Ionic transport and luminescence properties in sodium- and fluorine-co-doped rare-earth molybdates NaLn4Mo3O15F (Ln = Sm-Tb)

被引：0

作者：

Orlova, Ekaterina ^{[1
,2
]}

Morkhova, Yelizaveta ^{[3
,4
]}

Sorokin, Timofei ^{[1
]}

Zakharova, Elena ^{[5
]}

Kharitonova, Elena ^{[1
,2
]}

Lyskov, Nikolay ^{[6
]}

Shendrik, Roman ^{[7
]}

Kabanov, Artem ^{[8
]}

Yapaskurt, Vasiliy ^{[9
]}

Alekseeva, Olga ^{[1
]}

机构：

[1] Natl Res Ctr, Kurchatov Inst, Shubnikov Inst Crystallog, Kurchatov Complex Crystallog & Photon, Moscow, Russia

[2] Lomonosov Moscow State Univ, Fac Phys, Moscow, Russia

[3] Samara State Tech Univ, Samara 443100, Russia

[4] Russian Acad Sci, Nanomat Res Ctr, Lab Nat Inspired Technol & Environm Safety Arctic, Kola Sci Ctr, Apatity 184209, Russia

[5] Lomonosov Moscow State Univ, Dept Chem, Moscow, Russia

[6] Russian Acad Sci, Fed Res Ctr Problems Chem Phys & Med Chem, Chernogolovka, Russia

[7] Russian Acad Sci, AP Vinogradov Inst Geochem, Siberian Branch, Irkutsk, Russia

[8] Russian Acad Sci, PN Lebedev Phys Inst, Samara Branch, Samara, Russia

[9] Lomonosov Moscow State Univ, Fac Geol, Moscow, Russia

来源：

DALTON TRANSACTIONS | 2025年 / 54卷 / 24期

基金：

俄罗斯科学基金会;

关键词：

CRYSTAL-STRUCTURES; CONDUCTIVITY; CONDUCTORS; EU3+; PR; ND; LA;

D O I：

10.1039/d5dt00809c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Halogenated rare-earth molybdates of the NaLn4Mo3O15F (Ln = Sm-Tb) nominal composition were synthesized via a solid-state route and investigated for their structural, thermal, IR spectroscopic, luminescent, and ionic transport properties. The study demonstrated that lanthanide cation size critically governs structural symmetry. Guided by symmetry analysis, Sm and Eu were prioritized for investigation as they stabilize the cubic fluorite-like framework, which exhibits superior ionic conductivity, whereas smaller cations (Gd, Tb) form low-conductivity monoclinic oxymolybdates. Fluorine incorporation and oxidative annealing significantly modulated oxygen interstitial content, as evidenced by lattice parameter variations and luminescence spectroscopy, which confirmed europium's oxidation state transition (Eu2+ <-> Eu3+). Here, the conductive properties of NaSm4Mo3O15F (NSMF) and NaEu4Mo3O15F (NEMF) were studied for the first time. Crystal chemical analysis of ionic conductivity revealed approximately equal oxygen migration barriers, with an estimated value of about 0.5 eV for 3D oxygen diffusion. The results of kinetic Monte Carlo simulations demonstrated oxygen ionic conductivity of about 10-2-10-3 S cm-1 at 800 degrees C. To estimate the electronic contribution, density functional theory calculations were performed for band gaps calculations, which turned out to be ca. 0.6 eV. Conductivity measurements demonstrated a similar order of anionic conductivity, with enhanced electronic contributions under reducing conditions. Thermal analysis linked suppressed phase transitions in NSMF/NEMF to lattice rigidity caused by smaller lanthanides, contrasting with flexible lattices in MLn4Mo3O15F (M = Li, Na; Ln = La, Pr, Nd). These findings highlight fluorine's role in tuning oxygen mobility and underscore the interplay between cation size, lattice dynamics, and conductivity for intermediate-temperature solid oxide fuel cell applications.

