Inorganics

13 pages, 3616 KiB

Open AccessArticle

Synthesis, Structure, and Luminescence Properties of Zinc(II) Complex with a Spacer-Armed Tetradentate N₂O₂-Donor Schiff Base

by Alexey Gusev, Elena Braga, Kirill Mamontov, Mikhail Kiskin and Wolfgang Linert

Inorganics 2025, 13(5), 173; https://doi.org/10.3390/inorganics13050173 - 19 May 2025

Abstract

A zinc complex bearing a pyrazolone-based azomethine ligand has been synthesized for blue-emitting organic light-emitting diodes (OLEDs). The azomethine ligand H₂L and the complex [ZnL·H₂O] were characterized by IR, 1H NMR, XRD, and TGA/DSC techniques. According to a single-crystal [...] Read more.

A zinc complex bearing a pyrazolone-based azomethine ligand has been synthesized for blue-emitting organic light-emitting diodes (OLEDs). The azomethine ligand H₂L and the complex [ZnL·H₂O] were characterized by IR, 1H NMR, XRD, and TGA/DSC techniques. According to a single-crystal X-ray diffraction analysis, the complex [ZnL·H₂O] has a molecular structure. Its solid-state PL maxima appear to be at 416 nm and emit moderate blue emission with a quantum yield (QY) of 2%, with a dehydrated form of the complex showing greater efficiency with a QY of 55.5%. ZnL-based electroluminescent devices for OLED applications were fabricated. The devices exhibit blue emission with brightness up to 5300 Cd/A. Full article

(This article belongs to the Section Coordination Chemistry)

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13 pages, 2343 KiB

Open AccessArticle

Structural and Optical Properties of BaWO₄ Obtained by Fast Mechanochemical Treatment

by Maria Gancheva, Reni Iordanova, Iovka Koseva, Iskra Piroeva and Petar Ivanov

Inorganics 2025, 13(5), 172; https://doi.org/10.3390/inorganics13050172 - 18 May 2025

Abstract

This work investigated the optical characteristics of BaWO₄ nanoparticles that were produced through direct mechanochemical synthesis at varying speeds and times. This research expands upon our previous study. We demonstrated that the mechanochemical activation of the precursor of BaCO₃ and WO [...] Read more.

This work investigated the optical characteristics of BaWO₄ nanoparticles that were produced through direct mechanochemical synthesis at varying speeds and times. This research expands upon our previous study. We demonstrated that the mechanochemical activation of the precursor of BaCO₃ and WO₃, at elevated milling speeds (850 rpm), facilitates the formation of tetragonal BaWO₄ in a reduced reaction time. The final products were characterized by scanning electron microscopy (SEM), as well as Raman, infrared (IR), UV-Vis diffuse reflectance, and photoluminescence spectroscopies. The crystallite sizes and particles shapes were determined by X-ray diffraction and SEM analysis. Round particles with a size below 50 nm formed under different milling conditions. The Raman spectra of the synthesized samples confirmed the presence of a scheelite-type structure with the typical six distinct vibrational peaks. The symmetry of the structural WO₄ groups was determined by IR spectroscopy. The absorption spectra of both samples exhibited intensive peaks at 210 nm, and the calculated optical band gaps of BaWO₄ were 5.10 eV (3 h/500 rpm) and 5.24 eV (1 h/850 rpm). A strong (400 nm) and weak (465 nm) emission were observed for the BaWO₄ that was obtained at a higher milling speed, while wider emission at 410 nm was visible for the BaWO₄ that was prepared at a lower milling speed. The CIE coordinates of the mechanochemically synthesized BaWO₄ were located within the blue area, exhibiting various positions. Full article

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21 pages, 3742 KiB

Open AccessArticle

Mixed 3d-3d’-Metal Complexes: A Dicobalt(III)Iron(III) Coordination Cluster Based on Pyridine-2-Amidoxime

by Sotiris G. Skiadas, Christina D. Polyzou, Zoi G. Lada, Rodolphe Clérac, Yiannis Sanakis, Pierre Dechambenoit and Spyros P. Perlepes

Inorganics 2025, 13(5), 171; https://doi.org/10.3390/inorganics13050171 (registering DOI) - 17 May 2025

Abstract

In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH₂paoH) in Fe-Co chemistry. The 1:1:3 Fe^III(NO₃)₃·9H₂O/Co^II(ClO₄)₂·6H₂O/NH₂paoH reaction mixture [...] Read more.

