Reduction of colloidal Ag2S to binary Ag2–XS/Ag nanoparticles under UV and visible irradiation

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Ag2S/Ag3PO4/Ni复合薄膜的制备及其光催化性能

采用电化学方法制备Ag₂S/Ag₃PO₄/Ni复合薄膜,以扫描电子显微镜（SEM）、X射线衍射（XRD）、紫外-可见漫反射光谱（UV-Vis DRS）对薄膜的表面形貌、晶相结构、光谱特性及能带结构进行了表征,以罗丹明B为模拟污染物对薄膜的光催化活性和稳定性进行了测定,采用向溶液中加入活性物种捕获剂的方法对薄膜的光催化机理进行了探索。结果表明：最佳工艺制备的Ag₂S/Ag₃PO₄/Ni是由均匀的球形纳米颗粒构成的薄膜,其光催化活性明显优于纯Ag₃PO₄/Ni薄膜和纯Ag₂S/Ni薄膜,且在保持薄膜光催化活性基本不变的前提下可循环使用6次。提出了可见光下Ag₂S/Ag₃PO₄/Ni复合薄膜光催化降解罗丹明B的反应机理。     

Ag2S/Ag3PO4/Ni复合薄膜的制备及其光催化性能

采用电化学方法制备Ag_2S/Ag_3PO_4/Ni复合薄膜,以扫描电子显微镜(SEM)、X射线衍射(XRD)、紫外-可见漫反射光谱(UVVis DRS)对薄膜的表面形貌、晶相结构、光谱特性及能带结构进行了表征,以罗丹明B为模拟污染物对薄膜的光催化活性和稳定性进行了测定,采用向溶液中加入活性物种捕获剂的方法对薄膜的光催化机理进行了探索。结果表明:最佳工艺制备的Ag_2S/Ag_3PO_4/Ni是由均匀的球形纳米颗粒构成的薄膜,其光催化活性明显优于纯Ag_3PO_4/Ni薄膜和纯Ag_2S/Ni薄膜,且在保持薄膜光催化活性基本不变的前提下可循环使用6次。提出了可见光下Ag_2S/Ag_3PO_4/Ni复合薄膜光催化降解罗丹明B的反应机理。     

亚微米级Ag2S空心球的乳液法合成

Hollow Ag₂S spheres have been prepared via hydrolyze reaction of Ag₂S₂O₃， which formed from the reaction of AgNO₃ with Na₂S₂O₃， in cyclohexane/water/polyglycol emulsion system. It was found that the component of the reaction system has a significant influence on the formation of hollow Ag₂S spheres. The possible formation mech-anism of the hollow Ag₂S spheres in the emusion system was also discussed.     

Ag2S/Al2O3纳米复合物的水热合成及表征

采用水热技术结合煅烧的方法,成功制备了Ag2S/Al2O3纳米复合物。 通过SEM、EDX、XRD等测试技术对产品进行了表征,证明得到的产品是Ag2S/Al2O3纳米复合物;无孔Al2O3和多孔Al2O3作反应模板得到的复合物的形态和分布不同。     

Ag3PO4/Ag2S/g-C3N4复合光催化剂的制备与性能

通过沉积法和离子交换法成功地制备了Ag_3PO_4/Ag_2S/g-C_3N_4复合型光催化剂。利用X射线多晶粉末衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、N_2吸附-脱附等温线、紫外-可见漫反射光谱、荧光光谱等手段对样品进行了表征。通过降解罗丹明B考察其可见光催化活性及稳定性,研究了硫化钠与磷酸银物质的量的比值(n_(Na_2S)/n_(Ag_3PO_4))、g-C_3N_4添加量对所制备复合光催化材料性能的影响,同时对光催化机理进行了探讨。结果表明,随着n_(Na2S)/n_(Ag3PO4)的增加,所得复合催化材料活性先增加后降低;当n_(Na2S)/n_(Ag_3PO_4)为1.5%、g-C_3N_4与Ag_3PO_4的质量比为3∶7时制备的催化剂ASC1.5的光催化活性最好,在可见光照射下,40 min内可将罗丹明B完全降解,且5次循环使用后仍保持较高的催化活性。和Ag_3PO_4相比,Ag_3PO_4/Ag_2S/g-C_3N_4复合型光催化材料的活性与稳定性都得到明显提高,这主要归因于复合催化剂比表面积和孔结构的增加,载流子分离效率的提高。光催化机理研究表明,空穴(h~+)、超氧阴离子自由基(·O~(2-))和羟基自由基(·OH)都是光催化过程中的主要活性物种。三者作用大小依次为:h~+·O~(2-)·OH。     

Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(μ-S-pySH)2(PPh3)2] and [Ag2Br2(μ-S-pySH)2(PPh3)2] complexes

Reaction of silver(I) halides with PPh₃ in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag₂X₂(μ-S-pySH)₂(PPh₃)₂] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag₂S₂ cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state ³¹P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.     

A fluorescent Eu(Ⅲ) MOF for highly selective and sensitive sensing of picric acid

A metal-organic framework [Eu_3L_3(CH_3COO)_2(H_2O)_2(μ_3-OH)]·3 DMF,(EuL, H_2L=9H-carbazole-2,7-dicarboxylic acid,DMF=N,N-dimethylformamide) has been synthesized under solvothermal conditions and structurally characterized. In EuL,Eu_6O_8 clusters are four-bridged by carboxylates to form parallel-aligned Eu–O–C chains, which are further linked by the carbazole moieties of L~(2-) ligands to form the three-dimensional framework with rhombic channels. The EuL material with characteristic emission of Eu~(3+) ion exhibits significant luminescence quenching response for picric acid(PA) and the linear Stern-Volmer plot was observed in the concentration range of 0.05–0.15 mM with K_(sv) of 98074 M~(-1). As far as we know, this Ksv is among the highest values for COFs and MOFs in detection of PA. The excellent anti-interference ability and repeatability were also verified by experiments. Lastly, we investigated the luminescence quenching mechanism in the EuL sensing system.     

Ag2S或CuS掺杂的Zn0.5Cd0.5S纳米晶体：溶剂热法合成及光致发光性能

以异丙醇为溶剂,醇热法制备Zn_0.5Cd_0.5S和Ag₂S或CuS掺杂的Zn_0.5Cd_0.5S纳米晶体,考察了这些纳米晶体在可见光区域的光致发光性能。结果表明,反应温度和反应时间、掺杂剂的浓度和种类对Zn_0.5Cd_0.5S的发光性能有很大的影响,相比未掺杂Zn_0.5Cd_0.5S纳米晶体而言,Ag₂S或CuS掺杂后其光致发光强度明显增强、半高宽更宽。     

Simple and rapid surface-enhanced Raman Spectroscopy assay for safranine T and its application in highly sensitive determination of mercury (Ⅱ)

A simple and sensitive surface-enhanced Raman spectroscopy (SERS) method for the detection of safranine T (ST) and Hg²⁺ using silver nanoparticles (AgNPs) as substrate was developed. ST can absorb on the surface of AgNPs through electrostatic interaction, the electromagnetic effect combined with chemical adsorption effect give a notable Raman enhancement for ST. The presence of Hg²⁺ well decreased the absorbed ST molecules on AgNPs, leading to a significant decrease of SERS signals thus enabling to detect Hg²⁺. The determination conditions for SERS, including the amount of AgNPs, the concentration of NaCl, the concentration of HCl, the concentration of ST and the reaction time, were optimised. Under the optimised experimental conditions, good linear responses were obtained for ST and Hg²⁺ in the concentration ranges of 0.01–4.0 μmol L^?1 (3.5–1403.4 ng mL^?1) and 0.01–2.0 μmol L^?1 (2.0–401.2 ng mL^?1), the limit of detection were 3.0 nmol L^?1 (1.1 ng mL^?1) and 2.0 nmol L^?1 (0.4 ng mL^?1), respectively. The present method was subsequently applied to the determination of ST in tomato sauces and Hg²⁺ in environmental waters, the recoveries of ST and Hg²⁺ in spiked samples are 95.5–107.8% and 91.4–110.8 %, respectively.     

