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Inorganics
Volume 10
Issue 4
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Inorganics, Volume 10, Issue 4 (April 2022) – 16 articles

Cover Story (view full-size image): We have investigated a class of Schiff base oxidovanadium (V) complexes containing ligands with the potential to inhibit the growth of a representative bacterium, Mycobacterium smegmatis. An anticancerous, non-toxic Schiff base vanadium complex, the most potent of several related complexes, was, nevertheless, only a weak growth inhibitor, while free catecholates were more potent inhibitors of Mycobacterium smegmatis growth. Spectroscopic methods verified whether complexes remained intact in the cell culture medium used to evaluate vanadium complex effects on bacterial growth.  Together, these studies suggested that hydrophobicity and steric properties of vanadium-complexes were critical to their anticancer activity and bacterial toxicity. View this paper.
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19 pages, 4015 KiB  
Review
Size Dependent Properties of Reactive Materials
by Deepshikha Shekhawat, Maximilian Vauth and Jörg Pezoldt
Inorganics 2022, 10(4), 56; https://doi.org/10.3390/inorganics10040056 - 18 Apr 2022
Cited by 12 | Viewed by 4148
Abstract
The nature of the self-sustained reaction of reactive materials is dependent on the physical, thermal, and mechanical properties of the reacting materials. These properties behave differently at the nano scale. Low-dimensional nanomaterials have various unusual size dependent transport properties. In this review, we [...] Read more.
The nature of the self-sustained reaction of reactive materials is dependent on the physical, thermal, and mechanical properties of the reacting materials. These properties behave differently at the nano scale. Low-dimensional nanomaterials have various unusual size dependent transport properties. In this review, we summarize the theoretical and experimental reports on the size effect on melting temperature, heat capacity, reaction enthalpy, and surface energy of the materials at nano scale because nanomaterials possess a significant change in large specific surface area and surface effect than the bulk materials. According to the theoretical analysis of size dependent thermodynamic properties, such as melting temperature, cohesive energy, thermal conductivity and specific heat capacity of metallic nanoparticles and ultra-thin layers varies linearly with the reciprocal of the critical dimension. The result of this scaling relation on the material properties can affect the self-sustained reaction behavior in reactive materials. Resultant, powder compacts show lower reaction propagation velocities than bilayer system, if the particle size of the reactants and the void density is decreased an increase of the reaction propagation velocity due to an enhanced heat transfer in reactive materials can be achieved. Standard theories describing the properties of reactive material systems do not include size effects. Full article
(This article belongs to the Section Inorganic Materials)
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16 pages, 3762 KiB  
Article
Supramolecular Frameworks and a Luminescent Coordination Polymer from New β-Diketone/Tetrazole Ligands
by Delia Blasi, Pierluigi Mercandelli and Lucia Carlucci
Inorganics 2022, 10(4), 55; https://doi.org/10.3390/inorganics10040055 - 18 Apr 2022
Cited by 3 | Viewed by 2311
Abstract
Mixed multidentate linkers with donor groups of different types can be fruitfully exploited in the self-assembly of coordination polymers (CPs) and Metal-Organic Frameworks (MOFs). In this work we develop new ligands containing a β-diketone chelating functionality, to better control the stereochemistry at the [...] Read more.
