Chemical effects on x‐ray fluorescence yield of Ag+ compounds

X‐ray fluorescence measurements were carried out for silver metal and a number of silver compounds containing Ag⁺ ions such as Ag₂CO₃, Ag₂SO₄, AgNO₃, AgCl, AgBr and AgI using 59.6 keV γ‐rays, emitted from ²⁴¹Am, as the excitation source, to evaluate the value of Kβ/Kα x‐ray intensity ratio. For silver metal the value of this parameter is found to be 0.206 ± 0.003 and wide variations, 0.190 ≤ Kβ/Kα≤ 0.207, were observed for these compounds. The results are explained in terms of the charge transfer occurring between Ag⁺ and the coordinating anions. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of Hierarchical (BiO)2CO3 Nanosheets Microspheres toward Efficient Photocatalystic Reduction of CO2 into CO

In this paper, hierarchical (BiO)₂CO₃ nanosheets microspheres were synthesized with dry ice as carbon source, and characterized by X-ray diffraction (XRD) patterns, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), high-resolution transmission electron microscopy (HRTEM) and UV–vis diffuse reflectance spectra (DRS). The photocatalytic results showed that (BiO)₂CO₃ display much higher photocatalytic activity than BiOCl and TiO₂ for photocatalystic reduction of CO₂ under UV-visible light. The photocatalytic mechanism study revealled that (BiO)₂CO₃ display better separation efficiency of photoinduced charge carriers due to the large interlayer spacing (1.3675 nm).     

EPR and optical spectra of Ni2+-VAg in silver chloride and silver bromide

The optical absorption and EPR spectra of Ni²⁺-V_Ag centres in the AgCl:Ni²⁺ and AgBr:Ni²⁺ systems have been investigated theoretically on the basis of the complete energy matrices including the electron–electron repulsion interaction, the ligand field interaction, the spin–orbit coupling interaction, and Zeeman interaction. Because the charge compensation forms a silver ion vacancy (V_Ag) which makes the attractive force acted on the each ligand ion different, it was determined that the Ni–X (X = Cl, Br) distance next to V_Ag is shorter than others for both AgCl:Ni²⁺ and AgBr:Ni²⁺ systems in the tetragonal symmetry. Besides, it was found that the local lattice structure of (NiX₆)^4? clusters in AgCl and AgBr crystals exhibit a compression distortion. This compression distortion may be ascribed to the fact that the Ni²⁺ ion has a smaller ionic radius and more effective charge than the Ag⁺ ion.     

Preparation, characterization, and photocatalytic properties of silver carbonate

Silver carbonate (Ag₂CO₃) short rods were prepared using a precipitation method. It was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflective spectra (DRS) and photocatalytic degradation of organic pollutants and destruction of E. coli measurements. The results of DRS suggested that the optical transition of Ag₂CO₃ was indirectly allowed, and its band gap was determined to be 2.08 eV. The prepared Ag₂CO₃ displayed a high activity towards degradation of phenol and MB under visible light. The total organic carbon (TOC) value decreased during the photocatalytic process, which suggests that phenol was truly photodegraded. The stability of Ag₂CO₃ was greatly improved when Na₂CO₃ was added into the photocatalytic system. In addition, Ag₂CO₃ displayed enhanced photocatalytic activities for the destruction of E. coli due to its photogenerated electron-hole pairs.     

The Synthesis of Chiral Ag4Pd2(SR)8 by Nonreplaced Galvanic Reaction

Galvanic reaction is a classic reaction and widely applied in nanoscience and nanotechnology. However, it is rarely employed in the synthesis of doped metal nanoclusters with size less than ≈2 nm and remains to be exploited in nanocluster (NC) community. Herein, it is reported the synthesis of chiral Ag₄Pd₂(SR)₈ starting from Ag₂₅(SR)₁₈ NC via a galvanic reaction and the characterization of the as‐obtained NC by multiple techniques such as single crystal X‐ray crystallography and X‐ray photoelectron spectroscopy.     

