Sequential Anion and Cation Exchange Reactions for Complete Material Transformations of Nanoparticles with Morphological Retention

Ion exchange reactions of colloidal nanocrystals provide access to complex products that are synthetically challenging using traditional hot‐injection methods. However, such reactions typically achieve only partial material transformations by employing either cation or anion exchange processes. It is now shown that anion and cation exchange reactions can be coupled together and applied sequentially in one integrated pathway that leads to complete material transformations of nanocrystal templates. Although the product nanocrystals do not contain any of the original constituent elements, the original morphology is retained, thereby fully decoupling morphology and composition control. The sequential anion/cation exchange process was applied to pseudo‐spherical CdO nanocrystals and ZnO tetrapods, producing fully transformed and shape‐controlled nanocrystals of copper and silver sulfides and selenides. Furthermore, hollow core–shell tetrapod ZnS@CdS heterostructures were readily accessible.     

Influence of Pretreatment on the Interaction of Oxygen with Silver and the Catalytic Activity of Ag／SiO2 Catalysts for CO Selective Oxidation in H2

The interactions of oxygen with pre~reduced silver catalysts as well as their catalytic propertiesfor CO selective oxidation in H2 after oxygen pre-treatment are studied in this paper. It is found that the pretreatment exerts a strong influence on the activity and selectivity of the silver catalyst. A drop in activity and selectivity is observed after treating a pre-reduced catalyst with oxygen at low temperatures,whereas a converse result is obtained after an oxidizing treatment at high temperatures (T≥350℃). O2-TPD results show that surface oxygen species adsorbs on silver surface after the oxygen treatment at low temperatures. However, penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile the surface oxygen species disappear. No other silver species except metallic silver are observed on all the catalysts by XRD, and the size of silver particle is not changed after the treatment with oxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also be removed by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorption and diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing the decrease in CO oxidation activity, in other words, it is important to obtain a clean silver surface for increasing the catalyst activity in CO removal from H2-rich feed gas. The differences in activity and selectivity due to the oxygen pretreatment at different temperatures axe discussed in terms of the changes in the surface/subsurface oxygen species of the silver particles.     

Preparation of Large-area Controllable Patterned Silver Nanocrystals for High Sensitive and Stable Surface-enhanced Raman Spectroscopy

A novel and facile method for fabricating large-area patterned silver nanocrystals was introduced and the investigation on the high sensitive and stable surface-enhanced Raman spectroscopy(SERS) of the nanocrystals was carried out. Nanostructured silicon substrate was processed by laser interference and used as a template for growing silver nanocrystals via galvanic battery reaction method. The substrate with large area for violent chemical reaction was tailored into a nanocell array. The limited reaction area hindered the growth of silver nanocrystals and made their size uniform and controllable. The size and gaps of the nanocrystals could be controlled by template period and ratio, which were easily reproduced by laser interference. Taking 10^-8 to 10^-11 mol/L Rh6G for example, the optimized silver arrays exhibited great potential for ultrasensitive molecular sensing in terms of its high SERS enhancement ability, favorable stability, and excellent reproducibility.     

In situ transmission electron microscopy observation of silver oxidation in ionized/atomic gas

The interaction between silver and ionized and atomic gas was observed directly by in situ transmission electron microscopy with an environmental cell for the first time. The electron beam provides dual functions as the source of both gas ionization and imaging. The concentration of ionized gas was tuned via adjusting the current density of the electron beam. Oxidation of the silver is observed in situ, indicating the presence of ionized and/or atomic oxygen. The evolution of microstructure and phase constituents was characterized. Then the oxidation rate was measured, and the relationships among grain size, mass transport rate, and electron flux were characterized. The role of the electron beam is discussed, and the results are rationalized with respect to ex situ results from the literature.     

