Layered Minerals and Materials: Crystal Structures, Properties and Applications

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Crystallography and Physical Chemistry of Minerals & Nanominerals".

Deadline for manuscript submissions: closed (1 August 2020) | Viewed by 18123

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Guest Editor
Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, St. Petersburg 199034, Russia
Interests: minerals; Earth sciences; crystallography; X-ray diffraction; inorganic chemistry; layered minerals and materials; exhalative minerals
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Special Issue Information

Dear Colleagues,

Layered minerals and inorganic materials include compounds structurally based on two-dimensional tetrahedral or heteropolyhedral complexes. Nowadays, layered minerals and related synthetic compounds are extensively investigated in very different fields, from mineralogy, geochemistry, and biogeochemistry to solid-state physics, inorganic chemistry, and materials science. The most well-known class of layered compounds with a wide range of applications is represented by clay minerals, which include a number of different groups: kaolinite–serpentine, talc and pyrophyllite, smectite, chlorite, etc. The relatively recent discovery of clay minerals in meteorites allowed to suggest that the formation of minerals with a layered structure was an important prerequisite for the appearance of self-replicating organic compounds on Earth. In addition to clay minerals, such layered materials as layered double hydroxides (LDH), hybrid organo-inorganic compounds, titanosilicates, etc. are obtained using a wide variety of synthesis methods in the chemical industry. Most of the layered materials used in our days in various industries are analogues of known minerals or related mineral-like phases.

This Special Issue welcomes contributions on layered minerals and materials, layered crystal structures, and on applications of clay minerals and layered double hydroxides, composite materials.

Dr. Oleg Siidra
Guest Editor

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Keywords

  • layered materials
  • layered minerals
  • layered double hydroxides (LDH)
  • clay minerals
  • sorbents
  • composite materials
  • organically templated materials
  • layered minerals and materials characterization methods

Published Papers (5 papers)

