Silver aggregates and twofold-coordinated tin centers in phosphate glass: A photoluminescence study

The optical properties of silver species in various oxidation and aggregation states and of tin centers in melt-quenched phosphate glasses have been assessed by optical absorption and photoluminescence (PL) spectroscopy. Glasses containing silver and tin, or either dopant, were studied. Emission and excitation spectra along with time-resolved and temperature-dependent PL measurements were employed in elucidating the different emitting centers observed and investigating on their interactions. In regard to silver, the data suggests the presence of luminescent single Ag⁺ ions, Ag⁺-Ag⁺ and Ag⁺-Ag⁰ pairs, and nonluminescent Ag nanoparticles (NPs), where Ag⁺-Ag⁰→Ag⁺-Ag⁺ energy transfer is indicated. Tin optical centers appear as twofold-coordinated Sn centers displaying PL around 400 nm ascribed to triplet-to-singlet electronic transitions. The optically active silver centers were observed in glasses where 8 mol% of both Ag₂O and SnO, and 4 mol% of Ag₂O were added. Heat treatment (HT) of the glass with the high concentration of silver and tin leads to chemical reduction of ionic silver species resulting in a large volume fraction of silver NPs and the vanishing of silver PL features. Further characterization of such heat-treated glass by transmission electron microscopy and X-ray photoelectron spectroscopy appears consistent with silver being present mainly in nonoxidized form after HT. On the other hand, HT of the glass containing only silver results in the quenching of Ag⁺-Ag⁰ pairs emission that is ascribed to nonradiative energy transfer to Ag NPs due to the positioning of the pairs near the surface of NPs during HT. In this context, an important finding is that a faster relaxation was observed for this nanocomposite in relation to a heat-treated glass containing both silver and tin (no silver pairs) as revealed by degenerate four-wave mixing spectroscopy. Such result is attributed to Ag NP→Ag⁺-Ag⁰ plasmon resonance energy transfer. The data thus indicates that energy transfer between Ag⁺-Ag⁰ pairs and NPs is bi-directional.     

银团簇上吸附氧原子与氢气作用的研究

The interactions between Ag_nO^-(n=1-8) and H₂ (or D₂) were explored by combination of the mass spectroscopy experiments and density function theory (DFT) calculations. The experiments found that all oxygen atoms in Ag_nO^-(n=1-8) are inert in the interactions with H₂ or D₂ at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation (PROX) of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between Ag_nO^-(n=1-8) and H₂ were explored using DFT calculations. The results indicated that adsorption of H₂ on any site of Ag_nO^-(n=1-8) is extremely weak, and oxidation of H₂ by any kind of oxygen in Ag_nO^-(n=1-8) has an apparent barrier strongly dependent on the adsorption style of the "O". These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts.     

Influence of silver on the Sm<Superscript>3+</Superscript> luminescence in “Aerosil” silica glasses

The introduction of silver into the samarium-containing silica glasses prepared by the original solgel method leads to the formation of complex optical centers involving samarium ions and simple and/or complex silver ions. These centers are characterized by the effective sensitization of Sm³⁺ luminescence by Ag⁺, (Ag₂)⁺, and (Ag⁺)₂ ions according to the exchange mechanism for, at least, Sm³⁺-Ag⁺ centers. The formation of Sm-Ag centers is accompanied by an increase in the concentration of nonbridging oxygen ions, which prevent the reduction of silver ions by hydrogen. Silver nanoparticles formed in small amounts upon this reduction are effective quenchers of luminescence from the corresponding excited states of Sm³⁺ ions.     

Spectroscopic evidence of positive clusters in Ag colloids obtained by laser ablation in aqueous solutions

We have found evidence of positive cluster formation during the laser ablation process of a silver target in aqueous solutions. In particular, by employing in situ shot-by-shot UV–vis spectroscopy in the early stages of the ablation, we observed a weak and unstable absorption band around 266 nm and a more stable one around 290 nm, which could be assigned to charged clusters like Ag ₃ ²⁺ and Ag ₄ ²⁺ , respectively. Surface-enhanced Raman scattering experiments performed with a test molecule adsorbed on a silver colloid obtained in pure water were compatible with the presence of Ag ₄ ²⁺ active sites on the surface of the Ag nanoparticles.     