Pt nanocrystals: shape control and Langmuir-Blodgett monolayer formation

We report the synthesis of monodisperse Pt nanocrystals with three different shapes-cubes, cuboctahedra, and octahedra, selectively, with similar sizes of 9-10 nm by a modified polyol process. We found that addition of silver ion enhances the crystal growth rate along 100, and essentially determines the shape and surface structure of the Pt nanocrystals. After the reaction, the silver species can be easily removed by repetitive precipitation giving pure Pt nanoparticles. Two-dimensional arrays of the Pt nanocrystals were assembled by using the Langmuir-Blodgett (LB) method. The particles were evenly distributed on the entire substrate, and their surface coverage and density can be precisely controlled by tuning the surface pressure. The resulting Pt LB layers are potential candidates for 2-D model catalysts as a result of their high surface area and the structural uniformity of the metal nanocrystals.     

Hollow Ag/MnO2 Nanostructures with Controllable Shells: Synthesis and Oxygen Reduction Reaction Catalytic Performance

Novel hollow Ag/MnO₂ nanostructures with controlled shell composition and structure were designed and synthesized. In the present synthetic procedure, silver nanocrystals were oxidized by KMnO₄, and MnO₂ was heterogeneously formed on the surface of silver nanocrystals, then released Ag⁺ was photoreduced to silver adjacent to MnO₂. By simply changing the photoreduction moment, simultaneously with or after the addition of KMnO₄, hollow Ag/MnO₂ structures with different shell architectures—a monolayered shell composed of evenly mixed silver and MnO₂ and a double‐layered shell composed of an inner MnO₂ layer and an outer silver layer—can be obtained. Furthermore, the morphology of the hollow structure can be tuned by selecting different silver precursors, and the ratio of silver to MnO₂ in the shell can also be controlled by adjusting the ratio in the original reaction mixture. Electrochemical measurements revealed significantly enhanced catalytic performance in the oxygen reduction reaction for the prepared hollow structures. Compared with the Ag/MnO₂ composite, the onset potentials positively shift by about 50.0 mV and limiting current densities are nearly 2.0 times higher.     

Enhancement of nitrogen physisorption in coadsorption with oxygen on free, positively charged silver clusters

The coadsorption of molecular nitrogen and oxygen on small cationic silver clusters in the gas phase is experimentally studied. The presence of oxygen enhances the adsorption probabilities of N2. This indicates a partial charge transfer out of the finite free electron reservoir of the small silver particles into the chemisorbed oxygen molecule.     

Über die Flüchtigkeit von Silber im Sauerstoffstrom

Vaporization of Silver in a Stream of Oxygen Using a transport equipment the vaporization of silver at 611–721°C in a stream of oxygen has been measured. Experiments with detachable cuffs of silver or with wools of silver in a bulb made from quartzglass or silver lead to the same results. By variation of the O₂-pressure and the activity of silver is observed that the vaporization happens as Ag₂O,g, see “Inhaltsübersicht”. The solid was at first pure silver. During long lasting experiments, however, it is covered with a thin layer of oxygen or silver oxide, which lowers the concentration of Ag₂O,g in the equilibrium gas to a smaller, yet constant value. The following measurements using N₂ as carrier gas lead to the decomposition of this layer and ends with the very small vapor pressure of silver. The layer of oxygen or silver oxide on the metal could be shown after Davies [2] using mercury.     

MPT-AES法同时测定航空润滑油中铁、银和镍

用微波等离子体炬原子发射光谱法(MPT-AES)同时测定未使用过的航空润滑油中铁、银和镍的方法。详细考察了微波功率、载气流量、工作气流量、氧屏蔽气压力等实验参数对铁、银和镍发射强度的影响,并进行了系统优化。测得铁、银和镍的检出限分别为21.94ng/mL0、.36ng/mL9、.82ng/mL,线性范围分别为0.1~100μg/mL、0.001~8μg/mL、0.05~8μg/mL,各元素测定结果的相对标准偏差均小于3.95%,回收率在93.1%~107.4%之间。     

