Cu<Subscript>4</Subscript>RbCl<Subscript>3</Subscript>I<Subscript>2</Subscript> solid superionic conductor in thermodynamic study of three-component copper chalcogenides

The Cu-B-Se (B = In, As, Sb, Bi) systems are studied by measurement of EMF for concentration circuits vs. a copper electrode in the temperature range of 300–430 K. A solid superionic Cu₄RbCl₃I₂ conductor is used as an electrolyte. Diagrams of solid-phase equilibriums in the studied systems are constructed. Partial molar functions of alloyed copper are calculated on the basis of the equations of the temperature dependences of EMF. Potential-forming reactions corresponding to the measured EMF values are determined on the basis of the phase diagrams and standard thermodynamic formation functions and standard entropies of ternary compounds are calculated.     

Thermodynamic study of glasses in Ag-As-Se system using EMF method with Ag<Subscript>4</Subscript>RbI<Subscript>5</Subscript> solid electrolyte

The EMF method with Ag₄RbI₅ solid electrolyte was used to study silver solubility in Ag-As-Se glasses on the basis of the cross-sections of (I) Ag-As_0.25Se_0.75, (II) Ag-As_0.33Se_0.67, (III) Ag-As_0.4Se_0.6, and (IV) Ag-As_0.5Se_0.5. It is found that silver solubility reaches 30 and 40 at % in sections (I), (IV) and (II), (III), accordingly. The data of EMF measurements were used as a basis for calculation of partial polar functions of Ag in glasses. The Gibbs-Duhem equations were integrated to calculate thermodynamic functions of silver dissolution in vitreous As _x Se_{1 − x} (x = 0.25; 0.33; 0.4; 0.5), from which the corresponding data for the latter were used to obtain the standard integral thermodynamic functions of the mixing of glasses. The obtained results were compared with the thermodynamic data for crystalline silver selenoarsenites.     

Thermodynamic Properties of AgIn<Subscript>2</Subscript>Te<Subscript>3</Subscript>I and AgIn<Subscript>2</Subscript>Te<Subscript>3</Subscript>Br,Determined by EMF Method

Differential thermal analysis (DTA), X-ray diffraction (XRD), and electromotive force (EMF) are used to triangulate Ag–In–Te–I(Br) systems in the vicinity of compounds AgIn₂Te₃I and AgIn₂Te₃Br. The three-dimensional position of the AgIn₂Te₃I–InTe–Ag₂Te–AgI and AgIn₂Te₃Br–InTe–Ag₃TeBr phase areas with respect to the figurative points of silver is used to create equations of potential-determining chemical reactions. The potential-determining reactions are conducted in (?)C|Ag|Ag₃GeS₃I(Br) glass|D|C(+) electrochemical cells (ECCs), where C stands for inert (graphite) electrodes, Ag and D are ECC electrodes (D denotes alloys of one-, three-, and four-phase areas), and Ag₃GeS₃I and Ag₃GeS₃Br glasses are membranes with purely ionic Ag⁺ conductivity. Linear parts of the temperature dependences of the cell EMFs are used to calculate the standard integral thermodynamic functions of saturated solid solutions based on AgIn₂Te₃I and AgIn₂Te₃Br, and the relative partial thermodynamic functions of silver in the stoichiometric quaternary compounds.     

Thermodynamic study of the Ag-As-Se and Ag-S-I systems using the EMF method with a solid Ag<Subscript>4</Subscript>RbI<Subscript>5</Subscript> electrolyte

The EMF method with a solid Ag₄RbI₅ superionic conductor was used to study the Ag-As-Se and Ag-S-I systems in the composition ranges of Ag₂Se-As₂Se₃-Se and Ag₂S-AgI-S, accordingly. Their solid-phase equilibrium diagrams are constructed or specified. The existence of ternary AgAs₃Se₅, AgAsSe₂, Ag₃AsSe₃, Ag₇AsSe₆, Ag₃SI compounds is confirmed. The standard partial and integral thermodynamic formation functions and also standard entropies were calculated for these compounds for the first time.     

The heat capacity of solid antimony telluride Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>

The literature data on the heat capacity of solid antimony telluride over the range 53–895 K were analyzed. The heat capacity of Sb₂Te₃ was measured over the range 350–700 K on a DSM-2M calorimeter. The equation for the temperature dependence was suggested. The thermodynamic functions of Sb₂Te₃ were calculated over the range 298.15–700 K.     

