宏观长Ag2S纳米线簇的制备及其温度电导特性和光电导特性

以固态离子学方法制备的宏观长银(Ag)纳米线簇为基础,采用气-固反应法制备出宏观长硫化银(Ag₂S)纳米线簇.利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能量色散谱(EDS)和X射线光电子能谱(XPS)等手段对样品形貌和成分进行表征.将厘米长的Ag₂S纳米线簇两端涂敷金胶作为电极,并与外电路连接.在不同温度或采用不同波长的光束辐照下,测试了样品的输运性质.无光照时,在144—380 K的温度范围内,样品的电导随温度上升而非线性增大.室温下,Ag关键词： 硫化银纳米线 温度电导 光电导     

The irradiation influence on the properties of silver sulfide (Ag2S) colloidal nanoparticles

The aqueous solutions of different stability containing silver sulfide (Ag₂S) nanoparticles are studied. The stable, transparent, and turbid solutions have been subjected to daylight for 7 months, to ultraviolet and laser irradiation, as well as to an electron beam. Solar radiation is found to favor the Ag₂S reduction to Ag and/or the formation of Ag₂S/Ag hybrid nanoparticles in the solution. At a high amount of hybrid nanoparticles, the exciton–plasmon interaction causes asymmetry in the absorption spectra. The exposure of Ag₂S particles precipitated from the solution with the electron beam leads to the reversible growth of Ag threads. The possible exciton–plasmon interplay mechanisms in Ag₂S/Ag hybrid nanoparticles are considered. The physical mechanisms of the changing Ag₂S stoichiometry, the formation of metallic Ag and Ag₂S/Ag hybrid nanoparticles are the generation of hot carriers and the energy transfer (exciton–plasmon interaction) in a metal–semiconductor hybrid nanosystem are elucidated, as well.

     

Photoinduced Degradation of the Optical Properties of Colloidal Ag<Subscript>2</Subscript>S and CdS Quantum Dots Passivated by Thioglycolic Acid

The results of studying degradation of the optical properties of colloidal Ag₂S and CdS quantum dots (QDs) 2.6–3.2 nm in size passivated by thioglycolic acid (TGA) are presented. The photoluminescence intensity of colloidal Ag₂S QDs has been found to decrease under laser irradiation at a wavelength of 445 nm, beginning with the effective power of 10 mW. The observed effect is interpreted as a photochemical reaction of formation of new nonradiative-recombination channels in Ag₂S QDs upon excitation. It is established for colloidal CdS QDs passivated by TGA that a decrease in the optical density in the entire absorption spectrum and the luminescence intensity is accompanied by precipitation of the colloidal particles in a cell and related to photodegradation of the passivating shell.     

PAC study of ionic motion in silver compound superionic conductors

Ionic motion in superionic conductors, Ag₂S, Ag₂Se and Ag₃SI was investigated by γ-γ PAC on¹¹¹Cd. Diffusion constant measurements showed that probe ions migrate almost as fast as Ag⁺ ions above 500K in Ag₂S and Ag₂Se and above 700K in Ag₃SI. Multivalent impurities were found to be unstable in AgI and Ag₂Te. The correlation time of ionic motion was deduced from the observed relaxation rate together with the diffusion constants. The correlation time and its activation energy increase in order of Ag₂S, Ag₂Se and Ag₃SI.The flight distance of Ag⁺ ions remains almost constant in the measured temperature range.     

Spin resonance of conduction electrons and EPR of localized moments in a low-dimensional organic conductor [Pd(dddt)2]Ag1.5Br3.5

The EPR spectra of a quasi-two-dimensional organic metal [Pd(dddt)₂]Ag_1.5Br_3.5 contain signals due to the spin resonance of conduction electrons (CESR) and signals due to the localized magnetic moments of Ag²⁺. The system of Ag²⁺ ions exhibits a strong indirect antiferromagnetic exchange interaction characterized by the Weiss constant Θ=−280(25) K, which leads to magnetic ordering at a temperature of T ₀=70(10) K. The same temperature T ₀ corresponds to a strong anomaly in the CESR linewidth. The observed anomaly in the CESR linewidth, as well as some features of the temperature dependence of conductivity in the system studied, are explained by the interaction between conduction electrons and Ag²⁺ ions localized in the anion layers (π-d interaction) and by antiferromagnetic ordering of the spins of Ag²⁺ magnetic ions.     

