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Recent Advances in Novel Compositions for Electrochemical Applications

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Materials Science".

Deadline for manuscript submissions: closed (31 July 2023) | Viewed by 19086

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Dr. Almaz A. Zagidullin

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A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 420088 Kazan, Russia
Interests: organic synthesis; organometallics; electrochemistry; homogeneous catalysis; coordination chemistry; organphosphorus compounds; functional materials; MOFs

Dr. Mikhail N. Khrizanforov

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A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 420088 Kazan, Russia
Interests: electrochemistry; solid-state electrochemistry; HOMO-LUMO; electrochemical compositions; electrochemical sensors; electrochemical energy storage; fuel cells; MOFs; electrocatalysis; coordination chemistry
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Special Issue Information

Dear Colleagues,

This Special Issue is dedicated to various approaches to the preparation and modification of compositions for electrochemical applications based on organic, inorganic compounds, and polymers (CPs, COFs, MOFs).

In the last decade, electrochemical compositions with various morphologies, which possess advanced redox, catalytic, luminescent, magnetic, and other useful properties, were prepared. Such compositions lead to the production of molecular materials such as capacitors, supercapacitors, electrochemical sensors, fuel cells, solar cells, and other electrochemical devices.

The main goal of this Special Issue on “Recent Advances in Novel Compositions for Electrochemical Applications” is to become an open and broad forum where researchers can share their research and discoveries in this promising field.

Papers related to original experimental work, theoretical studies, and review articles that investigate the compositions for electrochemical applications with the state of the art and advances are within the scope of this Topic. Research on interdisciplinary contributions offering new methodologies or ideas is especially welcome.

Dr. Almaz A. Zagidullin
Dr. Mikhail N. Khrizanforov
Guest Editors

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Keywords

electrochemistry
electrochemical compositions
electrochemical sensors
functional materials
electrochemical energy storage
fuel cells
electrocatalysis
morphology

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Published Papers (10 papers)

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Editorial

Jump to: Research

5 pages, 219 KiB

Open AccessEditorial

Recent Advances in Novel Compositions for Electrochemical Applications

by Almaz Zagidullin and Mikhail Khrizanforov

Int. J. Mol. Sci. 2023, 24(20), 15388; https://doi.org/10.3390/ijms242015388 - 20 Oct 2023

Viewed by 925

Abstract

In recent years, there has been a significant rise in innovative developments in the field of electrochemical composites [...] Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

Research

Jump to: Editorial

20 pages, 8205 KiB

Open AccessArticle

Li₃V₂(PO₄)₃ Cathode Material: Synthesis Method, High Lithium Diffusion Coefficient and Magnetic Inhomogeneity

by Tatiana Gavrilova, Yulia Deeva, Anastasiya Uporova, Tatiana Chupakhina, Ivan Yatsyk, Alexey Rogov, Mikhail Cherosov, Ruslan Batulin, Mikhail Khrizanforov and Sergey Khantimerov

Int. J. Mol. Sci. 2024, 25(5), 2884; https://doi.org/10.3390/ijms25052884 - 1 Mar 2024

Cited by 1 | Viewed by 1344

Abstract

Li₃V₂(PO₄)₃ cathodes for Li-ion batteries (LIBs) were synthesized using a hydrothermal method with the subsequent annealing in an argon atmosphere to achieve optimal properties. The X-ray diffraction analysis confirmed the material’s single-phase nature, while the scanning electron microscopy revealed a granular structure, indicating a uniform particle size distribution, beneficial for electrochemical performance. Magnetometry and electron spin resonance studies were conducted to investigate the magnetic properties, confirming the presence of the relatively low concentration and highly uniform distribution of tetravalent vanadium ions (V⁴⁺), which indicated low lithium deficiency values in the original structure and a high degree of magnetic homogeneity in the sample, an essential factor for consistent electrochemical behavior. For this pure phase Li₃V₂(PO₄)₃ sample, devoid of any impurities such as carbon or salts, extensive electrochemical property testing was performed. These tests resulted in the experimental discovery of a remarkably high lithium diffusion coefficient D = 1.07 × 10⁻¹⁰ cm²/s, indicating excellent ionic conductivity, and demonstrated impressive stability of the material with sustained performance over 1000 charge–discharge cycles. Additionally, relithiated Li₃V₂(PO₄)₃ (after multiple electrochemical cycling) samples were investigated using scanning electron microscopy, magnetometry and electron spin resonance methods to determine the extent of degradation. The combination of high lithium diffusion coefficients, a low degradation rate and remarkable cycling stability positions this Li₃V₂(PO₄)₃ material as a promising candidate for advanced energy storage applications. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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25 pages, 4146 KiB

