Inorganics

18 pages, 8401 KiB

Open AccessArticle

Mg₂(Co_1/3Fe_1/3Ni_1/3), Mg₂(Cu_1/3Fe_1/3Ni_1/3), Mg₂(Co_1/3Cu_1/3Fe_1/3), Mg₂(Co_1/3Cu_1/3Ni_1/3), and Mg₂(Co_1/4Cu_1/4Fe_1/4Ni_1/4) Materials for Hydrogen Storage

by Eduardo David Ruiz-Santacruz, Paula del Carmen Cintrón Núñez, Nidia Libia Torres García and Karina Suárez-Alcántara

Inorganics 2025, 13(5), 135; https://doi.org/10.3390/inorganics13050135 (registering DOI) - 26 Apr 2025

Abstract

Hydrogen is a promising energy vector; however, its storage in solid-state materials is still an unresolved problem. Hydrogen storage on Mg-based materials is an ongoing research area. Here, five materials, Mg₂(Co_1/3Fe_1/3Ni_1/3), Mg₂(Cu_1/3 [...] Read more.

Hydrogen is a promising energy vector; however, its storage in solid-state materials is still an unresolved problem. Hydrogen storage on Mg-based materials is an ongoing research area. Here, five materials, Mg₂(Co_1/3Fe_1/3Ni_1/3), Mg₂(Cu_1/3Fe_1/3Ni_1/3), Mg₂(Co_1/3Cu_1/3Fe_1/3), Mg₂(Co_1/3Cu_1/3Ni_1/3), and Mg₂(Co_1/4Cu_1/4Fe_1/4Ni_1/4), are reported for hydrogen storage. The hydriding and dehydriding reactions in these materials proceed via two steps. The first step is associated with the Mg/MgH₂ equilibrium, while the second step is related to the simultaneous formation of mixtures of hydrided Mg-intermetallics. All of the studied materials demonstrate easy hydriding in mild conditions (15 bar, 300 °C). Mg₂(Co_1/3Fe_1/3Ni_1/3) can be considered the best material among the studied series, with a hydrogen storage capacity of 3.8 wt. % and a dehydriding onset temperature of 243 °C. The presence of Cu modified the equilibrium pressure of the second hydriding step and induced partial dehydriding at 250 °C in pressure-composition isothermal testing. The presence of Fe favored the hydrogen uptake in the first hydriding reaction, from 0.5 wt. % at the material without Fe to 1.1–2.2 wt. % in the Fe materials. The elements Co, Co, Cu, and Fe demonstrated synergistic effects on hydriding/dehydriding reactions. Full article

(This article belongs to the Special Issue Advanced Inorganic Nanomaterials for Energy Conversion and Catalysis Applications)

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17 pages, 5573 KiB

Open AccessArticle

Heteroleptic β-Diketonate Fe³⁺ Complex: Spin-Crossover and Optical Characteristics

by Denis V. Starichenko, Valerya E. Vorobeva, Matvey S. Gruzdev, Ulyana V. Chervonova, Alexander A. Ksenofontov, Aleksey S. Volegov and Ivan V. Yatsyk

Inorganics 2025, 13(5), 134; https://doi.org/10.3390/inorganics13050134 (registering DOI) - 25 Apr 2025

Abstract

The heteroleptic halogen-substituted Fe³⁺ complex of formula [FeL₂Bipy]Cl, where L is 1-(4-fluoro-phenyl)-3-(4-bromo-phenyl)-propane-1,3-dione and Bipy is 2,2′-bipyridine, was synthesized, and its optic and magnetic properties were studied. Magnetic measurements showed that the complex at high temperatures (T > 75 K) [...] Read more.

