 2000 Academic Press.     

First preparation of nanocrystalline zinc silicate by chemical vapor synthesis using an organometallic single-source precursor

A method is presented to prepare nanocrystalline alpha-Zn(2)SiO(4) with the smallest crystal size reported so far for this system. Our approach combines the advantages of organometallic single-source precursor routes with aerosol processing techniques. The chemical design of the precursor enables the preferential formation of pure zinc silicates. Since gas-phase synthesis reduces intermolecular processes, and keeps the particles small, zinc silicate was synthesized from the volatile organometallic precursor [[MeZnOSiMe(3)](4)], possessing a Zn-methyl- and O-silyl-substituted Zn(4)O(4)-heterocubane framework (cubane), under oxidizing conditions, using the chemical vapor synthesis (CVS) method. The products obtained under different process conditions and their structural evolution after sintering were investigated by using various analytical techniques (powder X-ray diffraction, transmission electron microscopy, EDX analysis, solid-state NMR, IR, Raman, and UV/Vis spectroscopy). The deposited aerosol obtained first (processing temperature 750 degrees C) was amorphous, and contained agglomerates with primary particles of 12 nm in size. These primary particles can be described by a [Zn-O-Si] phase without long-range order. The deposit obtained at 900 degrees C contained particles with embedded nanocrystallites (3-5 nm) of beta-Zn(2)SiO(4), Zn(1.7)SiO(4), and ZnO in an amorphous matrix. On further ageing, the as-deposited particles obtained at 900 degrees C form alpha-Zn(2)SiO(4) imbedded in amorphous SiO(2). The crystallite sizes and primary particle sizes in the formed alpha-Zn(2)SiO(4) were found to be below approximately 50 nm and mainly spherical in morphology. A gas-phase mechanism for the particle formation is proposed. In addition, the solid-state reactions of the same precursor were studied in detail to investigate the fundamental differences between a gas-phase and a solid-state synthesis route.     

Core-shell structured SiO2@YVO4:Dy3+/Sm3+ phosphor particles: sol-gel preparation and characterization

Spherical SiO(2) particles have been coated with YVO(4):Dy(3+)/Sm(3+) phosphor layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO(2)@YVO(4):Dy(3+)/Sm(3+) particles. X-ray diffraction (XRD), Fourier-transform IR spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO(2)@YVO(4):Dy(3+)/Sm(3+) core-shell phosphors. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 300 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (20 nm for one deposition cycle). The core-shell particles show strong characteristic emission from Dy(3+) for SiO(2)@YVO(4):Dy(3+) and from Sm(3+) for SiO(2)@YVO(4):Sm(3+) due to an efficient energy transfer from YVO(4) host to them. The PL intensity of Dy(3+) and Sm(3+) increases with raising the annealing temperature and the number of coating cycles.     

利用SnO2:Sb干凝胶部分升华产物处理ZnS:Mn荧光粉

以SnCl2•2H2O、SbCl3为原料, 通过溶胶-凝胶法制备SnO2:Sb干凝胶. 利用干凝胶氧化过程中的部分升华产物对新制的ZnS:Mn荧光粉进行了表面处理. 在固定氧气流量和氧化时间的条件下, 考察了SnO2:Sb干凝胶与ZnS:Mn荧光粉的质量比和氧化温度对处理后荧光粉电阻率的影响. 当干凝胶粉与荧光粉的质量比为3.0, 氧化温度为500 ℃处理后荧光粉的电阻率明显下降. 对处理后的荧光粉进行了室温光致荧光(PL)光谱、X射线衍射(XRD)以及透射电镜(TEM)分析. 结果表明对荧光粉进行表面处理没有改变荧光粉的光致发光性质和晶体结构.