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Inorganics, Volume 10, Issue 5 (May 2022) – 12 articles

Cover Story (view full-size image): Hybrid solid-state batteries, consisting of a bilayer of two different electrolyte materials, may offer advantages over using a single solid electrolyte as the interfaces can be tailored to both the anode and cathode. However, this introduces a new interface between the two electrolytes, which can strongly impede Li+ transport. In this work, the interfaces between a polymer electrolyte and two different ceramic electrolytes, an oxide and a sulfide, are investigated both electrochemically and chemically. At the polymer electrolyte/sulfide electrolyte interface, a relatively low resistance to Li+ transport is observed, despite the electrolytes having reacted chemically to form an interphase. By contrast, at the polymer electrolyte/oxide electrolyte interface, no chemical reactivity is observed, but the resistance to Li+ transport is relatively high. View this paper
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Editorial
New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry
Inorganics 2022, 10(5), 68; https://doi.org/10.3390/inorganics10050068 - 22 May 2022
Viewed by 512
Abstract
Vanadium was discovered twice [...] Full article
Article
TiO2-La2O3 as Photocatalysts in the Degradation of Naproxen
Inorganics 2022, 10(5), 67; https://doi.org/10.3390/inorganics10050067 - 22 May 2022
Viewed by 536
Abstract
The indiscriminate use of naproxen as an anti-inflammatory has been the leading cause of pollution in sewage effluents. Conversely, titanium dioxide is one of the most promising photocatalyst for the degradation of pollutants. Ti-La mixed oxides containing 0, 1, 3, 5, and 10 [...] Read more.
The indiscriminate use of naproxen as an anti-inflammatory has been the leading cause of pollution in sewage effluents. Conversely, titanium dioxide is one of the most promising photocatalyst for the degradation of pollutants. Ti-La mixed oxides containing 0, 1, 3, 5, and 10 wt.% of lanthanum were synthetized by sol-gel and tested as photocatalysts in the degradation of naproxen (NPX). The materials were further characterized by X-ray diffraction (XRD), nitrogen physisorption (BET), scanning electron microscopy (SEM), UV-Vis and Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The XRD patterns resembled that of anatase titania. The Eg values, determined from the UV-Vis spectra, vary from 2.07 to 3.2 eV corresponded to pure titania. The photocatalytic activity of these materials showed a degradation of naproxen from 93.6 to 99.8 wt.% after 4 h under UV irradiation. Full article
(This article belongs to the Special Issue Nanocomposites for Photocatalysis)
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Article
A Tetranuclear Dysprosium Schiff Base Complex Showing Slow Relaxation of Magnetization
Inorganics 2022, 10(5), 66; https://doi.org/10.3390/inorganics10050066 - 21 May 2022
Viewed by 699
Abstract
A tetranuclear dysprosium Schiff base complex was isolated by reacting dysprosium chloride with 2-hydroxy-3-methoxybenzaldehyde and 2-(aminomethyl)pyridine in-situ under basic conditions. The isolated Dy(III) complex was characterized by elemental analyses, single crystal X-ray diffraction and molecular spectroscopy. The complex crystallizes in the triclinic space [...] Read more.
A tetranuclear dysprosium Schiff base complex was isolated by reacting dysprosium chloride with 2-hydroxy-3-methoxybenzaldehyde and 2-(aminomethyl)pyridine in-situ under basic conditions. The isolated Dy(III) complex was characterized by elemental analyses, single crystal X-ray diffraction and molecular spectroscopy. The complex crystallizes in the triclinic space group P-1 with unit cell parameters of a = 10.2003 (4), b = 13.8602 (5), c = 14.9542 (6), α = 94.523 (3), β = 109.362 (4), and γ = 99.861 (3). The magnetic properties of 1 have been investigated by DC and AC susceptibility measurements. The DC measurements reveal weak exchange coupling of antiferromagnetic nature. In the AC measurement, the complex shows a slow relaxation of magnetization in the absence of an external magnetic field. Full article
(This article belongs to the Special Issue Synthesis, Structure and Properties of f-Block Complexes)
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Article
Spontaneous Adsorption and Efficient Photodegradation of Indigo Carmine under Visible Light by Bismuth Oxyiodide Nanoparticles Fabricated Entirely at Room Temperature
Inorganics 2022, 10(5), 65; https://doi.org/10.3390/inorganics10050065 - 19 May 2022
Viewed by 448
Abstract
Bismuth oxyiodide (BiOI) is a targeted material for its relative safety and photocatalytic activity under visible light. In this study, a successful simple and energy-saving route was applied to prepare BiOI through a sonochemical process at room temperature. The characterization of the prepared [...] Read more.