Controlled synthesis and self-assembly of highly monodisperse Ag and Ag(2)S nanocrystals

A facile method to control the synthesis and self‐assembly of monodisperse Ag and Ag₂S nanocrystals with a narrow‐size distribution is described. Uniform Ag nanoparticles of less than 4 nm were obtained by thermolysis of Ag–oleate complexes in the presence of oleic acid and dodecylamine, and monodisperse Ag nanoparticles of less than 10 nm were also prepared in one step by using dodecylamine and oleic acid as capping agents. Moreover, the surface‐enhanced Raman scattering (SERS) properties of the Ag substrates have also been investigated. It is worth mentioning that these Ag nanoparticles and assemblies show great differences in the SERS activities of Rhodamine B dye. In addition, the superlattices of Ag₂S nanocrystals were synthesized with Ag–oleate complexes, alkanethiol, and sulfur as the reactants. The resulting highly monodisperse nanocrystals can easily self‐assemble into interesting superstructures in the solution phase without any additional assembly steps. This method may be extended to the size‐controlled preparation and assembly of many other noble‐metal and transition‐metal chalcogenide nanoparticles. These results will aid the study of the physicochemical properties of the superlattice assemblies and construction of functional macroscopic architectures or devices.     

'Thiacalix[4]aniline' as a highly specific extractant for Au(III) and Pd(II) ions

Thiacalix[4]aniline (4), a cyclic tetramer of p-tert-butylaniline bridged with four sulfides, extracted Au(III) and Pd(II) ions specifically from acidic solutions among 41 metal ions including soft metal ions such as Hg(II), Cd(II), Zn(II), Pb(II), and Cu(II).     

Synthesis of a novel poly(para‐phenylene ethynylene) for highly selective and sensitive sensing mercury (II) ions

A new poly(p‐phenylene ethynylene) derivative with pendant 2,2′‐bipyridyl groups and glycol units (PPE‐bipy) has been prepared, and its metal ion sensing properties were investigated. The polymer of PPE‐bipy exhibited high selectivity for Hg²⁺ as compared with Li⁺, Na⁺, K⁺, Ba²⁺, Ca²⁺, Mg²⁺, Al³⁺, Mn²⁺, Ag⁺, Zn²⁺, Pb²⁺, Ni²⁺, Cd²⁺, Cu²⁺, Co,²⁺ and Fe³⁺ in THF/EtOH (1:1, v/v) solution. The fluorescence of PPE‐bipy was efficiently quenched by Hg²⁺ ions, and the detection limit was found to be 8.0 nM in a THF/EtOH (1:1, v/v) solvent system. PPE‐bipy also showed a selective chromogenic behavior toward Hg²⁺ ions by changing the color of the solution from slight yellow to colorless, which can be detected with the naked eye. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1998–2007, 2008     

Ag(nic)2 (nic = nicotinate): a spin-canted quasi-2D antiferromagnet composed of square-planar S = 1/2 Ag(II) ions

Square-planar S = 1/2 Ag(II) ions in polymeric Ag(nic)(2) are linked by bridging nic monoanions to yield 2D corrugated sheets. Long-range magnetic order occurs below T(N) = 11.8(2) K due to interlayer couplings that are estimated to be about 30 times weaker than the intralayer exchange interaction.     