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Research

10 pages, 2072 KiB  
Article
Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi2CuO3]SO4 and [Ln2O2]SO4 (Ln = Dy and Ho)
by Oleg Siidra, Dmitri Charkin, Igor Plokhikh, Evgeny Nazarchuk, Astrid Holzheid and Georgy Akimov
Minerals 2020, 10(10), 887; https://doi.org/10.3390/min10100887 - 07 Oct 2020
Cited by 2 | Viewed by 2002
Abstract
During the last decades, layered structures have attracted particular and increasing interest due to the multitude of outstanding properties exhibited by their representatives. Particularly common among their archetypes, with a significant number of mineral and synthetic species structural derivatives, is that of litharge. [...] Read more.
During the last decades, layered structures have attracted particular and increasing interest due to the multitude of outstanding properties exhibited by their representatives. Particularly common among their archetypes, with a significant number of mineral and synthetic species structural derivatives, is that of litharge. In the current paper, we report the structural studies of two later rare-earth oxysulfates, [Ln2O2]SO4 (Ln = Dy, Ho), which belong indeed to the grandreefite family, and a novel compound [Bi2CuO3]SO4, which belongs to a new structure type and demonstrates the second example of Cu2+ incorporation into litharge-type slabs. Crystals of [Bi2CuO3]SO4 were obtained under high-pressure/high-temperature (HP/HT) conditions, whereas polycrystalline samples of [Ln2O2]SO4 (Ln = Dy, Ho) compounds were prepared via an exchange solid-state reaction. The crystal structure of [Bi2CuO3]SO4 is based on alternation of continuous [Bi2CuO3]2+ layers of edge-sharing OBi2Cu2 and OBi3Cu tetrahedra and sheets of sulfate groups. Cu2+ cations are in cis position in O5Bi2Cu2 and O6Bi2Cu2 oxocentered tetrahedra in litharge slab. The crystal structure of [Ln2O2]SO4 (Ln = Dy, Ho) is completely analogous to those of grandreefite and oxysulfates of La, Sm, Eu, and Bi. Full article
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23 pages, 22182 KiB  
Article
Fedorite from Murun Alkaline Complex (Russia): Spectroscopy and Crystal Chemical Features
by Ekaterina V. Kaneva, Roman Yu. Shendrik, Tatiana A. Radomskaya and Ludmila F. Suvorova
Minerals 2020, 10(8), 702; https://doi.org/10.3390/min10080702 - 07 Aug 2020
Cited by 12 | Viewed by 3978
Abstract
Fedorite is a rare phyllosilicate, having a crystal structure characterized by SiO4-tetrahedral double layers located between continuous layers formed by edge-sharing (Ca,Na)-octahedra, and containing interlayer K, Na atoms and H2O molecules. A mineralogical-petrographic and detailed crystal-chemical study of fedorite [...] Read more.
Fedorite is a rare phyllosilicate, having a crystal structure characterized by SiO4-tetrahedral double layers located between continuous layers formed by edge-sharing (Ca,Na)-octahedra, and containing interlayer K, Na atoms and H2O molecules. A mineralogical-petrographic and detailed crystal-chemical study of fedorite specimens from three districts of the Murun alkaline complex was performed. The sequence of the crystallization of minerals in association with fedorite was established. The studied fedorite samples differ in the content of interlayer potassium and water molecules. A comparative analysis based on polyhedral characteristics and deformation parameters was carried out. For the first time, EPR, optical absorption and emission spectra were obtained for fedorite. The raspberry-red coloration of the mineral specimens could be attributed to the presence of Mn4+ ions. Full article
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12 pages, 5203 KiB  
Article
Organically Templated Layered Uranyl Molybdate [C3H9NH+]4[(UO2)3(MoO4)5] Structurally Based on Mineral-Related Modular Units
by Evgeny Nazarchuk, Dmitri Charkin, Oleg Siidra and Stepan Kalmykov
Minerals 2020, 10(8), 659; https://doi.org/10.3390/min10080659 - 25 Jul 2020
Cited by 3 | Viewed by 2262
Abstract
A new organically templated uranyl molybdate [C3H9NH+]4[(UO2)3(MoO4)5] was prepared by a hydrothermal method at 220 °C. The compound is monoclinic, Сс, a = 16.768(6), b = [...] Read more.
A new organically templated uranyl molybdate [C3H9NH+]4[(UO2)3(MoO4)5] was prepared by a hydrothermal method at 220 °C. The compound is monoclinic, Сс, a = 16.768(6), b = 20.553(8), c = 11.897(4) Å, β = 108.195(7), V = 3895(2) Å3, R1 = 0.05. The crystal structure is based upon [(UO2)3(MoO4)5]4− uranyl molybdate layers. The isopropylammonium cations are located in the interlayer. The layers in the structure of [C3H9NH+]4[(UO2)3(MoO4)5] are considered as modular architectures. Topological analysis of layers with UO2:TO4 ratio of 3:5 (TVI = S, Cr, Se, Mo) was performed. Modular description is employed to elucidate the relationships between different structural topologies of [(UO2)3(TO4)5]4− layers and inorganic uranyl-based nanotubules. The possible existence of uranyl molybdate nanotubules is discussed. Full article
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9 pages, 1521 KiB  
Article
Synthesis of Zn-Saponite Using a Microwave Circulating Reflux Method under Atmospheric Pressure
by Bing-Sheng Yu, Wei-Hsiang Hung, Jiann-Neng Fang and Yu-Ting Yu
Minerals 2020, 10(1), 45; https://doi.org/10.3390/min10010045 - 01 Jan 2020
Cited by 4 | Viewed by 2178
Abstract
Smectite is a common clay mineral in nature. Due to its tendency to swell and its strong cation exchange capacity (CEC), smectite is prevalently used in industrial and technological applications. Numerous scholars have explored smectite synthesis, which usually involves autoclaving under high pressure. [...] Read more.
Smectite is a common clay mineral in nature. Due to its tendency to swell and its strong cation exchange capacity (CEC), smectite is prevalently used in industrial and technological applications. Numerous scholars have explored smectite synthesis, which usually involves autoclaving under high pressure. However, this approach requires an array of expensive equipment, and the process consumes time and energy. This study adopted self-developed equipment to synthesize zinc saponite (Zn-saponite), a type of trioctahedral smectite, using a microwave circulating reflux method under atmospheric pressure. Compared with the conventional hydrothermal methods, the proposed method entails fewer constraints regarding the synthesis environment and can be more easily applied to large-scale synthesis. The phase purity of the synthetic product was examined using X-ray diffraction and the CEC of the product was tested. The results revealed that the microwave circulating reflux method could synthesize Zn-saponite in 16 h under atmospheric pressure, and the CEC of the product reached 120 cmol(+)/kg. In addition, the product exhibited larger basal spacing and a 32% increase in CEC compared with Zn-saponite synthesized using a hot-plate under atmospheric pressure. Full article
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16 pages, 7595 KiB  
Article
Crystal Chemistry of Chlormagaluminite, Mg4Al2(OH)12Cl2(H2O)2, a Natural Layered Double Hydroxide
by Elena S. Zhitova, Sergey V. Krivovichev, Igor V. Pekov and Vasiliy O. Yapaskurt
Minerals 2019, 9(4), 221; https://doi.org/10.3390/min9040221 - 08 Apr 2019
Cited by 13 | Viewed by 5988
Abstract
Chlormagaluminite is the only Cl-dominated hydrotalcite-supergroup mineral species with M2+:M3+ = 2:1. The holotype sample of chlormagaluminite from the Kapaevskaya volcanic pipe (Irkutsk Oblast, Siberia, Russia) has been chemically and structurally characterized. The average chemical composition of the mineral [...] Read more.
Chlormagaluminite is the only Cl-dominated hydrotalcite-supergroup mineral species with M2+:M3+ = 2:1. The holotype sample of chlormagaluminite from the Kapaevskaya volcanic pipe (Irkutsk Oblast, Siberia, Russia) has been chemically and structurally characterized. The average chemical composition of the mineral is (electron microprobe, OH content is calculated by stoichiometry and H2O from the crystal-structure data, wt. %): MgO 33.85, FeO 1.09, Al2O3 22.07, Cl 14.72, H2Otot 30.96, Cl=O −3.39, total 99.30. The empirical formula based on Mg + Al + Fe = 6 atoms per formula unit (apfu) is [Mg3.91Fe2+0.07Al2.02(OH)12]Cl2.02(H2O)2.0(2). The crystal structure has been solved from single-crystal X-ray diffraction data in the space group P63/mcm, a = 5.268(3), c = 15.297(8) Å and V = 367.6(4) Å3. The refinement converged to R1 = 0.083 on the basis of 152 unique reflections with I > 2σ(I) collected at room conditions. The powder pattern contains standard reflections of a 2H polytype and two additional reflections [(010), d010 = 4.574 Å; (110), d110 = 2.647 Å] indicative of Mg and Al ordering according to the 3 × 3 superstructure. The structure is based upon brucite-type octahedral layers with an ordered distribution of Mg and Al over octahedral sites. The Cl anions and H2O molecules reside in the interlayer, providing a three-dimensional integrity of the structure. Full article
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