The heteroleptic halogen-substituted Fe³⁺ complex of formula [FeL₂Bipy]Cl, where L is 1-(4-fluoro-phenyl)-3-(4-bromo-phenyl)-propane-1,3-dione and Bipy is 2,2′-bipyridine, was synthesized, and its optic and magnetic properties were studied. Magnetic measurements showed that the complex at high temperatures (T > 75 K) is predominantly in the high-spin (HS) state of Fe³⁺ ions (S = 5/2, γ_HS¹ = 93%) with a small admixture of low-spin (LS) state (S = 1/2, γ_LS¹ = 7%). At T* ≈ 46 K, a partial spin-crossover transition (SCO, 5/2↔1/2) occurs. This process is accompanied not only by a change in the magnetic state (γ_HS² = 76%, γ_LS² = 24%), but also by the appearance of AFM interactions (θ_II = −2.3 K) between neighboring Fe³⁺ ions. A theoretical model was proposed to describe magnetic susceptibility, χ(T). As a result of the analysis of the ground spin state M(H) at 2.0 K, it was established that the majority of the LS states, as well as part of the HS states of Fe³⁺ ions (γ_HS ~ 53%), do not participate in exchange interactions. EPR studies confirmed the presence of HS and LS Fe³⁺ centers and made it possible to isolate I-type and II-type HS centers, corresponding to strong low-symmetry and weak distorted octahedral fields. SCO was also detected and the temperature dependences of the EPR intensities, I(T), of the HS and LS centers were analyzed. Full article

(This article belongs to the Section Coordination Chemistry)

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12 pages, 5253 KiB

Open AccessArticle

Synthesis of Titanium Dioxide Photoanodes by Anodization in a Sodium Chloride Electrolyte

by Briseyda Del Angel-Hernández, Reinaldo David Martínez-Orozco, Ricardo García-Alamilla, Adriana Isabel Reyes de la Torre, E. Terrés and Ulises Páramo-García

Inorganics 2025, 13(5), 133; https://doi.org/10.3390/inorganics13050133 - 25 Apr 2025

Abstract

Titanium dioxide photoanodes were synthesized using the anodization method at low potentials in a 0.3 M sodium chloride electrolyte at room temperature. The morphology of the materials was analyzed with optical microscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM); the crystalline [...] Read more.

Titanium dioxide photoanodes were synthesized using the anodization method at low potentials in a 0.3 M sodium chloride electrolyte at room temperature. The morphology of the materials was analyzed with optical microscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM); the crystalline phase of the synthesized materials was analyzed by X-ray diffraction and Raman spectroscopy; meanwhile, the hydrophobic–hydrophilic properties were assessed through contact angles measurements, and all the synthesized samples possess hydrophilic properties. The samples anodized at 15 and 20 volts exhibited the formation of titanium dioxide in the anatase phase. Full article

(This article belongs to the Section Inorganic Materials)

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10 pages, 8796 KiB

Open AccessCommunication

Photocatalysis and Electrocatalysis Properties of a Keggin-Type Inorganic–Organic Hybrid SiW₁₂O₄₀@Ag

by Xin-Xin Hu, Tai-Dan Chen, Xiao-Jie Gong, Jiu-Yu Ji, Li-Ping Zhao, Wen-Xuan Xie and Kun Zhou

Inorganics 2025, 13(5), 132; https://doi.org/10.3390/inorganics13050132 - 25 Apr 2025

Abstract

An example of an inorganic–organic hybrid compound {[Ag₄(SiW₁₂O₄₀)(HBTA)₈][Ag₄(SiW₁₂O₄₀)(HBTA)₈(H₂O)]}_n·(1) modified by the Keggin-type [SiW₁₂O₄₀]⁴⁻ polyoxoanion was synthesized [...] Read more.

An example of an inorganic–organic hybrid compound {[Ag₄(SiW₁₂O₄₀)(HBTA)₈][Ag₄(SiW₁₂O₄₀)(HBTA)₈(H₂O)]}_n·(1) modified by the Keggin-type [SiW₁₂O₄₀]⁴⁻ polyoxoanion was synthesized hydrothermally, which was determined by single crystal X-ray diffraction. Two 1-dimensional (1D) chains are present in 1: chain a is connected by Ag···Ag interactions and chain b is connected by π···π stacking. Finally, they were extended into 2D and 3D supramolecular structures by hydrogen bonding. The photodegradation of methylene blue (MB) was investigated under visible light irradiation, and the degradation rate reached 99.4% within 200 min. In addition, 1 catalyzes the reduction of sodium nitrite and can be used as a potential electrocatalytic material. Full article

(This article belongs to the Special Issue Advances in Inorganic–Organic Composite Photocatalysts for Energy and Environmental Applications)

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17 pages, 1754 KiB

Open AccessArticle

Sustainable Semicrystalline/Nanocrystalline UiO-66-Type Zr-MOFs as Photodegraders of Rhodamine B

by Jemal M. Yassin, Abi M. Taddesse and Manuel Sánchez-Sánchez

Inorganics 2025, 13(5), 131; https://doi.org/10.3390/inorganics13050131 - 24 Apr 2025

Abstract

UiO-type Zr-BDC MOFs have garnered the interest of the scientific community due to their exceptional diversity in composition, structure, and chemical environment, as well as their high thermal and chemical stabilities. This work demonstrates the sustainable synthesis of a series of nanocrystalline/semicrystalline UiO-66(Zr) [...] Read more.