A Novel Fluorescent Nanoparticle for Sensitive Detection of Cry1Ab Protein In Vitro and In Vivo

Here, we report the synthesis and characterization of CoFe₂O₄ doping Ag₂S dendrimer-modified nanoparticles (CoFe₂O₄-Ag₂S DMNs) in Cry1Ab protein detection and imaging. The near-infrared Ag₂S quantum dots were first prepared by using the thermal decomposition method, followed by modification of the water-soluble quantum dots using the method of solvent evaporation and ligand exchange, and finally the fluorescent magnetic bifunctional nanoparticles were obtained by binding with CoFe₂O₄. As-prepared CoFe₂O₄-Ag₂S DMNs were characterized by fluorescence (FL) spectroscopy and transmission electron microscopy (TEM). Results showed that Ag₂S DMNs could sensitively detect Cry1Ab both in vitro and in vivo. In vitro, the enhanced FL intensity as a function of the concentration is notably consistent with the Langmuir binding isotherm equation in the range of 0–200 ng/mL of Cry1Ab proteins. The detection limit of this method was found to be 0.2 ng/mL. Meanwhile, the fluorescence wavelength was extended to the second near-infrared range (NIR-II, 1.0~1.4 μm), which enables in vivo imaging. This study highlights the importance of NIR QDs doping magnetic materials as a new method to trace Bacillus thuringiensis (Bt) in insects and their potential applications in in vivo NIR tissue imaging.     

Synaptic behaviors and modeling of a metal oxide memristive device

Nanoscale memristive devices using tungsten oxide as the switching layer have been fabricated and characterized. The devices show the characteristics of a flux-controlled memristor such that the conductance change is governed by the history of the applied voltage signals, leading to synaptic behaviors including long-term potentiation and depression. The memristive behavior is attributed to the migration of oxygen vacancies upon bias which modulates the interplay between Schottky barrier emission and tunneling at the WO _X /electrode interface. A physical model incorporating ion drift and diffusion effects using an internal state variable representing the area of the conductive region has been proposed to explain the observed memristive behaviors. A SPICE model has been further developed that can be directly incorporated into existing circuit simulators. This type of device can be fabricated with low-temperature processes and has potential applications in synaptic computations and as analog circuit components.     

Effect of Coulomb blockade on the switching time of Ag–Ag2S–Pt atomic switches

A theoretical model based on the single electron tunneling phenomenon is employed to calculate the time-dependent electrical resistance of an Ag–Ag₂S–Pt atomic switch at different applied voltages. While a negative voltage is applied to Pt electrode, Ag atoms precipitate on the surface of Ag₂S electrode where they form Ag clusters. The resistance of switch decreases as Ag clusters grow larger between two electrodes. Our model calculations imply the time required to decrease the resistance of switch below the resistance quantum (switching time) is mainly determined by the Coulomb blockade effect of Ag clusters. The switching time is found to decrease exponentially with increasing the applied voltage, which agrees very well with the experimental observations.     

Charge‐transfer contributions in surface‐enhanced Raman scattering from Ag,Ag2S and Ag2Se substrates

The degree of charge‐transfer in Ag–4‐mercaptopyridine (Mpy) and Ag₂S–4‐Mpy systems is investigated by use of surface‐enhanced Raman spectroscopy (SERS). Ag₂S and Ag₂Se nanoparticles are prepared on the basis of the former formation of Ag nanoparticles to make the SERS analytical objects comparable. We utilize the intensity of the non‐totally symmetric modes (either b₁ or b₂) as compared with the totally symmetric a₁ modes to measure the degree of charge‐transfer. We find ~25% of charge‐transfer contribution for Ag–4‐Mpy, whereas 81 ~ 93% for Ag₂S–4‐Mpy. It means that the charge‐transfer resonance contribution dominates the overall enhancement in SERS of Ag₂S–4‐Mpy. Energy level diagram is applied to discuss the likely charge‐transfer transition between Ag, Ag₂S, Ag₂Se and 4‐Mpy. This article may point out the link among the three main resonance sources and could enable some insights into the electronic pathways available to the metal‐molecule and semiconductor‐molecule systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Metal/TiO<Subscript>2</Subscript> interfaces for memristive switches

The interfaces between metal electrodes and the oxide in TiO₂-based memristive switches play a key role in the switching as well as in the I–V characteristics of the devices in different resistance states. We demonstrate here that the work function of the metal electrode has a surprisingly minor effect in determining the electronic barrier at the interface. In contrast, Ti oxides can be readily reduced by most electrode metals. The amount of oxygen vacancies created by these chemical reactions essentially determines the electronic barrier at the device interfaces.     