Bismuth oxyiodide (BiOI) is a targeted material for its relative safety and photocatalytic activity under visible light. In this study, a successful simple and energy-saving route was applied to prepare BiOI through a sonochemical process at room temperature. The characterization of the prepared BiOI was conducted by physical means. The transmission electron microscope (TEM) image showed that the BiOI comprises nanoparticles of about 20 nm. Also, the surface area of the BiOI was found to be 34.03 m2 g−1 with an energy gap of 1.835 eV. The adsorption and photocatalytic capacities of the BiOI were examined for the indigo carmine dye (IC) as a model water-pollutant via the batch experiment methodology. The solution parameters were optimized, including pH, contact time, IC concentration, and temperature. Worth mentioning that an adsorption capacity of 185 mg·g−1 was obtained from 100 mg L−1 IC solution at 25 °C within 60 min as an equilibrium time. In addition, the BiOI showed a high degradation efficiency towards IC under tungsten lamb (80 W), where 93% was removed within 180 min, and the complete degradation was accomplished in 240 min. The fabricated BiOI nanoparticles completely mineralized the IC under artificial visible light, as indicated by the total organic carbon analysis. Full article
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Article
Quantifying Lithium Ion Exchange in Solid Electrolyte Interphase (SEI) on Graphite Anode Surfaces
Inorganics 2022, 10(5), 64; https://doi.org/10.3390/inorganics10050064 - 17 May 2022
Viewed by 599
Abstract
Solid Electrolyte Interphase (SEI) has been identified as the most important and least understood component in lithium-ion batteries. Despite extensive studies in the past two decades, a few mysteries remain: what is the chemical form of and degree of mobility of Li+ [...] Read more.
Solid Electrolyte Interphase (SEI) has been identified as the most important and least understood component in lithium-ion batteries. Despite extensive studies in the past two decades, a few mysteries remain: what is the chemical form of and degree of mobility of Li+ in the interphase? What fraction of Li+ is permanently immobilized in the SEI, while the rest are still able to participate in the cell reactions via the ion-exchange process with Li+ in the electrolyte? This study attempted to answer, in part, these questions by using 6Li and 7Li-isotopes to label SEIs and electrolytes, and then quantifying the distribution of permanently immobilized and ion-exchangeable Li+ with solid-state NMR and ToF-SIMS. The results showed that the majority of Li+ were exchanged after one SEI formation cycle, and a complete exchange after 25 cycles. Ion exchange by diffusion based on concentration gradient in the absence of applied potential also occurred simultaneously. This knowledge will provide a foundation for not only understanding but also designing better SEIs for future battery chemistries. Full article
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Review
Functionalization of Porphyrins Using Metal-Catalyzed C–H Activation
Inorganics 2022, 10(5), 63; https://doi.org/10.3390/inorganics10050063 - 13 May 2022
Viewed by 3080
Abstract
The review is devoted to the C–H functionalization of porphyrins. Porphyrins exhibit the properties of organic semiconductors, light energy converters, chemical and electrochemical catalysts, and photocatalysts. The review describes the iridium- and palladium-catalyzed direct functionalization of porphyrins, with more attention given to the [...] Read more.
The review is devoted to the C–H functionalization of porphyrins. Porphyrins exhibit the properties of organic semiconductors, light energy converters, chemical and electrochemical catalysts, and photocatalysts. The review describes the iridium- and palladium-catalyzed direct functionalization of porphyrins, with more attention given to the results obtained in our laboratory. The development and improvement of synthetic methods that do not require preliminary modification of the substrate with various functional groups are extremely important for the preparation of new organic materials based on porphyrins. This makes it possible to simplify the synthetic procedure, to make the synthesis more economical, environmentally safe, and simple to perform. Full article
(This article belongs to the Special Issue Metal-Catalyzed C−H Functionalization)
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Article
Influence of Polymorphism on the Electrochemical Behavior of Dilithium (2,3-Dilithium-oxy)-terephthalate vs. Li
Inorganics 2022, 10(5), 62; https://doi.org/10.3390/inorganics10050062 - 10 May 2022
Viewed by 663
Abstract
Organic electrode materials offer obvious opportunities to promote cost-effective and environmentally friendly rechargeable batteries. Over the last decade, tremendous progress has been made thanks to the use of molecular engineering focused on the tailoring of redox-active organic moieties. However, the electrochemical performance of [...] Read more.
