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Solvated Metal Ions: From Solution to Solid
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Solvated Metal Ions: From Solution to Solid

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (20 May 2022) | Viewed by 17628

Special Issue Editor

Dr. Mikhail Skripkin

E-Mail Website
Guest Editor
Department of General and Inorganic Chemistry, Saint Petersburg State University, St Petersburg, Russia
Interests: solvated ions; solution structure; solution-solid transformation; solvocomplexes; acidocomplexes; ion pairs; coordination polyhedra; solubility phenomenon; vibrational spectroscopy

Special Issue Information

Dear Colleagues,

Solvated metal ions play a crucial role in different fields. They are present in natural and industrial waters, brines, biological liquids, and in different solids including functional materials like sorbents, catalysts, etc. The study of metal-solvent bonding and its dependence on the properties of interacting particles (metal ion size and charge, solvent donor number, softness of the components) is essential for the development of new methods of metal extraction from the ores, its recovery from the industrial wastes, the production of new sorbents and catalysts with optimized properties and also for the solution of some medical problems closely related to metal ion transformation both in liquids (blood, lymph) and in solids (bones). 

The analysis of literature shows that a lot of published data is concerned with the structure of solvated ions in solutions and solids. Most of them are devoted to hydrated ions; as for the non-aqueous and especially mixed solvents, those are studied to a far lesser degree. Also, in a majority of papers, only the experimental data, like the form of coordination polyhedron and bond distances, are given. The discussion of the effects of counter-ions on the solvated metal ions structures in solutions and solids is very rare. Moreover, the problem of the conditions for the preservation/modification of metal ion environment upon solution – solid transitions still remains unsolved. We hope that this issue will contribute significantly in the solution of the abovementioned problems of solution chemistry.  

Dr. Mikhail Skripkin
Guest Editor

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Keywords

  • solvated ions
  • solution structure
  • solvocomplexes
  • acidocomplexes
  • ion pairs
  • solution – solid transformation
  • solubility phenomena

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Published Papers (6 papers)

