Synthesis of CdSe, ZnSe, and ZnxCd1-xSe nanocrystals and their silica sheathed core/shell structures

Uniform ZnxCd1-xSe nanocrystals have been prepared at the artificially designed water-oil interface using Na2SeO3, Cd(NO3)2, and Zn(NO3)2 as precursors. The chemical composition and band gap of the ZnxCd1-xSe nanocrystals can be adjusted via different combinations of source material. The coating of a SiO2 shell could transform the hydrophobic particles into hydrophilic particles. An advantage of this method is that a water phase could be added to the oleic acid (OLEA) synthesis system, which could be extended to make the synthesis of various nanocrystals more simple and flexible.     

Single nanocrystals of anatase-type TiO2 prepared from layered titanate nanosheets: formation mechanism and characterization of surface properties

Anatase-type TiO2 single nanocrystals with boatlike, comblike, sheetlike, leaflike, quadrate, rhombic, and wirelike particle morphologies were prepared by hydrothermal treatment of a layered titanate nanosheet colloidal solution. The formation reactions and surface properties of the TiO2 nanocrystals were investigated using XRD, TEM, TG-DTA analyses, and measurements of BET specific surface area, photocatalytic activity, and ruthenium dye (N719) adsorption. The crystal morphology can be controlled by reaction temperature, pH value of reaction solution, and exfoliating agent. The titanate nanosheets were transformed to the TiO2 nanocrystals by two types of reactions. One is an in situ topotactic structural transformation reaction, and the other is a dissolution-deposition reaction on the surface. The anatase nanocrystals formed by the in situ topotactic structural transformation reaction retain the sheetlike particle morphology of the precursor, and they preferentially expose the (010) plane of anatase structure. The crystal surface of anatase nanocrystals prepared in this study showed higher photocatalytic activity and higher ruthenium dye adsorption capacity than did the Ishihara ST-01 sample, a standard anatase nanocrystal sample. The results indicated the (010) plane of the anatase structure has high photocatalytic activity and high ruthenium dye adsorption ability.     

Strong room-temperature ferromagnetism in Co2+-doped TiO2 made from colloidal nanocrystals

Colloidal cobalt-doped TiO(2) (anatase) nanocrystals were synthesized and studied by electronic absorption, magnetic circular dichroism, transmission electron microscopy, magnetic susceptibility, cobalt K-shell X-ray absorption spectroscopy, and extended X-ray absorption fine structure measurements. The nanocrystals were paramagnetic when isolated by surface-passivating ligands, weakly ferromagnetic (M(s) approximately 1.5 x 10(-)(3) micro(B)/Co(2+) at 300 K) when aggregated, and strongly ferromagnetic (up to M(s) = 1.9 micro(B)/Co(2+) at 300 K) when spin-coated into nanocrystalline films. X-ray absorption data reveal that cobalt is in the Co(2+) oxidation state in all samples. In addition to providing strong experimental support for the existence of intrinsic ferromagnetism in cobalt-doped TiO(2), these results demonstrate the possibility of using colloidal TiO(2) diluted magnetic semiconductor nanocrystals as building blocks for assembly of ferromagnetic semiconductor nanostructures with potential spintronics applications.     

Photochromism-based detection of volatile organic compounds by W-doped TiO2 nanofibers

W-doped TiO(2) nanofibers with various compositions (W/Ti: 2-8%) were fabricated by the electrospinning method from respective precursor solutions containing tungsten(V) pentaethoxide, titanium tetraisopropoxide (TTIP), and polyvinylpyrrolidone (PVP), followed with calcination at 550 °C. Morphological and structural characteristics of these nanofibers were studied with SEM, XRD and XPS. W-doping inhibited the crystal growth and anatase-to-rutile transformation of TiO(2) nanofibers. W-doped TiO(2) nanofiber mats showed good photocatalytic oxidation abilities for acetone. Obvious color change from white to blue of mats during the photocatalysis process can be detected by naked eyes, which provides a good way in detection of pollutants in indoor air, especially for the volatile organic compounds (VOCs).     