Mixed multidentate linkers with donor groups of different types can be fruitfully exploited in the self-assembly of coordination polymers (CPs) and Metal-Organic Frameworks (MOFs). In this work we develop new ligands containing a β-diketone chelating functionality, to better control the stereochemistry at the metal center, and tetrazolyl multidentate bridging groups, a combination not yet explored for networking with metal ions. The new ligands, 1,3-bis(4-(1H-tetrazol-5-yl)phenyl)-1,3-propanedione (H3L1) and 1-phenyl-3-(4-(1H-tetrazol-5-yl)phenyl)-1,3-propanedione (H2L2), are synthesized from the corresponding nitrile precursors by [2+3] dipolar cycloaddition of azide under metal-free catalytic conditions. Crystal structure analysis evidences the involvement of tetrazolyl fragments in multiple hydrogen bonding giving 2D and 1D supramolecular frameworks. Reactivity of the new ligands with different metal salts indicates good coordinating ability, and we report the preparation and structural characterization of the tris–chelate complex [Fe(HL1)3]3− (1) and the homometallic 2D CP [ZnL2(DMSO)] (2). In compound 1 only the diketonate donor is used, whereas the partially deprotonated tetrazolyl groups are involved in hydrogen bonding, giving rise to a 2D supramolecular framework of (6,3)IIa topological type. In compound 2 the ligand is completely deprotonated and uses both the diketonate donor (chelating) and the tetrazolate fragment (bridging) to coordinate the Zn(II) ions. The resulting neutral 2D network of sql topology shows luminescence in the solid state, which is red shifted with respect to the free ligand. Interestingly, it can be easily exfoliated in water to give a luminescent colloidal solution. Full article
(This article belongs to the Special Issue Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher)
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9 pages, 2147 KiB  
Article
Enhanced Photocatalytic Activity of WS2/TiO2 Nanofibers for Degradation of Phenol under Visible Light Irradiation
by Engy Ahmed Nada, Heba Hassan El-Maghrabi, Patrice Raynaud, Hager Rabea Ali, Saad Abd El-Wahab, Dina Yahea Sabry, Yasser Mohamed Moustafa and Amr Ahmed Nada
Inorganics 2022, 10(4), 54; https://doi.org/10.3390/inorganics10040054 - 18 Apr 2022
Cited by 19 | Viewed by 2814
Abstract
Binary composite WS2/TiO2 nanofibers (WTN) were elaborated by electrospinning technique. The photocatalytic efficiency of the binary nanofibers was changed via different ratios between WS2 and TiO2. The structural, morphological and optical properties of the prepared nanofibers were [...] Read more.
Binary composite WS2/TiO2 nanofibers (WTN) were elaborated by electrospinning technique. The photocatalytic efficiency of the binary nanofibers was changed via different ratios between WS2 and TiO2. The structural, morphological and optical properties of the prepared nanofibers were evaluated by Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and UV-Vis diffuse reflectance spectroscopy (UV-vis/DRS), respectively. The prepared nanofibers showed a remarkable performance in photocatalytic efficiency of phenol compound degradation under visible light. WTN nanofibers showed superior photocatalytic activity (83%) and high stability of several cycles under visible light. Therefore, WS2/TiO2 nanofibers have great prospects for the treatment of wastewater from toxic organic contamination due to their excellent photocatalytic performance reusability and recyclability. Full article
(This article belongs to the Section Inorganic Materials)
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11 pages, 15181 KiB  
Article
Electrocatalyst Derived from NiCu–MOF Arrays on Graphene Oxide Modified Carbon Cloth for Water Splitting
by Lisha Jia, Pawel Wagner and Jun Chen
Inorganics 2022, 10(4), 53; https://doi.org/10.3390/inorganics10040053 - 13 Apr 2022
Cited by 9 | Viewed by 3376
Abstract
Electrocatalysts are capable of transforming water into hydrogen, oxygen, and therefore into energy, in an environmentally friendly and sustainable manner. However, the limitations in the research of high performance catalysts act as an obstructer in the development of using water as green energy. [...] Read more.
