Inorganics

17 pages, 2500 KiB

Open AccessArticle

Combining a Low Valent Molybdenum(0) Center with a Strongly σ-Donating Mesoionic Carbene Chelate Ligand—Synthesis and Structural Characterization

by Benedict Josua Elvers, Paul Schulan, Sebastian Pätsch, Christian Fischer and Carola Schulzke

Inorganics 2022, 10(11), 216; https://doi.org/10.3390/inorganics10110216 - 20 Nov 2022

Viewed by 1679

Abstract

Triazolylidene ligands belong to a class of N-heterocyclic carbenes of growing chemical interest. Their precursors are readily available using Click chemistry and, therefore, highly modular for tuning their electronic characteristics. Due to their notable donor properties, these ligands are particularly suitable for modulating [...] Read more.

Triazolylidene ligands belong to a class of N-heterocyclic carbenes of growing chemical interest. Their precursors are readily available using Click chemistry and, therefore, highly modular for tuning their electronic characteristics. Due to their notable donor properties, these ligands are particularly suitable for modulating the electronic properties of the central ions of their complexes. Here, a bidentate bistriazolylidene which is a particularly strong donor ligand is combined with a low valent molybdenum(0) center and four carbon monoxide molecules as co-ligands. The novel complex exhibits characteristic electrochemical and IR-spectroscopic behavior. An X-ray structural analysis provides metrical details which are not entirely in agreement with spectroscopic data, likely going back to crystal packing effects. In comparison with precursor and ligand SCXRD data, notable geometrical changes induced by the coordination of the ligand to the metal can be observed. The analyses strongly support the bistriazolylidene ligand as being a particularly good donor of electron density towards the central metal. Potentially, these findings may support, in the future, the design of potent catalysts for the reductive activation of small molecules. Full article

(This article belongs to the Special Issue N-Heterocyclic Carbene Metal Complexes: Synthesis, Properties and Applications)

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11 pages, 3896 KiB

Open AccessArticle

Preparation of SBA-15-Supported Metals by Vapor-Phase Infiltration

by Ching-Yu Wang, Kai Shen, Raymond J. Gorte and John M. Vohs

Inorganics 2022, 10(11), 215; https://doi.org/10.3390/inorganics10110215 - 19 Nov 2022

Cited by 6 | Viewed by 1410

Abstract

A simple method is presented for incorporating various catalytic metals into the pores of SBA-15 using vapor-phase infiltration. The precursors used in Atomic Layer Deposition (ALD) for Pt, Pd, Rh, Ru, and Ni were exposed to an evacuated SBA-15, resulting in monolayer films [...] Read more.

A simple method is presented for incorporating various catalytic metals into the pores of SBA-15 using vapor-phase infiltration. The precursors used in Atomic Layer Deposition (ALD) for Pt, Pd, Rh, Ru, and Ni were exposed to an evacuated SBA-15, resulting in monolayer films of the adsorbed precursors inside the mesopores. The metal particles that formed after removal of the precursor ligands remained in the pores and had particle sizes ranging from 3.8 nm for Pt to 5.2 nm for Ni, as determined by Transmission Electron Microscopy (TEM), XRD, and CO chemisorption. Metal loadings for saturation exposures ranged from 5.1-wt% for Ni to 9.1-wt% for Pt; however, uniform deposition was demonstrated for lower loadings of Pd by decreasing the amount of precursor. To determine the effect of the surface composition of the mesopores, Pd particles were also added to SBA-15 that was coated with a 0.2-nm film of ZrO₂. Full article

(This article belongs to the Special Issue Recent Advancements of Metal Oxide in Catalysis)

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29 pages, 2490 KiB

Open AccessArticle

Convenient Access to Ferrocene Fused aza-Heterocycles via the Intramolecular Ritter Reaction: Synthesis of Novel Racemic Planar-Chiral 3,4-Dihydroferroceno[c]pyridines and 1H-Ferroceno[c]pyrroles

by Yuliya S. Rozhkova, Irina V. Plekhanova, Alexey A. Gorbunov and Yurii V. Shklyaev

Inorganics 2022, 10(11), 214; https://doi.org/10.3390/inorganics10110214 - 19 Nov 2022

Cited by 1 | Viewed by 1462

Abstract

An efficient and easy approach to the synthesis of novel racemic planar-chiral 3,4-dihydroferroceno[c]pyridines and 1H-ferroceno[c]pyrroles via the intramolecular Ritter reaction of 2-ferrocenyl-3,3-dimethylbutan-2-ol with nitriles and thiocyanates in the presence of MeSO₃H was developed. Aromatic and [...] Read more.

An efficient and easy approach to the synthesis of novel racemic planar-chiral 3,4-dihydroferroceno[c]pyridines and 1H-ferroceno[c]pyrroles via the intramolecular Ritter reaction of 2-ferrocenyl-3,3-dimethylbutan-2-ol with nitriles and thiocyanates in the presence of MeSO₃H was developed. Aromatic and aliphatic nitriles, phenylacetonitriles, and β-oxonitriles produced exclusively 3,4-dihydroferroceno[c]pyridines. The condensation of 2-ferrocenyl-3,3-dimethylbutan-2-ol with various thiocyanates, including alkyl thiocyanates, benzyl thiocyanate, and ethyl 2-thiocyanatoacetate, yielded not only 3,4-dihydroferroceno[c]pyridines but also 1H-ferroceno[c]pyrroles. The selectivity of these reactions depended on the temperature and the order of addition. The size of substituents at the α-position to the sulfur atom of thiocyanates also had a significant effect on the distribution of products. Full article

(This article belongs to the Special Issue Ferrocene and Its Derivatives: Celebrating the 70th Anniversary of Its Discovery)

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15 pages, 4456 KiB

Open AccessArticle

Electrodeposited PPy@TiO₂ and PEDOT@TiO₂ Counter Electrodes for [Co(bpy)₃]^2+/3+ Redox Mediator-Based Dye-Sensitized Solar Cells

by Abdelaal S. A. Ahmed, Xie Yi, Xiujian Zhao, Wanchun Xiang and Mohammed Abdelmotallieb

Inorganics 2022, 10(11), 213; https://doi.org/10.3390/inorganics10110213 - 18 Nov 2022

Cited by 2 | Viewed by 1880

Abstract

The main goal of this work is to enhance the catalytic performance of PPy and PEDOT films toward the Co²⁺/Co³⁺ redox couple. PPy and PEDOT films were electrodeposited separately on a porous TiO₂ template to assess their suitability as [...] Read more.

The main goal of this work is to enhance the catalytic performance of PPy and PEDOT films toward the Co²⁺/Co³⁺ redox couple. PPy and PEDOT films were electrodeposited separately on a porous TiO₂ template to assess their suitability as alternative catalysts in dye-sensitized solar cells (DSSC) based on the [Co(bpy)₃]^2+/3+ redox shuttle. The obtained PPy@TiO₂ and PEDOT@TiO₂ counter electrodes displayed much rougher surfaces. Electrochemical studies indicate the superior catalytic activity of both the electrodeposited electrodes toward Co³⁺ reduction, as indicated by lower charge transfer resistance than that of pristine films and even that of Pt electrodes. Therefore, the fabricated DSSC devices with these counter electrodes achieved higher power conversion efficiencies compared to cells with pristine PPy and PEDOT counter electrodes, or even with a Pt counter electrode. Interestingly, the assembled DSSC device with a PEDOT@TiO₂ counter electrode displayed the highest performance among all with a power conversion efficiency of 6.62%, which is better than that obtained by the device with a Pt electrode (6.07%). Full article

(This article belongs to the Collection Coordination Complexes for Dye-Sensitized Solar Cells (DSCs))

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13 pages, 5210 KiB

Open AccessArticle

A New Approach for the Synthesis of Powder Zinc Oxide and Zinc Borates with Desired Properties

by Irina V. Kozerozhets, Varvara V. Avdeeva, Grigorii A. Buzanov, Evgeniy A. Semenov, Yulia V. Ioni and Sergey P. Gubin

Inorganics 2022, 10(11), 212; https://doi.org/10.3390/inorganics10110212 - 17 Nov 2022

Cited by 9 | Viewed by 1559

Abstract

Zinc borates are widely used in industry due to their thermal stability as a flame retardant in the production of plastics, rubber, and other polymer compositions. We have developed a simple and effective approach for the synthesis of zinc borate powders with desired [...] Read more.

