Preparation of Au/Ag multilayers via layer-by-layer self-assembly in spherical polyelectrolyte brushes and their catalytic activity

Spherical polyelectrolyte brushes(SPBs) consisting of polystyrene(PS) core and poly(2-aminoethyl methacrylate hydrochloride)(PAEMH) shell were prepared by photo-emulsion polymerization. Au nanoparticles(Au-NPs) with controlled size and size distribution were synthesized in situ using SPBs as nanoreactors. Via layer-by-layer deposition technique on the surface of SPBs, nano-composite particles with Au/Ag-NPs bilayer and Au/Ag/Au-NPs trilayer were prepared. The structures of the as-prepared Au/Ag multilayer SPBs were characterized by UV-Vis spectroscopy, TEM, ICP-AES and DLS. The charge reversal of the nano-composite particles observed by zeta potential confirmed the success of layer-by-layer assembly. The Au/Ag-NPs bilayer nano-composite particles showed high catalytic efficiency with an apparent activation energy of about 41.2 k J/mol in the reduction reaction of 4-nitrophenol to 4-aminophenol in the existence of sodium borohydride monitored. The catalytic activity of Au/Ag-NPs multilayer SPBs close to that of Au-NPs SPBs and much higher than that of Ag-NPs SPBs reveals its potential applications in cost-effective catalysts with high-performance.     

Au/γ-MnO2催化剂催化无溶剂条件下甲苯氧化反应

采用氧化还原法制备了α, δ, γ-MnO₂载体, 采用原位还原法制备了Au负载量为0.5%-3.0%的Au/γ-MnO₂催化剂, 并采用X射线衍射、扫描电镜、透射电镜和N₂物理吸附等手段对其进行了表征. 透射电镜照片表明Au/γ-MnO₂催化剂中Au颗粒的大小约为10 nm. 采用无溶剂存在下的甲苯氧化反应测试所制备样品的催化活性. 结果表明, 甲苯转化率随着Au负载量的增加而增大. 这是由于Au颗粒数量增多, 尺寸减小的缘故. 同时, 负载Au颗粒对苯甲醛具有较高的选择性. Au/γ-MnO₂催化剂具有良好的重复使用性.     

Gold nanoparticles located at the interface of anatase/rutile TiO2 particles as active plasmonic photocatalysts for aerobic oxidation

Visible-light irradiation (λ > 450 nm) of gold nanoparticles loaded on a mixture of anatase/rutile TiO(2) particles (Degussa, P25) promotes efficient aerobic oxidation at room temperature. The photocatalytic activity critically depends on the catalyst architecture: Au particles with <5 nm diameter located at the interface of anatase/rutile TiO(2) particles behave as the active sites for reaction. This photocatalysis is promoted via plasmon activation of the Au particles by visible light followed by consecutive electron transfer in the Au/rutile/anatase contact site. The activated Au particles transfer their conduction electrons to rutile and then to adjacent anatase TiO(2). This catalyzes the oxidation of substrates by the positively charged Au particles along with reduction of O(2) by the conduction band electrons on the surface of anatase TiO(2). This plasmonic photocatalysis is successfully promoted by sunlight exposure and enables efficient and selective aerobic oxidation of alcohols at ambient temperature.     

Au/TiO2催化剂制备条件对巴豆醛选择加氢的影响

采用沉积-沉淀法制备了纳米Au/TiO2催化剂, 以X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等手段对催化剂进行了系统的表征, 并考察了该催化剂在巴豆醛液相加氢制巴豆醇反应中的催化性能. 通过改变活化气氛、负载量和还原温度, 能够调节Au粒子的尺寸及金属与载体间的相互作用. 在673 K还原条件下制备Au质量分数为9.2%的Au/TiO2 催化剂上, Au粒子的平均粒径为2 nm, 初始加氢速率达到13.7×10-5 mol·s-1·g-1, 同时巴豆醇最高收率可达69.9%. 结合表征结果, 该催化剂良好的巴豆醛选择加氢性能归属为载体TiO2在还原条件下产生的氧缺陷位对Au纳米粒子的锚定作用及给电子作用.     

A compilation of infinite dilution resonance integrals,I

The resonance integrals for 59 isotopes were determined by neutron activation in reactor Thetis. The irradiations were carried out with and without Cd cover. The ratios of the thermal to epithermal fluxes were calculated from the Cd ratio of a Au monitor. From the induced activities in 36 elements, measured by means of γ-spectrometry with Ge(Li) and NaI(Tl) detectors, the values of I₀/σ_th were obtained.     