X-ray study of c-axis parameters in disordered stage II Agχ TiS2

X-ray measurements have been performed on disordered Stage II Ag_χ TiS₂ crystals with χ = 0.18 and 0.19. The c-axis structure was determined using the 00.l reflections for 4 ?l? 29. A principal result is that the intercalation of Ag⁺ between S layers produces unequal TiS distances in the adjacent TiS₂. The charge transfer to the Ti layer produces an expanded TiS distance adjacent to the Ag layer. The TiS distance away from the Ag ions is accordingly contracted. This effective (indirect) repulsive interaction between Ag⁺ and Ti may provide a mechanism for staging in these materials by keeping the Ag layers as far apart as possible.     

Spectral Optical Properties of Polymer Composite Nanomaterials Based on Carbon Nanotubes in a High-Density Polyethylene Matrix

Spectral, kinetic, and nonlinear optical regularities that demonstrate the exchange of electronic excitations between the components of hybrid associates of Ag₂S colloid quantum dots (1.7–1.8 nm) in gelatin with molecules of thiazine dyes (Ds) are found. When the IR luminescence of Ag₂S quantum dots (QDs) is excited by radiation from the thionine absorption region, its enhancement due to nonradiative resonant energy transfer is observed. The association with methylene-blue molecules blocked the IR luminescence of Ag₂S QDs upon its excitation by radiation from the absorption region of the dye due to the transfer of charge carriers. It is demonstrated that the hybrid association of thionine molecules and Ag₂S QDs adversely affects the nonlinear optical properties of the latter, which manifests itself in inverse saturated absorption by the action of 10-ns second-harmonic pulses (532 nm) of a Nd³⁺:YAG laser. For the associates of Ag₂S QDs with methylene-blue molecules, the radiation focusing caused by the transfer of charge carriers from the dye and the change in the population of small traps in nanocrystals is found. It is concluded that the direction of the transfer of electronic excitations and the photophysical processes in these objects are determined by the mutual arrangement of the HOMO–LUMO levels of the dye with respect to the levels of dimensional quantization of the Ag₂S QDs.     

Ag2S nanoparticle encapsulated in mesoporous material nanoparticles and its application for photocatalytic degradation of dye in aqueous solution

Semiconductor loaded mesoporous materials in general possess greater photocatalytic activity than pure semiconductors. Hence, with an attempt to achieve higher photocatalytic activity, Ag₂S/MCM-41 photocatalysts were prepared by ion exchange method and used for the photocatalytic degradation of methylene blue. The materials were characterized by different analytical techniques such as transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and BET (Brunauer-Emmert-Teller) experiments. The effect of Ag₂S, MCM-41 support and different wt% of Ag₂S over the support on the photocatalytic degradation and influence of parameters such as Ag₂S loading, catalyst a mount, pH and initial concentration of dye on degradation are evaluated. The degradation reaction follows pseudo-first order kinetics. It was seen that 0.6 g/L of photocatalyst is an optimum value for the dosage of photocatalyst. The degradation efficiency was decreased in dye concentration above 3.2 ppm for dye.     

光电子成像研究AgOCH3-和Ag-(CH3OH)x (x=1, 2)

用光电子成像技术和从头算法研究Ag^-(CH₃OH)_x (x=1, 2)和AgOCH₃^-. 从AgOCH₃^-振动分辨的光电子谱得 到AgOCH₃^-的绝热和垂直电离能分别为1.29(2)和1.34(2) eV. Ag^-(CH₃OH)_{1,2相似文献}   

Phase transitions in CuS–Ag2S nanoparticle system

(Ag₂)_xCu_1?xS, x = .2, .4, .6 and .8 nanoparticles were synthesized by the solvothermal method. The as-synthesized nanoparticles were characterized by X-ray diffraction to study the crystal structure and size. The surface morphologies of the above samples were studied using scanning electron microscope. As there is continuous shift in the lower wavelength absorption edge of the UV–VIS spectrum of these samples with concentration, (Ag₂)_xCu_1?xS nanoparticles can be tuned to different band gap energies by varying the composition. The D.C. electrical resistance was measured in the temperature range 310–485 K. As Ag₂S transforms from monoclinic to bcc at around 450 K, copper sulfide nanoparticles also shows a phase transition at around 470 K, the effects of these two transitions are seen in the resistance measurements and in the UV–VIS spectra of the entire system. The electrical resistance of (Ag₂)_xCu_1?xS nanoparticles rapidly reduces as more and more copper sulfide is added.     

