Size-controlled and large-scale synthesis of organic-soluble Ag nanocrystals in water and their formation mechanism

Organic-soluble Ag nanocrystals (NCs) with tunable sizes in the range from 5.4 to 22.1 nm were synthesized by a facile, reproducible and easily scaled up route usin g water as solvent in the presence of oleic acid and an alkylamine. The synthetic Ag NCs exhibits excellent hydrophobicity and can be well re-dispersed in various non- or weak-polar media. The tunable sizes of the Ag NCs were achieved by simply adjusting the initial precursor AgNO3 concentration. Large-scale synthesis of the Ag NCs was realized at a high AgNO3 concentration (0.4 mol/L). As much as 16.2 g highly uniform organic-soluble Ag NCs with 5 nm average diameter can be readily synthesized at low cost in a single reaction only usin g 400 mL water as solvent, which is adaptable to the industrial scale production. The structure of the obtained Ag NCs was investigated in detail by X-ray diffract ometry, transmission electron microscopy, Fourier transform infrared and thermal gravimetric analysis measurements. The results reveal that the surface of the organic-soluble Ag NCs is coated with the monolayer surfactants consisting of oleic acid and the alkylamine. In addition, on the basis of the sufficient evidences, a proposed mechanism based on the “bilayer surfactant-controlled reaction” successfully demonstrates the formation of high quality organic-sol uble Ag NCs in the aqueous solution.     

Structural and electrical properties of HCl-polyaniline-Ag composites synthesized by polymerization using Ag-coated (NH4)2S2O8 powder

Ag nanoparticles were sputter-deposited on ammonium persulfate ((NH₄)₂S₂O₈) powder to obtain (NH₄)₂S₂O₈-Ag powder, which was used to synthesize the HCl-doped polyaniline-Ag (HCl-PANI-Ag) composite via a polymerization procedure. The Ag nanoparticles were dispersed in the HCl-PANI matrix, and their sizes mainly ranged from 3 to 6 nm. The Ag nanoparticles did not affect the structure of emeraldine salt in the composite, and they increased the ordered crystalline regions in the HCl-PANI matrix. The HCl-PANI-Ag composite had a conductivity of (6.8 ±0.1) S/cm, which is about four times larger than that of the HCl-PANI. The charge transport mechanism in the composite is explained by the three-dimensional Mott variable-range hopping (3D-Mott-VRH).     

Novel Ag nanocrystals based dental resin composites with enhanced mechanical and antibac terial propert ies

The aim of this work was to investigate the effect of trace addition of oleic acid coated Ag nanocrystals(Ag NCs) on mechanical and antibacterial properties of dental resin composites.Composites(70 wt%of silica loading) with 25 ppm,50 ppm,75 ppm and 100 ppm(wt) Ag NCs were prepared and the composite without Ag NCs served as a control.The experimental results showed that the addition of Ag NCs significantly improved the strength and modulus of the resin composite without compromising the shade.For the composite with 50 ppm Ag NCs,fiexural strength(140.3 MPa),modulus(13.2 GPa)and compressive strength(347.2 MPa) were increased by 4.1%,22.2%,13.3%,respectively,compared with the control.The antibacterial test demonstrated that trace Ag NCs provided the resin composites with an antibacterial effect.Such strong and antibacterial dental resin composites might be advantageous to prevent secondary caries and be potential for future clinical applications.     

Ethylene tetramerization with a highly active and long-lifetime trinuclear diphenylphosphinoamine/Cr（III）/MAO catalyst

The synthesis and characterization of a novel trinuclear diphosphinoamine ligand 2 are reported. The ligand combined with Cr(III), activated with methylaluminoxane, lead to highly active and long-lifetime catalytic systems for the tetramerization of ethylene to form 1-octene. The effects of reaction temperature, reaction pressure, molar ratio of Al/Cr and bis(diphenylphosphino)amine/Cr on the catalytic activity and product selectivity were studied. Compared with its mononuclear analogue 1, ligand 2 showed a higher catalytic activity and longer lifetime for ethylene tetramerization in the presence of methylaluminoxane as cocatalyst. High molecular weight polyethylene was generated as a by-product with extremely broad molecular weight distributions.     

