Abstract
Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs2(HSO4)(H2AsO4). The title compound crystallizes in the monoclinic system with the P21/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm−1and 1200–50 cm−1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs2(HSO4)(H2AsO4) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10−4 Ω−1 cm−1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.
Similar content being viewed by others
References
Baranov AI, Merinov BV, Tregubchenko AB, Shuvalov LA, Shchagina NM (1988) Phase Transitions, structure, protonic conductivity and dielectric properties of Cs3H(SeO4)2 and Cs3(H,D)(SeO4)2. Ferroelectrics 81:187–191
Baranov AI, Tregubchenko AV, Shuvalov LA, Shchagina NM (1987) Structural phase transitions and proton conductivity of Cs3H(SeO4)2 and (NH4)3H(SeO4)2 crystals. Sov Phys, Solid State 29:1448–1449
Belushkim AV, Adams MA (1997) Lattice dynamics of KH2PO4 at high pressure. Physica B 234-236:37–39
Kreuer KD (1996) Proton conductivity: materials and applications. Chem Matter 8:610–641
Zhu B, Albirsson I, Mellander BE, Meng G (1999) Intermediate-temperature proton-conducting fuel cells—present experience and future opportunities. Solid State Ionics 125:439–446
Guin M, Tietz F (2015) Survey of the transport properties of sodium superionic conductor materials for use in sodium batteries. Power Sources 273:1056–1064
Bouchet R, Miller S, Duclot M (2001) A thermodynamic approach to proton conductivity in acid-doped polybenzimidazole. Solid State Ionics 145:69–78
Chisholm CRI, Haile SM (1999) Structure and thermal behavior of the new superprotonic conductor Cs2(HSO4)(H2PO4). Acta Crystallogr B55:937–946
Averbuch-Pouchot MT, Durif A (1980) Crystal structure of KHSO4·KH2PO4. Res Bull 15:427–430
Stiewe A, Sonntag R, Troyanov SI, Hansen T, Kemnitz E (2000) Synthesis and structure determination of Rb2(HSO4)(H2PO4) and Rb4(HSO4)3(H2PO4) by x-ray single crystal and neutron powder diffraction. Sol State Chem 149:9–15
Averbuch-Pouchot MT (1981) Hydrogen bonding in NH4HSO4·NH4H2PO4. Mater Res Bull 16:407–411
Boubia M, Averbuch-Pouchot MT, Durif A (1985) Ordered AsO4 and SO4 tetrahedra in diammonium trihydrogenarsenate sulfate. Acta Crystallogr C41:1562–1564
Matsuo Y, Hatori J, Nakashima Y, Ikehata S (2004) Superprotonic and ferroelastic phase transition in K3H(SO4)2. Solid State Commun 130:269–274
Noda Y, Uchiyama S, Kafuku K (1990) Structure analysis and hydrogen bond character of K3H(SO4)2. Phys Soc Jpn 59:2804–2810
Jaouadi K, Zouari N, Mhiri T, Giorgi M (2009) Synthesis, structural study and thermal behaviour of a new superprotonic compound: Cs2(HSeO4)(H2AsO4). Phys Procedia 2:1185–1194
Sheldrick GM (1995) SORTAV user guide. University of Göttingen, Göttingen
International Tables for X-ray Crystallography Vol. C (1992). Kluwer Academic Publishers, Dordrecht
Sheldrick GM (1990) SHELXS-97, program for the solution of crystal structures. University of Göttingen, Göttingen
Sheldrick GM (1997) SHELXL-97, program for crystal structure determination. University of Göttingen, Göttingen
Zouari N, Jaouadi K, Mhiri T, Giorgi M (2005) X-ray single crystal, vibrational and phase transitions in the mixed Rb2(HSeO4)(H2PO4). Phase Transit 78:627–638
Itoh K, Ukeda T, Ozaki T, Nakamura E (1990) Redetermination of the structure of caesium hydrogensulfate. Acta Crystallogr C46:358–361
Pakhomov VI, Sil’nitskaya GB, Semin GK, Gerken VA, Kalashnikova II (1985) Structural perfection of CsH2AsO4 crystals. Inorg Mater 21:142–143
Novak A (1974) Hydrogen bonding in solids correlation of spectroscopic and crystallographic data. Struct Bond 18:177–216
Amri M, Zouari N, Mhiri T, Pechev S, Gravereau P, Von Der Muhll R (2007) Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4). Phys Chem Solids 68:1281–1292
Naili H, Mhiri T, Jaud J (2001) Crystal structure and characterization of CsH5(AsO4)2: a new cesium pentahydrogen arsenate, and comparison with CsH5(PO4)2 and RbH5(AsO4)2. Sol State Chem 161:9–16
Le Calve N, Romain F, Limage MH, Novak A (1989) Etude par spectroscopic Raman et infrarouge des verres de pseudo-spin Rb0,65(NH4)0,35H2PO4. Mol Struct (Theochem) 200:131–147
Romain F, Novak A (1991) Raman study of the high-temperature phase transition in CsH2PO4.Molecular. Structure 263:69–74
Naili H, Mhiri T, Daoud A (1999) Crystal structure, characterisation and vibrational study of a mixed compound Cs0.4Rb0.6H2PO4. Phase Transit 71:271–286
Marchon B, Novak A (1983) Vibrational study of CsH2PO4 and CsD2PO4 single crystals. Chem Phys 78:2105–2120
Hubert Joe I, Jayakumar VS, Aruldhas G (1995) FT-IR and polarized Raman spectra of N(CH3)4H2PO4·H2O. Sol State Chem 120:343–352
Fillaux F, Marchon B, Novak A (1984) Raman OH stretching band shape of and proton dynamics in CsH2PO4. Chem Phys 86:127–136
Colomban P (1992) Proton conductors: solids, membranes, and gels materials and devices. Cambridge University Press, Chemistry of Solid State Materials
Howell FS, Bose RA, Macedo PB, Moynihan CT (1974) Electrical relaxation in a glass-forming molten salt. Phys Chem 78:639–648
Martin SW, Angell CA (1986) Dc and ac conductivity in wide composition range Li2O-P2O5 glasses. Non-Cryst Solids 83:185–207
Chowdari BVR, Gopalakrishnan R (1987) ac conductivity analysis of glassy silver iodomolybdate system. Solid State Ionics 23:225–233
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Nouiri, N., Jaouadi, K., Mhiri, T. et al. Structure, thermal behavior, and dielectric properties of new cesium hydrogen sulfate arsenate: Cs2(HSO4)(H2AsO4). Ionics 22, 1611–1623 (2016). https://doi.org/10.1007/s11581-016-1679-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11581-016-1679-0