In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH₂paoH) in Fe-Co chemistry. The 1:1:3 Fe^III(NO₃)₃·9H₂O/Co^II(ClO₄)₂·6H₂O/NH₂paoH reaction mixture in MeOH gave complex [Co^III₂Fe^III(NH₂pao)₆](ClO₄)₂(NO₃) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [Co^III₂Fe^III(NH₂pao)₆]³⁺ which are strictly linear by symmetry. The central high-spin Fe^III ion is connected to each of the terminal low-spin Co^III ions through the oximato groups of three 2.1110 (Harris notation) NH₂pao⁻ ligands, in such a way that the six O atoms are bonded to the octahedral Fe^III center ({Fe^IIIO₆} coordination sphere). Each terminal octahedral Co^III ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH₂pao⁻ groups ({Co^IIIN₆} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO₄⁻ and NO₃⁻ counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d⁶ cobalt(III) and a charge-transfer NH₂pao⁻ → Fe^III band. The δ and ΔΕ_Q ⁵⁷Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin Fe^III center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of Fe^III. A critical discussion of the importance of NH₂paoH and its anionic forms (NH₂pao⁻, NHpao²⁻) in homo- and heterometallic chemistry is also attempted. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Novel Coordination and Organometallic Complexes)

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12 pages, 2422 KiB

Open AccessArticle

A Pt(II) Complex with a PNN Type Ligand Dppmaphen Exhibits Selective, Reversible Vapor-Chromic Photoluminescence

by Yuanyuan Hu, Jiangyue Wang, David James Young, Hong-Xi Li, Yuxin Lu and Zhi-Gang Ren

Inorganics 2025, 13(5), 170; https://doi.org/10.3390/inorganics13050170 - 16 May 2025

Abstract

The reaction of PtCl₂ with a PNN type ligand dppmaphen (N-(diphenylphosphanylmethyl)-2-amino-1,10-phenanthroline) yielded a new Pt(II) complex [Pt(dppmaphen)Cl]Cl·H₂O (1). Upon excitation at 370 nm, compound 1 emits yellow phosphorescence at 539 and 576 nm at room temperature. Exposure of [...] Read more.

The reaction of PtCl₂ with a PNN type ligand dppmaphen (N-(diphenylphosphanylmethyl)-2-amino-1,10-phenanthroline) yielded a new Pt(II) complex [Pt(dppmaphen)Cl]Cl·H₂O (1). Upon excitation at 370 nm, compound 1 emits yellow phosphorescence at 539 and 576 nm at room temperature. Exposure of compound 1 to MeOH vapor induces a shift in its emission to 645 nm, which can be attributed to the substitution of MeOH molecules for H₂O, resulting in the disruption and reorganization of weak interactions in 1. This response is selective for MeOH and, to a lesser extent, EtOH, the orange photoluminescence recovered in air. The emission change of 1 was reversible and visible to the naked eye. Full article

(This article belongs to the Special Issue Editorial Board Members’ Collection Series in “Featuring Ligands and Their Applications in Coordination Chemistry”, 2nd Edition)

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14 pages, 3340 KiB

Open AccessArticle

Synthesis, Molecular Structure, and Computational Studies of Dinuclear d⁰ Titanium(IV) Complex with P-P-Bonded Diphosphine Ligand

by Tomoyuki Toda, Yuya Toma, Miku Nishiguchi and Katsuhiko Takenaka

Inorganics 2025, 13(5), 169; https://doi.org/10.3390/inorganics13050169 - 16 May 2025

Abstract

Diphosphine compounds have been used as ligands for a variety of metals, and studies on their structures and reactivities are still of interest. We investigated the coordination chemistry of P–P-bonded diphosphine by conducting reactions of bis(1,1′-dibenzophospholyl) (Db)₂P–P(Db)₂ 1 with [...] Read more.

Diphosphine compounds have been used as ligands for a variety of metals, and studies on their structures and reactivities are still of interest. We investigated the coordination chemistry of P–P-bonded diphosphine by conducting reactions of bis(1,1′-dibenzophospholyl) (Db)₂P–P(Db)₂ 1 with d⁰-titanium(IV) reagents. The reaction of 1 with TiCl₄ afforded the dinuclear titanium complex Cl₃Ti{μ-(Db)₂P–P(Db)₂}(μ-Cl)₂TiCl₃ 2. The final structure of titanium complex 2 was determined by single-crystal X-ray structural analysis. The molecular structure of the complex was found to be a dinuclear d⁰-titanium complex coordinated to diphosphine on the same side, and the central titanium atoms were bridged to each other by chlorides. To further elucidate this complex, density functional theory (DFT) calculations were conducted to analyze its structure. Full article