Open AccessArticle

Hybrids of Sterically Hindered Phenols and Diaryl Ureas: Synthesis, Switch from Antioxidant Activity to ROS Generation and Induction of Apoptosis

by Elmira Gibadullina, Margarita Neganova, Yulia Aleksandrova, Hoang Bao Tran Nguyen, Alexandra Voloshina, Mikhail Khrizanforov, Thi Thu Nguyen, Ekaterina Vinyukova, Konstantin Volcho, Dmitry Tsypyshev, Anna Lyubina, Syumbelya Amerhanova, Anna Strelnik, Julia Voronina, Daut Islamov, Rakhmetulla Zhapparbergenov, Nurbol Appazov, Beauty Chabuka, Kimberley Christopher, Alexander Burilov, Nariman Salakhutdinov, Oleg Sinyashin and Igor Alabugin Show full author list Hide full author list

Int. J. Mol. Sci. 2023, 24(16), 12637; https://doi.org/10.3390/ijms241612637 - 10 Aug 2023

Cited by 5 | Viewed by 2556

Abstract

The utility of sterically hindered phenols (SHPs) in drug design is based on their chameleonic ability to switch from an antioxidant that can protect healthy tissues to highly cytotoxic species that can target tumor cells. This work explores the biological activity of a family of 45 new hybrid molecules that combine SHPs equipped with an activating phosphonate moiety at the benzylic position with additional urea/thiourea fragments. The target compounds were synthesized by reaction of iso(thio)cyanates with C-arylphosphorylated phenols containing pendant 2,6-diaminopyridine and 1,3-diaminobenzene moieties. The SHP/urea hybrids display cytotoxic activity against a number of tumor lines. Mechanistic studies confirm the paradoxical nature of these substances which combine pronounced antioxidant properties in radical trapping assays with increased reactive oxygen species generation in tumor cells. Moreover, the most cytotoxic compounds inhibited the process of glycolysis in SH-SY5Y cells and caused pronounced dissipation of the mitochondrial membrane of isolated rat liver mitochondria. Molecular docking of the most active compounds identified the activator allosteric center of pyruvate kinase M2 as one of the possible targets. For the most promising compounds, 11b and 17b, this combination of properties results in the ability to induce apoptosis in HuTu 80 cells along the intrinsic mitochondrial pathway. Cyclic voltammetry studies reveal complex redox behavior which can be simplified by addition of a large excess of acid that can protect some of the oxidizable groups by protonations. Interestingly, the re-reduction behavior of the oxidized species shows considerable variations, indicating different degrees of reversibility. Such reversibility (or quasi-reversibility) suggests that the shift of the phenol-quinone equilibrium toward the original phenol at the lower pH may be associated with lower cytotoxicity. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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21 pages, 6196 KiB

Open AccessArticle

Enhancement of Arc Erosion Resistance in AgCuO Electrical Contact Materials through Rare Earth Element Doping: First-Principles and Experimental Studies

by Haitao Wang, Yanling Wang, Jingqin Wang, Qinglong Cai and Dekao Hu

Int. J. Mol. Sci. 2023, 24(16), 12627; https://doi.org/10.3390/ijms241612627 - 10 Aug 2023

Cited by 2 | Viewed by 1564

Abstract

To investigate the stability and electrical and physical properties of undoped CuO and CuO doped with rare earth elements, electronic structures and elastic constants were calculated using first-principles density functional theory. Additionally, experimental verification was carried out on AgCuO and AgCuO-X (La, Ce, Y) electrical contacts, which were prepared using sol–gel and powder metallurgy methods. The contacts were tested under an 18 V/15 A DC resistive load using the JF04D contact material testing system. Arc parameters were analyzed, and three-dimensional surface profilometry and scanning electron microscopy were used to study the altered erosion morphology of the electrically contacted materials; moreover, the potential mechanisms behind their arc erosion behavior were investigated in depth. The results demonstrate that the doping of rare earth elements can improve the electrical conductivity and physical properties of the contacts, optimize the arc parameters, and enhance their resistance to arc erosion. Notably, AgCuO-Ce exhibited the highest electrical conductivity and the least amount of material transfer; moreover, it had excellent arc time and energy parameters, resulting in the best resistance to arc erosion. This study provides a theoretical basis for the screening of doping elements to enhance the performance of AgCuO contact materials and offers new ideas and scientific references for this field. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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15 pages, 3387 KiB