Preparation of highly uniform Ag/TiO2 and Au/TiO2 supported nanoparticle catalysts by photodeposition

Photodeposition of Ag nanoparticles on commercial TiO2 particles and nanoparticles was performed in order to provide direct visualization of the spatial distribution of photoactive sites on sub-micrometer-scale and nanoscale TiO2 particle surfaces and to create materials for potential catalytic applications. HRTEM (high-resolution transmission electron microscopy) and HAADF-STEM (high-angle annular dark-field scanning transmission electron microscopy) were used to characterize these materials. The size and spatial distributions of the Ag nanoparticles on the commercial TiO2 were not uniform; the concentration of Ag was higher on grain boundaries and at the edges of these submicrometer particles. In the case of TiO2 nanoparticles, the size distribution of the Ag nanoparticles deposited was relatively uniform and independent of irradiation time and photon energy. The amount of Ag deposited on TiO2 nanoparticles was at least 6 times higher than that on the commercial samples for comparable irradiation conditions. Compared to the case of Ag photodeposition, the difference in the amount of Au photodeposited on TiO2 particles and nanoparticles was even greater, especially at low precursor concentrations. Photodeposition on TiO2 nanoparticles is suggested as a potential method for the preparation of Au/TiO2 catalysts, as loadings in excess of 10 wt % of uniform 1 nm metal particles were achieved in this work.     

Bis(2-mercaptobenzoxazolato)mercury(II) and bis(2-pyridinethiolato)mercury(II) complexes as carriers for thiocyanate selective electrodes

Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on bis(2-mercaptobenzoxazolato)mercury(II) [Hg(MBO)₂] and bis(2-pyridinethiolato)mercury(II) [Hg(PT)₂] complexes as new carriers for thiocyanate-selective electrodes are reported. The electrodes were prepared by coating the membrane solution containing PVC, plasticizer, carriers and additives on the surface of graphite electrodes. Influence of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses towards thiocyanate over a wide concentration range of 1×10⁻⁶ to 0.1 M, with slopes of 60.6±0.8 and 57.5±1.2 mV per decade of thiocyanate concentration for Hg(MBO)₂ and Hg(PT)₂ carriers, respectively, over a wide pH range of 3-11. The limit of detection for both electrodes was ∼6×10⁻⁷ M. The sensors have response times of ≤5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show fairly good discrimination of thiocyanate over several inorganic and organic anions. The electrodes were successfully applied to direct determination of thiocyanate in saliva and as indicator electrodes in precipitation titrations.     

Tunable fabrication on iron oxide/Au/Ag nanostructures for surface enhanced Raman spectroscopy and magnetic enrichment

Novel lanthanum borate (LaBO₃) hollow nanospheres of size 34 ± 2 nm have been reported for the first time by soft-template self-assembly process. Poly(styrene-b-acrylic acid-b-ethylene oxide) (PS-PAA-PEO) micelle with core–shell–corona architecture serves as an efficient soft template for fabrication of LaBO₃ hollow particles using sodium borohydride (NaBH₄) and LaCl₃?7H₂O as the precursors. In this template, the PS block (core) acts as a template of the void space of hollow particle, the anionic PAA block (shell) serves as reaction field for metal ion interactions, and the PEO block (corona) stabilizes the polymer/lanthana composite particles. The PS-PAA-PEO micelles and the resulting LaBO₃ hollow nanospheres were thoroughly characterized by dynamic light scattering (DLS), transmission electron microscope (TEM), X-ray diffraction, magic angle spinning-nuclear magnetic resonance (¹¹B MAS NMR), energy dispersive X-ray analysis, thermal analyses, Fourier transform infra red spectroscopy, and nitrogen adsorption/desorption analyses. The nitrogen adsorption/desorption analyses and TEM observation of the hollow particles confirmed the presence of disordered mesopores in the LaBO₃ shell domain. The solid state ¹¹B MAS NMR spectra of LaBO₃ hollow nanospheres revealed that the shell part contains both trigonal and tetrahedral boron species. The LaBO₃ hollow particles were applied to anode materials in lithium-ion rechargeable batteries (LIBs). The hollow particles exhibited high coulombic efficiency and charge–discharge cycling capacities of up to 100 cycles in the LIBs.