Anomalous X-ray scattering studies on superionic glassy (As2Se3)-(AgX) systems (X = halides)

Anomalous X-ray scattering experiments for glassy room-temperature superionic conductors (As₂Se₃)_0.4 (AgI)_0.6 and (As₂Se₃)_0.4(AgBr)_0.6 were performed close to the As, Se, Ag, and Br K edges using a third-generation synchrotron radiation facility, ESRF. The differential structure factors, Δ_iS(Q), were obtained from detailed analyses, indicating that Δ_AsS(Q) and Δ_SeS(Q) of both the glassy superionic semiconductors are similar to those of glassy As₂ Se₃ except the prepeak in Δ_SeS(Q). The Δ_AgS(Q) spectrum of (As₂Se₃)_0.4 (AgI)_0.6 looks molten salt-like. However, the Δ_Ag S(Q) of (As₂Se₃)_0.4(AgBr)_0.6 glass have quite different features from that of (As₂Se₃)_0.4 (AgI)_0.6 glass in the low Q range, and the Δ_BrS(Q) has even a pre-shoulder around 13 nm^? 1 unlike molten salts. In the differential pair distribution functions Δ_ig(r) obtained from the Fourier transforms of Δ_iS(Q), the first peaks of Δ_Asg(r) and Δ_Seg(r) show no correlation with those of Δ_Agg(r) and Δ_Brg(r), and vice versa. From these results, it can be concluded that a pseudo-binary mixture of the As₂Se₃ network matrix and AgX-related ionic conduction pathways is a good structural model for these superionic glasses. Differences between the AgBr- and AgI mixtures were found in the second-neighbor structures around the Ag atoms, which may reflect those in the crystal structures of the AgX salts.     

Electrical properties of a new Ag+ ion conducting glassy system: x[0.75AgI:0.25AgCl] : (1−x)[Ag2O : P2O5]

A new fast Ag⁺ ion conducting glassy system: x[0.75AgI:0.25AgCl]: (1−x)[Ag₂O: P₂O₅], where 0.1 ≤ x ≤ 1 in molar weight fraction, has been synthesized by melt-quench technique using a high-speed twin roller-quencher. An alternate host salt: ‘quenched [0.75AgI: 0.25AgCl] mixed system/ solid solution’, has been used in place of the traditional host AgI. The compositional dependence conductivity studies on the glassy systems: x[0.75AgI:0.25AgCl]: (1−x)[Ag₂O: P₂O₅] as well as xAgI: (1−x)[Ag₂O: P₂O₅] prepared identically, indicated that the composition at x=0.75 exhibited the highest room temperature conductivity. The composition: 0.75[0.75AgI: 0.25AgCl]: 0.25[Ag₂O: P₂O₅] has been referred to as optimum conducting composition (OCC). The study also revealed that the new/ alternate host yielded better electrolyte system. The activation energy (E_a), involved in the thermally activated conductivity process has been computed from ‘log σ − 1/T’ Arrhenius plot. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

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.

     

On the third order elastic constants of AgCl-AgBr mixed system

Lowdin's many body effect is accounted to explain the violation of Cauchy's relation (C₁₂=C₄₄) in silver halides. Lundqvists potential model with many body effect has been used to evaluate the third order elastic constants of AgCl and AgBr. A modified Lundqvist potential model is used to calculate the third order elastic constants for the simple AgCl- AgBr mixed system with varying concentration of AgCl and AgBr.     

Impact of Extracellular Polymeric Substance in the Inactivation of Harmful Algae by Ag2O/g-C3N4 under Visible Light

Photocatalysis has attracted much attention as an emerging algae removal technology, but the inactivation performance is inevitably affected by the extracellular polymeric substance (EPS) produced by algae. In this study, a photocatalyst (Ag₂O/g-C₃N₄) with efficient algae inactivation is adopted to investigate the interactions with EPS, and the impact of EPS on photocatalytic algae removal is studied. The results show that EPS can adhere to the surface of Ag₂O/g-C₃N₄ by electrostatic force. The interaction with EPS decreases the surface zeta potential of the Ag₂O/g-C₃N₄ from 7.71 to −22.3 mV with the increase in EPS concentration, and the maximum ratio of particle size increases from 825 to 1281 nm. In addition, the interaction with EPS inhibits the release of Ag⁺ in Ag₂O/g-C₃N₄ by half, thus, the toxicity of metal ions will be alleviated. Meanwhile, EPS can also be degraded by Ag₂O/g-C₃N₄, indicating that EPS can work as a radical scavenger to protect the algae cells. Without the protection of EPS, 97.8% of algae cells are inactivated after 5 h photocatalysis. Therefore, more attention should be given to the interaction between EPS and photocatalyst to promote the design and application of the photocatalytic.     