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28 pages, 14487 KiB

Open AccessReview

Research Status of Silver Nanoparticles for Dental Applications

by Yanyan Guo, Xiaomei Hou, Sanjun Fan and Chanyuan Jin

Inorganics 2025, 13(5), 168; https://doi.org/10.3390/inorganics13050168 - 16 May 2025

Abstract

Silver nanoparticles (AgNPs) have emerged as a promising antimicrobial agent in dentistry due to their distinctive physicochemical characteristics and broad-spectrum biocidal activity. For example, silver nanoparticles can be incorporated into oral hygiene products in preventive dentistry, composite resins in restorative treatment, irrigation solutions [...] Read more.

Silver nanoparticles (AgNPs) have emerged as a promising antimicrobial agent in dentistry due to their distinctive physicochemical characteristics and broad-spectrum biocidal activity. For example, silver nanoparticles can be incorporated into oral hygiene products in preventive dentistry, composite resins in restorative treatment, irrigation solutions in endodontic treatment, membranes for guided tissue regeneration in periodontal treatment, acrylic resins and porcelains in prosthodontic treatment, coatings in dental implant treatment, and brackets and wires in orthodontic treatment. This paper focuses on summarizing the current knowledge on the antimicrobial use of silver nanoparticles in dentistry, highlighting their antimicrobial mechanism and potential applications in clinical treatment. The literature indicates that silver nanoparticles are a promising antimicrobial agent in dentistry. However, there are still many issues including fundamental antibacterial mechanisms that need to be completely elucidated before clinical applications. Full article

(This article belongs to the Special Issue Development of Nanocomposite Materials for Environmental Remediation and Biomedical Application)

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16 pages, 4695 KiB

Open AccessArticle

Hematite Nanoparticles Synthesized by Green Route: Characterization, Anticancer and Antioxidant Activities

by Safa Ezzine, Hela Ferjani, Oluwasayo E. Ogunjinmi and Damian C. Onwudiwe

Inorganics 2025, 13(5), 167; https://doi.org/10.3390/inorganics13050167 - 15 May 2025

Abstract

Recently, attention has shifted towards the green synthesis of nanoparticles using plant extracts rich in phytochemicals like phenols and flavonoids, offering an alternative method that avoids harmful chemicals and enables large-scale, low-cost production. This study introduces a straightforward and eco-friendly approach to synthesizing [...] Read more.

Recently, attention has shifted towards the green synthesis of nanoparticles using plant extracts rich in phytochemicals like phenols and flavonoids, offering an alternative method that avoids harmful chemicals and enables large-scale, low-cost production. This study introduces a straightforward and eco-friendly approach to synthesizing hematite α-Fe₂O₃ nanoparticles utilizing an aqueous extract of Musa paradisiaca. The variation in the calcination temperature resulted in the formation of nanoparticles presented as Fe₂O₃ (1), Fe₂O₃ (2), and Fe₂O₃ (3), obtained at 650, 750, and 900 °C for 4 h, respectively. This variation allowed for an investigation into the impact of different reaction temperatures on the structural and optical properties of the nanoparticles. Structural analysis was conducted using X-ray diffraction (XRD), while scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to examine morphology. Optical properties were assessed via UV-vis spectroscopy, revealing a reduction in the energy band gap (from 2.5 to 1.87 eV), attributed to an increase in crystallite size resulting from longer calcination temperatures (650–900 °C). A biological assay was carried out to evaluate the antioxidant and anticancer potentials of the nanoparticles. Both Fe₂O₃ (1) and Fe₂O₃ (2) with IC₅₀ values of 46.84 and 46.14 µg/mL, respectively, showed similar antioxidant potentials, while peel extract exhibited the least activity with an IC₅₀ of 79.26 µg/mL. The nanoparticles, peels, and 5-FU (used as standard) showed a stronger inhibitory effect on the Human Embryonic Kidney (HEK) 293 cells compared to the HeLa cells. This implies that the HEK 293 cells might be more susceptible to the drug samples and a lower concentration might even be sufficient to achieve the inhibition of normal cell proliferation. These results indicate a better therapeutic window with a lesser inhibitory effect compared to standard drugs used as controls. Full article

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14 pages, 2784 KiB

Open AccessArticle

Preparation and Photocatalytic Hydrogen Production of Pink ZnS

by Shangjie Gao, Yongxin Lu, Teng Ma, Haixia Liu and Jie Zhang

Inorganics 2025, 13(5), 166; https://doi.org/10.3390/inorganics13050166 - 15 May 2025

Abstract

With the continuous growth of global energy demand and the increasingly severe environmental issues, the extensive utilization of traditional fossil fuels has led to serious energy crises and environmental pollution problems. In this study, a hydrothermal method was employed, and by adding ethanolamine [...] Read more.