Electrocatalysts are capable of transforming water into hydrogen, oxygen, and therefore into energy, in an environmentally friendly and sustainable manner. However, the limitations in the research of high performance catalysts act as an obstructer in the development of using water as green energy. Here, we report on a delicate method to prepare novel bimetallic metal organic framework derived electrocatalysts (C–NiCu–BDC–GO–CC) using graphene oxide (GO) modified carbon cloth as a 3D flexible and conductive substrate. The resultant electrocatalyst, C–NiCu–BDC–GO–CC, exhibited very low electron transfer resistance, which benefited from its extremely thin 3D sponge-like morphology. Furthermore, it showed excellent oxygen evolution reaction (OER) activity, achieving 10 mA/cm2 at a low overpotential of 390 mV in 1 M KOH electrolyte with a remarkable durability of 10 h. Full article
(This article belongs to the Section Inorganic Materials)
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21 pages, 2231 KiB  
Review
The Intriguing Role of Iron-Sulfur Clusters in the CIAPIN1 Protein Family
by Simone Ciofi-Baffoni and Claudia Andreini
Inorganics 2022, 10(4), 52; https://doi.org/10.3390/inorganics10040052 - 13 Apr 2022
Cited by 2 | Viewed by 3302
Abstract
Iron-sulfur (Fe/S) clusters are protein cofactors that play a crucial role in essential cellular functions. Their ability to rapidly exchange electrons with several redox active acceptors makes them an efficient system for fulfilling diverse cellular needs. They include the formation of a relay [...] Read more.
Iron-sulfur (Fe/S) clusters are protein cofactors that play a crucial role in essential cellular functions. Their ability to rapidly exchange electrons with several redox active acceptors makes them an efficient system for fulfilling diverse cellular needs. They include the formation of a relay for long-range electron transfer in enzymes, the biosynthesis of small molecules required for several metabolic pathways and the sensing of cellular levels of reactive oxygen or nitrogen species to activate appropriate cellular responses. An emerging family of iron-sulfur cluster binding proteins is CIAPIN1, which is characterized by a C-terminal domain of about 100 residues. This domain contains two highly conserved cysteine-rich motifs, which are both involved in Fe/S cluster binding. The CIAPIN1 proteins have been described so far to be involved in electron transfer pathways, providing electrons required for the biosynthesis of important protein cofactors, such as Fe/S clusters and the diferric-tyrosyl radical, as well as in the regulation of cell death. Here, we have first investigated the occurrence of CIAPIN1 proteins in different organisms spanning the entire tree of life. Then, we discussed the function of this family of proteins, focusing specifically on the role that the Fe/S clusters play. Finally, we describe the nature of the Fe/S clusters bound to CIAPIN1 proteins and which are the cellular pathways inserting the Fe/S clusters in the two cysteine-rich motifs. Full article
(This article belongs to the Special Issue Assembly and Reactivity of Iron–Sulfur Clusters)
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16 pages, 2828 KiB  
Article
Reduction of Hf via Hf/Zr Substitution in Mechanically Alloyed (Hf,Ti)CoSb Half-Heusler Solid Solutions
by Ioanna Ioannou, Andreas Delimitis, Yaniv Gelbstein and Theodora Kyratsi
Inorganics 2022, 10(4), 51; https://doi.org/10.3390/inorganics10040051 - 13 Apr 2022
Cited by 6 | Viewed by 2266
Abstract
(Hf,Zr,Ti)Co(Sb,Sn) Solid solutions were prepared by mechanical-alloying followed by hot-press method as an attempt to reduce Hf concentration and therefore the material’s cost without negatively affecting the thermoelectric performance. To this end, two different methods were applied: (a) Hf substitution with its lighter [...] Read more.