Synthesis,characterization and excellent photocatalytic activity of Ag/AgBr/MoO3 composite photocatalyst

A novel composite photocatalyst Ag/AgBr/MoO₃ was successfully synthesized via a simple precipitation method at room temperature. The obtained products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy and UV–vis diffuse reflectance spectroscopy in detail. The photocatalytic activity of the samples was evaluated by monitoring the degradation of rhodamine B (RhB) solution under visible-light irradiation. The results showed that the photocatalytic activity of Ag/AgBr/MoO₃ composite significantly enhanced and the degradation ratio of RhB reached 97.7 % after 15 min only. The excellent photocatalytic activity might be closely related to the large surface area, porosity structure and efficient separation of photoinduced electron–hole pairs. The possible reaction mechanism was also discussed.     

Construction of Ag/AgCl nanostructures from Ag nanoparticles as high-performance visible-light photocatalysts

A combined strategy of in situ oxidation and assembly is developed to prepare Ag/AgCl nanospheres and nanocubes from Ag nanoparticles under room temperature. It is a new facile way to fabricate Ag/AgCl with small sizes and defined morphologies. Ag/AgCl nanospheres with an average size of 80 nm were achieved without any surfactants, while Ag/AgCl nanocubes with a mean edge length of 150 nm were obtained by introduction of N-dodecyl-N,N-dimethyl-2-ammonio-acetate. The possible formation mechanism involves the self-assembly of AgCl nanoparticles, Ostwald ripening and photoreduction of Ag⁺ into Ag⁰ by the room light. The as-prepared Ag/AgCl nanospheres and nanocubes exhibit excellent photocatalytic activity and stability toward degradation of organic pollutants under visible-light irradiation. It is demonstrated that Ag/AgCl nanocubes display enhanced photocatalytic activity in comparison with Ag/AgCl nanospheres due to the more efficient charge transfer. This work may pave an avenue to construct various functional materials via the assembly strategy using nanoparticles as versatile building blocks.

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Graphical abstract A combined strategy of in situ oxidation and assembly was developed to construct Ag/AgCl nanospheres and nanocubes from Ag nanoparticles, which exhibited highly photocatalytic activity and good stability for degrading methyl orange under visible light irradiation.

     

Physical properties of glasses in the Ag2GeS3-AgBr system

Glasses have been prepared by quenching melts in the Ag₂GeS₃-AgBr system in a range of 0–53 mol % AgBr. The concentration dependences of density, microhardness, glass transition temperatures, and crystallization of alloys have been established. The conductivity of glasses has been investigated by the dc probe method in a range of 240–420 K. The models of the drift motion of silver and halogen ions have been proposed.     

Laser-induced voltage (LIV) enhancement of La2/3Sr1/3MnO3 films with Ag addition

La_2/3Sr_1/3MnO₃:Ag _x (LSMO:Ag _x , x=0, 0.04, 0.08, 0.10, 0.20, 0.30) films were grown on vicinal cut LaAlO₃ (LAO) substrates by pulsed laser deposition technique (PLD). It is found that laser-induced voltage (LIV) of LSMO:Ag _x films is improved and enhanced by Ag addition. With x increasing, figure of merit (F _m ) and anisotropic Seebeck coefficient (ΔS) of LSMO:Ag _x (x=0.08) films reach the maximum values of 28.25 mV/ns and 0.38 μV/K, respectively. The results suggest that the LIV enhancement of LSMO:Ag _x films is due to the anisotropy of the Seebeck tensor, which is produced by long range cooperative Jahn–Teller distortions with Ag addition.     

Synthesis and characterization of the efficient visible-light-induced photocatalyst AgBr and its photodegradation activity

AgBr photocatalysts were prepared with the 1-hexadecyl-3-methylimidazolium bromide ([C₁₆mim]Br) reactable ionic liquid at different temperatures by one-step hydrothermal method, in which the ionic liquid acted as a precursor and a template to control the size of AgBr crystal. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), the Brunauer–Emmett–Teller (BET) surface area and diffuse reflectance spectroscopy (DRS). Methyl orange (MO) dye was chosen as a model pollutant to investigate the photocatalytic activity and the stability of the samples under visible light irradiation. The results indicated that the AgBr photocatalysts showed high efficiency in the degradation of MO under visible light irradiation. The kinetic property of the reaction followed the first-order reaction model. During the photocatalytic degradation reaction, AgBr was transformed to the Ag⁰/AgBr composite. However, the photocatalytic efficiency was still high and the photocatalytic activity was stable. The possible photocatalytic mechanism of the photocatalysts was also eventually proposed.     

