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

Galina O Kalashnikova; Sergey V Krivovichev; Victor N Yakovenchuk; Ekaterina A Selivanova; Margarita S Avdontceva; Gregory Yu Ivanyuk; Yakov A Pakhomovsky; Darya V Gryaznova; Natalya A Kabanova; Yelizaveta A Morkhova; Olga Yu Sinel'shchikova; Vladimir N Bocharov; Anatoly I Nikolaev; Olga F Goychuk; Sergei N Volkov; Taras L Panikorovskii

doi:10.3390/ma17010111

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

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

Authors

Galina O Kalashnikova¹, Sergey V Krivovichev^{1

2}, Victor N Yakovenchuk^{1

3}, Ekaterina A Selivanova^{1

3}, Margarita S Avdontceva², Gregory Yu Ivanyuk¹, Yakov A Pakhomovsky^{1

3}, Darya V Gryaznova¹, Natalya A Kabanova^{4

5}, Yelizaveta A Morkhova⁶, Olga Yu Sinel'shchikova⁷, Vladimir N Bocharov⁸, Anatoly I Nikolaev^{1

9}, Olga F Goychuk^{1

4}, Sergei N Volkov¹⁰, Taras L Panikorovskii⁴

Affiliations

¹ Laboratory for Synthesis and Research of the Properties of Mineral-Like Functional Materials, Nanomaterial Research Center of the Kola Science Centre, Russian Academy of Sciences, Fersmana str. 14, 184209 Apatity, Russia.
² Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, 7-9 University Emb., 199034 St. Petersburg, Russia.
³ Geological Institute, Kola Science Center of Russian Academy of Sciences, 14 Fersman Street, 184200 Apatity, Russia.
⁴ Laboratory of Nature-Inspired Technologies and Environmental Safety of the Arctic, Nanomaterial Research Center of the Kola Science Centre, Russian Academy of Sciences, Fersmana str. 14, 184209 Apatity, Russia.
⁵ Samara Center for Theoretical Materials Science, Samara State Technical University, Molodogvardeyskaya Str. 244, 443100 Samara, Russia.
⁶ Institute of Experimental Medicine and Biotechnology, Samara State Medical University, Chapayevskaya Srt. 89, 443099 Samara, Russia.
⁷ Laboratory of Physicochemical Design and Synthesis of Functional Materials, Institute of Silicate Chemistry of Russian Academy of Sciences, 2 Adm. Makarova, 199034 St. Petersburg, Russia.
⁸ Geo Environmental Centre "Geomodel", St. Petersburg State University, Universitetskaya nab., 7/9, 199034 St. Petersburg, Russia.
⁹ Tananaev Institute of Chemistry of the Kola Science Centre, Russian Academy of Sciences, Academic Town, 26a, 184209 Apatity, Russia.
¹⁰ Laboratory of Arctic Mineralogy and Material Sciences, Nanomaterial Research Center of the Kola Science Centre, Russian Academy of Sciences, Fersmana str. 14, 184209 Apatity, Russia.

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.

Grants and funding

21-77-10103/Russian Science Foundation