Crystallization at "Soft" Chemistry Conditions of New Inorganic Fluoride Nanomaterials and Their Application Prospects

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Abstract

Peculiarities of formation and growth of crystals of metal fluorides MF2 (where M — Ca, Sr, Pb) and MF3 (where M — Sc, La, Ln) as a result of interaction between components of an aqueous solution of metal salt and gaseous hydrogen fluoride at planar interface at room temperature are considered. Compounds with different crystal structures: PbF2 (pr. gr. Pnma, Fm3m), ScF3 (pr. gr. Pm3m, P6/mmm), LaF3 (pr. gr. P3c1) were chosen as model objects. The factors that have a significant influence on the morphology, size, and ordering of the formed crystals have been determined. The possibility of synthesis of 1D and 2D crystals is shown for some compounds. Probable fields of application of nanomaterials based on synthesized compounds are analyzed. The conclusion is made about the possibility of the interface technique developing for the design of new solid electrolytes, optically active materials, and functional coatings.

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L. B. Gulina

Saint Petersburg State University

Author for correspondence.
Email: l.gulina@spbu.ru
Russian Federation, Saint Petersburg

V. P. Tolstoy

Saint Petersburg State University

Email: l.gulina@spbu.ru
Russian Federation, Saint Petersburg

I. V. Murin

Saint Petersburg State University

Email: l.gulina@spbu.ru
Russian Federation, Saint Petersburg

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2. Fig. 1. SEM images of crystals synthesized on the surface of 0.02 M aqueous solutions of Ca(CH3COO)2 (a) and Sr(CH3COO)2 (b) as a result of their treatment with gaseous HF. a, b lowercase; µm replace with μm

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3. Fig. 2. X-ray diffraction patterns of SrF2 (a) and PbF2 (b) crystals synthesized as a result of interaction for 40 min with gaseous HF on the surface of 0.02 M aqueous solutions of Sr(CH3COO)2 and Pb(CH3COO)2, respectively. The positions of the maxima in the lower part of the figure characterize the crystal structure of fluorite of SrF2 [50] (a) and β-PbF2 [51] (b).

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4. Fig. 3. Optical (a, d) and SEM images (b, c, e) of PbF2 crystals synthesized on the surface of Pb(CH3COO)2 (a-c) and Pb(CH3COO)2/KCH3COO (d, e) solutions under the action of gaseous HF; f - Kikuchi picture of two-dimensional PbF2 crystal with indication of atomic planes indexing.

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5. Fig. 4. SEM images at different magnification of crystals synthesized on the surface of 0.1 M (a, b) and 0.05 M (c, d) aqueous solutions of ScCl3; 0.02 M Sc(NO3)3 (e) as a result of interaction with gaseous HF; f - image of ScF3 tube obtained by the NEIM method. a-e line; µm replaced by µm; nm

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6. Fig. 5. Results of the study of the crystal structure of materials based on scandium fluoride: a - X-ray film (45% c-ScF3); b - X-ray powder of rod-shaped crystals (96% h-ScF3); c - TEM images and electronogram of the ScF3 tube wall. a- lines in brackets; along the x-axis 2θ (CuKα), deg

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7. Fig. 6. SEM images of films synthesized on the surface of 0.035 M LaCl3 aqueous solution (a) and La(NO3)3 nitrate solution (b) as a result of their treatment with gaseous HF; c, d - SEM HF images of particles obtained on the surface of La(NO3)3 nitrate solution under the action of HF.

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8. Fig. 7. X-ray diffraction patterns of LaF3 films on the surface of single-crystalline silicon synthesized by 40 min of interaction with gaseous HF on the surface of 0.035 M aqueous LaCl3 solution at equilibrium pH (a) and 0.035 M La(NO3)3 solution in the presence of 1 M HNO3 (b).

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