With the continuous growth of global energy demand and the increasingly severe environmental issues, the extensive utilization of traditional fossil fuels has led to serious energy crises and environmental pollution problems. In this study, a hydrothermal method was employed, and by adding ethanolamine and controlling different temperatures, pink zinc sulfide with zinc vacancies was synthesized. UV-Vis DRS analysis indicated that the sample exhibited significant visible light absorption characteristics within the wavelength range of 500–550 nm. The presence of zinc vacancies was confirmed through XPS. Due to the existence of zinc vacancies, the sample demonstrated excellent photocatalytic hydrogen evolution activity without the need for co-catalysts, with the optimal sample achieving a hydrogen evolution rate of 7631.70 μmol h⁻¹ g⁻¹. Zinc vacancies can provide additional active sites, enhance catalytic efficiency, and promote the separation of photogenerated electrons and holes. Furthermore, the introduction of vacancies effectively reduces the bandgap of the material, significantly broadening its visible light absorption range. This work provides a new approach for enhancing hydrogen evolution in pure ZnS and offers novel strategies for the further design of ZnS-related photocatalysts. Full article

(This article belongs to the Special Issue Nanocomposites for Photocatalysis, 2nd Edition)

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11 pages, 3786 KiB

Open AccessArticle

AlF₃-Modified Carbon Anodes for Aluminum Electrolysis: Oxidation Resistance and Microstructural Evolution

by Guifang Xu, Yonggang Ding, Fan Bai, Youming Zhang, Jianhua Yin and Caifeng Chen

Inorganics 2025, 13(5), 165; https://doi.org/10.3390/inorganics13050165 - 15 May 2025

Abstract

The aluminum electrolysis industry faces significant challenges due to the high consumption and environmental impact of carbon anodes, which are prone to oxidation in high-temperature and strongly oxidizing environments. This study innovatively introduces aluminum fluoride (AlF₃) as an additive to enhance [...] Read more.

The aluminum electrolysis industry faces significant challenges due to the high consumption and environmental impact of carbon anodes, which are prone to oxidation in high-temperature and strongly oxidizing environments. This study innovatively introduces aluminum fluoride (AlF₃) as an additive to enhance the oxidation resistance of carbon anodes for aluminum electrolysis. By systematically exploring microstructural evolution through SEM, XRD, Raman spectroscopy, and permeability analyses, it reveals that AlF₃ inserts fluorine atoms into carbon interlayers, forming F-C bonds that reduce interlayer spacing while promoting graphitization. Simultaneously, AlF₃-derived α-Al₂O₃ particles densify the anode and make it more compact, reaching the optimum when 7 wt.% AlF₃ is doped. The bulk density of the carbon anode increased to 2.08 g/cm³, porosity decreased to 0.315, and air permeability reached a minimum of 2.3 nPm. In addition, the fluorine intercalation reduces the electrical resistance to 2.12 Ω via conductive F-C clusters. The demonstrated efficacy of AlF₃ additives in enhancing the oxidation resistance and conductivity of carbon anodes suggests strong potential for industrial adoption, particularly in optimizing anode composition to reduce energy consumption. Full article

(This article belongs to the Special Issue Carbon-Based Hybrid Materials for Environmental and Energy Applications)

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21 pages, 12869 KiB

Open AccessArticle

The Coumarin-Based Silver(I) Complex Showed Enhanced Antitumor and Antimicrobial Activity than Ligand Itself

by Jakub Kurjan, Zuzana Jendželovská, Viktória Dečmanová, Mária Vilková, Katarina Ćirković, Ivana Radojević, Miroslava Litecká, Rastislav Jendželovský and Ivan Potočňák

Inorganics 2025, 13(5), 164; https://doi.org/10.3390/inorganics13050164 - 14 May 2025

Abstract

In this study, a novel silver(I) complex [Ag(HL¹)₂]NO₃ (AgHL¹) with coumarin derivative (3E)-3-(1-{[(pyridin-2-yl)methyl]amino}ethylidene)-3,4-dihydro-2H-benzopyran-2,4-dione (HL¹) was prepared. The compounds HL¹ and AgHL¹ were characterized by IR and [...] Read more.