Photogenerated singlet oxygen over zeolite-confined carbon dots for shape selective catalysis

Singlet oxygen as an activated oxygen species played an important role in organic synthesis. Suitable catalyst for converting ubiquitous oxygen molecule to singlet oxygen under mild conditions has attracted a wide range of attention. Herein, carbon dots have been confined into mesopores of silicalite-1 nanocrystals framework and acted as active sites for generation of singlet oxygen. The high oxygen-adsorption capacity of zeolite nanocrystals facilitated the photocatalytic generation rate of singlet oxygen, outpacing the free-standing carbon dots for 14-fold. The integrated carbon dot-zeolite nanocrystal hybrid also exhibited a special size-dependent selectivity for organic synthesis by using the in situ formed and confined singlet oxygen as active oxygen species.     

The silver-oxygen system in catalysis: new insights by near ambient pressure X-ray photoelectron spectroscopy

We addressed the interaction of oxygen with silver by synchrotron based near ambient pressure X-ray photoelectron spectroscopy at temperatures relevant for industrial oxidation reactions performed with silver catalysts. For silver single crystals, polycrystalline foils and powders in equilibrium with gas phase O(2), we observed the dynamics of the formation of five different atomic oxygen species with relative abundances depending on the temperature and time. Correlation of their formation kinetics with spectroscopic features and thermal stability indicates that these are distinct species with different electronic structures, which might relate to the different roles of silver in oxidation reactions.     

Size-controlled synthesis of highly water-soluble silver nanocrystals

We describe a modified polyol process for the synthesis of silver nanocrystals with uniform sizes ranging from several nanometers to 20 nm. The use of polyacrylic acid, in place of polyvinylpyrrolidone in the conventional polyol process, significantly limits the growth of silver nanocrystals, prevents the interparticle aggregation and fusion, and leads to a uniform population of samples with high water solubility. The size of nanocrystals can be conveniently tuned by controlling the reaction time, the concentration and chain length of the polymeric surfactants, and the reaction temperature. Uniform silver nanocrystals within sizes below 20 nm are preferred candidates over larger particles for applications where high density of optical absorption is required, for example, for photothermal conversion in cancer therapy.     

A facile one-pot synthesis of uniform core-shell silver nanoparticle@mesoporous silica nanospheres

The uniform core-shell silver nanoparticle@mesoporous silica nanospheres have been prepared by a simple one-pot synchronous method, which combines several steps into one, including the generation of silver nanocrystals and mesoporous silica, transfer and aggregation of silver nanoparticles in an incompact silica framework.     

Chirality of silver nanoparticles synthesized on DNA

Silver nanocrystals grown on a poly(dG)-poly(dC) double stranded DNA scaffold displayed circular dichroism at their surface plasmon excitation band. This chiral plasmon signature was not observed in a control experiment where silver nanocrystals of similar size were produced without the DNA template and adsorbed to the DNA. It is concluded that the DNA templated Ag nanocrystals had a preferred structural handedness.     

Solventless nanoparticles synthesis under low pressure

In the present study, metal nanocrystals were obtained by the very easy, economical, and nontoxic thermal decomposition method and stabilized by coating oleate without any solvent. These nanocrystals have a highly crystalline structure due to a high decomposition temperature (~563-573 K) at low pressure and very narrow distribution. The prepared Fe3O4 nanocrystals were controlled by the annealing time and vacuum pressure. A TEM image of monodispersed Fe3O4 nanocrystals showed the 2D assembly of nanocrystals, demonstrating their uniformity. The particle size is 10.6 +/- 1.2 nm. TEM images of silver nanocrystals a showed 2D assembly with 9.5 +/- 0.7 nm. An electron diffraction image and X-ray diffraction of the nanocrystals showed the highly crystalline nature of metal nanocrystals.     