Catalytic combustion properties of nanocomplex oxide for natural gas

The catalysts of copper oxide supported on cerium dioxide were prepared by different methods for methane catalytic combustion. The effects of copper content in the catalysts and calcination temperatures of the catalysts on the catalytic activity are investigated. Results show that the complex oxide catalyst exhibits high catalytic activity for methane combustion due to the synergistic effect of CuO and CeO₂. The catalyst prepared by impregnation is more active than that prepared by controlled coprecipitation even if CuO content is the same. When W(CuO)<13%, the light-off temperature and full conversion temperature for the CH₄ reaction decrease with the increasing of CuO content in the catalysts. However, when the copper content is above 13%, the excess CuO has a negative effect on the catalytic activity owing to the formation of bulk CuO particles. A proper calcinations temperature of 650 ℃ can lead to a high dispersion of CuO and accordingly can enhance the catalytic activity of the composites.     

Thermal performance and reduction kinetic analysis of cold-bonded pellets with CO and H<Subscript>2</Subscript> mixtures

Cold-bonded pellets, to which a new type of inorganic binder was applied, were reduced by H₂–CO mixtures with different H₂/CO molar ratios (1:0, 5:2, 1:1, 2:5, and 0:1) under various temperatures (1023, 1123, 1223, 1323, and 1423 K) in a thermogravimetric analysis apparatus. The effects of gas composition, temperature, and binder ratio on the reduction process were studied, and the microstructure of reduced pellets was observed by scanning electron microscopy–energy-dispersive spectrometry (SEM-EDS). The SEM-EDS images show that binder particles exist in pellets in two forms, and the form that binder particles completely surround ore particles has a more significant hinder effect on the reduction. The reduction equilibrium constant, effective diffusion coefficient, and the reaction rate constant were calculated on the basis of the unreacted core model, and the promotion effect of temperature on reduction was further analyzed. The results show that no sintering phenomenon occurred at low temperatures and that the increasing reaction rate constant and high gas diffusion coefficient could maintain the promotion effect of temperature; however, when the sintering phenomenon occurs at high temperatures, gas diffusion is hindered and the promotion effect is diminished. The contribution of the overall equilibrium constant to the promotion effect depends on the gas composition.     

Activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag and their application to the recycling of Ni-Co-Fe-based end-of-life superalloys via remelting

To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni-Co-Fe-based end-of-life (EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO-Al₂O₃-SiO₂ slag. The activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag both show a positive deviation from Raoult's law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B=(%CaO)/(%SiO₂)=1, where B is the basicity. We observed that controlling the slag composition at approximately B=1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.     

The Composite Cathode of Ag and LSCF for SOFC Working under Intermediate Temperature

1 Introduction The composite electrode of La0.6Sr0.4Co0.2Fe0.8O3(LSCF) and Ag was studied as a new air electrode system for reduced-temperature SOFCs.The LSCF/Ag composite electrodes were prepared by baking the LSCF electrode with various Ag solution infiltrated in the pores of the electrode.In all cases,the cathode polarization resistance was reduced,which may be brought from the catalytic activity of Ag metal.For example,the power density of LSCF electrode on anode supported cell was increased from 0.28 W/cm2 to 0.34 W/cm2 at 600 ℃ by baking the infiltrated Ag solution into the electrode.     

A designed core-shell structural composite of lithium terephthalate coating on Li4Ti5O12 as anode for lithium ion batteries

A core-shell structural composite was synthesized with lithium terephthalate（Li₂C₈H₄O₄） coated on spinel Li₄Ti₅O₁₂（LTO）. The composite displays a capacity of about 200 mA h g^-1 and a good rate capability with two charge/discharge platforms at 1.55 and 0.8 V. The excellent cycling performance of the composite is attributed to the successful combination of high cycling stability of LTO and high specific capacity of Li₂C₈H₄O₄. In addition, an interesting phenomena is observed for the first time for this composite which is that lithium ions transfer between LTO and Li₂C₈H₄O₄ at a fast speed. This is investigated in details via the asymmetric charge/discharge measurement and cyclic voltammogram（CV）.The LTO/Li₂C₈H₄O₄ composite may have potential applications to be used as an anode material for the electric vehicle batteries, which is shallowly charged/discharged at ordinary times using the charge/discharge platform of LTO and fully charged/discharged at emergency to release the extra high capacity from Li₂C₈H₄O₄.     

Study on anti-pollution nano-preparation or dimethomorph and its performance

The photocatalysis of nanometer TiO2/Ag was modified by sodium dodecyl sulfate, and its behavior of adsorption for pesticide was investigated on the surface of catalyst. Four kinds of water-solubility preparations were prepared by using TiO2/Ag, modified TiO2/Ag by 0.5% SDS, TiO2 and nothingness as photocatalyst with dimethomorph as effective component. They were besmeared on a piece of glass, and the photocatalytic experiment was done in sunlight. Degradation rates of 1.2 % dimethomorph are 71.5 %, 68.0 %, 45.5% and 28.3%, respectively, when it was degraded in five days. Degradation rate of 10% dimethomorph is 97.3% in eight days in sunlight and ti/2 is 2.8 d in nano-preparation, when it was sprayed on small cabbages after being diluted in rudimental experiments of toxicity for crop. The nano-preparation is of better biologic activity, the virulence of which is 1.235 times as great as original pesticide and 1.245 times as ordinary preparation under the same condition.     