Controlled synthesis, growth mechanism, and properties of monodisperse CdS colloidal spheres

Highly monodisperse submicrometer CdS colloidal spheres (CSCS) with a controllable and tunable size (between 80 and 500 nm) have been synthesized through a facile solvothermal technique. Owing to the controllability of the reaction process, the growth mechanism of the colloidal spheres has been elucidated in detail. The whole growth process can be summarized as homogenous and slow nucleation of nanocrystals, formation of "cores" through 3D-oriented attachment of nanocrystals, and further surface-induced growth to monodisperse colloidal spheres through in situ formation and random attachment of additional nanocrystals. It has been demonstrated that the obtained CSCS colloidal particles are able to be assembled into films which show characteristic stop band gaps of photonic crystals. By using the CSCS as a template, Ag2S, Bi2S3, Cu2S, HgS, and Sb2S3 colloidal spheres, which are difficult to obtain directly, have also been prepared successfully through ion exchange.     

Colloidal synthesis of organic-capped ZnO nanocrystals via a sequential reduction-oxidation reaction

A nonhydrolytic route to quantum-sized (d < 9 nm) ZnO nanocrystals in homogeneous organic solutions is presented. Nearly spherical ZnO nanocrystals were grown in a surfactant mixture of hexadecylamine and oleic acid (OLEA) by means of a two-step chemical process, based on the hot reduction (at 180-250 degrees C) of a zinc halide by superhydride (LiBEt3H) followed by oxidation of the resulting product. The experimental results suggested that the controlled growth of ZnO in the nanosized regime depended both on the OLEA-assisted generation of intermediate metallic nanoparticles and on the adjustment of their oxidation conditions by using a mild oxidant, trimethylamine-N-oxide, rather than molecular oxygen. The present synthetic approach demonstrates to be particularly suitable to prepare organic-soluble ultra-small ZnO nanocrystals of low size dispersion and of stable size, which are appealing for optoelectronic, catalytic, and sensing purposes.     

Sol-gel low-temperature synthesis of stable anatase-type TiO2 nanoparticles under different conditions and its photocatalytic activity

In this work, TiO(2) nanoparticles in anatase phase was prepared by sol-gel low temperature method from titanium tetra-isopropoxide (TTIP) as titanium precursor in the presence of acetic acid (AcOH). The effects of synthesis parameters such as AcOH and water ratios, sol formation time, synthesis and calcination temperature on the photocatalytic activity of TiO(2) nanoparticles were evaluated. The resulting nanoparticles were characterized by X-ray diffraction, UV-Vis reflectance spectroscopy, transmission electron microscopy and Brunauer-Emmett-Teller techniques. Photocatalytic activity of anatase TiO(2) nanoparticles determined in the removal of C. I. Acid Red 27 (AR27) under UV light irradiation. Results indicate that with increasing AcOH/TTIP molar ratio from 1 to 10, sol formation time from 1 to 3 h and synthesis temperature from 0 to 25°C, increases crystallite size of synthesized nanoparticles. It was found that optimal conditions for low temperature preparation of anatase-type TiO(2) nanoparticles with high photocatalytic activity were as follows: TTIP:AcOH:water molar ratio 1:1:200, sol formation time 1 h, synthesis temperature 0°C and calcination temperature 450°C.     

Eu3+掺杂TiO2纳米晶的制备及光催化降解部分水解聚丙烯酰胺

以四异丙氧基钛(TTIP)为钛源, 采用溶胶-凝胶及水热合成方法, 制备了不同Eu3+含量的TiO2纳米晶催化剂, 运用载射线衍射谱、紫外-可见漫反射光谱仪、X射线光电子能谱仪和电感耦合等离子体原子发射光谱仪等手段对催化剂晶型、微晶尺寸、表面状态、组成及光学性能进行表征.结果表明, 所制备的样品均为锐钛矿型纳米晶, 粒子尺寸在9 nm左右, 铕以Eu2O3的形式存在于TiO2的晶格间隙. 在紫外光条件下降解部分水解聚丙烯酰胺(HPAM), 通过比较Eu3+的不同掺杂量对催化活性的影响, 得出Eu3+的最佳掺杂量为2.4%(w), 矿化率最终可达67%. 通过液质联机测定HPAM降解的中间产物, 推断了Eu3+/TiO2降解HPAM的机理.     

Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction

Successive ion layer adsorption and reaction (SILAR) originally developed for the deposition of thin films on solid substrates from solution baths is introduced as a technique for the growth of high-quality core/shell nanocrystals of compound semiconductors. The growth of the shell was designed to grow one monolayer at a time by alternating injections of air-stable and inexpensive cationic and anionic precursors into the reaction mixture with core nanocrystals. The principles of SILAR were demonstrated by the CdSe/CdS core/shell model system using its shell-thickness-dependent optical spectra as the probes with CdO and elemental S as the precursors. For this reaction system, a relatively high temperature, about 220-240 degrees C, was found to be essential for SILAR to fully occur. The synthesis can be readily performed on a multigram scale. The size distribution of the core/shell nanocrystals was maintained even after five monolayers of CdS shell (equivalent to about 10 times volume increase for a 3.5 nm CdSe nanocrystal) were grown onto the core nanocrystals. The epitaxial growth of the core/shell structures was verified by optical spectroscopy, TEM, XRD, and XPS. The photoluminescence quantum yield (PL QY) of the as-prepared CdSe/CdS core/shell nanocrystals ranged from 20% to 40%, and the PL full-width at half-maximum (fwhm) was maintained between 23 and 26 nm, even for those nanocrystals for which the UV-vis and PL peaks red-shifted by about 50 nm from that of the core nanocrystals. Several types of brightening phenomena were observed, some of which can further boost the PL QY of the core/shell nanocrystals. The CdSe/CdS core/shell nanocrystals were found to be superior in comparison to the highly luminescent CdSe plain core nanocrystals. The SILAR technique reported here can also be used for the growth of complex colloidal semiconductor nanostructures, such as quantum shells and colloidal quantum wells.     

Seeded growth of asymmetric binary nanocrystals made of a semiconductor TiO2 rodlike section and a magnetic gamma-Fe2O3 spherical domain

Asymmetric binary nanocrystals (BNCs), comprising one c-axis elongated anatase TiO2 section and one gamma-Fe2O3 spherical domain attached together, are synthesized by heterogeneous nucleation of iron oxide onto the longitudinal facets of TiO2 nanorods in a ternary surfactant mixture. The topologically controlled composition of the BNCs is ascertained by a combination of powder X-ray diffraction, Raman and M?ssbauer spectroscopy, high-angle annular dark-field imaging, and high-resolution transmission electron microscopy lattice fringe mapping, while their size-dependent magnetic behavior is demonstrated by ac susceptibility measurements. The heteroepitaxial growth proceeds through a mechanism never observed before for colloidal nanoheterostructures: the two domains share a restricted and locally curved junction region, which accommodates efficiently the interfacial strain and retards the formation of misfit dislocations. It is believed that these BNCs, which combine the properties of two technologically relevant oxide materials, can pave the way to reinforced applications in several fields of nanoscience, such as in photocatalysis, in malignant cell treatments, and in nanocrystal assembly.     

A general templated method to homogeneous and composition-tunable hybrid TiO2 nanocomposite fibers

Sequential impregnations of metal ions and titanium tetraisopropoxide (TTIP) into activated carbon fibers (ACF) followed by a solvothermal treatment has been found to be a general method in the preparations of homogeneous and composition-tunable hybrid TiO(2) hierarchical nanocomposite fibers like WO(3)/TiO(2), Fe(2)O(3)/TiO(2) and SnO(2)/TiO(2).     