(Hf,Zr,Ti)Co(Sb,Sn) Solid solutions were prepared by mechanical-alloying followed by hot-press method as an attempt to reduce Hf concentration and therefore the material’s cost without negatively affecting the thermoelectric performance. To this end, two different methods were applied: (a) Hf substitution with its lighter and cheaper homologue Zr; and (b) fine tuning of carrier concentration by the substitution of Sb with Sn. The isoelectronic substitution of Hf with Zr was investigated in Hf0.6-xZrxTi0.4CoSb0.8Sn0.2 solid solutions and resulted in lower power factors and ZTs. However, the low thermal conductivity of Hf0.4Zr0.2Ti0.4CoSb0.8Sn0.2 contributed in achieving a relatively good ZT~0.67 at 970 K. The effect of charge carrier concentration was investigated by preparing Hf0.4Zr0.2Ti0.4CoSb1-ySny (y = 0.15–0.25) compounds. Hf0.4Zr0.2Ti0.4CoSb0.83Sn0.17 composition prepared by six hours milling reached the highest ZT of 0.77 at 960 K. Full article
(This article belongs to the Special Issue Advances of Thermoelectric Materials)
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22 pages, 3358 KiB  
Article
Exploring Growth of Mycobacterium smegmatis Treated with Anticarcinogenic Vanadium Compounds
by Zeyad Arhouma, Heide A. Murakami, Jordan T. Koehn, Xiaorong Li, Deborah A. Roess, Dean C. Crick and Debbie C. Crans
Inorganics 2022, 10(4), 50; https://doi.org/10.3390/inorganics10040050 - 2 Apr 2022
Cited by 9 | Viewed by 2875
Abstract
A major problem with patient treatments using anticancer compounds is accompanying bacterial infections, which makes more information on how such compounds impact bacterial growth desirable. In the following study, we investigated the growth effects of an anticancerous non-toxic Schiff base oxidovanadium(V) complex ( [...] Read more.
A major problem with patient treatments using anticancer compounds is accompanying bacterial infections, which makes more information on how such compounds impact bacterial growth desirable. In the following study, we investigated the growth effects of an anticancerous non-toxic Schiff base oxidovanadium(V) complex (N-(salicylideneaminato)-N′-(2-hydroxyethyl)ethane-1,2-diamine) coordinated to the 3,5-di-tert-butylcatecholato ligand on a representative bacterium, Mycobacterium smegmatis (M. smeg). We prepared the Schiff base V-complexes as reported previously and selected a few complexes to develop a V-complex series. Biological studies of M. smeg growth inhibition were complemented by spectroscopic studies using UV-Vis spectrophotometry and NMR spectroscopy to determine which complexes were intact under biologically relevant conditions. We specifically chose to examine (1) the growth effects of Schiff base oxidovanadium complexes coordinated to a catechol, (2) the growth effects of respective free catecholates on M. smeg, and (3) to identify complexes where the metal coordination complex was more potent than the ligand alone under biological conditions. Results from these studies showed that the observed effects of Schiff base V-catecholate complex are a combination of catechol properties including toxicity, hydrophobicity, and sterics. Full article
(This article belongs to the Special Issue Metal-Based Anticancer Drugs)
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10 pages, 3809 KiB  
Article
The Flower-like Co3O4 Hierarchical Microspheres for Methane Catalytic Oxidation
by Changpeng Lv, Dan Du, Chao Wang, Yingyue Qin, Jinlong Ge, Yansong Han, Junjie Zhu and Muxin Liu
Inorganics 2022, 10(4), 49; https://doi.org/10.3390/inorganics10040049 - 2 Apr 2022
Cited by 2 | Viewed by 2411
Abstract
The development of non-noble Co3O4 catalysts exposing highly active crystal planes to low-temperature methane oxidation is still a challenge. Hence, a facile solvothermal method was adapted to construe flower-like Co3O4 hierarchical microspheres (Co3O4-FL), [...] Read more.