Phenidone Oxidation during Photoinitiated Chemical Reduction of AgBr Nanocrystals in Water Pools of Reverse Micelles

Photoinitiated chemical reduction of AgBr nanocrystals (synthesized in water pools of reverse micelles of Aerosol OT and sodium dodecyl sulfate) with phenidone was shown to yield 1-phenyl-3-hydroxypyrazole along with reduced silver. This becomes possible because of irreversible oxidation of phenidone (1-phenyl-3-pyrazolidone) used as a reducing agent, and the rate of 1-phenyl-3-hydroxypyrazole accumulation significantly increases in the presence of a silver halogenide. The formation of the dissociated form of 1-phenyl-3-hydroxypyrazole becomes more probable with decreasing diameter of the water pool of reverse micelles formed by both surfactants.     

Large-scale synthesis of uniform silver orthophosphate colloidal nanocrystals exhibiting high visible light photocatalytic activity

Silver orthophosphate nanocrystals with controlled particle size have been synthesized using a simple, reproducible and easily scaled up route based on the reaction between silver ions, oleylamine and phosphoric acid. The obtained nanocrystals are highly uniform in size and exhibit high visible light activity for the photodecomposition of organic compounds.     

Synthesis of Ag and AgI quantum dots in AOT-stabilized water-in-CO2 microemulsions

Silver and silver iodide nanocrystals have been synthesized in the water-in-CO(2) reverse microemulsions formed by the commonly used surfactant, sodium bis(2-ethylhexyl)sulfosuccinate (AOT), in the presence of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol as cosurfactant. The nanometer-sized aqueous domains in the microemulsion cores not only act as nanoreactors, but the surfactant interfacial monolayer also helps the stabilization of the metal and semiconductor nanoparticles. The transmission electron microscopy results show that silver and silver iodide nanocrystals with average diameters of 6.0 nm (standard deviation, SD=1.3 nm) and 5.7 nm (SD=1.4 nm), respectively, were formed. The results indicate that the method can be utilized as a general and economically viable approach for the synthesis of metal and semiconductor quantum dots in environmentally benign supercritical carbon dioxide.     

琥珀酸二异辛酯磺酸钠微乳体系中纳米银的制备及其连续相的影响

在琥珀酸二异辛酯磺酸钠(AOT)为表面活性剂、环己烷为连续相形成的微乳体系中, 利用水合肼还原AgNO₃制备了分散性良好的纳米银. 利用紫外-可见(UV-Vis)光谱和透射电镜(TEM)对所得产物进行了表征, TEM显微图像表明形成粒子为球形结构, 平均粒径为5.10 nm, 标准偏差为2.84 nm. 分别利用正己烷、正庚烷、正辛烷、环己烷和十二烷等作连续介质, 研究了微乳液中连续相对纳米银形成的影响. 随着正烷烃碳链长度的增加, 微乳液中胶束之间的交换速率增大, 形成粒子的平均粒径逐渐减小. 十二烷形成的微乳体系制备的纳米银溶胶具有最宽的共振吸收峰, 所得的纳米银粒子平均粒径最小. 环己烷形成的微乳液中反胶束具有特殊的界面强度, 导致纳米银晶核的形成速率过低, 纳米银晶粒的生长不完全.     

The palladium/silver membrane focusing injector — A new inlet system for thermal desorption capillary gas chromatography

Summary A new sample focusing technique for capillary gas chromatography is described. The system is designed as a focusing inlet for thermally desorbed gas samples. A solid-sorbent trapped sample is thermally released from the sample tube, transferred to a palladium/silver membrane chamber by a hydrogen carrier gas stream and retained there by the gas separation membrane, which is highly permeable to the carrier gas. After focusing in the membrane chamber the sample is injected onto the separation column. This technique allows focusing and injection of highly volatile compounds in capillary gas chromatography without using any coolant. The injection performance for n-alkanes is shown to be comparable to the cryofocusing technique.