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Research

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10 pages, 2423 KiB  
Article
Sorption of 137Cs and 60Co on Titanium Oxide Films in Light Water Reactor Primary Circuit Environment
by Nikita A. Glukhoedov, Vitaliy N. Epimakhov, Sergey N. Orlov, Anastasiya A. Tsapko, Aleksandr A. Zmitrodan, Grigoriy A. Zmitrodan and Mikhail Yu. Skripkin
Materials 2022, 15(12), 4261; https://doi.org/10.3390/ma15124261 - 16 Jun 2022
Cited by 3 | Viewed by 1467
Abstract
This paper discusses the processes of the long-lived 137Cs and 60Co immobilization on titanium surfaces in simulated light water reactor primary circuit environments. This study is prompted by numerous problems in both the maintenance of equipment during reactor operation and the [...] Read more.
This paper discusses the processes of the long-lived 137Cs and 60Co immobilization on titanium surfaces in simulated light water reactor primary circuit environments. This study is prompted by numerous problems in both the maintenance of equipment during reactor operation and the dismantling of the reactor after the completion of the operation, which is associated with contamination of working surfaces with long-lived radionuclides. The composition of the oxide films formed on the surface of commercial titanium alloy ПT-3B has been studied with specimens prepared in autoclave test conditions and surface samples from the pipeline sections to which the primary coolant was applied. These films on the coolant pipeline surface consist of a titanium dioxide layer tightly adhered to the pipeline metal surface and weakly fixed deposits—crystallites comprised of titanium oxides and other corrosion products (oxides and hydrated oxides of iron, nickel, chromium etc.). The radionuclide composition of the samples was studied by gamma-spectrometry. It is shown that the mechanism of titanium-surface contamination with 137Cs is by physisorption, contamination level increases upon the presence of dispersed particles. For 60Co, both sorption and deposition onto surfaces are observed. Full article
(This article belongs to the Special Issue Solvated Metal Ions: From Solution to Solid)
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7 pages, 3077 KiB  
Article
Transparency- and Repellency-Enhanced Acrylic-Based Binder for Stimuli-Responsive Road Paint Safety Improvement Technology
by Won-Bin Lim, Ji-Hong Bae, Gyu-Hyeok Lee, Ju-Hong Lee, Jin-Gyu Min and PilHo Huh
Materials 2021, 14(22), 6829; https://doi.org/10.3390/ma14226829 - 12 Nov 2021
Cited by 3 | Viewed by 2132
Abstract
In the current study, an acrylic polymer binder applicable to road signs was successfully developed by mixing various acrylic, acrylate-type, and photoinitiator-based monomer species at different acrylate series/silicone acrylate ratios. An amorphous acrylic monomer was used, and the distance between the polymers was [...] Read more.
In the current study, an acrylic polymer binder applicable to road signs was successfully developed by mixing various acrylic, acrylate-type, and photoinitiator-based monomer species at different acrylate series/silicone acrylate ratios. An amorphous acrylic monomer was used, and the distance between the polymers was increased to improve transparency. The binder was designed with the purpose of reducing the yellowing phenomenon due to resonance by excluding the aromatic ring structure, which is the main cause of yellowing. The optical properties of the binder were determined according to the content of n-butyl methacrylate/methyl methacrylate and the composition of the crosslinking agent in the formulation. Allyl glycidyl ether and dilauroyl peroxide were used to improve the yellowing problem of benzoyl peroxide, an aromatic photoinitiator. Adding a silicone-based trivalent acrylic monomer, 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), was also found to have a significant effect on the transparency, shear properties, and water resistance of the binder. When 15 wt% TMSPMA was added, the best water repellency and mechanical properties were exhibited. The surface morphology of the improved binder and the peeling part were confirmed using field emission scanning electron microscopy. The acrylic polymer developed in this study can be applied in the coating and adhesive industries. Full article
(This article belongs to the Special Issue Solvated Metal Ions: From Solution to Solid)
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12 pages, 2898 KiB  
Article
Structures, Bonding and Sensor Properties of Some Alkaline o-Phthalatocuprates
by Sergey V. Gladnev, Mikhail V. Grigoryev, Mariya A. Kryukova, Evgenia M. Khairullina, Ilya I. Tumkin, Nikita A. Bogachev, Andrey S. Mereshchenko and Mikhail Y. Skripkin
Materials 2021, 14(19), 5548; https://doi.org/10.3390/ma14195548 - 24 Sep 2021
Viewed by 1856
Abstract
Comprehensive study of the structure and bonding of disodium, dipotassium and diammonium di-o-phthalatocuprates(II) dihydrates has been undertaken. The crystal structure of ammonium o-phthalatocuprate has been determined. The identity of structures of phthalatocuprate chains in potassium and ammonium salts [...] Read more.
Comprehensive study of the structure and bonding of disodium, dipotassium and diammonium di-o-phthalatocuprates(II) dihydrates has been undertaken. The crystal structure of ammonium o-phthalatocuprate has been determined. The identity of structures of phthalatocuprate chains in potassium and ammonium salts has been revealed. Vibrational spectra of all three compounds have been recorded, and the assignment of vibrational bands has been made. Force field calculations have shown a minor effect of outer-sphere cations (Na+, K+, NH4+) on both intraligand (C-O) and metal–ligand bond strengths. Synthesized compounds have been tested as electrochemical sensors on D-glucose, dopamine and paracetamol. Their sensitivity to analytes varied in the order of Na+ > K+ > NH4+. This effect has been explained by the more pronounced steric hindrance of copper ions in potassium and ammonium salts. Full article
(This article belongs to the Special Issue Solvated Metal Ions: From Solution to Solid)
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19 pages, 4541 KiB  
Article
Dendritic Iron(III) Carbazole Complexes: Structural, Optical, and Magnetic Characteristics
by Matvey Gruzdev, Ulyana Chervonova, Arkadiy Kolker, Nadezhda Fomina, Ekaterina Zueva, Valerya Vorobeva, Denis Starichenko and Alexander Korolev
Materials 2021, 14(18), 5445; https://doi.org/10.3390/ma14185445 - 20 Sep 2021
Cited by 7 | Viewed by 2285
Abstract
This paper focuses on the synthesis, structural characterization, and study of the optical, magnetic, and thermal properties of novel architectures combining metal ions as magnetoactive centers and photoactive blocks formed by carbazole units. For this purpose, a series of azomethine complexes of the [...] Read more.
This paper focuses on the synthesis, structural characterization, and study of the optical, magnetic, and thermal properties of novel architectures combining metal ions as magnetoactive centers and photoactive blocks formed by carbazole units. For this purpose, a series of azomethine complexes of the composition [Fe(L)2]X (L = 3,6-bis[(3′,6′-di-tert-butyl-9-carbazol)-9-carbazol]benzoyloxy-4-salicylidene-N′-ethyl-N-ethylenediamine, X = NO3−, Cl−, PF6−) were synthesized by the reaction of metal salts with Schiff bases in a mixture of solvents. The UV–Vis absorption properties were studied in dichloromethane and rationalized via time-dependent density functional theory (DFT) calculations. Upon excitation at 350 nm, the compounds exhibited an intense dual fluorescence with two emission bands centered at ~445 and ~485 nm, which were assigned to πcarb–π* intraligand and πcarb–dFe ligand-to-metal charge-transfer excited states. EPR spectroscopy and SQUID magnetometry revealed solid-state partial spin crossover in some compounds, and antiferromagnetic interactions between the neighboring Fe(III) ions. Full article
(This article belongs to the Special Issue Solvated Metal Ions: From Solution to Solid)
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14 pages, 835 KiB  
Article
Thermodynamic Description of Dilution and Dissolution Processes in the MgCl2−CsCl−H2O Ternary System
by Valeriia Baranauskaite, Maria Belysheva, Olga Pestova, Yuri Anufrikov, Mikhail Skripkin, Yuri Kondratiev and Vassily Khripun
Materials 2021, 14(14), 4047; https://doi.org/10.3390/ma14144047 - 20 Jul 2021
Cited by 2 | Viewed by 2813
Abstract
Thermodynamic data on the properties of the water-based electrolyte systems are very valuable for fundamental physical chemistry and for industrial applications. The missing data both on the dilution and dissolution enthalpies for the ternary CsCl−MgCl2−H2O mixed electrolyte system were [...] Read more.
Thermodynamic data on the properties of the water-based electrolyte systems are very valuable for fundamental physical chemistry and for industrial applications. The missing data both on the dilution and dissolution enthalpies for the ternary CsCl−MgCl2−H2O mixed electrolyte system were investigated by means of the calorimetry method. The dilution calorimetry was performed at 298 K for the set of solutions from diluted to concentrated at constant ratio Cs+/Mg2+=1.8. The relative partial molar enthalpies, ideal, total, and excess ones were calculated. By means of the dissolution calorimetry, the standard enthalpies of formation, the enthalpies, and entropies for the double salt formation from simple salts were evaluated. The results obtained indicate that entropy as the major factor affecting the formation of the joint compound, both in the liquid and solid phases. These data can be implemented in thermodynamic databases and allow for accurate thermodynamic calculations for the salts extraction from natural water sources and for its possible application as thermochemical energy storage. Full article
(This article belongs to the Special Issue Solvated Metal Ions: From Solution to Solid)
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Review