Organic electrode materials offer obvious opportunities to promote cost-effective and environmentally friendly rechargeable batteries. Over the last decade, tremendous progress has been made thanks to the use of molecular engineering focused on the tailoring of redox-active organic moieties. However, the electrochemical performance of organic host structures relies also on the crystal packing, like the inorganic counterparts, which calls for further efforts in terms of crystal chemistry to make a robust redox-active organic center electrochemically efficient in the solid state. Following our ongoing research aiming at elaborating lithiated organic cathode materials, we report herein on the impact of polymorphism on the electrochemical behavior of dilithium (2,3-dilithium-oxy-)terephthalate vs. Li. Having isolated dilithium (3-hydroxy-2-lithium-oxy)terephthalate through an incomplete acid-base neutralization reaction, its subsequent thermally induced decarboxylation mechanism led to the formation of a new polymorph of dilithium (2,3-dilithium-oxy-)terephthalate referred to as Li4-o-DHT (β-phase). This new phase is able to operate at 3.1 V vs. Li+/Li, which corresponds to a positive potential shift of +250 mV compared to the other polymorph formerly reported. Nevertheless, the overall electrochemical process characterized by a sluggish biphasic transition is impeded by a large polarization value limiting the recovered capacity upon cycling. Full article
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Article
Effect of Temperature on the Adhesion and Bactericidal Activities of Ag+-Doped BiVO4 Ceramic Tiles
Inorganics 2022, 10(5), 61; https://doi.org/10.3390/inorganics10050061 - 06 May 2022
Viewed by 528
Abstract
The aim of this research was to study the effect of temperature on the adhesion and disinfection activities of an Ag+-doped BiVO4 (Ag+/BiVO4) coating. Ag+/BiVO4 was prepared by a sol–gel method, and spraying [...] Read more.
The aim of this research was to study the effect of temperature on the adhesion and disinfection activities of an Ag+-doped BiVO4 (Ag+/BiVO4) coating. Ag+/BiVO4 was prepared by a sol–gel method, and spraying was used as the deposition method of coating. X-ray diffraction patterns showed that the monoclinic scheelite phase of the samples was unchanged by annealing at 450–650 °C. Scanning electron microscopy results showed that, at high temperatures, the particles melted and formed a dense coating, and the roughness of the coating decreased after initially increasing. The adhesion and disinfection activities were evaluated by ASTM D3359-08 and disinfection experiments. The results showed that the samples modified by silver had a good disinfection activity when annealed in the range of 450–650 °C. The adhesion increased upon increasing the annealing temperature. The sample annealed at 650 °C showed the best coating adhesion and completely killed Escherichia coli, Staphylococcus aureus, Shigella, and Salmonella after 2 h of visible-light irradiation. Full article
(This article belongs to the Special Issue Nanocomposites for Photocatalysis)
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Article
Interfaces between Ceramic and Polymer Electrolytes: A Comparison of Oxide and Sulfide Solid Electrolytes for Hybrid Solid-State Batteries
Inorganics 2022, 10(5), 60; https://doi.org/10.3390/inorganics10050060 - 26 Apr 2022
Viewed by 1351
Abstract
Hybrid solid-state batteries using a bilayer of ceramic and solid polymer electrolytes may offer advantages over using a single type of solid electrolyte alone. However, the impedance to Li+ transport across interfaces between different electrolytes can be high. It is important to [...] Read more.
Hybrid solid-state batteries using a bilayer of ceramic and solid polymer electrolytes may offer advantages over using a single type of solid electrolyte alone. However, the impedance to Li+ transport across interfaces between different electrolytes can be high. It is important to determine the resistance to Li+ transport across these heteroionic interfaces, as well as to understand the underlying causes of these resistances; in particular, whether chemical interphase formation contributes to giving high resistances, as in the case of ceramic/liquid electrolyte interfaces. In this work, two ceramic electrolytes, Li3PS4 (LPS) and Li6.5La3Zr1.5Ta0.5O12 (LLZTO), were interfaced with the solid polymer electrolyte PEO10:LiTFSI and the interfacial resistances were determined by impedance spectroscopy. The LLZTO/polymer interfacial resistance was found to be prohibitively high but, in contrast, a low resistance was observed at the LPS/polymer interface that became negligible at a moderately elevated temperature of 50 °C. Chemical characterization of the two interfaces was carried out, using depth-profiled X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, to determine whether the interfacial resistance was correlated with the formation of an interphase. Interestingly, no interphase was observed at the higher resistance LLZTO/polymer interface, whereas LPS was observed to react with the polymer electrolyte to form an interphase. Full article
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Article
Sacrificial Zinc Oxide Strategy-Enhanced Mesoporosity in MIL-53-Derived Iron–Carbon Composite for Methylene Blue Adsorption
Inorganics 2022, 10(5), 59; https://doi.org/10.3390/inorganics10050059 - 25 Apr 2022
Viewed by 704
Abstract
MOF-derived carbon-based materials have attracted widespread attention due to their relatively large surface area, morphology, and their stability in water. Considering these advantages, these materials present themselves as excellent adsorbents. In this work, a novel method was designed for the fabrication of a [...] Read more.