The development of non-noble Co3O4 catalysts exposing highly active crystal planes to low-temperature methane oxidation is still a challenge. Hence, a facile solvothermal method was adapted to construe flower-like Co3O4 hierarchical microspheres (Co3O4-FL), which are composed of nanosheets with dominantly exposed {112} crystal planes. The flower-like hierarchical structure not only promotes the desorption of high levels of active surface oxygen and enhances reducibility, but also facilitates an increase in lattice oxygen as the active species. As a result, Co3O4-FL catalysts offer improved methane oxidation, with a half methane conversion temperature (T50) of 380 °C (21,000 mL g−1 h−1), which is much lower than that of commercial Co3O4 catalysts (Co3O4-C). This study will provide guidance for non-noble metal catalyst design and preparation for methane oxidation and other oxidative reactions. Full article
(This article belongs to the Section Inorganic Materials)
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19 pages, 6862 KiB  
Article
An Experimental and Theoretical Study of the Optical Properties of (C2H7N4O)2BiCl5 for an Optoelectronic Application
by Hela Ferjani, Youssef Ben Smida, Damian C. Onwudiwe, Nuha Y. Elamin, Safa Ezzine and Norah S. Almotlaq
Inorganics 2022, 10(4), 48; https://doi.org/10.3390/inorganics10040048 - 1 Apr 2022
Cited by 6 | Viewed by 2342
Abstract
This study explores the electronic properties of (C2H7N4O)2BiCl5 using the density functional theory (DFT) method, which was compared with the experimental data. The band structure of the compound indicated that it is a direct [...] Read more.
This study explores the electronic properties of (C2H7N4O)2BiCl5 using the density functional theory (DFT) method, which was compared with the experimental data. The band structure of the compound indicated that it is a direct semiconductor with a band gap energy of 3.54 eV, which was comparable with the value (3.20 eV) obtained experimentally from the UV–vis spectroscopy. The density of state study showed that the conduction band was formed mainly by Bi 6p, C 2p, and N 2p states, while the valence band was formed mainly by Cl 2p, O 2p, and N 2p states. Hirshfeld surface analysis and enrichment ratio (E) were further used to investigate and quantify the intermolecular interactions within the compound. These studies established that the most important role in the stability of the structure of this crystalline material was provided by hydrogen bonding and π–π stacking interactions. The crystalline morphology of the compound was determined using BFDH simulation, based on the single-crystal structure result. Furthermore, Fourier transform infrared spectroscopy (FTIR) was used to study the vibrational modes of carbamoyl-ganidinium cations. The charge transfer process within the anionic chains of [BiCl5]∝, studied using photoluminescence spectroscopy, resulted in a broad emission band with two positions of maxima centered at 336 and 358 nm. This work offers a good understanding of the optical, structural, as well as the electrical properties of (C2H7N4O)2BiCl5, which are necessary in its applications in areas such as multifunctional magnetic, optoelectronic, and photonic systems. Full article
(This article belongs to the Special Issue Semiconductor Light-Emitting Chip: Structure, Design and Synthesis)
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11 pages, 1517 KiB  
Review
An Overview of Vanadium and Cell Signaling in Potential Cancer Treatments
by Valeria Alejandra Ferretti and Ignacio Esteban León
Inorganics 2022, 10(4), 47; https://doi.org/10.3390/inorganics10040047 - 1 Apr 2022
Cited by 27 | Viewed by 3989
Abstract
Vanadium is an ultratrace element present in higher plants, animals, algae, and bacteria. In recent years, vanadium complexes have been studied to be considered as a representative of a new class of nonplatinum metal anticancer drugs. Nevertheless, the study of cell signaling pathways [...] Read more.
Vanadium is an ultratrace element present in higher plants, animals, algae, and bacteria. In recent years, vanadium complexes have been studied to be considered as a representative of a new class of nonplatinum metal anticancer drugs. Nevertheless, the study of cell signaling pathways related to vanadium compounds has scarcely been reported on and reviewed thus far; this information is highly critical for identifying novel targets that play a key role in the anticancer activity of these compounds. Here, we perform a review of the activity of vanadium compounds over cell signaling pathways on cancer cells and of the underlying mechanisms, thereby providing insight into the role of these proteins as potential new molecular targets of vanadium complexes. Full article
(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)
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15 pages, 5594 KiB  
Article
Synergistic Effect of Co and Mn Co-Doping on SnO2 Lithium-Ion Anodes
by Adele Birrozzi, Angelo Mullaliu, Tobias Eisenmann, Jakob Asenbauer, Thomas Diemant, Dorin Geiger, Ute Kaiser, Danilo Oliveira de Souza, Thomas E. Ashton, Alexandra R. Groves, Jawwad A. Darr, Stefano Passerini and Dominic Bresser
Inorganics 2022, 10(4), 46; https://doi.org/10.3390/inorganics10040046 - 1 Apr 2022
Cited by 6 | Viewed by 3102
Abstract
The incorporation of transition metals (TMs) such as Co, Fe, and Mn into SnO2 substantially improves the reversibility of the conversion and the alloying reaction when used as a negative electrode active material in lithium-ion batteries. Moreover, it was shown that the [...] Read more.
