Special Issue "Metal Fluorides"

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Inorganic Solid-State Chemistry".

Deadline for manuscript submissions: closed (31 October 2018).

Special Issue Editor

Guest Editor
Prof. Dr. Erhard Kemnitz

Full University Professor, Chemistry Department, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, D-12489 Berlin, Germany
Website | E-Mail
Interests: mechanistic aspects of heterogeneously catalysed fluorination reactions, non-aqueous fluorolytic sol–gel synthesis of nanoscopic metal fluorides; nano metal fluorides as solid Lewis acids; nano metal hydroxide fluorides as biacidic Brønsted/Lewis acids and bases; metal fluoride sols for antireflective coating; inorganic–organic hybrid materials based on nano metal fluorides

Special Issue Information

Dear Colleagues,

Metal fluorides are of interest for many different applications in metallurgy, such as optical materials (e.g., solid-state lasers, luminophores, scintillators or antireflective coatings), uranium isotope separation, sensing (e.g., fluoride sensitive electrodes), and catalysis (e.g., heterogeneously catalysed fluorination reactions). An outstanding bust of interest over recent years arose from energy storage applications.

For many applications, nano metal fluorides have gained an enormous level of attraction over the past 20 years because properties of nanoscopic compounds usually differ drastically from those of classically-prepared analogues. The high potential of nanomaterials for industrial applications is the major driving force for scientists to search for new synthesis routes toward these materials. Consequently, a variety of new synthesis techniques has been developed over the past decades, which open the door to the fascinating world of new materials.

Inspired by the great potential of applications that these materials have gained, it is the intention of this Special Issue to provide an overview on several aspects of metal fluoride chemistry. This Special Issue “Metal Fluorides” in Inorganics will take stock of the efforts and results of the many groups that have made evident progress in the field of metal fluorides. 

Prof. Dr. Erhard Kemnitz
Guest Editor

Manuscript Submission Information

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Keywords

  • Metal fluorides
  • Synthesis
  • Mechanism
  • Properties
  • Metal fluoride applications
  • Nanomaterials

Published Papers (5 papers)