Thermodynamic study of Cu-Tl-Te system using EMF technique with Cu<Subscript>4</Subscript>RbCl<Subscript>3</Subscript>I<Subscript>2</Subscript> solid electrolyte

The EMF method with a solid Cu⁺-conducting electrolyte of Cu₄RbCl₃I₂ was sued to study the Cu-Tl-Te system in the temperature range of 300–420 K. A diagram of solid-phase equilibriums of this system is constructed, partial molar functions of copper in alloys, standard thermodynamic functions of formation and standard entropies of CuTlTe₂, CuTl₄Te₃, Cu₂TlTe₂, Cu₃TlTe₂, Cu₉TlTe₅ triple compounds and Cu _x Tl_{5 − x} Te₃ solid solutions (0 < x < 1) are calculated. The obtained results confirmed the assumption as to the possibility of using this modification for the EMF technique for thermodynamic studies of copper-containing triple systems, even if they contain a less noble component than copper.     

High temperature Ag<Superscript>+</Superscript>β”-alumina in situ sensor for sulfur-containing gases

The paper reports the development of high temperature in situ fully solid electrochemical sensor for sulfur-containing gases monitoring. The sensor is based on Ag⁺β”-Al₂O₃ membrane with Ag₂S or Ag₂SO₄ layer on its surface. Silver beta alumina was manufactured by high temperature ion exchange technique in AgNO₃ melt. The original design of the in situ sensor was developed. Three types of galvanic cells were used for the investigation of electromotive force (EMF) response on SO₂ partial pressure both in oxygen-free and oxygen-containing atmosphere in the temperature range 673–923 K. The data obtained was compared with following Nernst equations. The applicability of the sensor for in situ measurements in industrial processes is discussed.     

Study and 3D modeling of the phase diagram of the Ag–Ge–Se system

In view of the contradictoriness of the literature data, phase equilibria in the Ag–Ge–Se system were restudied by differential thermal analysis and X-ray powder diffraction analysis. A number of polythermal sections and an isothermal section at room temperature of the phase diagram were constructed, and so was the projection of the liquidus surface. The primary crystallization fields of phases and the types and coordinates of in- and monovariant equilibria were determined. It was shown that, in the system, a single ternary compound, Ag₈GeSe₆, forms, which undergoes congruent melting at 1175 K and a polymorphic transformation at 321 K. The formation of the compounds Ag₂GeSe₃ and Ag₈GeSe₅, which was previously reported in the literature, was not confirmed. Based on the phase diagrams of boundary binary systems and the results of the differential thermal analysis of a number of samples of the ternary system, equations were obtained for calculation and 3D modeling of the liquidus and phase-separation surfaces.     

Composition-induced phase transition in a [Ag<Subscript>2</Subscript>HgI<Subscript>4</Subscript>:0.2AgI] mixed composite system doped with CuI

A novel composite superionic system, [Ag₂HgI₄:0.2AgI]:xCuI, (x = 0.2, 0.4, 0.6 mol. wt.%), was prepared and [Ag₂HgI₄:0.2AgI] mixed system was used as the host. Electrical conductivity was measured to study the transition behavior at frequencies of 100 Hz, 120 Hz, 1 kHz, and 10 kHz in the temperature range 90°–170°C by a Gen Rad 1659 RLC Digibridge. Sharp increase in conductivity was observed for β-α phase transitions. As a result of increase in the dopant-to-host ratio, the conductivity of the system exhibited Arrhenius (thermally activated)-type behavior. X-ray powder diffraction, differential scanning calorimetry (DSC), differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA) studies confirmed the doping effect on the transition in the host, the phase transition temperature increased with an increase in the dopant concentration. Activation energies for the system in eV both for the pretransition and post-transition phase transformations are reported. The addition of CuI to [Ag₂HgI₄:0.2AgI] shifted the phase transition of the host [Ag₂HgI₄:0.2AgI], due to an interaction between [Ag₂HgI₄:0.2AgI] and CuI.     

A Sulfide (Selenide)-Centered Nonanuclear Silver Cluster: A Distorted and Flexible Tricapped Trigonal Prismatic Ag<Subscript>9</Subscript> Framework

Two luminescent, monoanionic chalcogenide-centered nonanuclear silver clusters stabilized by dichalcogenophosphates were synthesized and fully characterized by various spectroscopies including multinuclear NMR and ESI-mass. Single crystal X-ray diffraction studies on both cluster anions, [Ag₉(S){S₂P(OEt)₂}₈]^?, 1, and [Ag₉(Se){Se₂P(OEt)₂}₈]^?, 2, reveal that the nine silver atoms form an extremely distorted tricapped trigonal prism, which has an encapsulating chalcogenide. The coordination geometry of the central chalcogenide appears to be monocapped trigonal prismatic, which was analyzed by DFT calculations. The origin of the yellow emission is assigned by TDDFT calculations to originate from a chalcogen (ligand + encapsulated) → silver charge transfer.     