Zinc borates are widely used in industry due to their thermal stability as a flame retardant in the production of plastics, rubber, and other polymer compositions. We have developed a simple and effective approach for the synthesis of zinc borate powders with desired properties, including desired particle size, low bulk density, high reactivity, etc. Zinc borates were prepared by the thermal treatment of a concentrated water–carbohydrate solution of a zinc salt until finely dispersed ZnO was formed, followed by its hydrothermal treatment at 90–300 °C as part of a suspension based on a hot aqueous solution of H₃BO₃. According to X-ray powder diffraction, IR spectroscopy, and TG–DSC data, depending on the temperature of hydrothermal treatment, a decrease in the water content in the structure of synthesized zinc borate particles is observed. TEM and SEM data indicate the formation of isometrically shaped zinc borate particles in the nanometer range during hydrothermal treatment above 250 °C. Varying the temperature of the hydrothermal treatment affects the average size and fineness of the structure of the zinc borate particles. Full article

(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)

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18 pages, 5332 KiB

Open AccessArticle

Effect of CuO Loading on the Photocatalytic Activity of SrTiO₃/MWCNTs Nanocomposites for Dye Degradation under Visible Light

by Xuan Truong Mai, Duc Nguyen Bui, Van Khang Pham, Thi Ha Thanh Pham, Thi To Loan Nguyen, Hung Dung Chau and Thi Kim Ngan Tran

Inorganics 2022, 10(11), 211; https://doi.org/10.3390/inorganics10110211 - 16 Nov 2022

Cited by 4 | Viewed by 1568

Abstract

In this study, we report on the preparation of copper oxide/strontium titanate/multi-walled carbon nanotube (CuO/STO/MWCNTs) nanocomposites and their photocatalytic activity for degradation of dye under visible light. The crystalline structures of the nanocomposites were investigated by an X-ray diffraction (XRD) technique, which explored [...] Read more.

In this study, we report on the preparation of copper oxide/strontium titanate/multi-walled carbon nanotube (CuO/STO/MWCNTs) nanocomposites and their photocatalytic activity for degradation of dye under visible light. The crystalline structures of the nanocomposites were investigated by an X-ray diffraction (XRD) technique, which explored the successful fabrication of CuO/STO/MWCNTs nanocomposites, and the cubic STO phase was formed in all samples. For the morphological study, the transmission electron microscope (TEM) technique was used, which had proved the successful preparation of CuO and STO nanoparticles. The energy dispersive X-ray spectroscopy (EDX), dark field scanning transmission electron microscope (DF-STEM-EDX mapping), and X-ray photoelectron spectra (XPS) analysis were performed to evidence the elemental composition of CuO/STO/MWCNTs nanocomposites. The optical characteristics were explored via UV–Vis diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) techniques. These studies clearly indicate the effect of the presence of CuO and MWCNTs on the visible absorption of the CuO/STO/MWCNTs nanocomposites. The photocatalytic activity of CuO/STO/MWCNTs nanocomposites was evaluated by the degradation of methylene blue (MB) dye under visible light irradiation, following first-order kinetics. Among the different x% CuO/STO/MWCNTs nanocomposites, the 5 wt.% CuO/STO/MWCNTs nanocomposites showed the highest photocatalytic efficiency for the degradation of MB dye. Moreover, the 5% CuO/STO/MWCNTs showed good stability and recyclability after three consecutive photocatalytic cycles. These results verified that the optimized nanocomposites can be used for photocatalytic applications, especially for dye degradation under visible light. Full article

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14 pages, 5385 KiB

Open AccessArticle

Excellent Adsorption of Dyes via MgTiO₃@g-C₃N₄ Nanohybrid: Construction, Description and Adsorption Mechanism

by Abueliz Modwi, Mohamed R. Elamin, Hajo Idriss, Nuha Y. Elamin, Fatima A. Adam, Abuzar E. Albadri and Babiker Y. Abdulkhair

Inorganics 2022, 10(11), 210; https://doi.org/10.3390/inorganics10110210 - 15 Nov 2022

Cited by 16 | Viewed by 1647

Abstract

This report investigates the elimination of hazardous Rhodamine B dye (RhB) from an aqueous medium utilizing MgTiO₃@g-C₃N₄ nanohybrids manufactured using a facile method. The nanohybrid MgTiO₃@g-C₃N₄ was generated using an ultrasonic approach in [...] Read more.

This report investigates the elimination of hazardous Rhodamine B dye (RhB) from an aqueous medium utilizing MgTiO₃@g-C₃N₄ nanohybrids manufactured using a facile method. The nanohybrid MgTiO₃@g-C₃N₄ was generated using an ultrasonic approach in the alcoholic solvent. Various techniques, including HRTEM, EDX, XRD, BET, and FTIR, were employed to describe the fabricated MgTiO3@g-C3N4 nanohybrids. RhB elimination was investigated utilizing batch mode studies, and the maximum removal was attained at pH 7.0. The RhB adsorption process is more consistent with the Langmuir isotherm model. The highest adsorption capacity of MgTiO₃@g-C₃N₄ nanohybrids for RhB was determined to be 232 mg/g. The dye adsorption followed a pseudo-second-order model, and the parameters calculated indicated that the kinetic adsorption process was spontaneous. Using ethanol and water, the reusability of the nanomaterial was investigated, and based on the results; it can be concluded that the MgTiO₃@g-C₃N₄ nanohybrids are easily regenerated for dye removal. The removal mechanism for the removal of RhB dye into MgTiO₃@g-C₃N₄ nanohybrids was also investigated. Full article

(This article belongs to the Special Issue Nanocomposites for Photocatalysis)

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14 pages, 3137 KiB

Open AccessArticle

Synthesis of a New Dinuclear Ag(I) Complex with Asymmetric Azine Type Ligand: X-ray Structure and Biological Studies

by Mezna Saleh Altowyan, Saied M. Soliman, Dhuha Al-Wahaib, Assem Barakat, Ali Eldissouky Ali and Hemmat A. Elbadawy

Inorganics 2022, 10(11), 209; https://doi.org/10.3390/inorganics10110209 - 15 Nov 2022

Cited by 2 | Viewed by 1349

Abstract

Aspects of the molecular and supramolecular structure of the new dinuclear [Ag(L)(NO₃)]₂ complex, where L is 2-((E)-(((E)-1-(thiazol-2-yl)ethylidene)hydrazono)methyl)phenol, were discussed. The complex was crystallized in the monoclinic crystal system and P2₁/n space group. The unit [...] Read more.