Chemisorption of oxygen on the silver (111) surface

The interaction of oxygen with the (111) surface of a silver single crystal is studied, mainly in the pressure range from 10^?3 up to 1 torr and at temperatures from room up to 500°C. The experimental techniques employed were LEED, secondary electron spectroscopy, work function variation measurements, and desorption kinetics. Exposure to the high pressures was made with a sample isolation valve. The experimental procedures are examined in detail and critically discussed. The results obtained with the different techniques allow a correlation with many studies of other authors. The LEED technique indicates that in the range of pressures and temperatures examined, a surface superstructure is stable, having a unit mesh with sides four times greater than that of the silver (111) plane. The presence of this surface phase seems to be related to oxygen adsorbed in the dissociated form. On this assumption, an interpretation of the structure is proposed, which is based on a coincidence lattice formed by a (111) plane of Ag₂O on the (111) plane of the metal. This interpretation is also in agreement with the thermodynamic data.     

Surface-modified antibacterial TiO2/Ag nanoparticles: Preparation and properties

Studies were performed on surface modification of antibacterial TiO₂/Ag⁺ nanoparticles by grafting γ-aminopropyltriethoxysilane (APS). The interfacial structure of the modified particles was characterized by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis. The thickness of the surface layer was determined by using Auger electron spectroscopy (AES). The results show that APS is chemically bonded to the surface of antibacterial TiO₂/Ag⁺ nanoparticles. Furthermore, the modified particles were mixed in PVC to prepare composites whose antibacterial property was investigated. The results suggest that surface modification has no negative effect on antibacterial activity of TiO₂/Ag⁺ nanoparticles and PVC-TiO₂/Ag⁺ composites exhibits good antibacterial property.     

The effect of oxygen on sensitization of AgBrI crystals with anionic dye

A mechanism is suggested for the effect of oxygen on spectral sensitization of AgBrI microcrystals (MCs) with anionic dye adsorbed on the surface, which adequately describes the changes of both luminescent and spectral-sensitometric properties of this system. It is shown that the effect of oxygen on the spectral sensitization of AgBrI MC with anionic dye cannot be explained only by desensitization of the AgBrI MC sensitivity as has been suggested in the literature, but rather its effect on the spectral sensitization of AgBrI MC was not so unambiguous. In the framework of the suggested mechanism such ambiguity is due to the fact that the Ag⁺ and Ag₂⁺ silver centers that participate in the generation recombination processes and are different in structure, interact on the surface of the AgBrI MC with different aggregate forms of the dye, which are in turn differently affected by oxygen. Understanding physicochemical processes occurring in the considered system allows using the obtained results in holographic and spectrozonal photographic materials, gas-phase sensors, and in solar-energy systems.     

Dissociation channels of silver bromide cluster Ag<Subscript>2</Subscript>Br,silver cluster Ag<Subscript>3</Subscript> and their ions studied by using alkali metal target

Various dissociation channels of silver bromide cluster ion Ag₂Br⁺ and silver cluster ion Ag₃ ⁺ were observed in high-energy collisionally-activated dissociation (CAD) using a Cs target. The fragment patterns of the high-energy CAD were compared with those of the metastable dissociation and low-energy CAD. The difference in the fragment patterns between the high-energy CAD and the other dissociation methods was explained in terms of the internal energy distributions. The dissociation mechanisms of neutral silver bromide cluster Ag₂Br and silver cluster Ag₃ were also investigated by charge inversion mass spectrometry using the Cs target. While the fragment ions AgBr^- and Ag₂ ^- were dominantly observed in the charge inversion spectrum of Ag₂Br⁺, the undissociated ion Ag₃ ^- was observed as a predominant peak in the case of Ag₃ ⁺. The dissociation behavior of Ag₂Br^* can be explained on the basis of the calculated thermochemical data. Contrary to this, the predominant existence of the undissociated Ag₃ ^- cannot be explained by the reported thermochemical data. The existence of undissociated Ag₃ ^- suggests that the dissociation barrier is higher than the internal energy of Ag₃ ^* (theoretical: 1.03 eV, experimental: 2.31 eV) estimated from the ionization potentials of Ag₃ and Cs.     

SERS and XPS observation of the adsorption behavior of NO and NO2 on a silver powder surface

The influence of H₂O on the adsorption behavior of NO or NO₂ on a silver powder surface was studied by SERS and XPS at room temperature. Water vapor was found to be responsible for the adsorption of NO on the silver powder surface. When surface species such as Ag₂O are present on the surface, some of the NO₂ molecules are adsorbed on the surface species to produce NO^-₃, whereas NO molecules are adsorbed on a different site to produce NO^-₂.     