Open AccessArticle

Chemical and Electrochemical Reductions of Monoiminoacenaphthenes

by Vera V. Khrizanforova, Robert R. Fayzullin, Tatiana P. Gerasimova, Mikhail N. Khrizanforov, Almaz A. Zagidullin, Daut R. Islamov, Anton N. Lukoyanov and Yulia H. Budnikova

Int. J. Mol. Sci. 2023, 24(10), 8667; https://doi.org/10.3390/ijms24108667 - 12 May 2023

Cited by 6 | Viewed by 1981

Abstract

Redox properties of monoiminoacenaphthenes (MIANs) were studied using various electrochemical techniques. The potential values obtained were used for calculating the electrochemical gap value and corresponding frontier orbital difference energy. The first-peak-potential reduction of the MIANs was performed. As a result of controlled potential electrolysis, two-electron one-proton addition products were obtained. Additionally, the MIANs were exposed to one-electron chemical reduction by sodium and NaBH₄. Structures of three new sodium complexes, three products of electrochemical reduction, and one product of the reduction by NaBH₄ were studied using single-crystal X-ray diffraction. The MIANs reduced electrochemically by NaBH₄ represent salts, in which the protonated MIAN skeleton acts as an anion and Bu₄N⁺ or Na⁺ as a cation. In the case of sodium complexes, the anion radicals of MIANs are coordinated with sodium cations into tetranuclear complexes. The photophysical and electrochemical properties of all reduced MIAN products, as well as neutral forms, were studied both experimentally and quantum-chemically. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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10 pages, 2850 KiB

Open AccessCommunication

In-Situ Electrochemical Exfoliation and Methylation of Black Phosphorus into Functionalized Phosphorene Nanosheets

by Aidar M. Kuchkaev, Airat M. Kuchkaev, Aleksander V. Sukhov, Svetlana V. Saparina, Oleg I. Gnezdilov, Alexander E. Klimovitskii, Sufia A. Ziganshina, Irek R. Nizameev, Igor P. Asanov, Konstantin A. Brylev, Oleg G. Sinyashin and Dmitry G. Yakhvarov

Int. J. Mol. Sci. 2023, 24(4), 3095; https://doi.org/10.3390/ijms24043095 - 4 Feb 2023

Cited by 11 | Viewed by 2004

Abstract

Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most of the methods for BP functionalization with organic substrates require either the use of low-stable precursors of highly reactive intermediates or the use of difficult-to-manufacture and flammable BP intercalates. Herein we report a facile route for simultaneous electrochemical exfoliation and methylation of BP. Conducting the cathodic exfoliation of BP in the presence of iodomethane makes it possible to generate highly active methyl radicals, which readily react with the electrode’s surface yielding the functionalized material. The covalent functionalization of BP nanosheets with the P–C bond formation has been proven by various microscopic and spectroscopic methods. The functionalization degree estimated by solid-state ³¹P NMR spectroscopy analysis reached 9.7%. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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10 pages, 1469 KiB

Open AccessArticle

Non-Noble-Metal Mono and Bimetallic Composites for Efficient Electrocatalysis of Phosphine Oxide and Acetylene C-H/P-H Coupling under Mild Conditions

by Maxim V. Tarasov, Olga D. Bochkova, Tatyana V. Gryaznova, Asiya R. Mustafina and Yulia H. Budnikova

Int. J. Mol. Sci. 2023, 24(1), 765; https://doi.org/10.3390/ijms24010765 - 1 Jan 2023

Cited by 4 | Viewed by 1755

Abstract

The present work describes an efficient reaction of electrochemical phosphorylation of phenylacetylene controlled by the composition of catalytic nanoparticles based on non-noble-metals. The sought-after products are produced via the simple synthetic protocol based on room temperature, atom-economical reactions, and silica nanoparticles (SNs) loaded by one or two d-metal ions as nanocatalysts. The redox and catalytic properties of SNs can be tuned with a range of parameters, such as compositions of the bimetallic systems, their preparation method, and morphology. Monometallic SNs give phosphorylated acetylene with retention of the triple bond, and bimetallic SNs give a bis-phosphorylation product. This is the first example of acetylene and phosphine oxide C-H/P-H coupling with a regenerable and recyclable catalyst. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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11 pages, 5009 KiB

Open AccessArticle

Conductive Mediators in Oxidation Based on Ferrocene Functionalized Phosphonium Ionic Liquids

by Vadim V. Ermolaev, Liliya R. Kadyrgulova, Mikhail N. Khrizanforov, Tatiana P. Gerasimova, Gulnaz R. Baembitova, Anna A. Lazareva and Vasili A. Miluykov

Int. J. Mol. Sci. 2022, 23(24), 15534; https://doi.org/10.3390/ijms232415534 - 8 Dec 2022