Aspects of the molecular and supramolecular structure of the new dinuclear [Ag(L)(NO₃)]₂ complex, where L is 2-((E)-(((E)-1-(thiazol-2-yl)ethylidene)hydrazono)methyl)phenol, were discussed. The complex was crystallized in the monoclinic crystal system and P2₁/n space group. The unit cell parameters are a = 10.3274(2) Å, b = 11.4504(3) Å, c = 12.7137(3) Å and β = 108.2560(10)°. The asymmetric unit comprised one [Ag(L)(NO₃)] formula in which the azine and nitrate ligand groups act as NN- and OO-bidentate chelates, respectively. The coordination environment of the Ag(I) is completed by one weak Ag-O bond with another [Ag(L)(NO₃)] unit, leading to the dinuclear formula [Ag(L)(NO₃)]₂. This was clearly revealed by Hirshfeld analysis. Additionally, the Ag…C, O…H and C…C intermolecular interactions played an important role in the molecular packing of the studied complex. The antimicrobial, antioxidant and cytotoxic activities of the [Ag(L)(NO₃)]₂ complex and the free ligand (L) were discussed. While the [Ag(L)(NO₃)]₂ complex showed very weak antioxidant activity, the results of the antifungal and cytotoxic activities were promising. The inhibition zone diameters (IZD) and the minimum inhibitory concentration (MIC) values were determined to be 31 mm and 20 μg/mL, respectively, against A. fumigatus, which is compared to 17 mm and 156 μg/mL, respectively, for the positive control Ketoconazole. Generally, the Ag(I) complex has better antimicrobial activities than the free ligand against all microbes except for S. aureus, where the free ligand has higher activity. Additionally, the IC₅₀ value against colon carcinoma (HCT-116 cell line) was determined to be 12.53 ± 0.69 µg/mL, which is compared to 5.35 ± 0.49 µg/mL for cis-platin. Additionally, the Ag(I) complex displays better cytotoxicity than the free ligand (L) (242.92 ± 8.12 µg/mL). Full article

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12 pages, 3009 KiB

Open AccessArticle

Graphite Felt Electrode Modified by Quaternary Ammonium for Vanadium Redox Flow Battery with an Ultra-Long Cycle Life

by Xuejiao Liu, Junping Hu, Jun Liu, Hongyi Liu, Sha Fu, Xiongwei Wu and Yuping Wu

Inorganics 2022, 10(11), 208; https://doi.org/10.3390/inorganics10110208 - 15 Nov 2022

Viewed by 1844

Abstract

Vanadium redox flow batteries (VRFBs) are one of the most attractive devices for grid-scale energy storage due to their advantages of high safety, flexible assembly, and electrolyte-class recycling. However, the conventional graphite felt electrodes usually possess inferior electrocatalytic activity for vanadium ion redox [...] Read more.

Vanadium redox flow batteries (VRFBs) are one of the most attractive devices for grid-scale energy storage due to their advantages of high safety, flexible assembly, and electrolyte-class recycling. However, the conventional graphite felt electrodes usually possess inferior electrocatalytic activity for vanadium ion redox reactions, vastly limiting the rate and lifespans of VRFBs. Herein, we demonstrate a high-rate and ultra-stable vanadium redox flow battery based on quaternary ammonium salt-modified graphite felt electrodes. At a high current density of 200 mA cm⁻², the constructed VRFB exhibited a superior cycling life of up to 1000 cycles. This work affords a straightforward approach for developing efficient, environmentally friendly, and low-cost graphite felt electrodes for ultra-stable and high-rate VRFBs. Full article

(This article belongs to the Special Issue Beyond Lithium-Ion Battery Technology)

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14 pages, 3384 KiB

Open AccessArticle

How to Protect ortho-Carborane from Decapitation—Practical Synthesis of 3,6-Dihalogen Derivatives 3,6-X₂-1,2-C₂B₁₀H₁₀ (X = Cl, Br, I)

by Akim V. Shmal’ko, Sergey A. Anufriev, Kyrill Yu. Suponitsky and Igor B. Sivaev

Inorganics 2022, 10(11), 207; https://doi.org/10.3390/inorganics10110207 - 13 Nov 2022

Cited by 3 | Viewed by 1437

Abstract

The 3-halogen and 3,6-dihalogen derivatives of ortho-carborane 3-X-1,2-C₂B₁₀H₁₁ and 3,6-X₂-1,2-C₂B₁₀H₁₀ (X = Cl, Br, I) were prepared by Cu-assisted halodeboronation of the corresponding pinacolborate derivatives 3-Bpin-1,2-C₂B₁₀H [...] Read more.

The 3-halogen and 3,6-dihalogen derivatives of ortho-carborane 3-X-1,2-C₂B₁₀H₁₁ and 3,6-X₂-1,2-C₂B₁₀H₁₀ (X = Cl, Br, I) were prepared by Cu-assisted halodeboronation of the corresponding pinacolborate derivatives 3-Bpin-1,2-C₂B₁₀H₁₁ and 3,6-(Bpin)₂-1,2-C₂B₁₀H₁₀. It was shown that decapitation of 3-Cl-1,2-C₂B₁₀H₁₁, similarly to the corresponding bromo and iodo derivatives, proceeds regioselectively with the retention of the B-Cl bond. Crystal structures of 3,6-Cl₂-1,2-C₂B₁₀H₁₀ and Cs [3-Cl-7,8-C₂B₉H₁₁] were determined by single crystal X-ray diffraction. Full article

(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)

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17 pages, 3372 KiB

Open AccessArticle

12-Vertex closo-3,1,2-Ruthenadicarbadodecaboranes with Chelate POP-Ligands: Synthesis, X-ray Study and Electrochemical Properties

by Anastasiya M. Zimina, Nikolay V. Somov, Yulia B. Malysheva, Nadezhda A. Knyazeva, Alexander V. Piskunov and Ivan D. Grishin

Inorganics 2022, 10(11), 206; https://doi.org/10.3390/inorganics10110206 - 11 Nov 2022

Cited by 1 | Viewed by 1198

Abstract

A class of so-called POP ligands (Xanthos, NiXantphos, DPEphos) are of a great interest to the coordination chemistry due to their wide P-M-P bite angles and ability to show either κ²- or κ³-binding modes. Such κ²–κ³ [...] Read more.

A class of so-called POP ligands (Xanthos, NiXantphos, DPEphos) are of a great interest to the coordination chemistry due to their wide P-M-P bite angles and ability to show either κ²- or κ³-binding modes. Such κ²–κ³-rearrangement is valuable for catalytic application and internal stabilization of intermediates. To widen the scope of ruthenium-based catalysts for Atom Transfer Radical Polymerization (ATRP) two new approaches to the synthesis of closo-ruthenacarboranes with aforementioned POP ligands were developed and six new 17-e (3,3-(POP)-3-Cl-closo-3,1,2-RuC₂B₉H₁₁; 2, 4, 7) and 18-e (3,3-(POP)-3-NCCH₃-closo-3,1,2-RuC₂B₉H₁₁; 3, 5, 8) clusters were synthesized and characterized by means of NMR or ESR spectroscopy, MALDI mass-spectrometry and single crystal X-ray diffraction studies. The unique 18-e complex of Ru(II) with dioxygen ligand 3,3-(DPEphos)-3-(η²-O₂)-closo-3,1,2-RuC₂B₉H₁₁ (9) was isolated and characterized by X-ray diffraction. It was shown that aforementioned POP ligands coordinate to ruthenium by two phosphorus atoms in a κ²-fashion. The performed electrochemical studies have shown reversible Ru(II)-Ru(III) transition making the complexes suitable for application in catalysis of polymerization. The test experiments on methyl methacrylate (MMA) polymerization indicate the proceeding of the process in according with an ATRP mechanism. Full article

(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)

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16 pages, 2651 KiB

Open AccessArticle

Synthesis of Novel Ferrocene-Benzofuran Hybrids via Palladium- and Copper-Catalyzed Reactions

by Enikő Nagy, Márk Váradi, Zoltán Nagymihály, László Kollár, Krisztina Kovács, Kitti Andreidesz, Ágnes Gömöry, Nikolay Tumanov, Johan Wouters and Rita Skoda-Földes

Inorganics 2022, 10(11), 205; https://doi.org/10.3390/inorganics10110205 - 11 Nov 2022

Cited by 1 | Viewed by 1483

Abstract

The combination of the ferrocene skeleton with pharmacophores often leads to molecules with interesting biological properties. Five ferrocene-benzofuran hybrids of different structures were synthesized by transition metal catalyzed reactions. The efficiency of both homogeneous and heterogeneous catalytic methods was tested. The products were [...] Read more.