Investigations on field desorption products from silver surfaces by mass spectrometry

Field evaporation of silver and field desorption of silver surface compounds were investigated by analysing positive ions with a mass spectrometer. In particular, the well known adsorption states of oxygen, and further the interactions of H₂O, NH₃, H₂, CO and CH₄ were measured in the field ion mass spectrometer under steady state fields of > 0.1 V/Å with a sensitivity of < 0.1 ions s^?1 and at temperatures between 80 °K and 425 °K. Although oxygen is usually chemisorbed at Ag surfaces, no AgO⁺, AgO⁺₂ or other Ag-O compounds could be detected as positive ions, Ag⁺ and O₂⁺ are the only observed ions at best image fields in oxygen up to fields of field evaporation of Ag⁺(≈ 2.2 V/Å). Even after the actual adsorption of oxygen with zero-field (6 × 10⁵ Langmuir at 10^?3 Torr) at 323 °K and 473 °K and subsequent application of the desorption field at 210°K no silver-oxygen compounds were found in positive ionic form. Small quantities of AgO⁺ and AgO⁺₂ were only formed — besides Ag(H₂O)_x⁺ complexes — if atomic oxygen was supplied by the field induced dissociation of water.Gases which do not adsorb on silver under zero-field conditions (H₂, CO, CH₄, N₂) yield the ions Ag(H₂)_n, Ag(CO)_n⁺, n=1, 2; AgCH₄⁺, AgN₂⁺. The situation with H₂O and NH₃ is more complicated: Molecular ions [Ag(H₂O)_n]⁺·mH₂O, n=1,…, 4, m=1,…, 8 and [Ag(NH₃)_n]⁺·mNH₃, n=1, 2, m=1,…, 6 are found besides Ag⁺.From the temperature and field dependence conclusions are drawn about the mechanisms of evaporation and formation of ionic surface complexes. The activation energies of evaporation of Ag⁺ are found to depend on the square root of the field strength. In general, the generation of surface compounds can be described by field induced reactions rather than usual gas adsorption.     

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.     

Sensing and fluorescence behaviors of complex formation between new lariat crown ethers bearing fluorescence sidearm and metal ions in methanol solution

Fluorescence spectroscopic properties of the complex formation between six new C-pivot16-crown-5 ethers bearing fluorescence side arms and metal ions are studied. Six new C-pivot 16-crown-5 ethers that carry fluorescence side arms were synthesized. The research also included the examination of different fluorescent behavior of the new lariat ethers in the presence of silver and sodium ions (Ag⁺ and Na⁺) in methanol. Because of the good fit of the cavity size of these 16-crown-5 ethers with the Ag⁺ and Na⁺ ions, remarkable change in fluorescent spectra were observed. The results showed that the new lariat crown ethers exhibited enhanced selectivity towards sodium ion, but silver ion show quenching abilities towards the ligands. Cooperative participations of the C-pivot side arm oxygen with the ring oxygen molecules in complexation was also confirmed by the single crystal X-ray crystallography of the complex, (C₂₇H₃₀O₇)·NaClO₄. The freezing of crown ring conformation and the diminishment of the chance of sidearm oscillation that occurred upon complexation with sodium ion are the main causes of fluorescent enhancement. The quenching caused by the addition of silver ion was found to explainable by the photo-induced electron transfer that results in the reduction of silver ions.     

Photoemission study of oxygen adsorbed on coldly deposited silver films

UPS spectra of coldly deposited silver films differ from those of films deposited at room temperature by electronic states localized at surface defects with an energy about 4.2 eV below E_F. Changes after exposure at 140 K to oxygen only occur in the presence of these defects, demonstrating that oxygen is only adsorbed at defects. Raman vibrational spectroscopy shows that oxygen is adsorbed nominally as O₂^? and O₂^2?. Possible assignments of the oxygen related UPS structures are discussed.     

129I-Mössbaurer study of superionic glasses AgI−Sb2S3: Local structure and diffusion effects

The local environment and the short-range diffusional displacements of the iodide ions induced by the hoppingAg ⁺ ions have been studied inAgI?Sb ₂ S ₃ superionic glasses using¹²⁹ I-Mössbauer spectroscopy in the temperature range 4.2 K to 240 K. It was found that the nearest neighbours of the iodide ions are only silver ions; the local environment of iodide is therefore close to that in the crystalline superionic conductorAg ₃ SI. Diffusion effects are observed above 140 K by characteristic changes in isomer shift, electric-quadrupole interaction and recoil-free fraction. The derived activation energy for theAg ⁺ ion local hopping is 2 times larger than that of crystallineAg ₃ SI.     