The incorporation of transition metals (TMs) such as Co, Fe, and Mn into SnO2 substantially improves the reversibility of the conversion and the alloying reaction when used as a negative electrode active material in lithium-ion batteries. Moreover, it was shown that the specific benefits of different TM dopants can be combined when introducing more than one dopant into the SnO2 lattice. Herein, a careful characterization of Co and Mn co-doped SnO2 via transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray diffraction including Rietveld refinement is reported. Based on this in-depth investigation of the crystal structure and the distribution of the two TM dopants within the lattice, an ex situ X-ray photoelectron spectroscopy and ex situ X-ray absorption spectroscopy were performed to better understand the de-/lithiation mechanism and the synergistic impact of the Co and Mn co-doping. The results specifically suggest that the antithetical redox behaviour of the two dopants might play a decisive role for the enhanced reversibility of the de-/lithiation reaction. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Professor Michel Armand on the Occasion of His 75th Birthday)
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11 pages, 3619 KiB  
Article
Ionic Conductivity of LiSiON and the Effect of Amorphization/Heterovalent Doping on Li+ Diffusion
by Siyuan Wu, Ruijuan Xiao, Hong Li and Liquan Chen
Inorganics 2022, 10(4), 45; https://doi.org/10.3390/inorganics10040045 - 31 Mar 2022
Cited by 2 | Viewed by 2810
Abstract
The search for and design of suitable superior lithium ion conductors is a key process for developing solid state batteries. In order to realize a large range of applications, we researched the ionic conductivity of LiSiON, an example oxynitride mainly composed of elements [...] Read more.
The search for and design of suitable superior lithium ion conductors is a key process for developing solid state batteries. In order to realize a large range of applications, we researched the ionic conductivity of LiSiON, an example oxynitride mainly composed of elements with high abundance and a similar mixed anion size. Both its amorphous and heterovalent-doped phases were studied through density functional theory simulations. The Li+ ion diffusion behaviors and related properties are discussed. These elements are abundant in nature, and we found that amorphization or doping with P obviously enhanced the ionic conductivity of the system. General strategies to improve the kinetic properties of a candidate structure are presented, to help in the design of solid state electrolytes for lithium batteries. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Professor Michel Armand on the Occasion of His 75th Birthday)
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12 pages, 3380 KiB  
Article
A Simple Method to Obtain Protective Film against Acid Rain
by Ana-Maria Mocioiu, Diana-Irinel Băilă, Cosmin Iulian Codrea and Oana Cătălina Mocioiu
Inorganics 2022, 10(4), 44; https://doi.org/10.3390/inorganics10040044 - 31 Mar 2022
Cited by 2 | Viewed by 2814
Abstract
Acid rain is a major problem for animals, plants, buildings, and also for the top glass of photovoltaic (PV) solar panels and greenhouses. Air pollutants such as NOx, NH3, and H2S can mix with water in the atmosphere to [...] Read more.