The combination of the ferrocene skeleton with pharmacophores often leads to molecules with interesting biological properties. Five ferrocene-benzofuran hybrids of different structures were synthesized by transition metal catalyzed reactions. The efficiency of both homogeneous and heterogeneous catalytic methods was tested. The products were characterized using ¹H, ¹³C NMR and FTIR spectroscopy, HRMS and cyclic voltammetry. The structure of one of the new compounds was also proved with X-ray crystallography. The new hybrids showed moderate cytotoxicity on MCF-7 and MDA-MB-231 cell lines. It is remarkable that the less curable MDA-MB-231 cell line was more sensitive to treatment with three ferrocene derivatives. Full article

(This article belongs to the Special Issue Ferrocene and Its Derivatives: Celebrating the 70th Anniversary of Its Discovery)

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10 pages, 3354 KiB

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Enhancement in the Performance of Dye Sensitized Solar Cells (DSSCs) by Incorporation of Reduced Graphene Oxide (RGO) and Carbon Nanotubes (CNTs) in ZnO Nanostructures

by Ahmed Alshahrie, Ahmed A. Alghamdi, Prince M. Z. Hasan, Faheem Ahmed, Hanadi Mohammed Eid Albalawi, Ahmad Umar and Abdullah Alsulami

Inorganics 2022, 10(11), 204; https://doi.org/10.3390/inorganics10110204 - 11 Nov 2022

Cited by 3 | Viewed by 1430

Abstract

In this work, a fast, environment-friendly and economic route was used to prepare ZnO and their nanocomposites containing reduced graphene oxide (RGO) and carbon nanotubes (CNTs) for the fabrication of dye-sensitized solar cells (DSSCs). The prepared nanostructures were well-characterized by X-ray diffraction (XRD), [...] Read more.

In this work, a fast, environment-friendly and economic route was used to prepare ZnO and their nanocomposites containing reduced graphene oxide (RGO) and carbon nanotubes (CNTs) for the fabrication of dye-sensitized solar cells (DSSCs). The prepared nanostructures were well-characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and Raman measurements. The XRD, Raman and TEM results confirmed that the ZnO nanostructures were crystallized into the hexagonal phase, and the nanocomposites containing RGO and CNTs. Morphological studies performed by using FESEM and TEM images showed that the ZnO possessed tube-like morphology with length and diameter in the range of ~1 micron and 90–200 nm, respectively, which were uniform and densely covered on the surface of the carbon materials. The DSSCs were fabricated using prepared nanostructures as a working electrode and platinum as a counter electrode with ruthenium-based dyes and iodide electrolytes. To further improve the efficiency of fabricated solar cells, nanocomposites of prepared nanostructures of ZnO with RGO and CNTs were synthesized, and their results were compared with the pristine samples. The results showed that the ZnO/CNTs (0.5 wt%) nanocomposites electrode exhibited the highest power conversion efficiency (PCE) of DSSCs with a maximum value of 0.612% compared to 0.326% of DSSC with pure ZnO, and 0.574% of DSSC with ZnO/RGO. Significantly, this technique could be used for large-scale production using the existing economical and highly effective DSSC fabrication technique. Full article

(This article belongs to the Special Issue Graphene and Its Composites for Energy Storage Applications)

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10 pages, 1515 KiB

Open AccessArticle

Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine

by Peter A. Cleaves, Ben Gourlay, Margot Marseglia, Daniel J. Ward and Stephen M. Mansell

Inorganics 2022, 10(11), 203; https://doi.org/10.3390/inorganics10110203 - 11 Nov 2022

Cited by 1 | Viewed by 1405

Abstract

The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (19) with one and two equivalents of [AuCl(tht)] was attempted in order to selectively form the mono and digold species, respectively. The digold species [(AuCl)₂(19)] (21) was synthesized in 32% yield [...] Read more.

The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (19) with one and two equivalents of [AuCl(tht)] was attempted in order to selectively form the mono and digold species, respectively. The digold species [(AuCl)₂(19)] (21) was synthesized in 32% yield and comprehensibly characterized (multinuclear NMR spectroscopy, elemental analysis, mass spectrometry and single-crystal X-ray diffraction). The monogold species showed no ³¹P nuclear magnetic resonance at 25 °C but two resonances at −70 °C due to rapid exchange of AuCl between the phosphinine donors at 25 °C and was also susceptible to redistribution reactions to form the digold species. Analogous reactions of [AuCl(tht)] with 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (22) revealed preferential coordination of the AuCl unit to the PPh₂ donor first, with coordination to the phosphinine achieved upon reaction with the second equivalent of [AuCl(tht)]. Unexpectedly, the digold complex was not stable, undergoing decomposition to give an unidentified black precipitate. Structural information could only be obtained on the digold hydrolysis product [(AuCl)₂(1-OH-2-PPh₂-3-MePC₅H₄)], which showed an aurophilic interaction. Full article

(This article belongs to the Special Issue Synergy between Main Group and Transition Metal Chemistry)

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13 pages, 3963 KiB

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A 2D Porous Zinc-Organic Framework Platform for Loading of 5-Fluorouracil

by Liang Qin, Fenglan Liang, Yan Li, Jiana Wu, Shiyuan Guan, Meiyin Wu, Shiling Xie, Manshi Luo and Deyun Ma

Inorganics 2022, 10(11), 202; https://doi.org/10.3390/inorganics10110202 - 09 Nov 2022

Cited by 118 | Viewed by 2342

Abstract

A hydrostable 2D Zn-based MOF, {[Zn(5-PIA)(imbm)]·2H₂O}_n (1) (5-H₂PIA = 5-propoxy-isophthalic acid, imbm = 1,4-di(1H-imidazol-1-yl)benzene), was synthesized and structurally characterized. Complex 1 shows good water and thermal stability based on the TGA and PXRD analyses and displays [...] Read more.

A hydrostable 2D Zn-based MOF, {[Zn(5-PIA)(imbm)]·2H₂O}_n (1) (5-H₂PIA = 5-propoxy-isophthalic acid, imbm = 1,4-di(1H-imidazol-1-yl)benzene), was synthesized and structurally characterized. Complex 1 shows good water and thermal stability based on the TGA and PXRD analyses and displays a 2D framework with 1D channels of 4.8 × 13.8 and 10.0 × 8.3 Å² along the a axis. The 5-fluorouracil (5-FU) payload in activated complex 1 (complex 1a) is 19.3 wt%, and the cumulative release value of 5-FU at 120 h was about 70.04% in PBS (pH 7.4) at 310 K. In vitro MTT assays did not reveal any cytotoxic effect of NIH-3T3 and HEK-293 cells when the concentration of 1 was below 500 μg/mL and 5 μg/mL, respectively. No morphological abnormalities were observed on zebrafish exposed to complex 1. Full article

(This article belongs to the Special Issue Inorganics: 10th Anniversary)

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17 pages, 3675 KiB

Open AccessArticle

The Effect of Short Chain Carboxylic Acids as Additives on the Crystallization of Methylammonium Lead Triiodide (MAPI)

by Chiara Dionigi, Meriem Goudjil, Giampiero Ruani and Luca Bindi

Inorganics 2022, 10(11), 201; https://doi.org/10.3390/inorganics10110201 - 08 Nov 2022

Viewed by 1684

Abstract

Due to their exceptional properties, the study of hybrid perovskite (HyP) structures and applications dominate current photovoltaic prospects. Methylammonium lead tri-iodide perovskite (MAPI) is the model compound of the HyP class of materials that, in a few years, achieved, in photovoltaics, a power [...] Read more.