In this study, a novel silver(I) complex [Ag(HL¹)₂]NO₃ (AgHL¹) with coumarin derivative (3E)-3-(1-{[(pyridin-2-yl)methyl]amino}ethylidene)-3,4-dihydro-2H-benzopyran-2,4-dione (HL¹) was prepared. The compounds HL¹ and AgHL¹ were characterized by IR and NMR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. Specifically, the single crystal X-ray analysis determined the structures of both compounds HL¹ and AgHL¹ in their solid state, while NMR spectroscopy was used for structural determination in a solution. The HL¹ proved to be a monodentate ligand and is coordinated to the Ag(I) atom through a nitrogen atom from the 2-picolylamine fragment. In the complex AgHL¹, two molecules of neutral HL¹ are coordinated forming a nearly linear N-Ag-N arrangement. An uncoordinated nitrate anion balances the positive charge of the complex cation. NMR spectroscopy also confirmed the stability of AgHL¹ in DMSO-d₆ for 3 days. In vitro cytotoxicity of HL¹ and AgHL¹ was performed over two cancerous cell lines A549 and HT-29 and their selectivity was verified on a healthy CCD-18Co cell line. AgHL¹ exhibited low anticancer nonselective activity while the ligand was inactive. Also, the complex shows better antimicrobial activity than the positive controls on the Pseudomonas aeruginosa standard and clinical strain as well as on the tested molds. Full article

(This article belongs to the Special Issue Functional Inorganic Biomaterials for Molecular Sensing and Biomedical Applications)

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5 pages, 156 KiB

Open AccessEditorial

Advanced Inorganic Semiconductor Materials, 2nd Edition

by Sake Wang, Minglei Sun and Nguyen Tuan Hung

Inorganics 2025, 13(5), 163; https://doi.org/10.3390/inorganics13050163 - 14 May 2025

Abstract

Building upon our previous edition [...] Full article

(This article belongs to the Special Issue Advanced Inorganic Semiconductor Materials, 2nd Edition)

40 pages, 7391 KiB

Open AccessReview

Preparation Methods and Photocatalytic Performance of Kaolin-Based Ceramic Composites with Selected Metal Oxides (ZnO, CuO, MgO): A Comparative Review

by Dikra Bouras, Lotfi Khezami, Regis Barille, Neçar Merah, Billel Salhi, Gamal A. El-Hiti, Ahlem Guesmi and Mamoun Fellah

Inorganics 2025, 13(5), 162; https://doi.org/10.3390/inorganics13050162 - 13 May 2025

Abstract

The current review examines various methods for preparing photocatalytic materials based on ceramic substrates, with a focus on incorporating metal oxides such as ZnO, CuO, and MgO. This study compares traditional mixing, co-precipitation, sol–gel, and autoclave methods for synthesizing these materials. Kaolin-based ceramics [...] Read more.

The current review examines various methods for preparing photocatalytic materials based on ceramic substrates, with a focus on incorporating metal oxides such as ZnO, CuO, and MgO. This study compares traditional mixing, co-precipitation, sol–gel, and autoclave methods for synthesizing these materials. Kaolin-based ceramics (DD3 and DD3 with 38% ZrO₂) from Guelma, Algeria, were used as substrates. This review highlights the effects of different preparation methods on the structural, morphological, and compositional properties of the resulting photocatalysts. Additionally, the potential of these materials for the photocatalytic degradation of organic dyes, specifically Orange II, was evaluated. Results indicated that ceramic/ZnO/CuO and ceramic/MgO powders prepared via traditional mixing and co-precipitation techniques exhibited significantly faster degradation rates under visible light than Cu layers deposited on ceramic substrates using solution gradient processes. This enhancement was attributed to the increased effective surface area and the size of the spherical nanoparticles obtained through these methods, which facilitated accelerated pollutant absorption. This study highlights the ease and cost-effectiveness of preparing robust layers on ceramic substrates, which are advantageous for photocatalytic applications due to their straightforward removal after filtration. Notably, DD3Z/MgO powders demonstrated superior catalytic activity, achieving complete degradation of the organic dye in just 10 min, whereas DD3Z/ZnO-CuO powders achieved 93.6% degradation after 15 min. Additionally, experiments using kaolin-based ceramics as substrates instead of powders yielded a maximum dye decomposition rate of 77.76% over 6 h using ZnO thin layers prepared via the autoclave method. Full article

(This article belongs to the Special Issue Nanocomposites for Photocatalysis, 2nd Edition)

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17 pages, 7737 KiB

Open AccessArticle

Photocatalytic Efficiency of Pure and Palladium Co-Catalytic Modified Binary System

by Nina Kaneva and Albena Bachvarova-Nedelcheva

Inorganics 2025, 13(5), 161; https://doi.org/10.3390/inorganics13050161 - 11 May 2025

Abstract

The present work examines pure and palladium photofixed TiO₂ and binary (TiO₂/ZnO) photocatalysts for breaking down tartrazine, a food coloring agent, in distilled water. Powders with the following compositions are obtained using the sol-gel process: 100TiO₂, 10TiO₂ [...] Read more.

