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. 2023 Dec 25;17(1):111.
doi: 10.3390/ma17010111.

The AM-4 Family of Layered Titanosilicates: Single-Crystal-to-Single-Crystal Transformation, Synthesis and Ionic Conductivity

Galina O Kalashnikova  1 , Sergey V Krivovichev  1   2 , Victor N Yakovenchuk  1   3 , Ekaterina A Selivanova  1   3 , Margarita S Avdontceva  2 , Gregory Yu Ivanyuk  1 , Yakov A Pakhomovsky  1   3 , Darya V Gryaznova  1 , Natalya A Kabanova  4   5 , Yelizaveta A Morkhova  6 , Olga Yu Sinel'shchikova  7 , Vladimir N Bocharov  8 , Anatoly I Nikolaev  1   9 , Olga F Goychuk  1   4 , Sergei N Volkov  10 , Taras L Panikorovskii  4
Affiliations

The AM-4 Family of Layered Titanosilicates: Single-Crystal-to-Single-Crystal Transformation, Synthesis and Ionic Conductivity

Galina O Kalashnikova et al. Materials (Basel). .

Abstract

Flexible crystal() structures, which exhibit() single-crystal()-to-single-crystal() (SCSC) transformations(), are attracting attention() in many applied aspects: magnetic() switches, catalysis, ferroelectrics and sorption. Acid treatment() for titanosilicate material() AM-4 and natural() compounds with the same structures led to SCSC transformation() by loss() Na+, Li+ and Zn2+ cations with large structural() changes (20% of the unit()-cell() volume()). The conservation() of crystallinity through complex() transformation() is possible due() to the formation() of a strong hydrogen bonding() system(). The mechanism() of transformation() has been characterized using single-crystal() X-ray() diffraction analysis(), powder() diffraction, Rietvield refinement, Raman spectroscopy and electron microscopy. The low migration() energy() of cations in the considered materials() is confirmed using bond()-valence and density() functional() theory() calculations, and the ion conductivity of the AM-4 family's materials() has been experimentally verified.

Keywords: AM-4; K3; L3; SCSC; arctic minerals; impedance spectroscopy; ion-migration modeling; ionic conductivity; kukisvumite; lintisite; microporous; mineral-mimetic material; transformation.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Minerals and mineral-mimetic materials belonging to the AM-4 family: (a) kukisvumite (1); (b) punkaruaivite (2); (c) lintisite (3); (d) manganokukisvumite (4); (e) eliseevite (5); (f) synthetic AM-4 (6).
Figure 2
Figure 2
The initial crystal of kukisvumite (a) and the same crystal after 0.5 HCl treatment (b).
Figure 3
Figure 3
Reconstructed sections of reciprocal space obtained for (h0l) and (0kl) sections for kukisvumite (a,b) and K3 form (c,d).
Figure 4
Figure 4
Hodographs of impedance measured at AM-4 sample with silver electrodes after calcination at 550 °C. Black markers indicate points corresponding to the 1 kHz frequency.
Figure 5
Figure 5
Powder X-ray diffraction patterns of Li-modification AM-4 phases with Li-metasilicate (a) and sitinakite (b) phases.
Figure 6
Figure 6
Backscattered images of (a) synthetic AM-4 (1) and (b) L3 (2) (AM-4 after HCl treatment).
Figure 7
Figure 7
Powder X-ray diffraction patterns of initial AM-4 and L3 phases.
Figure 8
Figure 8
Powder X-ray diffraction patterns of initial AM-4, L3, L3 + Li and L3 + Na phases.
Figure 9
Figure 9
The crystal structure of kukisvumite (a) and its protonated modification K3 (b). Projection on plane (001).
Figure 10
Figure 10
The crystal structure of lintisite (a) and its protonated modification L3 (b). Projection on plane (001).
Figure 11
Figure 11
Differences between two crystal structures of kukisvumite and lintisite. (a,c), (b,d)—two type of chains TiO6 octahedrons. Packing of TiO6 chains in kukisvumite (e) and lintisite structure (f). The signs + and − means different orientation of TiO6 octahedron chains.
Figure 12
Figure 12
Positions of the adjacent titanosilicate in kukisvuminte (a) and in K3 (b) and structural reconstruction involving shifts of the adjacent layers for crystal structure of kukisvumite. The same fragment of unit cell in the (100) plane in kukisvuminte (c) and K3 (d) structures. Shift of TiO6 tetrahedra during transition (e).
Figure 13
Figure 13
Intensity profile for the powder X-ray Rietveld refinement of Ti(Si2O5(OH))(OH). The observed and calculated profiles are represented in blue and red lines, respectively. The difference profile is plotted at the bottom. The vertical bars indicate the positions of the Bragg reflections.
Figure 14
Figure 14
Raman spectra of pristine lintisite (green curve) and the L3 form (light blue curve) (a) kukisvumite (black curve) and the K3 (blue curve) form (b). The most significant differences in the positions or intensities of both spectra are indicated by gray lines.
Figure 15
Figure 15
Natural tiling for lintisite structure calculated using means topological analysis.
Figure 16
Figure 16
One-dimensional migration paths (green areas) of Li+ (a) and three-dimensional pathways (blue areas) of H+ (b) in the lintisite derived from the BVSE approach.
Figure 17
Figure 17
Li+- and Zn2+-ionic (a) and protonic (b) conductivities in lintisite and kukisvumite from KMC modeling.
Figure 18
Figure 18
Fragments of AM-4, kukisvumite and lintisite structures, in which protons involved in charge transfer are presented in the energy isosurface, derived from the BVSE calculation with the distance between nearest ions. The atoms designation is the same with Figure 16.
Figure 19
Figure 19
Structure and energy barriers of Li+- and Na+-ion migration for models AM-4-I (a) and AM-4-II (b). TiO6 octahedra filled by blue, SiO4 tetrahedra –brown.
Figure 20
Figure 20
The values of the electrical conductivity of various samples depending on temperature.
Figure 21
Figure 21
Scheme of hydrogen bond interaction in the crystal structure of K3.
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