Due to their exceptional properties, the study of hybrid perovskite (HyP) structures and applications dominate current photovoltaic prospects. Methylammonium lead tri-iodide perovskite (MAPI) is the model compound of the HyP class of materials that, in a few years, achieved, in photovoltaics, a power conversion efficiency of 25%. The attention on HyP has recently moved to large single crystals as emerging candidates for photovoltaic application because of their improved stability and optoelectronic properties compared to polycrystalline films. To control the quality and symmetry of the large MAPI single crystals, we proposed an original method that consisted of adding short-chain carboxylic acids to the inverse temperature crystallization (ICT) of MAPI in γ-butyrolactone (GBL). The crystals were characterized by single-crystal X-ray diffraction (SC-XRD), X-ray powder diffraction (XRPD) and Raman spectroscopy. Based on SC-XRD analysis, MAPI crystals grown using acetic and trifluoroacetic acids adopt a tetragonal symmetry “I4cm”. MAPI grown in the presence of formic acid turned out to crystallize in the orthorhombic “Fmmm” space group demonstrating the acid’s effect on the crystallization of MAPI. Full article

(This article belongs to the Section Inorganic Materials)

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19 pages, 1480 KiB

Open AccessPerspective

Integrative Metallomics Studies of Toxic Metal(loid) Substances at the Blood Plasma–Red Blood Cell–Organ/Tumor Nexus

by Maryam Doroudian and Jürgen Gailer

Inorganics 2022, 10(11), 200; https://doi.org/10.3390/inorganics10110200 - 07 Nov 2022

Cited by 8 | Viewed by 1557

Abstract

Globally, an estimated 9 million deaths per year are caused by human exposure to environmental pollutants, including toxic metal(loid) species. Since pollution is underestimated in calculations of the global burden of disease, the actual number of pollution-related deaths per year is likely to [...] Read more.

Globally, an estimated 9 million deaths per year are caused by human exposure to environmental pollutants, including toxic metal(loid) species. Since pollution is underestimated in calculations of the global burden of disease, the actual number of pollution-related deaths per year is likely to be substantially greater. Conversely, anticancer metallodrugs are deliberately administered to cancer patients, but their often dose-limiting severe adverse side-effects necessitate the urgent development of more effective metallodrugs that offer fewer off-target effects. What these seemingly unrelated events have in common is our limited understanding of what happens when each of these toxic metal(loid) substances enter the human bloodstream. However, the bioinorganic chemistry that unfolds at the plasma/red blood cell interface is directly implicated in mediating organ/tumor damage and, therefore, is of immediate toxicological and pharmacological relevance. This perspective will provide a brief synopsis of the bioinorganic chemistry of As^III, Cd²⁺, Hg²⁺, CH₃Hg⁺ and the anticancer metallodrug cisplatin in the bloodstream. Probing these processes at near-physiological conditions and integrating the results with biochemical events within organs and/or tumors has the potential to causally link chronic human exposure to toxic metal(loid) species with disease etiology and to translate more novel anticancer metal complexes to clinical studies, which will significantly improve human health in the 21st century. Full article

(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)

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16 pages, 3807 KiB

Open AccessArticle

New Ferrocene-Based Metalloligand with Two Triazole Carboxamide Pendant Arms and Its Iron(II) Complex: Synthesis, Crystal Structure, ⁵⁷Fe Mössbauer Spectroscopy, Magnetic Properties and Theoretical Calculations

by Peter Antal, Ivan Nemec, Jiří Pechoušek and Radovan Herchel

Inorganics 2022, 10(11), 199; https://doi.org/10.3390/inorganics10110199 - 07 Nov 2022

Cited by 1 | Viewed by 1576

Abstract

The new ferrocene-based metalloligand bis (N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl])ferrocene carboxamide (L) was prepared through derivatization of 1,1′-ferrocenedicarboxylic acid with 4-amino-3,5-di(pyridyl)-4H-1,2,4-triazole. The composition and purity of L in the solid state was determined with elemental analysis, FT-IR spectroscopy, and its crystal [...] Read more.

The new ferrocene-based metalloligand bis (N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl])ferrocene carboxamide (L) was prepared through derivatization of 1,1′-ferrocenedicarboxylic acid with 4-amino-3,5-di(pyridyl)-4H-1,2,4-triazole. The composition and purity of L in the solid state was determined with elemental analysis, FT-IR spectroscopy, and its crystal structure with single-crystal X-ray analysis, which revealed that the substituted cyclopentadienyl rings adopt the antiperiplanar conformation and the crystal structure of L is stabilized by O–H···N and N–H···O hydrogen bonds. The molecular properties of L in solution were investigated with NMR and UV-VIS spectroscopies, and cyclic voltammetry disclosed irreversible redox behavior providing one oxidation peak at E_1/2 = 1.133 V vs. SHE. Furthermore, the polymeric Fe^II complex {Fe(L)(C(CN)₃)₂}_n (1) was prepared and characterized with elemental analysis, FT-IR spectroscopy, ⁵⁷Fe Mössbauer spectroscopy, and magnetic measurements. The last two methods confirmed that a mixture of low- and high-spin species is present in 1; however, the spin crossover properties were absent. The presented study was also supported by theoretical calculations at the DFT/TD-DFT level of theory using TPSS and TPSSh functionals. Full article

(This article belongs to the Special Issue Ferrocene and Its Derivatives: Celebrating the 70th Anniversary of Its Discovery)

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19 pages, 2873 KiB

Open AccessArticle

Electrochemical Performance of Potassium Hydroxide and Ammonia Activated Porous Nitrogen-Doped Carbon in Sodium-Ion Batteries and Supercapacitors

by Yuliya V. Fedoseeva, Elena V. Shlyakhova, Svetlana G. Stolyarova, Anna A. Vorfolomeeva, Alina D. Nishchakova, Mariya A. Grebenkina, Anna A. Makarova, Konstantin A. Kovalenko, Alexander V. Okotrub and Lyubov G. Bulusheva

Inorganics 2022, 10(11), 198; https://doi.org/10.3390/inorganics10110198 - 07 Nov 2022

Cited by 2 | Viewed by 1757

Abstract

Carbon nanomaterials possessing a high specific surface area, electrical conductivity and chemical stability are promising electrode materials for alkali metal-ion batteries and supercapacitors. In this work, we study nitrogen-doped carbon (NC) obtained by chemical vapor deposition of acetonitrile over the pyrolysis product of [...] Read more.