Metal Oxide Thin Films Containing Au Nano-Particles Prepared with Gas Diffusion Method

Au particles dispersed thin metal oxide films were prepared from precursor films containing HAuCl₄ with H₂S gas diffusion method. HAuCl₄ was uniformly dissolved in the films as promoted by hydroxypropyl cellulose (HPC). The mechanism of the Au particle formation was studied. It was found that HAuCl₄ was converted directly to Au metal particles upon contacting with H₂S gas. Au particles generated by this method were characterized with small particle size, sharp size distribution and high volume fraction in the films. The surface plasma resonance absorption of Au particles shifted to longer wavelength when TiO₂ component was introduced in the matrix.     

Size and shape of Au nanoparticles formed in ionic liquids by electron beam irradiation

Au nano-particles were synthesized via a reductive reaction in ionic liquid solution containing Au(3+) ions using a low-energy electron irradiation technique. In this study, we focused on how the electron beam conditions (acceleration energy, beam current and irradiation time) and the kinds of ionic liquid affected the size and shape of the prepared Au particles. The sizes of the primary particles increased with higher acceleration energy of the electron beam, whereas they did not depend so much on the beam current. Although the amount of secondary particles increased with longer irradiation time, the sizes of the primary particles remained constant. The anion of the ionic liquid strongly affected the size and shape of the primary particles, which was due to the different local structure of the ionic liquid around the Au particles. When the thickness of the ionic liquid layer was smaller than the penetration length of the electron beam, the formation of secondary particles was suppressed. The present results gave an important knowledge for controlling the size and shape of the metal particles, which is important for application of various catalyst or devices.     

Preparation of Au Nanoparticles on Surface of Two Supports by Adsorption Phase Synthesis

By utilizing adsorption phase synthesis (APS), Au nanoparticles were prepared on the surface of SiO₂ with or without modification by Ni(OH)₂. TEM, XRD, and UV‐vis were employed to characterize the morphology of Au particles on the surface of two kinds of supports. The results showed that the average size of Au particles on the SiO₂ surface modified by Ni(OH)₂ was less than 5 nm. Due to high surface isoelectric point, Au particles formed in the adsorption layer were prone to distribute on the surface of SiO₂ modified by Ni(OH)₂. With content of Ni(OH)₂ in samples increasing, more Au particles with small size appeared on the support surface.     

Electronic and geometric properties of Au nanoparticles on Highly Ordered Pyrolytic Graphite (HOPG) studied using X-ray Photoelectron Spectroscopy (XPS) and Scanning Tunneling Microscopy (STM)

Au nanoparticles grown on mildly sputtered Highly Ordered Pyrolytic Graphite (HOPG) surfaces were studied using Scanning Tunneling Microscopy (STM) and X-ray Photoelectron Spectroscopy (XPS). The results were compared with those of Ag nanoparticles on the same substrate. By varying the defect densities of HOPG and the Au coverages, one can create Au nanoparticles in various sizes. At high Au coverages, the structures of the Au films significantly deviate from the ideal truncated octahedral form: the existence of many steps between different Au atomic layers can be observed, most likely due to a high activation barrier of the diffusion of Au atoms across the step edges. This implies that the particle growth at room temperature is strongly limited by kinetic factors. Hexagonal shapes of Au structures could be identified, indicating preferential growth of Au nanostructures along the (111) direction normal to the surface. In the case of Au, XPS studies reveal a weaker core level shift with decreasing particle size compared to the 3d level in similarly sized Ag particles. Also taking into account the Auger analysis of the Ag particles, the core level shifts of the metal nanoparticles on HOPG can be understood in terms of the metal/substrate charge transfer. Ag is (partially) positively charged, whereas Au negatively charged on HOPG. It is demonstrated that XPS can be a useful tool to study metal-support interactions, which plays an important role for heterogeneous catalysis, for example.     

Influence Type and Temperature of Activation on the Catalytic Activity of Derived Form of Au 101 Nanocatalysts

Recently, gold nanoparticles attracted an increased attention due to unusual and somewhat unexpected catalytic properties especially pronounced in the oxidation of some organic compounds. Gold nanoparticles, which was immobilized on powder Norit® activated carbon as a support (1.0 wt % Au101/AC) exhibited high activity and selectivity for benzyl alcohol oxidation particularly with the gold catalysts subjected to a specific type of activation and temperature. The interaction between Au101 particles and its support was studied by measuring the catalytic activity and selectivity as a function of activation procedure. The first method included washing with a solvent (i.e., toluene) at elevated temperature, and/or followed by heat treatments at mild temperatures (i.e., 100 and 200°C for 3 h). The highest catalytic activity of benzyl alcohol oxidation was however obtained when gold catalysts were pre-washed with hot toluene at 100°C for 2 h followed by thermal treatment under vacuum. In these cases, the gold core diameters was ∼3.5 nm. In a number of experiments, the reaction time was 3 h, whereas in other runs it was extended to 24 h. The conversion level of benzyl alcohol oxidation was affected by the type of activation and its temperature related to the gold particles size.     