Preparation and photoelectrochemical performance of TiO<Subscript>2</Subscript>/Ag<Subscript>2</Subscript>Se interface composite film

Coupling TiO₂ with a narrow band gap semiconductor acting as the photosensitizer has attracted much attention in solar energy exploitation. In this work, the porous TiO₂ film was first formed on the conducting glass plate (CGP) substrate by the decomposition of polyethylene glycol (PEG) mixing in titanium hydroxide sol at 450°C. Then, the TiO₂/Ag²Se interface composite film was fabricated by interface reaction of AgNO₃ with NaSeSO₃ on the activated surface of porous TiO₂ film. The results of SEM and XRD analyses indicated that the porous TiO₂ layer was made up of the anatase crystal, and the Ag₂Se layer was made up of congregative small particles that have low-temperature α-phase structure. Due to its efficient charge separation for the photo-induced electron-hole pairs, the TiO₂/Ag₂Se interface composite film as-prepared has good photovoltaic property and high photocurrent response for visible light, which have been confirmed by the photoelectrochemical measurements.     

Quantum chemical simulation of propylene oxidation on Ag<Subscript>20</Subscript>

The adsorption of atomic oxygen and the mechanism of propylene (C₃H₆) oxidation to oxide (C₃H₆O) on an Ag₂₀ tetrahedral cluster were studied using density functional theory. The effects of cluster structure and active site structure on the mechanism of this reaction were considered. The oxidation of C₃H₆ can occur both on an edge and at the apex of the silver cluster. The C₃H₆O formation steps on the cluster edge are characterized by lower activation energies.     

Behavior of silver sulfide in the system Ag<Subscript>2</Subscript>S-Fe(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>-HNO<Subscript>3</Subscript>-H<Subscript>2</Subscript>O

Behavior of silver sulfide in the system Ag₂S-Fe(NO₃)₃-HNO₃-H₂O was studied at 25, 55, and 80°C using the method of the simplex-lattice experiment design. The quantitative dependences of Ag₂S oxidation on the concentrations of the acid and Fe³⁺ were determined. The isoconcentration diagrams were obtained.     

Application of solid electrolytes α-AgI and RbAg<Subscript>4</Subscript>I<Subscript>5</Subscript> for refining phase diagrams and determining standard thermodynamic functions of compounds in silver-containing systems

Standard thermodynamic properties of minerals and phases of ternary systems Ag-Au-X (X = S, Se, Te) are determined by measuring the EMF in the cells with a common gas space and Ag₄RbI₅ as the solid electrolyte. By this means, thermodynamic functions of the following minerals and phases are determined: Au₂S, Ag₃AuS₂ (uytenbogaardtite), AgAuS (petrovskaite), Ag₂Se (naumannite), AuSe, Ag₃AuSe₂ (fischesserite), and Ag₅Te₃ (stuetzite). Thermodynamics of a pyrite-pyrrhotite equilibrium in the Ag-Fe-S system is studied in a cell with a solid electrolyte based on silver iodide at 500–730 K and atmospheric pressure.     

Synthesis and characterization of ambient temperature superionic solids in the composite system CuI–Ag<Subscript>2</Subscript>O–TeO<Subscript>2</Subscript>

The present work deals with the composite system (CuI) _x –(Ag₂O–TeO₂)_{100– x} , where x=30, 35, 40, 45, 50, 55, 60, 65, 70 and 75 mol%, respectively, synthesized by a solid-state reaction route. Powder specimens were analysed using differential scanning calorimetry, X-ray diffraction and Fourier transform infrared techniques. These studies have revealed the formation of Cu₃TeO₆, AgI and/or other phases. The ambient temperature electrical conductivities obtained for the samples using a complex impedance method were found to lie in the range 10^–6–10^–4 Scm^–1, with low activation energies, thus indicating their superionic nature. The typical composition 35CuI–32.5Ag₂O–32.5TeO₂ was identified as the best conducting one, having an electrical conductivity of 6×10^–4 Scm^–1 at 296 K and an activation energy of 0.23 eV. Ion transport number measurements carried out using Wagner's polarization technique as well as by an electromotive force method suggested that silver ions were responsible for the observed transport features of the composite system. Electronic Publication     

High-temperature heat capacity and thermodynamic properties of Pb<Subscript>4</Subscript>V<Subscript>2</Subscript>O<Subscript>9</Subscript> and Pb<Subscript>8</Subscript>V<Subscript>2</Subscript>O<Subscript>13</Subscript>

The molar heat capacity of Pb₄V₂O₉ and Pb₈V₂O₁₃ in the temperature range 350–1000 K was measured by differential scanning calorimetry. It was determined that the plot C_p = f(T) for Pb₈V₂O₁₃ has an extremum within the range 416–516 K, which is due to a phase transition. A correlation was found between the heat capacity and composition of oxides in the PbO–V₂O₅ system. The data obtained allowed one to predict the specific heat capacity value for Pb(VO₃)₂.     