Carbon nanomaterials possessing a high specific surface area, electrical conductivity and chemical stability are promising electrode materials for alkali metal-ion batteries and supercapacitors. In this work, we study nitrogen-doped carbon (NC) obtained by chemical vapor deposition of acetonitrile over the pyrolysis product of calcium tartrate, and activated with a potassium hydroxide melt followed by hydrothermal treatment in an aqueous ammonia solution. Such a two-stage chemical modification leads to an increase in the specific surface area up to 1180 m² g⁻¹, due to the formation of nanopores 0.6–1.5 nm in size. According to a spectroscopic study, the pore edges are decorated with imine, amine, and amide groups. In sodium-ion batteries, the modified material mNC exhibits a stable reversible gravimetric capacity in the range of 252–160 mA h g⁻¹ at current densities of 0.05–1.00 A g⁻¹, which is higher than the corresponding capacity of 142–96 mA h g⁻¹ for the initial NC sample. In supercapacitors, the mNC demonstrates the highest specific capacitance of 172 F g⁻¹ and 151 F g⁻¹ at 2 V s⁻¹ in 1 M H₂SO₄ and 6 M KOH electrolytes, respectively. The improvement in the electrochemical performance of mNC is explained by the cumulative contribution of a developed pore structure, which ensures rapid diffusion of ions, and the presence of imine, amine, and amide groups, which enhance binding with sodium ions and react with protons or hydroxyl ions. These findings indicate that hydrogenated nitrogen functional groups grafted to the edges of graphitic domains are responsible for Na⁺ ion storage sites and surface redox reactions in acidic and alkaline electrolytes, making modified carbon a promising electrode material for electrochemical applications. Full article

(This article belongs to the Special Issue Beyond Lithium-Ion Battery Technology)

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16 pages, 16467 KiB

Open AccessArticle

Cold Sintering Process of Zinc Oxide Ceramics: Powder Preparation and Sintering Conditions Effects on Final Microstructure

by Andrey V. Smirnov, Maxim V. Kornyushin, Anastasia A. Kholodkova, Sergey A. Melnikov, Artem D. Stepanov, Elena V. Fesik and Yurii D. Ivakin

Inorganics 2022, 10(11), 197; https://doi.org/10.3390/inorganics10110197 - 05 Nov 2022

Cited by 5 | Viewed by 1949

Abstract

Although the activating effect of an acetate medium in the cold sintering process of zinc oxide ceramics is well known, some problems need to be solved on the effect of process conditions and the initial powder’s preparation methods on the ceramic’s density and [...] Read more.

Although the activating effect of an acetate medium in the cold sintering process of zinc oxide ceramics is well known, some problems need to be solved on the effect of process conditions and the initial powder’s preparation methods on the ceramic’s density and microstructure. This article describes an effect of the zinc acetate introduction method, its concentration in zinc oxide powder as well as that of the die sealing configuration on the density and microstructure of zinc oxide ceramics obtained by the cold sintering process at 244 °C. The activating additive of zinc acetate was applied in two ways: (1) impregnation in aqueous solution and (2) impregnation with subsequent treatment in water vapor. Zinc oxide powders and ceramics were analyzed using SEM, TGA/DSC/MS and XRD to reveal the effect of powder pre-treatment and sintering conditions on the material microstructure. Cold sintered ZnO ceramics samples with a relative density up to 0.99 and with average grain sizes from 0.28 to 1.71 μm were obtained. The die sealing by two Teflon sealing rings appeared to be the most effective. Full article

(This article belongs to the Special Issue Oxide Optical Ceramics and Precursor Powders Preparation for Luminescence and Laser Applications)

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13 pages, 2564 KiB

Open AccessArticle

New Aspects of the Synthesis of closo-Dodecaborate Nitrilium Derivatives [B₁₂H₁₁NCR]⁻ (R = n-C₃H₇, i-C₃H₇, 4-C₆H₄CH₃, 1-C₁₀H₇): Experimental and Theoretical Studies

by Alexey V. Nelyubin, Ilya N. Klyukin, Alexander S. Novikov, Andrey P. Zhdanov, Nikita A. Selivanov, Alexander Yu. Bykov, Alexey S. Kubasov, Konstantin Yu. Zhizhin and Nikolay T. Kuznetsov

Inorganics 2022, 10(11), 196; https://doi.org/10.3390/inorganics10110196 - 02 Nov 2022

Cited by 9 | Viewed by 1386

Abstract

The preparation of novel nitrilium derivatives of closo-dodecaborate anion [B₁₂H₁₁NCR]⁻, R = n-C₃H₇, i-C₃H₇, 4-C₆H₄CH₃, 1-C₁₀H₇ is [...] Read more.

The preparation of novel nitrilium derivatives of closo-dodecaborate anion [B₁₂H₁₁NCR]⁻, R = n-C₃H₇, i-C₃H₇, 4-C₆H₄CH₃, 1-C₁₀H₇ is described. Target compounds were obtained in good yields (up to 73%). The synthesis of target borylated nitrilium derivatives was characterised by the simplicity of the chemical apparatus and the absence of the necessity for the purification of desired compounds. The crystal structures of previously obtained [B₁₂H₁₁NCCH₃]⁻ and novel [B₁₂H₁₁NCC₃H₇]⁻ were established with the help of X-ray structure analysis. DFT-analysis of several nitrilium derivatives [B₁₂H₁₁NCR]⁻, R = CH₃, C₃H₇, 4-CH₃C₆H₄ was carried out. The main peculiarities of the C≡N bond of the exo-polyhedral substituent were revealed in terms of bond lengths, bond orders and atomic charges. The LUMO orbitals of the systems considered were examined for understanding of the electrophilic nature of the nitrilium derivatives of the closo-dodecaborate anion. Full article

(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)

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12 pages, 2349 KiB

Open AccessArticle

Highly Porous Cyanometallic Spin-Crossover Frameworks Employing Pyridazino[4,5-d]pyridazine Bridge

by Volodymyr M. Hiiuk, Sergiu Shova, Kostiantyn V. Domasevitch and Il’ya A. Gural’skiy

Inorganics 2022, 10(11), 195; https://doi.org/10.3390/inorganics10110195 - 02 Nov 2022

Viewed by 1465

Abstract

Single crystals of two spin-crossover (SCO) cyanometallic coordination polymers based on the pyridazino[4,5-d]pyridazine ligand (pp) of the composition [Fe(pp)M(CN)₄]∙G (where M = Pd, Pt; G = guest molecules) were obtained by a slow diffusion technique. A single-crystal [...] Read more.

Single crystals of two spin-crossover (SCO) cyanometallic coordination polymers based on the pyridazino[4,5-d]pyridazine ligand (pp) of the composition [Fe(pp)M(CN)₄]∙G (where M = Pd, Pt; G = guest molecules) were obtained by a slow diffusion technique. A single-crystal X-ray analysis showed that both compounds adopted the structure of porous 3D frameworks, consisting of heterometallic cyano-bridged layers and interlayer pillar pp ligands, with a total solvent accessible volume of ca. 160 Å³ per iron(II) ion (about 37% of the unit cell volume). These frameworks displayed hysteretic SCO behaviour with T_1/2 of 150/190 K (heating/cooling) for Pd complex and 135/170 K (heating/cooling) for Pt complex, which was confirmed by variable-temperature SCXRD experiments. This research shows the perspective of using pp ligand for building porous MOFs with spin transitions. Full article

(This article belongs to the Special Issue Inorganics: 10th Anniversary)

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16 pages, 3694 KiB

Open AccessArticle

Synthesis, Structure and Photoluminescence Properties of Cd and Cd-Ln Pentafluorobenzoates with 2,2′:6′,2′-Terpyridine Derivatives

by Maxim A. Shmelev, Julia K. Voronina, Maxim A. Evtyukhin, Fedor M. Dolgushin, Evgenia A. Varaksina, Ilya V. Taydakov, Aleksey A. Sidorov, Igor L. Eremenko and Mikhail A. Kiskin

Inorganics 2022, 10(11), 194; https://doi.org/10.3390/inorganics10110194 - 01 Nov 2022

Cited by 7 | Viewed by 1792

Abstract

Six new complexes [Cd(tpy)(pfb)₂] (1, tpy = 2,2′:6′,2″-terpyridine), [Ln₂Cd₂(tpy)₂(pfb)₁₀] (Ln = Eu (2_Eu), Tb (2_Tb)), [Ln₂Cd₂(tbtpy)₂(pfb)₁₀]·2MeCN (Ln = Eu (3_Eu [...] Read more.