The present work examines pure and palladium photofixed TiO₂ and binary (TiO₂/ZnO) photocatalysts for breaking down tartrazine, a food coloring agent, in distilled water. Powders with the following compositions are obtained using the sol-gel process: 100TiO₂, 10TiO₂/90ZnO, 50TiO₂/50ZnO, and 90TiO₂/10ZnO. The composite materials are analyzed using SEM-EDS, UV-Vis, DTA-TG, and X-ray diffraction. The synthesized gels are then photo-fixed with UV light to incorporate palladium ions and are also examined for tartrazine (E102) degradation. The photocatalytic tests were carried out in a cylindrical glass reactor illuminated by ultraviolet light. Compared to mixed binary catalysts, the prepared pure TiO₂ catalyst demonstrated greater activity in the photodegradation of tartrazine (E102). The further of a specific quantity of zinc oxide reduced the catalytic properties of TiO₂. The recombination of photoinduced electron-hole pairs in ZnO may account for this. In comparison to the pure samples, the co-catalytic palladium-modified gels exhibited higher photocatalytic efficiency. Heterojunction and palladium modification of the composites partially captured and transferred the electrons. Consequently, the longer lifetime of the photogenerated charges improved the catalytic activity of the palladium titanium dioxide and binary gels. Additionally, under UV light, pure and palladium photofixed TiO₂ and binary sol-gel samples displayed excellent stability for tartrazine photodegradation. Full article

(This article belongs to the Special Issue Metal Catalyst Discovery, Design and Synthesis)

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12 pages, 2833 KiB

Open AccessArticle

Glass Transition Temperature and Mean Bond Energy of Chalcogenide Glasses in the As₂Se₃-GeTe-CdTe System

by Ina Karadashka, Petya Romanova and Veronika Karadjova

Inorganics 2025, 13(5), 160; https://doi.org/10.3390/inorganics13050160 - 9 May 2025

Abstract

Chalcogenide samples from the As₂Se₃-GeTe-CdTe system were synthesized by the melt-quench technique. The surface topography of some of the samples was performed with the help of scanning electron microscopy. Various physical parameters of the chalcogenide glasses were calculated: the [...] Read more.

Chalcogenide samples from the As₂Se₃-GeTe-CdTe system were synthesized by the melt-quench technique. The surface topography of some of the samples was performed with the help of scanning electron microscopy. Various physical parameters of the chalcogenide glasses were calculated: the degree of cross-linking atom, the average heteropolar bond energy of the glasses, the content of chalcogen in the glass, the mean coordination number, and the average energy of the chemical bonds between the atoms of the metals in the glass. With their help, the components of the overall bond energy were calculated: the mean bond energy of the average cross-linking per atom and the average bond energy per atom of the “remaining matrix”. A linear dependence has been established between the glass transition temperature and the overall mean bond energy and between the glass transition temperature and the mean coordination number. The correlation between microhardness and glass transition temperature of chalcogenide glasses was investigated. The dependance between the composition and physical parameters of the As₂Se₃-GeTe-CdTe glasses was established and discussed. Full article

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25 pages, 4788 KiB

Open AccessArticle

Insight into the Oxygen-Sensing Mechanisms of TiO₂–CeO₂ Mixed Oxides Treated in a High-Energy Ball Mill: An XPS Analysis

by Jelena N. Stevanović, Ana G. Silva, Nenad Bundaleski, Dana Vasiljević-Radović, Milija Sarajlić, Orlando M. N. D. Teodoro and Srđan P. Petrović

Inorganics 2025, 13(5), 159; https://doi.org/10.3390/inorganics13050159 - 9 May 2025

Abstract

This study explored the oxygen-sensing mechanism of CeO₂ modified with TiO₂ via high-energy ball milling at different speeds. Different characterization techniques were employed to investigate the obtained materials. Quantitative surface analysis by X-ray photoelectron spectroscopy was conducted to elucidate their sensitivity [...] Read more.