Gas-bubble effects on the formation of colloidal iron oxide nanocrystals

This paper reports that gas bubbles can be used to tailor the kinetics of the nucleation and growth of inorganic-nanocrystals in a colloidal synthesis. We conducted a mechanistic study of the synthesis of colloidal iron oxide nanocrystals using gas bubbles generated by boiling solvents or artificial Ar bubbling. We identified that bubbling effects take place through absorbing local latent heat released from the exothermic reactions involved in the nucleation and growth of iron oxide nanocrystals. Our results show that gas bubbles display a stronger effect on the nucleation of iron oxide nanocrystals than on their growth. These results indicate that the nucleation and growth of iron oxide nanocrystals may rely on different types of chemical reactions between the iron-oleate decomposition products: the nucleation relies on the strongly exothermic, multiple-bond formation reactions, whereas the growth of iron oxide nanocrystals may primarily depend upon single-bond formation reactions. The identification of exothermic reactions is further consistent with our results in the synthesis of iron oxide nanocrystals with boiling solvents at reaction temperatures ranging from 290 to 365 °C, by which we determined the reaction enthalpy in the nucleation of iron oxide nanocrystals to be -142 ± 12 kJ/mol. Moreover, our results suggest that a prerequisite for effectively suppressing secondary nucleation in a colloidal synthesis is that the primary nucleation must produce a critical amount of nuclei, and this finding is important for a priori design of colloidal synthesis of monodispersed nanocrystals in general.     

Fluorescence quenching of meso-tetrakis (4-sulfonatophenyl) porphyrin by colloidal TiO(2)

A stable colloidal TiO(2) has been prepared. The interaction of meso-tetrakis (4-sulfonatophenyl) porphyrin (TSPP) with colloidal TiO(2) was studied by absorption and fluorescence spectroscopy. Upon excitation of its absorption band, the fluorescence emission of TSPP was quenched by colloidal TiO(2). The bimolecular quenching rate constant (k(q)) is 1.78 x 10(11)M(-1)s(-1). The porphyrin can participate in the quenching process by injecting electrons from its excited states into the conduction band of TiO(2). The quenching mechanism is discussed on the basis of the quenching rate constant as well as the reduction potential of the colloidal TiO(2). Rehm-Weller equation was applied for the calculation of free energy change (DeltaG(et)).     

Growth of InP nanostructures via reaction of indium droplets with phosphide ions: synthesis of InP quantum rods and InP-TiO2 composites

InP quantum rods were synthesized via the reaction of monodispersed colloidal indium droplets with phosphide ions. In(0) droplets, which do not act as a catalyst but rather a reactant, are completely consumed. The excess electrons that are produced in this reaction are most likely transferred to an oxide layer at the indium surface. For the synthesis of InP quantum rods with a narrow size distribution, a narrow size distribution of In(0) particles is also required because each indium droplet serves as a template to strictly limit the lateral growth of individual InP nanocrystals. Free-standing quantum rods, 60, 120, or 150 A in diameter, with aspect ratios of 1.6-3.5, and without the residual metallic catalyst at the rod tip, were synthesized from the diluted transparent solution of metallic indium particles. The same approach was used to synthesize InAs quantum rods. A photoactive InP-TiO(2) composite was also prepared by the same chemical procedure; InP nanocrystals grow as well-defined spherical or slightly elongated shapes on the TiO(2) surface.     

In situ one-pot synthesis of 1-dimensional transition metal oxide nanocrystals

One-dimensional colloidal metal oxide nanocrystals are of great importance in materials chemistry, but reports on these materials are rare due to lack of well-defined synthetic protocols. In this paper, we present a general and highly effective one-pot synthetic protocol to produce 1-dimensional nanostructures of transition metal oxide (e.g., W(18)O(49), TiO(2), Mn(3)O(4), and V(2)O(5)) through thermally induced crystal growth processes from a mixture of metal chloride and surfactants.     

Photocatalytic synthesis of silver nanoparticles stabilized by TiO2 nanorods: a semiconductor/metal nanocomposite in homogeneous nonpolar solution

A novel colloidal approach toward semiconductor/metal nanocomposites is presented. Organic-soluble anatase TiO(2) nanorods are used for the first time to stabilize Ag nanoparticles in optically clear nonpolar solutions in the absence of specific ligands for silver. Metallic silver is generated upon UV illumination of deaerated TiO(2) solutions containing AgNO(3). The Ag nanoparticles can be obtained in different size-morphological regimes as a function of the irradiation time, due to light-induced photofragmentation and ripening processes. A mechanism for the colloidal stabilization of the silver nanoparticles is tentatively suggested, which regards the TiO(2) nanorods as inorganic stabilizers, thus acting in the same manner as conventional surfactant molecules. The proposed photocatalytic approach offers a convenient method for producing TiO(2)/Ag nanocomposite systems with a certain control over the metal particle size without the use of surfactants and/or additives. Stable colloidal TiO(2)-nanorod-stabilized Ag nanoparticles can be potentially available for a number of applications that require "clean" metal surfaces, such as homogeneous organic catalysis, photocatalysis, and sensing devices.     

