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Title: Mixed sodium nickel-manganese sulfates: Crystal structure relationships between hydrates and anhydrous salts

Abstract

The present contribution provides new structural and spectroscopic data on the formation of solid solutions between hydrated and dehydrated sulfate salts of sodium-nickel and sodium-manganese in a whole concentration range: Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·yH{sub 2}O, 0≤ x≤1.0. Using powder XRD, electron paramagnetic resonance spectroscopy (EPR), IR and Raman spectroscopy it has been found that double sodium-nickel and sodium-manganese salts form solid solutions Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O with a blödite-type of structure within a broad concentration range of 0≤x≤0.49, while the manganese rich compositions Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O (0.97≤x≤1.0) crystallize in the kröhnkite-type of structure. The Ni-based blödites Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O dehydrate between 140 and 260 °C into anhydrous salts Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}, 0≤ x≤0.44, with a structure where Ni{sub 1−x}Mn{sub x}O{sub 6} octahedra are bridged into pairs by edge- and corner sharing SO{sub 4}{sup 2−} groups. Both TEM and EPR methods show that the Ni{sup 2+} and Mn{sup 2+} ions are homogenously distributed over three crystallographic positions of the large monoclinic cell. The dehydration of the kröhnkite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O yields the alluaudite phase Na{sub 2+δ}Mn{sub 2-δ/2}(SO{sub 4}){sub 3}, wheremore » the Na-to-Mn ratio decreases and all Ni{sup 2+} dopants are released from the structure. The process of the dehydration is discussed in terms of structural aspects taking into account the distortion degree of the Ni,MnO{sub 6} and SO{sub 4} polyhedra. - Graphical abstract: Thermal dehydration of the blödite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O (0≤ x≤0.49) yields nickel-manganese sulfates Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2} (0≤ x≤0.44) with a large monoclinic cell, while the alluaudite phase Na{sub 2+δ}Mn{sub 2-δ/2}(SO{sub 4}){sub 3} is obtained from the kröhnkite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O (0.97≤x≤1.0). - Highlights: • Blödite phases accommodate Mn{sup 2+} ions. • Blödite structure is transformed to a super-cell structure. • The kröhnkite phase accommodates only limited amounts of Ni{sup 2+} ions.« less

Authors:
; ; ;  [1];  [1];  [2];  [1]
  1. Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)
  2. (Bulgaria)
Publication Date:
OSTI Identifier:
22658287
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 250; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CRYSTAL STRUCTURE; CRYSTALS; DEHYDRATION; DOPED MATERIALS; ELECTRON SPIN RESONANCE; MANGANESE IONS; MONOCLINIC LATTICES; NICKEL IONS; RAMAN SPECTROSCOPY; SALTS; SOLID SOLUTIONS; X-RAY DIFFRACTION

Citation Formats

Marinova, Delyana M., Zhecheva, Ekaterina N., Kukeva, Rositsa R., Markov, Pavel V., Nihtianova, Diana D., Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, 1113 Sofia, and Stoyanova, Radostina K., E-mail: radstoy@svr.igic.bas.bg. Mixed sodium nickel-manganese sulfates: Crystal structure relationships between hydrates and anhydrous salts. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2017.03.015.
Marinova, Delyana M., Zhecheva, Ekaterina N., Kukeva, Rositsa R., Markov, Pavel V., Nihtianova, Diana D., Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, 1113 Sofia, & Stoyanova, Radostina K., E-mail: radstoy@svr.igic.bas.bg. Mixed sodium nickel-manganese sulfates: Crystal structure relationships between hydrates and anhydrous salts. United States. doi:10.1016/J.JSSC.2017.03.015.
Marinova, Delyana M., Zhecheva, Ekaterina N., Kukeva, Rositsa R., Markov, Pavel V., Nihtianova, Diana D., Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, 1113 Sofia, and Stoyanova, Radostina K., E-mail: radstoy@svr.igic.bas.bg. Thu . "Mixed sodium nickel-manganese sulfates: Crystal structure relationships between hydrates and anhydrous salts". United States. doi:10.1016/J.JSSC.2017.03.015.
@article{osti_22658287,
title = {Mixed sodium nickel-manganese sulfates: Crystal structure relationships between hydrates and anhydrous salts},
author = {Marinova, Delyana M. and Zhecheva, Ekaterina N. and Kukeva, Rositsa R. and Markov, Pavel V. and Nihtianova, Diana D. and Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, 1113 Sofia and Stoyanova, Radostina K., E-mail: radstoy@svr.igic.bas.bg},
abstractNote = {The present contribution provides new structural and spectroscopic data on the formation of solid solutions between hydrated and dehydrated sulfate salts of sodium-nickel and sodium-manganese in a whole concentration range: Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·yH{sub 2}O, 0≤ x≤1.0. Using powder XRD, electron paramagnetic resonance spectroscopy (EPR), IR and Raman spectroscopy it has been found that double sodium-nickel and sodium-manganese salts form solid solutions Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O with a blödite-type of structure within a broad concentration range of 0≤x≤0.49, while the manganese rich compositions Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O (0.97≤x≤1.0) crystallize in the kröhnkite-type of structure. The Ni-based blödites Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O dehydrate between 140 and 260 °C into anhydrous salts Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}, 0≤ x≤0.44, with a structure where Ni{sub 1−x}Mn{sub x}O{sub 6} octahedra are bridged into pairs by edge- and corner sharing SO{sub 4}{sup 2−} groups. Both TEM and EPR methods show that the Ni{sup 2+} and Mn{sup 2+} ions are homogenously distributed over three crystallographic positions of the large monoclinic cell. The dehydration of the kröhnkite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O yields the alluaudite phase Na{sub 2+δ}Mn{sub 2-δ/2}(SO{sub 4}){sub 3}, where the Na-to-Mn ratio decreases and all Ni{sup 2+} dopants are released from the structure. The process of the dehydration is discussed in terms of structural aspects taking into account the distortion degree of the Ni,MnO{sub 6} and SO{sub 4} polyhedra. - Graphical abstract: Thermal dehydration of the blödite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·4H{sub 2}O (0≤ x≤0.49) yields nickel-manganese sulfates Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2} (0≤ x≤0.44) with a large monoclinic cell, while the alluaudite phase Na{sub 2+δ}Mn{sub 2-δ/2}(SO{sub 4}){sub 3} is obtained from the kröhnkite phase Na{sub 2}Ni{sub 1−x}Mn{sub x}(SO{sub 4}){sub 2}·2H{sub 2}O (0.97≤x≤1.0). - Highlights: • Blödite phases accommodate Mn{sup 2+} ions. • Blödite structure is transformed to a super-cell structure. • The kröhnkite phase accommodates only limited amounts of Ni{sup 2+} ions.},
doi = {10.1016/J.JSSC.2017.03.015},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 250,
place = {United States},
year = {Thu Jun 15 00:00:00 EDT 2017},
month = {Thu Jun 15 00:00:00 EDT 2017}
}