This study explored the oxygen-sensing mechanism of CeO₂ modified with TiO₂ via high-energy ball milling at different speeds. Different characterization techniques were employed to investigate the obtained materials. Quantitative surface analysis by X-ray photoelectron spectroscopy was conducted to elucidate their sensitivity mechanisms and assess the impact of the introduction of TiO₂. A comparable concentration of oxygen vacancies was found in the samples milled at 350 and 450 rpm. Electrical measurements conducted at temperatures lower than required for semiconductor gas sensors revealed the higher sensitivity of these two samples in comparison to pure CeO₂ at an oxygen concentration above 10%. In contrast, the samples derived from precursors milled at the highest speed exhibited the lowest sensitivity. This may be linked to a slight decrease in the vacancy concentration and the presence of a differentially charged carbon-containing phase. Eventually, the C 1s line provided significant insight into the surface characteristics of the materials. The uniform and non-uniform charging found for pure TiO₂ and CeO₂, respectively, along with the high charging of CeO₂, suggest that TiO₂ promotes the contact between the sensing layer and the overlayer. Sensor testing showed the significantly lower resistance of mixed oxides in comparison to CeO₂, which increases the utility of metal oxide-based sensors. Full article

(This article belongs to the Special Issue Advanced Inorganic Semiconductor Materials, 3rd Edition)

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12 pages, 6312 KiB

Open AccessArticle

Nanocrystalline–Amorphous Transition in ZrN Nanofilms Induced by Helium Accumulation at Grain Boundaries

by Xin Xiao, Sen Sun, Wei Jiang, Xiaoling Qin, Qinxin Liu and Yuanxia Lao

Inorganics 2025, 13(5), 158; https://doi.org/10.3390/inorganics13050158 - 9 May 2025

Abstract

Helium (He) accumulation, a byproduct of nuclear transmutation, poses a significant reliability challenge for the materials used in nuclear reactors. Nanomaterials, with their high density of interfaces, offer superior He tolerance by absorbing He atoms and suppressing bubble growth. However, the long-term stability [...] Read more.

Helium (He) accumulation, a byproduct of nuclear transmutation, poses a significant reliability challenge for the materials used in nuclear reactors. Nanomaterials, with their high density of interfaces, offer superior He tolerance by absorbing He atoms and suppressing bubble growth. However, the long-term stability of these materials under continuous He accumulation remains a concern. This study investigated the microstructural and mechanical property responses of ZrN nanofilms to excessive He accumulation. Different doses of He atoms were introduced via magnetron sputtering. The results indicate that increasing the He dose induced a nanocrystalline-to-amorphous transition and instability in the mechanical properties. The structural and mechanical instability, characterized by surface blistering, softening, abnormal lattice shrinkage, and amorphization, was primarily triggered by the degradation of the grain boundaries with He accumulation, and an amorphization model of nanomaterials is proposed. Full article

(This article belongs to the Special Issue Recent Research and Application of Amorphous Materials)

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17 pages, 5659 KiB

Open AccessArticle

Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding

by Irina S. Aliyarova, Anastasiia V. Koziakova, Daniil M. Ivanov, Natalia S. Soldatova and Pavel S. Postnikov

Inorganics 2025, 13(5), 157; https://doi.org/10.3390/inorganics13050157 - 9 May 2025

Abstract

Three diaryliodonium dicyanoargentates(I), [MesIAr][Ag(CN)₂] (Ar = Ph 1, Mes 2, 4-MeC₆H₄ 3; Mes = 2,4,6-Me₃C₆H₂), were prepared by anion metathesis. The X-ray structural analyses for these crystals revealed [...] Read more.

Three diaryliodonium dicyanoargentates(I), [MesIAr][Ag(CN)₂] (Ar = Ph 1, Mes 2, 4-MeC₆H₄ 3; Mes = 2,4,6-Me₃C₆H₂), were prepared by anion metathesis. The X-ray structural analyses for these crystals revealed C–I^III∙∙∙N≡C halogen bonds (abbreviated as XB) between I atoms of diaryliodonium cations and N atoms of cyano groups, which provide different supramolecular organization. The noncovalent nature of these interactions was studied by density functional theory (DFT) calculations and topological analysis of the electron density distribution in the framework of the quantum theory of atoms in molecules (QTAIM) at the PBE-D3/jorge-DZP-DKH level of theory both in gas phase and crystal models. The philicities of partners in these contacts were confirmed by electron localization function (ELF) projections, electron density/electrostatic potential (ED/ESP) profiles, and Hirshfeld surfaces analysis. An analysis of the available crystallographic data from the literature allows us to find other examples of σ-hole interactions including the dicyanoargentate(I) anion, and the C–X∙∙∙N≡C (X = Br, I, Te) bonding were also confirmed theoretically. Full article