Instrumental activation analysis for determining the composition of micro-ingots of multi-constituent alloys

A procedure for the instrumental neutron activation analysis of micro-ingots of alloys containing In, Sb, Au, Ga, Ni, Sn and Bi is proposed. The non-destructive analysis of the irradiated samples is performed by γ-spectrometry techniques including one-crystal scintillation detectors, dual-crystal sum-coincidence scintillation detectors and Ge(Li) semiconductor detectors. As a result, the cumbersome operations of radiochemical separation can be eliminated. The sensitivity of quantitative determinations using scintillation detectors in alloys of the above composition is 10⁻¹⁰ g for indium, gold, antimony and gallium and 10⁻⁶ g for nickel and tin. The use of semiconductor detectors yields sensitivities of 10⁻¹⁰ g for indium and gold and 10⁻⁹ g for gallium and antimony.     

Epithermal instrumental neutron activation analysis for the determination of gold and arsenic in Ghanaian gold tailings using conventional and anti-coincidence counting

Epithermal instrumental neutron activation analysis (EINAA) together with both conventional and anti-coincidence counting techniques were used to analyze six different gold tailing samples from Ghana for Au and As. The method involves the use of the epi-cadmium site of the Dalhousie University Slowpoke-2 reactor facility for the irradiation of the samples. After irradiation, the samples were counted directly on the detectors. The identification and quantification of the elements were done using 411 keV photopeak of ¹⁹⁸Au and both 559 keV and 657 keV photopeaks of ⁷⁶As. The precision and accuracy of the method were evaluated. Values for Au in the samples ranged from 2.48 ppm and 6.76 ppm and for As between 1,550 ppm and 3,460 ppm. The values obtained using the two counting systems were in good agreement while the anti-coincidence counting system gave values of higher precision and accuracy. The detection limit for Au were 20 and 10 ppb for the conventional and anti-coincidence spectrometric systems, respectively, and 50 ppb for As in both cases. Details of the method and results are presented.     

单分散纳米金尺寸的分步晶种生长控制

以聚乙烯吡咯烷酮(poly(vinylpyrrolidone), PVP)为保护剂, 硼氢化钠为还原剂, 合成了尺寸为(1.9±0.4) nm的单分散金胶体, 再以其作为一级晶种, 并分别用抗坏血酸和PVP为还原剂和保护剂, 通过改变各步晶种尺寸和氯金酸与晶种的摩尔比分步逐级合成了尺寸为3.2、4.7、6.3、8.0、10.3、14.0 nm的系列金纳米颗粒. 以LaMer模型为基础, 对分步晶种生长过程中影响金胶体产物尺寸分布(单分散性)的主要因素进行了讨论. 缓慢加入抗坏血酸并降低氯金酸对晶种的相对量对于单分散金纳米颗粒的控制合成有决定性作用. 快速加入抗坏血酸会因二次成核而导致金颗粒尺寸分布范围变宽.     

Interaction of cobalt with ceria thin films and its influence on supported Au nanoparticles

The interaction of Co with ceria thin films and its influence on the sintering behavior of Au were investigated by scanning tunneling microscopy(STM), synchrotron radiation photoemission spectroscopy(SRPES) and X-ray photoelectron spectroscopy(XPS). The strong interaction between Co and CeO_2(111) leads to oxidation of Co to Co~(2+) at 300 K, accompanied by partial reduction of ceria surface at low Co coverages. Subsequent Co deposition results in an increasing fraction of metallic Co. Annealing to high temperatures induces Co~(2+)ions diffuse into the CeO_2 film, while the small metallic Co islands agglomerate into larger ones. The bimetallic Co–Au particles were prepared by deposition of Au on the existing Co particles on ceria surfaces. The sintering behavior of Co–Au bimetallic surfaces is found to be highly determined by the stoichiometry of ceria supports. The addition of Co to the Au/CeO_2 surface suppresses the sintering of Au particles at high temperatures in comparison with that of pure Au particles. However, Au particles are less stable on the Co/CeO_(1.82) layer than on CeO_(1.82) surface.     