Six new complexes [Cd(tpy)(pfb)₂] (1, tpy = 2,2′:6′,2″-terpyridine), [Ln₂Cd₂(tpy)₂(pfb)₁₀] (Ln = Eu (2_Eu), Tb (2_Tb)), [Ln₂Cd₂(tbtpy)₂(pfb)₁₀]·2MeCN (Ln = Eu (3_Eu), Tb (3_Tb), tbtpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine), [Eu₂Cd₂(tppz)(pfb)₁₀]n (4, tppz = 2,3,5,6-tetra-(pyridin-2-yl)pyrazine) based on pentafluorobenzoic acid (Hpfb) have been prepared and investigated. The effect of tridentate ligands on geometry heterometallic scaffolds synthesized complexes is discussed. The supramolecular crystal structures of the new compounds are stabilized by π-π, C-F···π, C-H···O, C-H...F, F….F interactions. Non-covalent interactions have been studied using Hirschfeld surface analysis. The obtained compounds were characterized by single-crystal and powder X-ray diffraction, luminescence spectroscopy, IR spectroscopy, CHN analysis. Complexes 2_Ln and 3_Ln exhibit metal-centered photoluminescence, but the presence of ligand luminescence bands indicates incomplete energy transfer from the d-block to the lanthanide ion. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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7 pages, 1318 KiB

Open AccessCommunication

NH₃ Sensor Based on ZIF-8/CNT Operating at Room Temperature with Immunity to Humidity

by Wenjun Yan, Shiyu Zhou, Min Ling, XinSheng Peng and Houpan Zhou

Inorganics 2022, 10(11), 193; https://doi.org/10.3390/inorganics10110193 - 31 Oct 2022

Cited by 2 | Viewed by 1584

Abstract

Humidity effects on resistive gas sensors operating at room temperature remain a serious bottleneck. In this work, we introduce a resistive gas sensor based on a zeolitic imidazolate framework-8/carbon nanotube (ZIF-8/CNT) composite for the detection of ammonia gas at room temperature. The composite [...] Read more.

Humidity effects on resistive gas sensors operating at room temperature remain a serious bottleneck. In this work, we introduce a resistive gas sensor based on a zeolitic imidazolate framework-8/carbon nanotube (ZIF-8/CNT) composite for the detection of ammonia gas at room temperature. The composite was prepared using a facile solution method. In this sensor, the basic mechanism was the charge transfer between ammonia molecules and CNTs; meanwhile, the ZIF-8 facilitated the adsorption of ammonia molecules as a preconcentrator, and prevented the adsorption of H₂O molecules due to its hydrophobicity; CNTs were threaded through the ZIF-8 to form a great conductive network for charge transfer. The obtained sensor showed good ammonia sensing, especially at room temperature, with great selectivity and immunity to humidity under moderately humid conditions (45–70 % RH). However, the ammonia response was reduced at very high humidity (90% RH) due to the competitive adsorption of H₂O molecules. This proved that the NH₃ sensor based on ZIF-8/CNT could be suitable for practical applications under moderately humid conditions. Full article

(This article belongs to the Special Issue Gas Sensors Based on Inorganic Materials)

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14 pages, 4720 KiB

Open AccessArticle

Effect of Remnant Carbon and Etching of Particles on Pyrolysis Bonded Silicon Carbide (PBSC)

by Mehrad Mehr, Mohamed S. Elbakhshwan, David J. Sprouster, Simerjeet K. Gill, Lynne E. Ecker, Ghatu Subhash and Juan C. Nino

Inorganics 2022, 10(11), 192; https://doi.org/10.3390/inorganics10110192 - 31 Oct 2022

Viewed by 1295

Abstract

Silicon carbide (SiC) formed through pyrolysis of preceramic polymers loaded with SiC particles has gained significant attention for applications such as coatings, composite matrix modifications, and most importantly additive manufacturing. This work presents combined synchrotron XRD, Raman spectroscopy, scanning electron microscopy, nano-indentation, and [...] Read more.

Silicon carbide (SiC) formed through pyrolysis of preceramic polymers loaded with SiC particles has gained significant attention for applications such as coatings, composite matrix modifications, and most importantly additive manufacturing. This work presents combined synchrotron XRD, Raman spectroscopy, scanning electron microscopy, nano-indentation, and Vickers indentation of pyrolysis bonded SiC to shed light on the changes of composition and mechanical properties of these materials. Characterization was performed on samples that were heat treated ranging from the synthesis 850 °C up to 1500 °C. Pre-treatments of the powders prior to pellet synthesis, such as heat treatment and etching using a hydrofluoric acid (HF), were investigated. It is shown that the degradation of mechanical properties when exposed to higher temperatures is due to the burnout of amorphous carbon clusters remnant of the pyrolysis process of the preceramic polymer. Furthermore, prior HF etching and removal of the native oxide layer of the powders showed improved density and hardness values in the final pellets. The average Vickers hardness of the control samples were 4.59 GPa and later 3.74 GPa when exposed to 1500 °C, while the samples synthesized using powders that were etched with HF had an average hardness value of 9.37 GPa and later 6.86 GPa when exposed to 1500 °C. Full article

(This article belongs to the Section Inorganic Solid-State Chemistry)

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12 pages, 1200 KiB

Open AccessArticle

Technoeconomic Analysis of Dye Sensitized Solar Cells (DSSCs) with WS₂/Carbon Composite as Counter Electrode Material

by Tajamul Hussain Syed and Wei Wei

Inorganics 2022, 10(11), 191; https://doi.org/10.3390/inorganics10110191 - 29 Oct 2022

Cited by 12 | Viewed by 3778

Abstract

Exploration of clean and renewable energy materials is necessary due to the coming energy crisis and environmental problems. Solar energy is one of the favorable energy sources because of the continuous energy reservoir and its affluence. Silicon-based solar devices are expensive due to [...] Read more.

Exploration of clean and renewable energy materials is necessary due to the coming energy crisis and environmental problems. Solar energy is one of the favorable energy sources because of the continuous energy reservoir and its affluence. Silicon-based solar devices are expensive due to their complicated production process, which limits this technology for urban and other commercial applications. Among the third generation of solar cells, Dye-Sensitized Solar Cells (DSSCs) have attracted widespread attention as potential cost-effective alternatives to silicon-based solar cells. In this paper, the commercializing potential of the DSSCs is investigated. A module is introduced where the materials, equipment, and distribution of direct manufacturing costs are calculated. The manufacturing costs and the Levelized Cost of Energy (LCOE) of these DSSCs for a system lifetime of 25 years were determined to be USD 22.40 per m² and USD 0.0438 per kWh and the module price of this technology is USD 0.18 per W and the total installed system cost is USD 0.88 per W in Kansas which suggest that this PV technology could challenge other leading PV technologies. Full article

(This article belongs to the Collection Coordination Complexes for Dye-Sensitized Solar Cells (DSCs))

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13 pages, 6415 KiB

Open AccessArticle

Syntheses and Applications of Symmetrical Dinuclear Half-Sandwich Ruthenium(II)–Dipicolinamide Complexes as Catalysts in the Transfer Hydrogenation of Ketones

by Robert Tettey Kumah, Sabathile Thandeka Mvelase and Stephen Otieno Ojwach

Inorganics 2022, 10(11), 190; https://doi.org/10.3390/inorganics10110190 - 29 Oct 2022

Cited by 2 | Viewed by 1652

Abstract

The treatment of [Ru(η⁶-p-cymene)Cl₂]₂ with N,N’-(1,2-phenylene)dipicolinamide (H₂L1) afforded the double salt complex [{Ru(η⁶-p-cymene)₂-µ-Cl}L1][Ru(η⁶-p-cymene)Cl₃], (Ru1) in moderate [...] Read more.