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26 pages, 5326 KiB  
Review
Dielectric Characteristics, Electrical Conductivity and Solvation of Ions in Electrolyte Solutions
by Vladimir V. Shcherbakov, Yuliya M. Artemkina, Irina A. Akimova and Irina M. Artemkina
Materials 2021, 14(19), 5617; https://doi.org/10.3390/ma14195617 - 27 Sep 2021
Cited by 39 | Viewed by 5657
Abstract
Solvation and association of ions in solutions largely depend on the dielectric properties of the solvent, the distance between ions in solutions, and temperature. This paper considers the effect of temperature on static dielectric constant (DC), dipole dielectric relaxation (DR) time, and limiting [...] Read more.
Solvation and association of ions in solutions largely depend on the dielectric properties of the solvent, the distance between ions in solutions, and temperature. This paper considers the effect of temperature on static dielectric constant (DC), dipole dielectric relaxation (DR) time, and limiting (ultimate) high frequency (HF) electrical conductivity (EC) of water and some polar solvents. In the investigated temperature range (0–370 °C), the static DC and DR time of water decrease, and limiting HF EC passes through a maximum at 250–300 °C with temperature growth. The dielectric characteristics of methanol, ethanol, and propanol behave in a similar way. It is shown that the existence of an HF EC temperature maximum is due to the different nature of the temperature dependences of DC and DR time. It is suggested that the same dependences are responsible for the presence of a maximum in the temperature dependences of the dissociation degree and the ionic product of water. The influence of non-electrolytes concentration as well as metal salts on the dielectric properties of their aqueous solutions is considered. The limiting HF EC of water determines the specific EC value of aqueous electrolyte solutions. Analysis of the absorption of microwave energy by polar solvents, as well as aqueous solutions of non-electrolytes and electrolytes, at a frequency of 2455 MHz is carried out. The optimal conditions for high-frequency heating of solutions have been established. The distance between ions in aqueous solutions of inorganic salts and in non-aqueous solutions of ionic liquids is calculated. It is shown that the maximum on the concentration dependence of the specific EC can be related to ions association. Full article
(This article belongs to the Special Issue Solvated Metal Ions: From Solution to Solid)
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