Surface modifications of Pt-based atomically ordered nanoparticles to improve catalytic performances for oxygen reduction reaction

Bimetallic platinum-cobalt (Pt–Co) nanostructure catalysts represent superior catalytic performances for oxygen reduction reaction (ORR). In a variety of Pt–Co catalyst structures, atomically ordered structure catalysts show excellent catalytic performances in the ORR. In this work, for promoting their catalytic performances, atomically ordered PtCo nanoparticles (PtCo/C) with carbon supported were successfully prepared by an improved impregnation method and annealing. Then, the ordered PtCo/C catalysts have been significantly improved by doped with ultralow amount of Au and Cr transition metal. The physical and electrochemical test results demonstrate the Cr–PtCo/C and Au–PtCo/C catalysts have superior catalytic performances including mass activity and stability compared to commercialized Johnson Matthey (JM) Pt/C, which was the result of the modified electronic properties of Pt surface and atomically ordered structure. The presence of Au and Cr enhances the stability of PtCo/C catalysts. This work represents a simple way to promote the catalytic performances of the atomically ordered catalysts.     

Size-controlled and large-scale synthesis of organic-soluble Ag nanocrystals in water and their formation mechanism

Organic-soluble Ag nanocrystals (NCs) with tunable sizes in the range from 5.4 to 22.1 nm were synthesized by a facile, reproducible and easily scaled up route using water as solvent in the presence of oleic acid and an alkylamine. The synthetic Ag NCs exhibits excellent hydrophobicity and can be well re-dispersed in various non- or weak-polar media. The tunable sizes of the Ag NCs were achieved by simply adjusting the initial precursor AgNO₃ concentration. Large-scale synthesis of the Ag NCs was realized at a high AgNO₃ concentration (0.4 mol/L). As much as 16.2 g highly uniform organic-soluble Ag NCs with 5 nm average diameter can be readily synthesized at low cost in a single reaction only using 400 mL water as solvent, which is adaptable to the industrial scale production. The structure of the obtained Ag NCs was investigated in detail by X-ray diffractometry, transmission electron microscopy, Fourier transform infrared and thermal gravimetric analysis measurements. The results reveal that the surface of the organic-soluble Ag NCs is coated with the monolayer surfactants consisting of oleic acid and the alkylamine. In addition, on the basis of the sufficient evidences, a proposed mechanism based on the “bilayer surfactant-controlled reaction” successfully demonstrates the formation of high quality organic-soluble Ag NCs in the aqueous solution.     

中孔Ag微米盘/ZnO纳米棒阵列异质结的构筑及光催化研究

利用简单的两步合成法制备得到新颖的中孔Ag微米盘（HMDs）/ZnO纳米棒（NRs）异质结,主要包括上晶种和异质外延生长.通过简单的合成参数调控,可以制备不同纳米直径、不同长度、不同形状的ZnO NRs,进而制成不同形貌的Ag/ZnO异质结.结构新颖的Ag/ZnO异质结由一维（1D）半导体和二维（2D）纳米结构元构成,Ag/ZnO异质结具有高比表面积和开放的空间结构,在光电领域具有很重要的应用潜力.在光催化测试中,Ag/ZnO异质结表现出优越的催化活性,主要归因于结构独特的Ag/ZnO异质结的协同效应.     

Near-infrared fluorescent aptamer-templated silver nanoclusters facilely synthesized for cellular imaging applications

Fluorescent metal nanoclusters(NCs)have received extensive attention for their potential uses in bionanotechnology.Here,we develop a facile strategy to synthesize near-infrared fluorescent silver nanoclusters(Ag NCs)stabilized by MUC1 aptamer.The MUC1-Ag NCs are characterized by UV–Vis absorption spectroscopy,fluorescence spectroscopy,transmission electron microscopy,and fluorescence lifetime.These results indicated that the MUC1-Ag NCs possess bright near-infrared luminescence,high stability,and excellent biocompatibility.The cellular imaging of MUC1-Ag NCs by confocal laser microscopy demonstrated them to be promising candidates as novel fluorescent probes for biomedical application.     