Singlet-Oxygen Sensitization by Associates of Methylene Blue with Colloidal Ag<Subscript>2</Subscript>S Quantum Dots Passivated by Thioglycolic Acid

Luminescence studies of singlet-oxygen photosensitization by methylene blue molecules in various solvents, as well as by hybrid associates of this dye with colloidal Ag₂S quantum dots with average sizes of 2.0, 2.4, and 2.7 nm, are performed. The conditions for simultaneous singlet-oxygen photosensitization and detection of the IR luminescence of colloidal Ag₂S quantum dots passivated by thioglycolic acid are determined.     

Ultrasonic enhancement of microdroplet-based interfacial reaction for improving the synthesis of Ag2S QDs

Ag₂S quantum dots (QDs) have aroused extensive concerns in intravital imaging field due to their merits of narrow bandgap, low biological toxicity and decent fluorescence emission properties in the second near-infrared (NIR-II) window. However, low quantum yield (QY) and poor uniformity of Ag₂S QDs are still main obstacles for its application. In this work, a novel strategy of utilizing ultrasonic field is presented, which can enhance the microdroplet-based interfacial synthesis of Ag₂S QDs. The ultrasound increases the presence of ions at the reaction sites by enhancing the ion mobility in the microchennels. Therefore, the QY is enhanced from 2.33 % (optimal QY without ultrasound) to 8.46 %, which is the highest value of Ag₂S ever reported without ion-doping. Also, the decrease of the corresponding full width at half maximum (FWHM) from 312 nm to 144 nm indicates the obvious uniformity improvement of the obtained QDs. Further mechanism exploration illustrates that ultrasonic cavitation significantly increases the interfacial reaction sites by splitting the droplets. Meanwhile, the acoustic flow field strengthens the ion renewal at the droplet interface. Consequently, the mass transfer coefficient increases by more than 500 %, which is favorable to improve both the QY and quality of Ag₂S QDs. This work serves both fundamental research and practical production for the synthesis of Ag₂S QDs.     

One-step synthesis of Ag<Subscript>2</Subscript>S/Ag@MoS<Subscript>2</Subscript> nanocomposites for SERS and photocatalytic applications

This paper reported a one-step synthesis of Ag₂S/Ag@MoS₂ nanocomposites and its applications in the surface-enhanced Raman scattering (SERS) detection and photocatalytic degradation of organic pollutants. The nanocomposites were well characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammograms (CV), the Brunauer-Emmett-Teller (BET), and Fourier transforms infrared spectra (FTIR). The AgNPs were uniformly dispersed on the MoS₂ nanosheets and the particle size of the AgNPs was about 10–30 nm. These Ag₂S/Ag@MoS₂ nanocomposites offered sensitive SERS signals for the detection of R6G with the limit of detections as low as 10^?10 M. The photocatalytic activity of the composite catalyst was studied by the degradation of methylene blue (MB) dye under light illumination. The apparent rate constant of MB degradation for the obtained catalyst could reach 6.6?×?10^?2 min^?1, indicating that the novel Ag₂S/Ag@MoS₂ nanocomposites can be explored for organic pollutant’s detection and degradation.

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Graphical abstract One-step synthesis of Ag₂S/Ag@MoS₂ nanocomposites for SERS and photocatalytic applications

     

插层化合物Ag1/4TiSe2电子结构的第一性原理研究

采用基于密度泛函理论的平面波赝势方法,选用局域密度近似对Ag_1/4TiSe₂及TiSe₂的几何结构进行了优化和总能量计算.计算得到的晶格常量与实验结果符合较好,负的形成能表明有序Ag_1/4TiSe₂系统的稳定性.布居数、键长、能带结构和态密度的计算结果显示：Ag以较强的离子性结合于Ag_1/4TiSe₂中.Ag的插入使得半金属性的TiSe_{2关键词： 1/4}TiSe₂')" href="#">Ag_1/4TiSe₂ 电子结构 插层化合物 第一性原理计算     

197Au and125Te Mössbauer spectroscopic study on the low temperature phases of Ag3AuX2 (X=S,Se, and Te)

¹⁹⁷Au and¹²⁵Te Mössbauer spectroscopy has been applied for the low-temperature β-phases of Ag₃AuX₂ (X=S, Se, and Te). The values of I. S. and Q. S. for¹⁹⁷Au suggest that the gold atoms, linearly coordinated by two chalcogen atoms in these phases, exist as monovalent cations. The¹²⁵Te Mössbauer spectra suggest that the tellurium atoms are substantially ionic for both Ag₂Te and Ag₃AuTe₂. The nature of X-Au-X bonds is discussed on the basis of the Mössbauer data and the bond distances.