Acid rain is a major problem for animals, plants, buildings, and also for the top glass of photovoltaic (PV) solar panels and greenhouses. Air pollutants such as NOx, NH3, and H2S can mix with water in the atmosphere to form acid rain. It was discovered that atmospheric water vapor adsorbed on the surface of glass can also lead to corrosion of the glass surface. The purpose of this work is to obtain a protective film for glasses used in different domains such as solar cells, windows, stained glass windows from historical buildings, etc. Thin film deposited on glass must be protective against acid rain, transparent in the visible domain with a band gap up to 3.2 eV, and have a vitreous structure (glass). Electron beam (e-gun) technology is a deposition technique for producing high-purity and dense coatings in a short time. It is well known that Ta2O5 is an oxide with anticorrosive properties, but it is expensive and cannot form glass by itself. ZnO is an oxide known as a glass former, exhibiting good optical properties. In this paper, a thin film obtained by the deposition of ZnO and Ta2O5 on a glass substrate using e-gun technology are studied. The simulated acid rain effect on the structure, morphology, and optical properties of thin films are studied after a 65% nitric acid attack on the surface. The X-ray diffraction (XRD) pattern shows the vitreous state of the thin film with a composition 50%ZnO 50%Ta2O5 before and after the acid attack. The morphology, composition, and thickness of the film are investigated using scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) and profilometry. Full article
(This article belongs to the Special Issue Novel Functional Ceramics)
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13 pages, 1178 KiB  
Article
Transition Metal Complexes of Schiff Base Ligands Prepared from Reaction of Aminobenzothiazole with Benzaldehydes
by Mahmoud Sunjuk, Lana Al-Najjar, Majed Shtaiwi, Bassam El-Eswed, Mousa Al-Noaimi, Luay Al-Essa and Kamal Sweidan
Inorganics 2022, 10(4), 43; https://doi.org/10.3390/inorganics10040043 - 30 Mar 2022
Cited by 24 | Viewed by 6427
Abstract
Schiff bases have played significant roles in the development of inorganic or coordination chemistry. Three Schiff base (NB, CB and HB) ligands, prepared for the reaction of 2-amino-6-methoxy-benzothiazole with 2-Nitrobenzaldehyde, 2-chlorobenzaldehyde and 2,4-Dihydroxybenzaldehyed, respectively, were investigated for their transition metal complexes, which were [...] Read more.
Schiff bases have played significant roles in the development of inorganic or coordination chemistry. Three Schiff base (NB, CB and HB) ligands, prepared for the reaction of 2-amino-6-methoxy-benzothiazole with 2-Nitrobenzaldehyde, 2-chlorobenzaldehyde and 2,4-Dihydroxybenzaldehyed, respectively, were investigated for their transition metal complexes, which were prepared by reacting the ligand (2:1 molar ratio) with Co(II), Ni(II), Cu(II), Cd(II), Cr(III) and Fe(III) chlorides. The nature of the interaction between the metal ions and ligands (L) was studied with the aid of magnetic susceptibility, elemental analysis, FTIR and 1H-NMR spectroscopy. Based on the magnetic superstability and elemental analysis results, octahedral structures of the complexes, such as [ML2Cl2] or [ML2Cl(OH)], were proposed for Cu(II), Cd(II), Co(II) and Ni(II) in which the ligand (L:NB, CB or HB) is bidentate through the azomethine and benzothiazole nitrogen. For Cr(III) and Fe(III) complexes, octahedral ML2Cl(OH)2 or ML2(OH)3 structures were proposed, where one ligand is monodentate and the other is bidentate. The azomethine ν(-HC=N-) and 1H-NMR peaks of NB and CB were shifted to a higher frequency and downfield, respectively, upon complexation with metal ions. The bonding of OH groups of HB to Co(II), Cu(II) and Ni(II) enables π-backdonation from these metals to the azomethine of Schiff bases and the consequent shift of ν(-HC=N-) to a lower frequency and changes in the intensity of the 1H-NMR peak of OH. On the other hand, this backdonation was not evidenced in the FTIR of HB complexes with high-charge Cr(III) and Fe(III) ions. Full article
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12 pages, 2895 KiB  
Article
Enabling Stable Interphases via In Situ Two-Step Synthetic Bilayer Polymer Electrolyte for Solid-State Lithium Metal Batteries
by Ying Liu, Fang Fu, Chen Sun, Aotian Zhang, Hong Teng, Liqun Sun and Haiming Xie
Inorganics 2022, 10(4), 42; https://doi.org/10.3390/inorganics10040042 - 29 Mar 2022
Cited by 8 | Viewed by 2998
Abstract
Poly(ethylene oxide) (PEO)-based electrolyte is considered to be one of the most promising polymer electrolytes for lithium metal batteries. However, a narrow electrochemical stability window and poor compatibility at electrode-electrolyte interfaces restrict the applications of PEO-based electrolyte. An in situ synthetic double-layer polymer [...] Read more.