Complex alpha-MoO(3) nanostructures with external bonding capacity for self-assembly

Through manipulating crystal growth directions, we devised a versatile synthetic method to fabricate complex alpha-MoO(3) nanostructures with external bonding capacity for self-organization. Using four-armed forklike alpha-MoO(3) as nanobuilding blocks, we assembled more complex crystal morphologies, such as centrally holed nanorods, tridents, and paintbrushes. With prolonged ultrasonic treatments, pristine forklike alpha-MoO(3) crystals can be turned into less armed nanostructures, giving away the secondary arms (width < 100 nm) at the same time. On the other hand, the resultant alpha-MoO(3) itself can act as a template to produce shaped TiO(2) and other nanocrystals. Square- and horseshoe-shaped nanocrystals of anatase TiO(2) are left undissolved after removing alpha-MoO(3) templates in basic medium.     

Colloidal gallium indium oxide nanocrystals: a multifunctional light-emitting phosphor broadly tunable by alloy composition

We demonstrate compositionally tunable photoluminescence in complex transparent conducting oxide nanocrystals. Alloyed gallium indium oxide (GIO) nanocrystals with variable crystal structures are prepared by a colloidal method throughout the full composition range and studied by different structural and spectroscopic methods, including photoluminescence and X-ray absorption. The structures and sizes of the GIO nanocrystals can be simultaneously controlled, owing to the difference in the growth kinetics of In(2)O(3) and Ga(2)O(3) nanocrystals and the polymorphic nature of both materials. Using the synthesized nanocrystal series, we demonstrate the structural and compositional dependences of the photoluminescence of GIO nanocrystals. These dependences, induced by the interactions between specific defect sites acting as electron donors and acceptors, are used to achieve broad emission tunability in the visible spectral range at room temperature. The nature of the photoluminescence is identified as donor-acceptor pair recombination and changes with increasing indium content owing to the changes in the energy states of, and interactions between, donors and acceptors. Structural analysis of GIO nanocrystals by extended X-ray absorption fine structure spectroscopy reveals that In(3+) occupies only octahedral, rather than tetrahedral, sites in the spinel-type γ-Ga(2)O(3) nanocrystal host lattice, until reaching the substitutional incorporation limit of ca. 25%. The emission decay dynamics is also strongly influenced by the nanocrystal structure and composition. The oxygen vacancy defects, responsible for the observed photoluminescence properties, are also implicated in other functional properties, particularly conductivity, enabling the application of colloidal GIO nanocrystals as integrated optoelectronic materials.     

Impact of growth kinetics on morphology and pore structure of TiO2-one-pot synthesis of macroporous TiO2 microspheres

Titanium dioxide was synthesized by the hydrolysis of titanium tetraisopropoxide (TTIP) in the presence of acetic acid, 2-propanol, and organic amines (octylamine, aniline, and isobutylamine). H2O was supplied by an esterification reaction between acetic acid and 2-propanol (denoted as H2Oe), and/or by intentionally adding it (denoted as H2Oa). It was found that the quantity of H2Oa plays a crucial role in the morphology and porous structure of the final TiO2 product. Without the addition of H2Oa, 1D and porous TiO2 was synthesized. With the addition of H2Oa, and when the H2Oa:TiO2 molar ratio was in the range of 1:1 to 60:1, macroporous TiO2 microspheres possessing a large surface area and high thermal stability were obtained. When the H2Oa:TiO2 molar ratio exceeded 60:1, porous TiO2 with an irregular shape was formed. The variation in the morphology and porous structure is attributed to the manipulation of the growth kinetics by the addition of water.     

Seeded growth of two-dimensional dendritic gold nanostructures

We show that seeded growth can be applied to creating two-dimensional (2D) dendritic Au nanostructures on sample grids, which can be directly characterized by transmission electron microscopy (TEM). The 2D synthesis of highly consistent structures offers a novel mechanistic perspective on the aggregation of colloidal Au nanocrystals on a surface.