Ag/TiO_2/AC光催化氧化NO性能研究

以活性炭(AC)为载体,采用溶胶-凝胶法和浸渍法制备新型光催化剂Ag/TiO_2/AC,利用SEM、XRD、BET和UV-Vis光谱等手段对样品进行了表征,并以模拟烟气中的NO为对象,进行光催化氧化性能测试。结果表明,Ag/TiO_2/AC的比表面积为895.21 m~2/g,且对光响应波长已扩展到可见光区,该催化剂在光催化氧化NO反应中具有优异的活性,NO的氧化率高于60.5%。     

铜纳米颗粒修饰多孔氮化硼高效还原对硝基苯酚的研究

为了寻找高催化活性、环境友好、价格低廉、稳定性好的催化剂,研究金属与载体之间的协同催化效应,采用煅烧前驱体法制备了表面富含羟基和氨基的高比表面积多孔h-BN载体,通过简单的液相还原法成功地制备出粒径分布均匀的Cu/h-BN纳米复合材料,并对复合材料的组成、微观结构和性能进行表征。结果显示,铜纳米粒子的引入并未破坏多孔h-BN的二维片状结构,但比表面积及孔径均有不同程度的下降。以对硝基苯酚(4-NP)还原为对氨基苯酚(4-AP)为模型反应,考察Cu/h-BN复合材料的催化性能,当Cu含量为6%(质量分数)时,复合纳米材料具有最高的催化性能(表观反应速率常数k=4.62×10^-2 s^-1)和稳定性,催化活性在5个循环内基本保持不变。因此,具有高比表面积的h-BN载体负载可稳定Cu纳米颗粒,它们之间的协同催化作用使Cu/h-BN具有优异的催化活性和稳定性。此研究为今后进一步研究金属与h-BN协同催化提供了理论基础。     

复合铌酸盐的合成和光催化活性的研究

利用光催化剂降解有机染料具有很好的应用前景,光催化材料在光催化反应中起着重要的作用,但是如何制备化学性质稳定、在可见光下具有高的催化活性的催化剂一直是人们探索的一个主题。以Ag2O、Nb2O5、Na2CO3为前驱物,经高温固相反应法合成了具有不同Na/Ag摩尔比的(AgNbO3)1-x(NaNbO3)x复合铌酸盐。采用X-射线粉末衍射(XRD)、紫外-可见漫反射谱(UV-vis DRS)等方法对样品的结构和光谱响应特征进行了表征,以亚甲基蓝的降解反应为探针考察不同Na/Ag摩尔比的(AgNbO3)1-x(NaNbO3)x复合铌酸盐在可见光下的光催化活性。结果表明,由高温固相法合成出的复合铌酸盐的结构随着Na/Ag摩尔比的变化而变化,光谱响应特征随Na/Ag摩尔比的减小逐渐红移,而对亚甲基蓝的降解性能随Na/Ag呈规律性变化,其中(AgNbO3)0.6(NaNbO3)0.4复合铌酸盐呈现最好的光催化活性。     

TiO2/AC复合催化剂的制备及光催化性能研究

以钛酸丁酯为前驱体,三乙醇胺为螯合荆,通过溶胶-凝胶法制备了TiO<,2>溶胶前驱体.然后,结合胶体浸渍-烧结法制得TiO<,2>/AC复合催化剂.主要讨论了制备过程中水,活性炭的预处理方式,以及不同烧结方式对复合催化剂光催化性能的影响.实验表明钛酸丁酯和水的质量比为17:1时制得的TiO<,2>前驱体与经HNO<,3...     

天然水体主要本底成分对催化臭氧氧化草酸的影响

采用浸渍法制备了Fe2O3负载活性炭（Fe2O3/AC）催化剂,考察了Fe2O3/AC催化臭氧氧化草酸的活性以及天然水体主要本底成分对Fe2O3/AC催化臭氧氧化草酸的影响. 结果表明,臭氧氧化草酸过程中Fe2O3/AC显示了良好的催化活性,草酸的去除主要基于催化贡献. HCO3-、CO32-及腐殖酸对Fe2O3/AC催化臭氧氧化草酸体系均有抑制作用. HCO3-和CO32-加入使催化臭氧氧化体系pH升高,进而降低Fe2O3/AC催化臭氧氧化草酸的活性. 此外,HCO3-和CO32-也是羟基自由基抑制剂,HCO3-、CO32-对体系的抑制作用从侧面验证Fe2O3/AC催化臭氧氧化草酸遵循羟基自由基机理. 腐殖酸加入体系后,与草酸形成竞争吸附和竞争氧化,从而抑制草酸的降解.