Metastable fragmentation of silver bromide clusters

The abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most abundant species are Ag_nBr_{n - 1} ⁺ and Ag_nBr_{n + 1} ^- and Ag₁₄Br₁₃ ⁺ is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-halide ionic clusters. From a certain size, Ag_nBr_{n - 1} ⁺ is no more the main series, and Ag_nBr _{n - 2, 3} ⁺ series become almost as important. The fast fragmentation induced by a UV laser makes the cations lose more bromine than silver ions and lead to more silver-rich clusters. Negative ions mass spectra contain also species with more silver atoms than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new experimental method. The large majority of the cations release mainly a neutral Ag₃Br₃ cluster. These decay channels are in full agreement with our recent ab initio DFT calculations, which show that Ag⁺-Ag⁺ repulsion is reduced due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr)₃ and to quasi-planar cyclic structures of (AgBr)_n clusters up to n = 6. We have shown that these two features may be extended to other silver halides, to silver hydroxides (AgOH)_n, and to cuprous halide compounds. Received 9 November 2000 and Received in final form 25 January 2001     

The influence of low-temperature silver-ion exchange on the spectral-luminescent properties of fluorophosphate glasses doped with PbSe

Changes in the absorption and luminescence spectra of fluorophosphate glasses doped with PbSe caused by low-temperature Ag⁺–Na⁺ ion exchange are considered. It is found that the silver distribution gradient in a near-surface layer about 16 μm thick leads to two different processes of interaction between metal and semiconductor nanoparticles. PbSe molecular clusters and quantum dots more efficiently grow in deep layers with a low silver concentration. The near-surface glass layers with a high silver concentration exhibit formation of Ag metal nanoparticles, on the surface of which interaction with PbSe molecular clusters leads to the formation of Ag–Se–Pb bonds, which transform into Ag₂Se layers in the process of heat treatment. The appearance of the new phase is confirmed by X-ray diffraction.     

Paramagnetic silver species in irradiated Ag−NaA zeolites. An EPR and ESEEM study

Several polymeric silver clusters have been observed in Ag_x?NaA zeolite (x=1,6) of varying water content, which was exposed to x-rays at 77 K and annealed at higher temperatures.¹⁰⁹Ag₁?NaA zeolite dehydrated at 130°C yields the dimer¹⁰⁹Ag₂ ⁺ and the trimer¹⁰⁹Ag₃ ²⁺ after irradiation at 77 K and annealing at 240 K. Owing to the use of one Ag isotope the EPR spectra of these species are highly resolved exhibitingg and hyperfine anisotropy. By irradiation of¹⁰⁹Ag_x?NaA zeolite (x=1,6) in hydrated form two new trimeric silver clusters I and II are produced. The ratio between I and II depends on the initial Ag content. ESEEM spectra of these species show interaction with aluminum nuclei of the framework and with distant water molecules. If Ag₆?NaA zeolite dehydrated at 130°C is irradiated the hexameric cluster Ag₆ ⁿ⁺ is formed. The ESEEM spectrum shows interaction only to aluminum nuclei. From ESEEM experiments on Ag₆ ⁿ⁺ with added adsorbates (D₂O, CD₃OD) it could be inferred that Ag₆ ⁿ⁺ is only stable if the neighbouring cages do not contain adsorbate molecules.     

Study of interfacial charge transfer in nanosemiconductor–molecule composites

Interaction of sol–gel synthesized Ce–Ag‐codoped ZnO (CSZO) nanocrystals with (E)‐1‐(naphthalen‐1‐yl)‐2‐styryl‐1H‐phenanthro[9,10‐d]imidazole has been analysed. The synthesized nanocrystals and their composites with naphthyl styryl phenanthrimidazole have been characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X‐ray spectroscopy, X‐ray diffractometry, X‐ray photoelectron spectroscopy (XPS) lifetime and Fourier transform infrared spectroscopy and cyclic voltammetry. XPS shows doped silver and cerium in Ag⁰ and Ce⁴⁺ states, respectively_. SEM and TEM images of CSZO nanoparticles show that they appear to be 3D trapezoid and cocoon‐like shape. The selected area electron diffraction pattern supports the nanocrystalline character of the synthesized material. The percentages of doping of cerium and silver in CSZO are 0.54 (at.) and 0.34 (at.), respectively. From the energy levels of the materials used in the imidazole–CSZO composite, the dominant CT direction has been analysed. Theoretical investigation shows that the binding energy and energy gap of the imidazole composites are highly dependent on the nature of the silver oxide cluster and that charge transfer in the imidazole–Ag₄O₄ composite is faster than the same in other composites. Molecular docking technique has also been carried out to understand the imidazole–DNA interactions. Copyright © 2016 John Wiley & Sons, Ltd.     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.     

IR Spectral Analysis of the Mixed Crystal System of AgNO3 and Sr(NO3)2

IR spectroscopy is utilized to analyse the mixed crystal system of AgNO₃ and Sr(NO₃)₂ in the ordered phase II and disordered phases of silver nitrate. The study aims mainly to clearify the change and the affect of partial replacement of Ag⁺ ion by Sr⁺⁺ ion in the mixed crystal system of the two metal nitrates. The change in the rotational energy barrier of the nitrate group was also checked.