Vibrational spectra of the layered monofluorophosphate (V), NH4Ag3(PO3F)2

The powder Fourier‐transform (FT) infrared (IR) and Raman spectra of the recently characterized NH₄Ag₃(PO₃F)₂ were recorded and are discussed with a site‐symmetry analysis based on its known structural data. Some comparisons are made with the solution spectra of the PO₃F²⁻ anion and with those of crystalline Ag₂PO₃F. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

Ag3PO4/rectorite nanocomposites: Ultrasound-assisted preparation,characterization and enhancement of stability and visible-light photocatalytic activity

To overcome the drawback of low stable brought by the transformation of Ag⁺ into Ag, a highly efficient and stable photocatalyst Ag₃PO₄/rectorite composite was successfully synthesized by ultrasound-assisted precipitation method. The as-prepared samples were characterized by field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, N₂ adsorption-desorption, room-temperature photoluminescence spectra, Fourier transform infrared spectrum measurements and UV–vis diffuse reflectance spectra. The absorption edges of the Ag₃PO₄/rectorite display a noticeable shift to the visible light region as compared to that of the Ag₃PO₄. Compared with bare Ag₃PO₄, the Ag₃PO₄/rectorite composite by ultrasound-assisted precipitation process exhibits significantly enhanced photocatalytic activity and stable for methyl orange (MO) degradation under visible light irradiation. The improved activity of the Ag₃PO₄/rectorite photocatalyst could be attributed to the expanded visible light absorption, the enhanced interfacial charge transfer and the inhibited recombination of electron-hole pairs. Therefore, the facile ultrasound-assisted preparation process provides some insight into the application of Ag₃PO₄/rectorite nanocomposites in photocatalytic degradation of organic pollutants.     

One-pot synthesis of Ag+ doped BiVO4 microspheres with enhanced photocatalytic activity via a facile hydrothermal method

The Ag⁺/BiVO₄ photocatalyst was fabricated through a facile hydrothermal method by using K₆V₁₀O₂₈·9H₂O as the vanadium source. The impact of Ag⁺ on the product's structure and morphology was studied. It was shown that the amount of Ag⁺ has no effect on the product’s crystal phases but plays an important role on the morphology of the nanoparticles that construct the shell of BiVO₄ microspheres. In addition, the Ag⁺-doped photocatalysts have much higher photocatalytic activities in removing RhB and MB under the UV light illumination than the pure BiVO₄. A possible photocatalytic mechanism was proposed in photoexcitation of the BiVO₄ electrons which subsequently captured by the dopant. The present work may offer a novel route to reach higher photocatalytic activity by doping the Ag⁺ in the semiconductor catalysts.     

Adsorption and reaction of bromine with Ag(110): A photoemission study

The adsorption of bromine on the (110) surface of silver has been studied by ultraviolet (hυ = 21.2 and 40.8 eV) photoelectron spectroscopy in the temperature range of 100–300 K. Four different adsorption and reaction states could be detected. For fractional monolayer coverages Br₂ adsorbs dissociatively on the Ag(110) surface. The chemisorption of bromide leads to new emission features at about 3 and 5.2 eV below E_F, which are assigned as occupied antibonding structures (3 eV) and as bonding Br4p_{x, y} orbitals (5.2 eV). At 100 K, further bromide adsorption leads to the formation of an AgBr layer with molecular adsorbed bromine on top of this corrosion layer. The He I spectrum is dominated by structures at 3.5, 5.8 and 7.5 eV which are due to emission from the π_g, π_u and σ_g molecular orbitals of Br₂. The buildup of the AgBr layer is clearly demonstrated by desorbing the molecular bromine at about 150 K. The resulting spectrum of the AgBr layer shows peaks at 2.5 and 3.4 eV with p- and mixed-in d-character and peaks at 4.1, 5.2 and 6.1 eV which are primarily d-like. Heating of the AgBr layer up to 300 K results in a transformation from a 2D layer into a 3D agglomeration of larger AgBr clusters on top of a Br/Ag(110) chemisorption layer.