Ionic Liquid Assisted Synthesis of Au–Pd Bimetallic Particles with Enhanced Electrocatalytic Activity

Morphology‐ and composition‐controlled synthesis of Au–Pd bimetallic particles was realized by a facile ionic liquid assisted route at room temperature. The morphologies of the synthesized particles, such as nanoflake‐constructed spheres with a core–shell structure, nanoparticle‐constructed spheres, and nanoparticle‐constructed dendrites, could be well controlled by the present route. The ionic liquid was found to play a key role in the formation of these interesting particles. Moreover, the composition (Au:Pd) of the particles could be modulated by means of the molar ratio of the metal precursors in the feeding solutions. The Au–Pd bimetallic particles exhibit high electrocatalytic activity toward oxidation of ethanol and formic acid. Furthermore, cyclic voltammetric studies on the as‐prepared Au–Pd bimetallic particles revealed good electroactivity for H₂O₂, which results in an effective amperometric H₂O₂ sensor.     

Determination of trace concentrations of transmuted stable nuclides in TMD detectors using PGAA

The capability of prompt gamma-ray activation analysis (PGAA) for neutron fluence dosimetry by means of transmutation detectors is reported. The metallic foils of Ni, Au, Cu and Nb and the small piece of Ge crystal, which were irradiated at the LVR-15 reactor at ?e? for several days, were selected for analysis by PGAA technique. Concentrations of transmuted stable nuclides in these foils were measured using the PGAA facility installed at the research reactor FRM II in Garching.     

Oxygen Reduction Reaction (ORR) on Huge Gold (Au) Particles Prepared by a Pyrolysis Process of AuCl3 Dissolved in Distilled Water in the Presence of MWCNTs

Gold (Au) huge particles were prepared by a pyrolysis process of AuCl₃ dissolved in distilled water in the presence of multi‐walled carbon nanotubes (MWCNTs). X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the obtained samples. The results showed that Au huge particles with a diameter close to 500 nm were fabricated. The electrocatalytic performance of the huge Au particles modified graphite electrode in the oxygen reduction reaction (ORR) was investigated using cyclic voltammetry (CV). It indicated that the pyrolysis time was a key factor that can affect the electrocatalysis of Au huge particles towards ORR. Developing a novel and simple method of pyrolysis for fabricating Au huge particles is the main contribution of this work, which will be very helpful in the preparation of Au huge particles on a large scale.     

Photoinduced dissolution and redeposition of Au nanoparticles supported on TiO2

Au particles (mean size ca. 3 nm) supported on TiO(2) particles were irradiated by UV light (>300 nm) in aqueous solutions at 278 K. Photo-induced dissolution of Au nanoparticles followed by redeposition occurred in aqueous solutions containing halogen ions. The dissolution of Au nanoparticles yielded a Au(III) complex with a halogen ion; subsequent reduction of the Au(III) complex caused precipitation of larger Au particles on TiO(2).     

Gold Nanoparticles Supported on Mesoporous Titania Thin Films with High Loading as a CO Oxidation Catalyst

In the present work, 2.4 nm gold nanoparticles (Au NPs) are uniformly dispersed on mesoporous titania thin films which are structurally tuned by controlling the calcination temperature. The gold content of the catalyst is as high as 27.8 wt %. To our knowledge, such a high loading of Au NPs with good dispersity has not been reported until now. Furthermore, the reaction rate of the gold particles is enhanced by one order of magnitude when supported on mesoporous titania compared to non‐porous titania. This significant improvement can be explained by an increase in the diffusivity of the substrate due to the presence of mesopores, the resistance to agglomeration, and improved oxygen activation.     

Nano-Sized NiO Immobilized on Au/CNT for Benzyl Alcohol Oxidation: Influences of Hybrid Structure and Interface

Tiny gold nanoparticles were successfully anchored on carbon nanotubes (CNT) with NiO decoration by a two-step synthesis. Characterizations suggested that Ni species in an oxidative state preferred to be highly dispersed on CNT. During the synthesis, in situ reduction by NaBH₄ and thermal treatment in oxidation atmosphere were consequently carried out, causing the formation of Au-Ni-O_x interfaces and bimetal hybrid structure depending on the Ni/Au atomic ratios. With an appropriate Ni/Au atomic ratio of 8:1, Ni atoms migrated into the sub-layers of Au particles and induced the lattice contraction of Au particles, whilst a higher Ni/Au atomic ratio led to the accumulation of NiO fractions surrounding Au particles. Both contributed to the well-defined Au-Ni-O_x interface and accelerated reaction rates. Nickel species acted as structure promoters with essential Au-Ni-O_x hybrid structure as well as the active oxygen supplier, accounting for the enhanced activity for benzyl alcohol oxidation. However, the over-layer of unsaturated gold sites easily occured under a high Ni/Au ratio, resulting in a lower reaction rate. With an Au/Ni atomic ratio of 8:1, the specific rate of AuNi₈/CNT reached 185 μmol/g/s at only 50 °C in O₂ at ordinary pressure.