Poly(ethylene oxide) (PEO)-based electrolyte is considered to be one of the most promising polymer electrolytes for lithium metal batteries. However, a narrow electrochemical stability window and poor compatibility at electrode-electrolyte interfaces restrict the applications of PEO-based electrolyte. An in situ synthetic double-layer polymer electrolyte (DLPE) with polyacrylonitrile (PAN) layer and PEO layer was designed to achieve a stable interface and application in high-energy-density batteries. In this special design, the hydroxy group of PEO-SPE can form an O-H---N hydrogen bond with the cyano group in PAN-SPE, which connects the two layers of DLPE at a microscopic chemical level. A special Li+ conducting mechanism in DLPE provides a uniform Li+ flux and fast Li+ conduction, which achieves a stable electrolyte/electrode interface.LiFePO4/DLPE/Li battery shows superior cycling stability, and the coulombic efficiency remains 99.5% at 0.2 C. Meanwhile, LiNi0.6Co0.2Mn0.2O2/DLPE/Li battery shows high specific discharge capacity of 176.0 mAh g−1 at 0.1 C between 2.8 V to 4.3 V, and the coulombic efficiency remains 95% after 100 cycles. This in situ synthetic strategy represents a big step forward in addressing the interface issues and boosting the development of high-energy-density lithium-metal batteries. Full article
(This article belongs to the Special Issue A Themed Issue in Honor of Professor Michel Armand on the Occasion of His 75th Birthday)
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14 pages, 4111 KiB  
Article
Cyano-Bridged Dy(III) and Ho(III) Complexes with Square-Wave Structure of the Chains
by Valentina D. Sasnovskaya, Leokadiya V. Zorina, Sergey V. Simonov, Artem D. Talantsev and Eduard B. Yagubskii
Inorganics 2022, 10(4), 41; https://doi.org/10.3390/inorganics10040041 - 29 Mar 2022
Viewed by 2476
Abstract
Four new cyano-bridged DyIII-CrIII, DyIII-FeIII, HoIII-CrIII and HoIII-FeIII bimetallic coordination polymers were synthesized by the reaction of [Ln(H2dapsc)(H2O)4](NO3)3 (Ln = [...] Read more.
Four new cyano-bridged DyIII-CrIII, DyIII-FeIII, HoIII-CrIII and HoIII-FeIII bimetallic coordination polymers were synthesized by the reaction of [Ln(H2dapsc)(H2O)4](NO3)3 (Ln = Dy, Ho); H2dapsc = 2,6-diacetylpyridinebis(semicarbazone)) with K3[M(CN)6] (M = Cr, Fe) in H2O, resulting in the substitution of two water molecules in the coordination sphere of rare earth by paramagnetic tricharged hexacyanides of Fe and Cr. The complexes are isostructural and consist of alternating [Ln(H2dapsc)(H2O)2]3+ and [M(CN)6]3− units linked by bridges of two cis-cyano ligands of the anion to form square-wave chains. The ac magnetic measurements revealed that the DyCr and DyFe complexes are field-induced single molecule magnets, while their Ho analogs do not exhibit slow magnetic relaxation. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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