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Subsolidus phase relations and structures of solid solutions in the systems K 2 MoO 4 –Na 2 MoO 4 –MMoO 4 (M = Mn, Zn). / Gulyaeva, Oksana A.; Solodovnikova, Zoya A.; Solodovnikov, Sergey F. et al.
In: Journal of Solid State Chemistry, Vol. 272, 01.04.2019, p. 148-156.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Subsolidus phase relations and structures of solid solutions in the systems K 2 MoO 4 –Na 2 MoO 4 –MMoO 4 (M = Mn, Zn)
AU - Gulyaeva, Oksana A.
AU - Solodovnikova, Zoya A.
AU - Solodovnikov, Sergey F.
AU - Yudin, Vasiliy N.
AU - Zolotova, Evgeniya S.
AU - Komarov, Vladislav Yu
PY - 2019/4/1
Y1 - 2019/4/1
N2 - Study of phase formation in the system K 2 MoO 4 –Na 2 MoO 4 at 500 °C showed the existence of the only double molybdate K 2-x Na x MoO 4 (0.4 ≤ x ≤ 1) of the glaserite-related type. Using these data, the subsolidus phase relations in the systems K 2 MoO 4 –Na 2 MoO 4 –MMoO 4 (M = Mn, Zn) were studied at 470–560 °C and the extended solid solutions based on the alluaudite-type Na 4−2x M 1+x (MoO 4 ) 3 were found. In the structure of K 1.71 Na 1.71 Mn 1.29 (MoO 4 ) 3 (sp. gr. C2/c, Z = 4, a = 13.0595(3) Å b = 13.7892(3) Å c = 7.2973(2) Å β = 111.339(1)° R = 0.0134), the potassium ions partially replace Na + in the channels running along c-axis. The structure of K 1.84 Na 2.11 Zn 1.02 (MoO 4 ) 3 (sp. gr. P1̅ Z = 2, a = 7.3258(8) Å b = 9.4128(10) Å c = 9.4302(10) Å α = 93.104(3)° β = 104.573(3)° γ = 104.432(3)° R = 0.0220) is isotypic with alluaudite-related α-K 4 Zn(WO 4 ) 3 and seems to be a result of stabilizing an unknown triclinic modification of K 4 Zn(MoO 4 ) 3 by substitution of sodium for potassium with the strong differentiation of alkali and zinc cations in the structure. In the structure of K 1.5 Na 0.5 Mn 2 (MoO 4 ) 3 (sp. gr. Pcca, Z = 8, a = 10.6160(7) Å b = 12.2714(8) Å c = 18.0275(11) Å R = 0.0155) of the α-K 2 Mn 2 (MoO 4 ) 3 type, one of three initial potassium positions is jointly occupied by (Na, Mn); a similar phenomenon occurs in isostructural Rb 3 Na 3 Sc 2 (MoO 4 ) 6 . The structure contains zigzag-like ribbons of edge-sharing MnO 6 octahedra linked with separate MnO 6 octahedra and МоО 4 tetrahedra into 3D containing channels along the c-axes filled by K + ions. BVS maps show possible one-dimensional sodium-ion conductivity for the structures of K 1.71 Na 1.71 Mn 1.29 (MoO 4 ) 3 and Rb 3 Na 3 Sc 2 (MoO 4 ) 6 .
AB - Study of phase formation in the system K 2 MoO 4 –Na 2 MoO 4 at 500 °C showed the existence of the only double molybdate K 2-x Na x MoO 4 (0.4 ≤ x ≤ 1) of the glaserite-related type. Using these data, the subsolidus phase relations in the systems K 2 MoO 4 –Na 2 MoO 4 –MMoO 4 (M = Mn, Zn) were studied at 470–560 °C and the extended solid solutions based on the alluaudite-type Na 4−2x M 1+x (MoO 4 ) 3 were found. In the structure of K 1.71 Na 1.71 Mn 1.29 (MoO 4 ) 3 (sp. gr. C2/c, Z = 4, a = 13.0595(3) Å b = 13.7892(3) Å c = 7.2973(2) Å β = 111.339(1)° R = 0.0134), the potassium ions partially replace Na + in the channels running along c-axis. The structure of K 1.84 Na 2.11 Zn 1.02 (MoO 4 ) 3 (sp. gr. P1̅ Z = 2, a = 7.3258(8) Å b = 9.4128(10) Å c = 9.4302(10) Å α = 93.104(3)° β = 104.573(3)° γ = 104.432(3)° R = 0.0220) is isotypic with alluaudite-related α-K 4 Zn(WO 4 ) 3 and seems to be a result of stabilizing an unknown triclinic modification of K 4 Zn(MoO 4 ) 3 by substitution of sodium for potassium with the strong differentiation of alkali and zinc cations in the structure. In the structure of K 1.5 Na 0.5 Mn 2 (MoO 4 ) 3 (sp. gr. Pcca, Z = 8, a = 10.6160(7) Å b = 12.2714(8) Å c = 18.0275(11) Å R = 0.0155) of the α-K 2 Mn 2 (MoO 4 ) 3 type, one of three initial potassium positions is jointly occupied by (Na, Mn); a similar phenomenon occurs in isostructural Rb 3 Na 3 Sc 2 (MoO 4 ) 6 . The structure contains zigzag-like ribbons of edge-sharing MnO 6 octahedra linked with separate MnO 6 octahedra and МоО 4 tetrahedra into 3D containing channels along the c-axes filled by K + ions. BVS maps show possible one-dimensional sodium-ion conductivity for the structures of K 1.71 Na 1.71 Mn 1.29 (MoO 4 ) 3 and Rb 3 Na 3 Sc 2 (MoO 4 ) 6 .
KW - Bond valence sum maps
KW - Complex molybdates
KW - Crystal structure
KW - Ionic conductivity
KW - Solid solutions
KW - Ternary systems
KW - BINARY MOLYBDATES
KW - CRYSTAL-STRUCTURE
KW - IONIC-CONDUCTIVITY
KW - CO
KW - STRUCTURE CRISTALLINE
KW - TUNGSTATES
KW - CHEMISTRY
KW - POTASSIUM
KW - NI
KW - DOUBLE MOLYBDATES
UR - http://www.scopus.com/inward/record.url?scp=85061430297&partnerID=8YFLogxK
U2 - 10.1016/j.jssc.2019.02.010
DO - 10.1016/j.jssc.2019.02.010
M3 - Article
AN - SCOPUS:85061430297
VL - 272
SP - 148
EP - 156
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
SN - 0022-4596
ER -
ID: 18485861