MOF-derived carbon-based materials have attracted widespread attention due to their relatively large surface area, morphology, and their stability in water. Considering these advantages, these materials present themselves as excellent adsorbents. In this work, a novel method was designed for the fabrication of a nano zero-valent-iron (nZVI) carbon composite. The utilization of zinc oxide nanorods (ZnONRs) in the role of sacrificial consumable nuclei for the synthesis of MIL-53 sacrificial zinc oxide nanorods (MIL-53-SNR) and the subsequent pyrolysis at 700 °C in the inert atmosphere led to a graphitic-supported nZVI material (Fe-C-SNR). Fe-C-SNR was compared with a commercial zinc oxide bulk (MIL-53-SB) and with a pristine MIL-53. By virtue of the ZnONRs, Fe-C-SNR exhibited a greatly improved mesoporous structure. Consequently, the pyrolyzed materials were applied as adsorbents for methylene blue. Fe-C-SNR’s performance increased to more than double of the pyrolyzed MIL-53 (Fe-C), with a remarkably fast adsorption time (10 min) for a concentration of 10 mg L−1 with only 200 mg L−1 adsorbent required. This functional composite also displayed exceptional recyclability; after ten complete cycles, Fe-C-SNR was still capable of completely adsorbing the methylene blue. The utilization of ZnONRs proves itself advantageous and could further be extended to other MOFs for a wide range of applications. Full article
(This article belongs to the Special Issue New Advances into Nanostructured Oxides)
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Article
Studies on Red Mud Material to Use for Combustion of Vietnam Pulverized Coal
Inorganics 2022, 10(5), 58; https://doi.org/10.3390/inorganics10050058 - 24 Apr 2022
Viewed by 679
Abstract
The catalytic effect of red mud on Vietnam anthracite’s combustion characteristics was investigated. The mineralogical composition of the red mud includes CaCO3, Fe2O3, FeO(OH), FeTiO3, and Al(OH)3. This red mud is rich in [...] Read more.
The catalytic effect of red mud on Vietnam anthracite’s combustion characteristics was investigated. The mineralogical composition of the red mud includes CaCO3, Fe2O3, FeO(OH), FeTiO3, and Al(OH)3. This red mud is rich in Na, Ca, Al, Fe, and Ti. The combustion characteristics were analyzed by the thermogravimetry method. The combustion effectiveness was assessed by thermogravimetric analysis. The results were derived from a combination of several parameters, such as the ignition temperature, the burnout efficiency, and the amount of heat release. The combustion characteristics of pulverized coal were improved by the introduction of red mud, and the greatest catalytic performance was achieved when the content reached 6%. With the optimal addition, the ignition temperature of anthracite was reduced by 12 °C, and the burnout efficiencies were increased by 2.59% compared to raw anthracite. The amount of heat released by anthracite was increased to 6.93 kJ/g by adding red mud. Full article
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Article
Electrochemical Synthesis of Precursors of Al2O3-ZrO2 Ceramic Stabilized with Cerium Oxide and Magnesium Aluminate
Inorganics 2022, 10(5), 57; https://doi.org/10.3390/inorganics10050057 - 20 Apr 2022
Viewed by 664
Abstract
This article presents a new approach to preparing the precursors of complex oxide systems Al2O3-ZrO2-MXOY (M = Mg, Ce). The approach is based on the electrogeneration and interaction of reagents with electrolyte components in [...] Read more.
This article presents a new approach to preparing the precursors of complex oxide systems Al2O3-ZrO2-MXOY (M = Mg, Ce). The approach is based on the electrogeneration and interaction of reagents with electrolyte components in a coaxial electrochemical reactor. The design of the electrolyzer provides the suspension homogenization due to the turbulence induced by the intensive hydrogen bubbles and electrolyte movement in opposite directions relative to the central electrode in a closed space. Hydrogen evolution leads to the mixing of the solution. The transfer of OH ions generated at the cathode into the electrolyte and interaction with metal ions (Zr, Al, Ce, Mg) leads to the formation of hydroxoaqua complexes of these metals. They participate in the polycondensation reaction, forming polymerized hydroxides and oxyhydroxides, which are the basis of the primary particles. The process of hydroxylation of nanoparticle surface of the formed precursors of oxide systems stabilizes the dispersion and prevents particle aggregation. The stabilized tetragonal t-ZrO2 was obtained by sintering the precursor of the synthesized oxide system at 1100 °C with the formation of an alumina phase (γ-Al2O3, or an aluminum–magnesium spinel MgAl2O4) with a low CeO2 content (2–3 wt%). Full article
(This article belongs to the Section Inorganic Materials)
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