Cited by 4 | Viewed by 1513

Abstract

Herein, the synthesis of ferrocene-containing salts is presented. Acylation of ferrocene (Fc) according to the Friedel–Crafts method led to ω-bromoacyl ferrocenes. The ω-bromoacyl ferrocenes were subsequently introduced to quaternization reaction with tri-tert-butyl phosphine, which resulted in phosphonium salts. Obtained phosphonium salts were characterized by physical methods. The electrochemical properties of phosphonium salts were studied by cyclic voltammetry (CV). It was found that the replacement of n-butyl fragments at the phosphorus atom by tert-butyl leads to a more anodic potential shift. In contrast to isolobal structures Fc-C(O)(CH₂)_nP⁺(n-Bu)₃X⁻ and Fc-(CH₂)_n+1P⁺(n-Bu)₃X⁻, the CV curves of Fc-C(O)(CH₂)_nP⁺(t-Bu)₃X⁻ and Fc-(CH₂)_n+1P⁺(t-Bu)₃X⁻ did not show a large discrepancy between forward and reverse currents. The transformation of the C=O groups to CH₂ fragments had a significant effect on the electrochemical properties of ferrocene salts, the oxidation potential of which is close to that of pure ferrocene. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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13 pages, 2454 KiB

Open AccessArticle

Complexes of Sodium Pectate with Nickel for Hydrogen Oxidation and Oxygen Reduction in Proton-Exchange Membrane Fuel Cells

by Irek R. Nizameev, Danis M. Kadirov, Guliya R. Nizameeva, Aigul’ F. Sabirova, Kirill V. Kholin, Mikhail V. Morozov, Lyubov’ G. Mironova, Rustem R. Zairov, Salima T. Minzanova, Oleg G. Sinyashin and Marsil K. Kadirov

Int. J. Mol. Sci. 2022, 23(22), 14247; https://doi.org/10.3390/ijms232214247 - 17 Nov 2022

Cited by 4 | Viewed by 1985

Abstract

A number of nickel complexes of sodium pectate with varied Ni²⁺ content have been synthesized and characterized. The presence of the proton conductivity, the possibility of the formation of a dense spatial network of transition metals in these coordination biopolymers, and the immobilization of transition ions in the catalytic sites of this class of compounds make them promising for proton-exchange membrane fuel cells. It has been established that the catalytic system composed of a coordination biopolymer with 20% substitution of sodium ions for divalent nickel ions, Ni (20%)-NaPG, is the leading catalyst in the series of 5, 15, 20, 25, 35% substituted pectates. Among the possible reasons for the improvement in performance the larger specific surface area of this sample compared to the other studied materials and the narrowest distribution of the vertical size of metal arrays were registered. The highest activity during CV and proximity to four-electron transfer during the catalytic cycle have also been observed for this compound. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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14 pages, 3403 KiB

Open AccessArticle

Assessment of Salt Stress to Arabidopsis Based on the Detection of Hydrogen Peroxide Released by Leaves Using an Electrochemical Sensor

by Jiancheng Zhang, Mei Lu, Han Zhou, Xihua Du and Xin Du

Int. J. Mol. Sci. 2022, 23(20), 12502; https://doi.org/10.3390/ijms232012502 - 18 Oct 2022

Cited by 5 | Viewed by 2091

Abstract

Salt stress will have a serious inhibitory effect on various metabolic processes of plant cells, this will lead to the excessive accumulation of reactive oxygen species (ROS). Hydrogen peroxide (H₂O₂) is a type of ROS that can severely damage plant cells in large amounts. Existing methods for assessing the content of H₂O₂ released from leaves under salt stress will cause irreversible damage to plant leaves and are unable to detect H₂O₂ production in real time. In this study, on the strength of a series of physiological indicators to verify the occurrence of salt stress, an electrochemical sensor for the detection of H₂O₂ released from leaves under salt stress was constructed. The sensor was prepared by using multi-walled carbon nanotube-titanium carbide–palladium (MWCNT-Ti₃C₂T_x-Pd) nanocomposite as substrate material and showed a linear response to H₂O₂ detection in the range 0.05–18 mM with a detection limit of 3.83 μM. Moreover, we measured the determination of H₂O₂ released from Arabidopsis leaves at different times of salt stress by the sensor, which was consistent with conventional method. This study demonstrates that electrochemical sensing is a desirable technology for the dynamic determination of H₂O₂ released by leaves and the assessment of salt stress to plants. Full article

(This article belongs to the Special Issue Recent Advances in Novel Compositions for Electrochemical Applications)

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