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Research

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Open AccessArticle
A Computational Study of AlF3 and ACF Surfaces
Inorganics 2018, 6(4), 124; https://doi.org/10.3390/inorganics6040124
Received: 18 October 2018 / Revised: 13 November 2018 / Accepted: 14 November 2018 / Published: 20 November 2018
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Abstract
By applying first principles density functional theory (DFT) methods, different metal fluorides and their surfaces have been characterized. One of the most investigated metal fluorides is AlF3 in different polymorphs. Its chloride-doped analogon AlClxF3−x (ACF) has recently attracted [...] Read more.
By applying first principles density functional theory (DFT) methods, different metal fluorides and their surfaces have been characterized. One of the most investigated metal fluorides is AlF3 in different polymorphs. Its chloride-doped analogon AlClxF3−x (ACF) has recently attracted much attention due to its application in catalysis. After presenting a summary of different first-principle studies on the bulk and surface properties of different main group fluorides, we will revisit the problem of the stability of different α -AlF3 surfaces and extend the investigation to chloride-doped counterparts to simulate the surface properties of amorphous ACF. For each material, we have considered ten different surface cuts with their respective terminations. We found that terminations of ( 01 1 ¯ 0 ) and ( 11 2 ¯ 0 ) yield the most stable surfaces for α -AlF3 and for the chlorine substituted surfaces. A potential equilibrium shape of the crystal for both α -AlF3 and ACF is visualized by a Wulff construction. Full article
(This article belongs to the Special Issue Metal Fluorides)
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Open AccessArticle
Atomic Layer Deposition of Lithium Fluoride Optical Coatings for the Ultraviolet
Received: 4 April 2018 / Revised: 26 April 2018 / Accepted: 28 April 2018 / Published: 4 May 2018
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Abstract
Lithium fluoride is an important material for ultraviolet optical systems, possessing among the largest optical bandgaps of dielectric materials. We report on the development of an atomic layer deposition (ALD) process for lithium fluoride that is capable of depositing thin films in a [...] Read more.
Lithium fluoride is an important material for ultraviolet optical systems, possessing among the largest optical bandgaps of dielectric materials. We report on the development of an atomic layer deposition (ALD) process for lithium fluoride that is capable of depositing thin films in a self-limiting manner, with an approximate deposition rate of approximately 0.15 Å per ALD cycle at a substrate temperature of 150 °C. Films are characterized by spectroscopic ellipsometry, atomic force microscopy, X-ray photoelectron spectroscopy, and far ultraviolet reflectometry. For substrate temperatures of 150 °C and greater, films showed significant microroughness with a correlated reduction in effective refractive index. This behavior was mitigated by a reduction in substrate temperature to as low as 100 °C. Films deposited on silicon substrates were subjected to long-term storage testing to evaluate the environmental sensitivity of the deposited layers. Protected aluminum mirrors were also fabricated with ALD LiF overcoats, yielding a reflectance of 84% at a wavelength of 125 nm. The performance relative to state-of-the-art LiF thin films deposited by physical vapor deposition methods is discussed, along with the prospects for future optimization. Full article
(This article belongs to the Special Issue Metal Fluorides)
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Open AccessArticle
The Melt of Sodium Nitrate as a Medium for the Synthesis of Fluorides
Received: 5 March 2018 / Revised: 23 March 2018 / Accepted: 28 March 2018 / Published: 29 March 2018
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Abstract
The preparation of NaLnF4 complexes, LnF3 (Ln = La, Ce, Y) rare earth binary fluorides, CaF2 and SrF2 alkali earth fluorides, as well as mixtures of these compounds from their nitrates dissolved in molten NaNO3 has been studied [...] Read more.
The preparation of NaLnF4 complexes, LnF3 (Ln = La, Ce, Y) rare earth binary fluorides, CaF2 and SrF2 alkali earth fluorides, as well as mixtures of these compounds from their nitrates dissolved in molten NaNO3 has been studied in order to select the ideal solvent for fluoride synthesis by spontaneous crystallization from flux. Sodium fluoride (NaF) was used as a fluorinating agent. The results of our experiments have confirmed that NaNO3 melt is one of the most promising media for precipitating said inorganic fluoride materials within a broad temperature range (300–500 °С). Also, in contrast with precipitation/co-precipitation from aqueous solutions, our syntheses have resulted in obtaining equilibrium phases only. Full article
(This article belongs to the Special Issue Metal Fluorides)
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Open AccessArticle
The Decomposition Products of Sulfur Hexafluoride (SF6) with Metals Dissolved in Liquid Ammonia
Received: 25 September 2017 / Revised: 10 October 2017 / Accepted: 11 October 2017 / Published: 13 October 2017
Cited by 2 | PDF Full-text (1989 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Sulfur hexafluoride is a highly chemically inert gas with several important industrial applications. It is stable against fused alkali, oxygen and ammonia, even at several hundred degrees Celsius. In this work, the reactions between metals (Li–Cs, Sr, Ba, Eu, Yb) dissolved in liquid [...] Read more.
Sulfur hexafluoride is a highly chemically inert gas with several important industrial applications. It is stable against fused alkali, oxygen and ammonia, even at several hundred degrees Celsius. In this work, the reactions between metals (Li–Cs, Sr, Ba, Eu, Yb) dissolved in liquid ammonia and SF6 are reported, leading to mono- or bivalent fluorides and sulfides. To this end, SF6 was passed into a cooled solution of the respective metal in liquid ammonia. The identity of the products was confirmed by powder X-ray diffraction and IR spectroscopy. The reactions could lead to a cheap and effective disposal method of the present amounts of stored SF6, for possible generation of H2S and HF. Full article
(This article belongs to the Special Issue Metal Fluorides)
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Review

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Open AccessReview
Fluorolytic Sol–Gel Synthesis of Nanometal Fluorides: Accessing New Materials for Optical Applications
Inorganics 2018, 6(4), 128; https://doi.org/10.3390/inorganics6040128
Received: 20 September 2018 / Revised: 20 November 2018 / Accepted: 28 November 2018 / Published: 3 December 2018
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Abstract
The potential of fluorolytic sol–gel synthesis for a wide variety of applications in the field of optical materials is reviewed. Based on the fluorolytic sol–gel synthesis of nanometal fluorides, sols of complex fluorometalates have become available that exhibit superior optical properties over known [...] Read more.
The potential of fluorolytic sol–gel synthesis for a wide variety of applications in the field of optical materials is reviewed. Based on the fluorolytic sol–gel synthesis of nanometal fluorides, sols of complex fluorometalates have become available that exhibit superior optical properties over known classical binary metal fluorides as, for instance, magnesium fluoride, calcium fluoride, or strontium fluoride, respectively. The synthesis of transparent sols of magnesium fluoroaluminates of the general composition MgxAlFy, and fluoroperovskites, [K1−xNax]MgF3, is reported. Antireflective coatings fabricated from MgF2, CaF2, MgxAlFy, and [K1−xNax]MgF3 sols and their relevant properties are comprehensively described. Especially the heavier alkaline earth metal fluorides and the fluorperovskites crystallizing in a cubic crystal structure are excellent hosts for rare earth (RE) metals. Thus, the second chapter reflects the synthesis approach and the properties of luminescent systems based on RE-doped alkaline earth metal fluorides and [K1−xNax]MgF3 phases. Full article
(This article belongs to the Special Issue Metal Fluorides)
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