引用

页码：9689 / 9700

页数：12

共 38 条

[1] High power lithium ion battery materials by computational design [J].

Adams, Stefan ;

Rao, R. Prasada .

PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE, 2011, 208 (08) :1746-1753

[2] Crystal structure of the oxygen conducting compound Nd5Mo3O16 [J].

Alekseeva, O. A. ;

Gagor, A. B. ;

Pietraszko, A. P. ;

Sorokina, N. I. ;

Bolotina, N. B. ;

Artemov, V. V. ;

Kharitonova, E. P. ;

Voronkova, V. I. .

ZEITSCHRIFT FUR KRISTALLOGRAPHIE-CRYSTALLINE MATERIALS, 2012, 227 (12) :869-875

[3] Structural features of sodium- and halogen-containing fluorite-like rare-earth molybdates [J].

Antipin, Alexander M. ;

Orlova, Ekaterina I. ;

Smirnova, Ekaterina S. ;

Trukhacheva, Maria P. ;

Sorokin, Timofei A. ;

Sidorova, Ekaterina V. ;

Kharitonova, Elena P. ;

Lyskov, Nikolay V. ;

Novikova, Natalia E. ;

Yapaskurt, Vasiliy O. ;

Sorokina, Natalia I. ;

Alekseeva, Olga A. ;

Voronkova, Valentina I. .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2025, 27 (07) :3897-3907

[4] Proton Conductivity in Rare-Earth Fluorine-Containing Molybdates NaLn4Mo3O15F [J].

Baldin, E. D. ;

Sorokin, T. A. ;

Orlova, E. I. ;

Gorshkov, N. V. ;

Kharitonova, E. P. ;

Lyskov, N. V. ;

Goffman, V. G. ;

Voronkova, V. I. .

RUSSIAN JOURNAL OF ELECTROCHEMISTRY, 2023, 59 (01) :54-59

[5] Eu3+ activated molybdates – Structure property relations [J].

Baur F. ;

Jüstel T. .

Optical Materials: X, 2019, 1

[6] The Fluorite-Like Phase Nd5Mo3O16±δ in the MoO3-Nd2O3 System: Synthesis, Crystal Structure, and Conducting Properties [J].

Biendicho, Jordi Jacas ;

Playford, Helen Y. ;

Rahman, Seikh M. H. ;

Norberg, Stefan T. ;

Eriksson, Sten G. ;

Hull, Stephen .

INORGANIC CHEMISTRY, 2018, 57 (12) :7025-7035

[7] ON EU3+ FLUORESCENCE IN MIXED METAL OXIDES .3. ENERGY TRANSFER IN EU3+-ACTIVATED TUNGSTATES AND MOLYBDATES OF TYPE LN2WO6 AND LN2MO06 [J].

BLASSE, G ;

BRIL, A .

JOURNAL OF CHEMICAL PHYSICS, 1966, 45 (07) :2350-&

[8] Analysis of migration paths in fast-ion conductors with Voronoi-Dirichlet partition [J].

Blatov, Vladislav A. ;

Ilyushin, Gregory D. ;

Blatova, Olga A. ;

Anurova, Nataly A. ;

Ivanov-Schits, Alexej K. ;

Dem'yanets, Lyudmila N. .

ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 2006, 62 (1010-1018) :1010-1018

[9] Applied Topological Analysis of Crystal Structures with the Program Package ToposPro [J].

Blatov, Vladislav A. ;

Shevchenko, Alexander P. ;

Proserpio, Davide M. .

CRYSTAL GROWTH & DESIGN, 2014, 14 (07) :3576-3586

[10] Intermediate temperature solid oxide fuel cells [J].

Brett, Daniel J. L. ;

Atkinson, Alan ;

Brandon, Nigel P. ;

Skinner, Stephen J. .

CHEMICAL SOCIETY REVIEWS, 2008, 37 (08) :1568-1578

← 1 2 3 4 →