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35 pages, 4708 KiB

Open AccessReview

Homo- and Hetero-Multinuclear Iridium(III) Complexes with Cytotoxic Activity

by Irena Kostova

Inorganics 2025, 13(5), 156; https://doi.org/10.3390/inorganics13050156 - 8 May 2025

Abstract

Towards the efforts to expand the bioactivity and to reduce toxic and adverse properties of known metal-based drugs, various multinuclear complexes have recently been studied. They have shown enhancement of target specificity and selectivity. Different from small organic compounds and traditional metal-based complexes [...] Read more.

Towards the efforts to expand the bioactivity and to reduce toxic and adverse properties of known metal-based drugs, various multinuclear complexes have recently been studied. They have shown enhancement of target specificity and selectivity. Different from small organic compounds and traditional metal-based complexes with anticancer activity, iridium(III) multinuclear or heteronuclear metallodrugs have confirmed potential advantages due to their unique biological and chemical diversities, better activity and different anticancer mechanisms. Ir(III) coordination compounds, similar to most Pt group compounds, are of excessive interest because of their potential cytotoxic activity, effective cellular uptake and tolerance by healthy cells. Although mononuclear Ir(III) complex compounds have been extensively studied as promising candidates for antitumor application, the research on the antineoplastic potential of homo- or hetero-multinuclear iridium(III) complexes is not as abundant; nevertheless, intensive investigations have been conducted in the recent years towards developing complexes that are anticipated to have improved therapeutic potential and biotarget selectivity. Multimetallic iridium(III) frameworks have offered interesting possibilities for designing new antitumor agents by exploiting the action of different metal cations at the same time. This method was very successful in the design of homo- and hetero-multinuclear cyclometalated and half-sandwich organometallic Ir(III) compounds. In the described background, many homonuclear and heteronuclear Ir(III) complexes have been estimated and have exposed promising advantages in cancer therapy. This review intends to summarize newly reported innovative and promising multinuclear Ir(III)-based complexes and to afford a wide-ranging overview of current development and perspectives for the practical impact of these complexes in the tumor therapy field. It is anticipated that this analysis will provide significant direction for the further progress of active homonuclear and heteronuclear iridium-based anticancer agents. Full article

(This article belongs to the Special Issue Metal Complexes Diversity: Synthesis, Conformations, and Bioactivity)

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14 pages, 5213 KiB

Open AccessArticle

Synthesis of M-Doped MoSe₂ (M = Fe, Co, Ni) via Chemical Vapor Deposition for an Electrocatalytic Hydrogen Evolution Reaction

by Xinya Chen, Xingchen Zhang, Jinying Zhang and Zhiyong Wang

Inorganics 2025, 13(5), 155; https://doi.org/10.3390/inorganics13050155 - 8 May 2025

Abstract

Given the high cost and limited availability of noble-metal-based catalysts in acidic media water electrolysis, developing cost-effective and high-performance non-noble metal catalysts is crucial for realizing large-scale hydrogen production. In this study, Fe-, Co-, and Ni-doped MoSe₂ nanomaterials were synthesized via chemical [...] Read more.

Given the high cost and limited availability of noble-metal-based catalysts in acidic media water electrolysis, developing cost-effective and high-performance non-noble metal catalysts is crucial for realizing large-scale hydrogen production. In this study, Fe-, Co-, and Ni-doped MoSe₂ nanomaterials were synthesized via chemical vapor deposition, and their electrocatalytic performance for the hydrogen evolution reaction (HER) was systematically evaluated. Characterization techniques including X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy were used to confirm the incorporation of doping elements and investigate their effects on the crystal structure and morphology of MoSe₂. Electrochemical tests, including linear sweep voltammetry and cyclic voltammetry, revealed that the doping of Fe, Co, and Ni significantly enhanced the HER catalytic activity of MoSe₂, with the Co-doped sample exhibiting the best performance, showing an overpotential of 0.293 V at 100 mA/cm⁻² and a Tafel slope of 47 mV/dec. Furthermore, density functional theory calculations were employed to analyze the adsorption energy of hydrogen atoms on the catalysts, providing deeper insights into the role of doping in tuning the catalytic activity of MoSe₂. This study offers new theoretical support and experimental evidence for the application of transition metal-doped MoSe₂ in electrocatalysis. Full article

(This article belongs to the Special Issue Advanced Electrocatalysis Materials Design: Innovations and Applications)

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