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Synthesis, Crystal Structure and Electrophysical Properties of Triple Molybdates Containing Silver, Gallium and Divalent Metals

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Synthesis, Crystal Structure and Electrophysical Properties of Triple Molybdates Containing Silver, Gallium and Divalent Metals Kotova I. Yu., Savina A. A., Vandysheva A. I., Belov D. A., Stefanovich S. Yu. Chimica Techno Acta. 2018. Vol. 5, No. 3. P. 132–143. ISSN 2409–5613 I. Yu. Kotovaa, A. A. Savinaa*, A. I. Vandyshevab, D. A. Belovc, S. Yu. Stefanovichc aBaikal Institute of Nature Management, Siberian Branch, Russian Academy of Sciences, 6 Sakh’yanova St., Ulan-Ude, 670047, Buryat Republic, Russian Federation bBuryat State University, 24a Smolin St., Ulan-Ude, 670000, Buryat Republic, Russian Federation cLomonosov Moscow State University, Leninskie Gory, 1, Moscow 119991, Russian Federation *E-mail: [email protected] DOI: 10.15826/chimtech.2018.5.3.02 Synthesis, crystal structure and electrophysical properties of triple molybdates containing silver, gallium and divalent metals A possibility of the triple molybdates formation with both NASICON-like and NaMg3In(MoO4)5 structures in the Ag2MoO4–AMoO4–Ga2(MoO4)3 (A = Mn, Co, Zn, Ni) systems was studied by powder X-ray diffraction analysis. It was established that NASICON-like phases Ag1−xA1−xGa1+x(MoO4)3 are not formed. The triple molyb- dates AgA3Ga (MoO4)5 (A = Mn, Co, Zn) isostructural to triclinic NaMg3In(MoO4)5 (sp. gr. P1, Z = 2) were synthesized and characterized. The structure of the obtained compounds was refined for AgZn3Ga(MoO4)5 according to the powder data by the Rietveld method. The structure consists of MoO4 tetrahedra, couples of edge-shared M(1)O6 octahedra, and trimers of edge-shared M(2)O6–, M(3)6– and M(4)O6 octahedra, which are linked by the common vertices to form a 3D framework. High-temperature conductivity measurements revealed that the –2 conductivity of AgMn3Ga(MoO4)5 at 500°С reaches 10 S / cm, which is close to one of the known NASICON-type ionic conductors. Keywords: triple molybdates; silver; gallium; solid-state synthesis; powder X-ray diffraction; Rietveld refinement; ionic conductivity. Received: 10.10.2018. Accepted: 22.10.2018. Published: 31.10.2018. © Kotova I. Yu., Savina A. A., Vandysheva A. I., Belov D. A., Stefanovich S. Yu., 2018 Introduction A synthesis and studying of com- lybdates, in particular triple ones, which plex oxide compounds, the development are among the fastest-growing groups of new materials with functionally sig- of complex oxide compounds containing nificant properties based on those are a tetrahedral anion and three different among the main areas of the materials cations. One of the largest families of these science. An important place in the study compounds is molybdates containing and obtaining of new phases with valuable 1-, 2- and 3-charged cations. In particular, physicochemical properties belongs to mo- silver-containing NASICON-like phases 132 Ag1–xA1–xR1+x(MoO4)3 (A = Mg Co, R = Al; obtained and their crystal structures were A = Mg, R = In) with different homoge- determined [1–9]. neity range and triclinic AgA3R(MoO4)5 The purpose of this work is to study (A = Mg, R = Cr, Fe, Ga; A = Mn, R = Al, the possibility of forming triple mo- Cr, Fe, Sc, In) having high ionic conduc- lybdates Ag1–xA1–xGa1+x(MoO4)3 and –3 –2 tivity (10 –10 S / cm) are of interest. For AgA3Ga(MoO4)5 (A = Mn, Co, Zn, Ni) and a number of phases: AgMg3R(MoO4)5 investigate crystal structure and electro- II III (R = Cr, Fe), AgMn 3 (Mn 0.26Al0.74) physical properties of the obtained com- (MoO4)5, Ag0.90Al1.06Co2.94(MoO4)5 and pounds. II III AgFe 3Fe (MoO4)5 single crystals were Experimental The initial materials were simple mo- obtained products was controlled by the lybdates of silver, manganese, cobalt, zinc, PXRD analysis before each increasing nickel, MoO3 and Ga2O3 (reagent grade). of the annealing temperature. Ag2MoO4 and molybdates of divalent PXRD patterns were collected at room metals were obtained by the step annealing temperature on a Bruker D8 ADVANCE of stoichiometric mixtures of AgNO3 (ana- diffractometer using Cu Kα radiation lytical grade), MnO, Co(NO3)2·6H2O, in the 2θ range from 5° to 100° with a step ZnO, MoO3 (all chemically pure), NiO of 0.02076°. Possible impurity phases were (reagent grade) at 350−450 °С (Ag2MoO4), checked by comparing their PXRD patterns 400−750 °С (MnMoO4), 300−700 °С with those in the Powder Diffraction File. (CoMoO4), 500−700 °С (ZnMoO4), The crystal structure refinement was car- 450−750 °С (NiMoO4) in the air with ried out with the GSAS [16] program suite intermittent grindings every 15 hours using PXRD data. Lattice parameters and for better sample homogenization. Power individual scale factors were established, X-ray diffraction (PXRD) patterns of the and five common peak-shape parameters prepared compounds do not contain reflec- of the pseudo-Voigt function (No. 2), one tions of starting or impurity phases. PXRD asymmetry parameter and one parameter and thermal characteristics of all prepared for the zero-point correction were used compounds agree well with corresponding to describe the powder patterns. The back- data reported in [10−15]. ground level was described by a combina- Sample compositions Ag1–xA1–xGa1+x tion of 15-order Chebyshev polynomials. (MoO4)3 (0 ≤ x ≤ 0.7, Δx = 0.1) and Isotropic displacement parameters (Uiso) AgA3Ga(MoO4)5 were prepared by the were refined, and grouped by chemical annealing of appropriate stoichiometric similarity by used constrains. mixtures of Ag2MoO4, АMoO4, MoO3 and Thermoanalytic studies were carried Ga2O3. The initial mixtures were annealed out on a STA 449 F1 Jupiter NETZSCH starting at 300 °C followed by raising the thermoanalyser (Pt crucible, heating rate temperature by 20–50 °C (in some cases, of 10 °С / min in Ar stream). 5–10 °C) with intermittent grindings every Ceramic disks for dielectric investi- 20–30 hours for sample homogenization. gations were prepared by the calcination The calcination time at each temperature of pressed powder at 600 °С for 2 h. The was 30–70 h. The phase composition of the disks were of 9–10 mm in diameter and 133 1–2 mm thick, the electrodes were depo- in the frequency range 1 Hz–1 MHz in the sited by painting the disk bases with col- temperature range 25–560 °C at the rate loid platinum followed by subsequent one of 4 °C / min at both heating and cooling hour annealing at about 580 °С. The di- using a Novocontrol Beta-N impedance rect current (DC) electric conductivity was analyzer. The activation energy of electrical measured with a V7–38 microammeter. conductivity was calculated from the slope To study the ion transfer, electrical con- of the straight lines corresponding to the ductivity was measured on an alternating Arrhenius dependence in lg (σT) – (103 / T) current (AC) by the two-contact method coordinates. Results and discussion PXRD characteristics 550 °C, but the PXRD data of the product The presence of NASICON-like phases are not given by the authors. It should be in the Ag2MoO4–AMoO4–Ga2(MoO4)3 sys- noted that in none of the later publications tems was determined according to PXRD (including those of the same authors) ad- analysis of samples Ag1−xA1−xGa1+x(MoO4)3 ditional information about this compound (0 ≤ x ≤ 0.7, Δх = 0.1) which were annealed was found. in the temperature range from 300 °C At the same time, in the Ag2MoO4– to melting point. The final annealed tem- AMoO4–Ga2(MoO4)3 systems triple mo- perature was 550–700 °C and depended lybdates of composition AgA3Ga(MoO4)5 on both the composition of the reaction were found. These compounds were syn- mixtures and the nature of the divalent thesized by the solid-state reactions at 550– metal. It was established that, despite the 600 °С (A = Mn), 540–550 °С (A = Zn), close values of the Al3+ (0.53) and Ga3+ 500–530 °С (A = Co) for 80–100 h. How- (0.62 Å [17]) radii, gallium containing ever, nickel-containing compound was not triple molybdates with NASICON-like obtained in the single-phase state, even after structure, apparently, do not exist. All our sintering at temperatures as high as 600– attempts to obtain rhombohedral phases 650 °C for 250–300 hours. This may be due 2+ Ag1−xA1−xGa1+x(MoO4)3 by solid state syn- to the smallest radius of Ni cation (0.69 Å thesis did not lead to a positive result, for CN = 6 [17]) in the studied series probably this is due to the low reactivity of simple molybdates of divalent metals. of gallium in the molybdate systems. Thus, The triple molybdates AgA3Ga(MoO4)5 the simple gallium molybdate Ga2(MoO4)3 (A = Zn, Mn, Co) were found to melt in- has not yet been obtained by ceramic congruently at temperatures of 644, 727, techno logy, and only recently it was syn- and 739 °C, respectively. thesized by the sol-gel method [18]. Be- The powder XRD patterns of as- sides, silver-gallium double molybdate is prepared single-phase compounds not synthesized either by ceramic tech- AgA3Ga(MoO4)5 are similar and show that nology or by co-precipitation. In [19] this these oxides are isostructural to triclinic compound was obtained by the calcining NaMg3In(MoO4)5 (sp. gr. P1, Z = 2) [20]. of mixtures of AgNO3, Ga2O3, MoO3 (in ra- The diffractograms of the AgA3Ga(MoO4)5 tio 2:1:4) at 350–400 °C for 8–10 h, fol- (A = Mn, Co, Zn) were indexed with tak- lowed by cooling, homogenization, and the ing into account our data obtained earlier repeated 12–20 hours annealing at 500– in the course of single-crystal structure de- 134 termination of AgMg3R(MoO4)5, R = Fe, cording to the Rietveld method [21], Cr [7].
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