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  • Accepted Manuscript: Sodium Transition Metal Vanadates from Hydrothermal Brines: Synthesis and Characterization of NaMn 4 (VO 4 ) 3 , Na 2 Mn 3 (VO 4 ) 3 , and Na 2 Co 3 (VO 4 ) 2 (OH) 2
Title: Sodium Transition Metal Vanadates from Hydrothermal Brines: Synthesis and Characterization of NaMn 4 (VO 4 ) 3 , Na 2 Mn 3 (VO 4 ) 3 , and Na 2 Co 3 (VO 4 ) 2 (OH) 2
Authors:
; ; ; ;
Award ID(s):
1808371 1806279 1655740
Publication Date:
NSF-PAR ID:
10215034
Journal Name:
European Journal of Inorganic Chemistry
Volume:
2020
Issue:
35
Page Range or eLocation-ID:
3408 to 3415
ISSN:
1434-1948
Sponsoring Org:
National Science Foundation
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    Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I , Rb 2 Mn 3 (VO 4 ) 2 CO 3 , crystallizes in the trigonal crystal system in the space group P 3̄1 c , and compound II , K 2 Co 3 (VO 4 ) 2 CO 3 , crystallizes in the hexagonal space group P 6 3 / m . Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO 6 octahedra and MO 5 trigonal bipyramids, respectively. The honeycombmore »and triangular layers are connected along the c -axis through tetrahedral [VO 4 ] groups. The MO 5 units are connected with each other by carbonate groups in the ab -plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO 6 -honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO 5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K 2 Co 3 (VO 4 ) 2 CO 3 ( II ) exhibits a canted antiferromagnetic ordering below T N = 8 K. The Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of −42 K suggesting a dominant antiferromagnetic coupling in the Co 2+ magnetic sublattices.« less
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