The treatment of [Ru(η⁶-p-cymene)Cl₂]₂ with N,N’-(1,2-phenylene)dipicolinamide (H₂L1) afforded the double salt complex [{Ru(η⁶-p-cymene)₂-µ-Cl}L1][Ru(η⁶-p-cymene)Cl₃], (Ru1) in moderate yields. Separately, the reactions of ligands (H₂L1), N,N’-(4,5 dimethyl-1,2-phenylene)dipicolinamide (H₂L2), and N,N’-(4-methoxy-1,2-phenylene)dipicolinamide (H₂L3) with the [Ru(η⁶-p-cymene)Cl₂]₂ in the presence of KPF₆ afforded the respective dinuclear half-sandwich Ru(II) complexes [{(Ru(η⁶-p-cymene)_2--µ-Cl}L1][PF₆] (Ru2), [{(Ru(η⁶-p-cymene)₂-µ-Cl}L2][PF₆] (Ru3), and [{(Ru(η⁶-p-cymene)₂-µ-Cl}L3][PF₆] (Ru4). NMR and FT-IR spectroscopies, ESI-MS spectrometry, and elemental analyses were used to establish the molecular structures of the new dinuclear ruthenium(II) complexes. Single crystal X-ray crystallography was used to confirm the piano-stool geometry of the dinuclear complexes Ru1 and Ru4, as containing N^N chelated ligand and bridging chlorido ligands in each Ru(II) atom. The complexes (Ru1-Ru4) showed good catalytic activities at low catalyst concentrations of 0.005 mol% in the transfer hydrogenation of a wide range of ketone substrates. Full article

(This article belongs to the Special Issue Metal-Catalyzed (De)Hydrogenation, Hydrogen Transfer and Hydroelementation Reactions)

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18 pages, 8289 KiB

Open AccessReview

Rational Design of Fluorescent/Colorimetric Chemosensors for Detecting Transition Metal Ions by Varying Functional Groups

by Jong-Kwon Park, Junhyeop Shin, Seohyeon Jang, Myeong-Lok Seol, Jihyeon Kang, Seyoung Choi, Hojong Eom, Ohhyun Kwon, Soomin Park, Dong-Youn Noh and Inho Nam

Inorganics 2022, 10(11), 189; https://doi.org/10.3390/inorganics10110189 - 29 Oct 2022

Cited by 3 | Viewed by 1687

Abstract

In recent decades, concerns about increasing biological and environmental contamination have necessitated the development of chemosensors with high selectivity, sensitivity, and cost-effectiveness. In principle, the sensing performance can be affected by the functional group(s) of receptor, the charge of the metal ion(s), and [...] Read more.

In recent decades, concerns about increasing biological and environmental contamination have necessitated the development of chemosensors with high selectivity, sensitivity, and cost-effectiveness. In principle, the sensing performance can be affected by the functional group(s) of receptor, the charge of the metal ion(s), and the electron configuration of the sensing molecule(s)e and metal ion(s). Fine controlling of the substituents can influence the electron density of the receptor to enhance the binding affinity to metal ions, which is an effective way to improve the photophysical properties of the sensors. This review explores the effect of functional group modification on the performance of various chemosensors represented by Pt(dithiolene)-based complexes (2012–2021). Then, recently developed Schiff base chemosensors (2014–2021) are discussed. The Schiff base is a good platform for controlling electron configuration due to a facile synthesis of various organic structures (aldehyde or ketone groups with primary amine derivatives). The discussion focuses on the detection type, physicochemical and optical properties, and applications of these chemosensors. Full article

(This article belongs to the Special Issue Colorimetric and Fluorescent Chemosensors for Metal Ions)

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14 pages, 12871 KiB

Open AccessArticle

A Graphene Oxide-Angiogenin Theranostic Nanoplatform for the Therapeutic Targeting of Angiogenic Processes: The Effect of Copper-Supplemented Medium

by Lorenzo Riela, Lorena Maria Cucci, Örjan Hansson, Tiziano Marzo, Diego La Mendola and Cristina Satriano

Inorganics 2022, 10(11), 188; https://doi.org/10.3390/inorganics10110188 - 29 Oct 2022

Cited by 3 | Viewed by 1503

Abstract

Graphene oxide (GO) nanosheets with different content in the defective carbon species bound to oxygen sp3 were functionalized with the angiogenin (ANG) protein, to create a novel nanomedicine for modulating angiogenic processes in cancer therapies. The GO@ANG nanocomposite was scrutinized utilizing UV-visible and [...] Read more.

Graphene oxide (GO) nanosheets with different content in the defective carbon species bound to oxygen sp3 were functionalized with the angiogenin (ANG) protein, to create a novel nanomedicine for modulating angiogenic processes in cancer therapies. The GO@ANG nanocomposite was scrutinized utilizing UV-visible and fluorescence spectroscopies. GO exhibits pro- or antiangiogenic effects, mostly attributed to the disturbance of ROS concentration, depending both on the total concentration (i.e., >100 ng/mL) as well as on the number of carbon species oxidized, that is, the C/O ratio. ANG is considered one of the most effective angiogenic factors that plays a vital role in the angiogenic process, often in a synergic role with copper ions. Based on these starting hypotheses, the GO@ANG nanotoxicity was assessed with the MTT colorimetric assay, both in the absence and in the presence of copper ions, by in vitro cellular experiments on human prostatic cancer cells (PC-3 line). Laser confocal microscopy (LSM) cell imaging evidenced an enhanced internationalization of GO@ANG than bare GO nanosheets, as well as significant changes in cell cytoskeleton organization and mitochondrial staining compared to the cell treatments with free ANG. Full article

(This article belongs to the Special Issue Bioactivity of Transition Metal-Based Complexes)

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11 pages, 1387 KiB

Open AccessReview

Cobalt-Based Perovskite Electrodes for Solid Oxide Electrolysis Cells

by Chi Zhang, Bin Lu, Haiji Xiong, Chengjun Lin, Lin Fang, Jile Fu, Dingrong Deng, Xiaohong Fan, Yi Li and Qi-Hui Wu

Inorganics 2022, 10(11), 187; https://doi.org/10.3390/inorganics10110187 - 28 Oct 2022

Cited by 7 | Viewed by 2160

Abstract

Recently, many efforts and much attention has been paid to developing environmentally friendly energy. Solid oxide electrolyte cells (SOECs) process in reverse to solid oxide fuel cells (SOFCs) producing hydrogen gas as a green energy source. However, in this application, high-performance catalysts are [...] Read more.

Recently, many efforts and much attention has been paid to developing environmentally friendly energy. Solid oxide electrolyte cells (SOECs) process in reverse to solid oxide fuel cells (SOFCs) producing hydrogen gas as a green energy source. However, in this application, high-performance catalysts are usually required to overcome the sluggish oxygen evolution reactions (OER) during water decomposition. For this reason, discovery of catalysts with high performance is a crucial issue for the wide application of SOECs. Owning to their inherent activity and adequate stability in electrochemical conditions, perovskite oxides have been intensively employed in SOECs. In this mini review, we summarize the currently available studies concerning the applications of cobalt-based perovskite oxide catalysts in SOECs. Particularly, their structural properties and corresponding electronic structures are discussed based on their electrochemical performance, both experimentally and theoretically. Full article

(This article belongs to the Special Issue Semiconducting Nanomaterials for Energy Storage)

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Inorganics, Volume 10, Issue 11 (November 2022) – 41 articles

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