Ag<Subscript>3</Subscript>PO<Subscript>4</Subscript>/Bi<Subscript>2</Subscript>MoO<Subscript>6</Subscript> heterostructures with enhanced visible light photocatalytic activity for the degradation of rhodamine B

Highly efficient visible-light-driven Ag₃PO₄/Bi₂MoO₆ hybrid photocatalysts with different mole ratios of Ag₃PO₄ were prepared via sonochemical method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that product are cubic Ag₃PO₄ nanoparticles supported on orthorhombic Bi₂MoO₆ nanoplates. Under visible light irradiation (>420 nm), the Ag₃PO₄/Bi₂MoO₆ photocatalysts displayed the higher photocatalytic activity than pure Bi₂MoO₆ for the decolorization of rhodamine B (RhB). Among the hybrid photocatalysts, 10% Ag₃PO₄/Bi₂MoO₆ exhibited the highest photocatalytic activity for the decolorization of RhB due to the efficient separation of electron–hole pairs.     

Thermodynamic Study of the 2PbTe–AgSbTe<Subscript>2</Subscript> System Using EMF Technique with the Ag<Subscript>4</Subscript>RbI<Subscript>5</Subscript> Solid Electrolyte

The work presents the results of studies of the 2PbTe–AgSbTe₂ system using the EMF technique with the Ag₄RbI₅ solid electrolyte in the temperature range of 300–430 K. Formation of a wide (0–80 mol % AgSbTe₂) region of PbTe-based solid solutions in the system is shown. Partial thermodynamic functions \(\left( {\overline {\Delta G} ,\overline {\Delta H} ,\overline {\Delta S} } \right)\) of alloyed silver are calculated on the basis of the equations of the temperature dependences of EMF. Potential-forming reactions are determined on the basis of the data on solid-phase equilibriums in the Ag₂Te–PbTe–Sb₂Te₃–Te system that are used to calculate standard thermodynamic functions of formation and standard entropies of (2PbTe) _x (AgSbTe₂)_1–x (x = 0.2; 0.4; 0.6; 08; 0.9) solid solutions.     

Thermodynamic study of solid solutions in the SnTe–AgSbTe<Subscript>2</Subscript> system by means of EMF with solid electrolyte Ag<Subscript>4</Subscript>RbI<Subscript>5</Subscript>

The results from studying the SnTe–AgSbTe₂ system by means of EMF with the solid electrolyte Ag₄RbI₅ in the temperature range of 300–430 K are presented. The formation of a wide (≥80 mol % of AgSbTe₂) region of solid solutions based on SnTe is confirmed. Partial thermodynamic functions ΔG?, ΔH?, and ΔS? of silver in alloys are calculated from the equations for the EMF temperature dependences. Based on the literature data regarding solid-phase equilibria in the Ag₂Te–SnTe–Sb₂Te₃–Te system, potential-determining reactions are identified that allow us to calculate the standard thermodynamic formation functions and standard entropies of solid solutions (2SnTe) _x (AgSbTe₂)_1?x (х = 0.2, 0.4, 0.6, 0.8, and 0.9).     

Synthesis and structure of the polymeric complex [Ag<Subscript>2</Subscript>(Ph<Subscript>3</Subscript>P)<Subscript>2</Subscript>B<Subscript>10</Subscript>H<Subscript>10</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A method for the synthesis of the silver(I) complex with the closo-decaborate anion and triphenylphosphine [Ag₂(Ph₃P)₂B₁₀H₁₀] _n was developed and the structure of this complex was studied. The polymeric chain of the complex is formed with participation of Ag(I) atoms, which coordinate the B₁₀H₁₀²⁻ anions through the apical (B(1)–B(2), B(9)–B(10)) and equatorial (B(3)–B(6), B(5)–B(8)) edges, the metalligand bonding occurring through three-center two-electron bonds (MHB). The P atoms of two triphenylphosphine molecules are also incorporated in the inner coordination sphere of the metal: the CN of the silver atom is 4 + 1.