UiO-type Zr-BDC MOFs have garnered the interest of the scientific community due to their exceptional diversity in composition, structure, and chemical environment, as well as their high thermal and chemical stabilities. This work demonstrates the sustainable synthesis of a series of nanocrystalline/semicrystalline UiO-66(Zr) metal–organic frameworks (MOFs) under facile conditions—specifically at room temperature, in water, with high yield, and without the use of modulators or toxic byproducts. The synthesis involves either deprotonating the linker or utilizing various ratios of water and DMF as solvents. The as-prepared materials obtained from both synthesis strategies share key structural features with conventional UiO-66(Zr) in their short- and medium-range physicochemical properties, while exhibiting significant differences in crystallinity and textural properties. Nonetheless, the materials generally lack long-range order (semicrystalline), in particular these synthesized following the deprotonation strategy. However, the materials prepared using mixed solvent strategy seem to exhibit characteristics of nanocrystalline UiO-66(Zr). Overall, both approaches successfully addressed various synthesis challenges related to the highly sought-after Zr-based metal–organic frameworks (MOFs). Some of these MOF materials were tested for the photodegradation of rhodamine B (RhB) under mercury light irradiation, evidencing high photocatalytic efficiency of up to 75 ± 0.078% within 120 min under the pseudo-first-order model. This suggests an interaction between the photocatalyst and the RhB dye, involving electron injection from RhB and the ability for ligand-to-metal charge transfer (LMCT), which enhances the efficient photocatalytic degradation of RhB. The trapping experiments indicated that superoxide radicals (•O₂⁻) and photogenerated holes (h⁺) are crucial in the photodegradation of RhB. Moreover, the materials showed good recyclability across five tested cycles. A plausible photocatalytic reaction mechanism has been proposed to explain these findings. Full article

(This article belongs to the Special Issue Advanced Inorganic Nanomaterials for Energy Conversion and Catalysis Applications)

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15 pages, 2194 KiB

Open AccessArticle

Boosting C-C Coupling for Electrochemical CO₂ Reduction over Novel Cu-Cubic Catalysts with an Amorphous Shell

by Hanlin Wang, Tian Wang, Gaigai Dong, Linbo Zhang, Fan Pan and Yunqing Zhu

Inorganics 2025, 13(5), 130; https://doi.org/10.3390/inorganics13050130 - 23 Apr 2025

Abstract

Currently, the electrochemical reduction of carbon dioxide faces significant challenges, including poor selectivity for C₂ products and low conversion efficiency. An effective strategy for optimizing the reduction reaction pathway and enhancing catalytic performance involves manipulating highly unsaturated atomic sites on the catalyst’s [...] Read more.

Currently, the electrochemical reduction of carbon dioxide faces significant challenges, including poor selectivity for C₂ products and low conversion efficiency. An effective strategy for optimizing the reduction reaction pathway and enhancing catalytic performance involves manipulating highly unsaturated atomic sites on the catalyst’s surface, thereby increasing the number of active sites. In this study, we employed sodium dodecylbenzenesulfonate (SDBS) as a surfactant in the electrodeposition method to synthesize copper cubes encapsulated with an amorphous shell (100 nm–250 nm) containing numerous defect sites on its surface. The electrocatalytic CO₂ reduction reactions in an H-type reactor showed that, compared to ED-Cu synthesized without additives, AS (amorphous shell)-Cu-5 exhibited a Faradaic efficiency value for ethylene that was 1.7 times greater than that of ED-Cu while significantly decreasing the Faradaic efficiency of hydrogen production. In situ attenuated total reflectance surface-enhanced infrared spectroscopy (ATR-SEIRAS) revealed that introducing an amorphous shell and abundant defects altered both the intermediate species and reaction pathways on the AS-Cu-5 catalyst’s surface, favoring C₂H₄ formation. The density functional theory (DFT) calculations further confirmed that amorphous copper lowers the energy barrier required for C-C coupling, resulting in a marked enhancement in FE-C₂H₄. Therefore, additive-assisted electrodeposition presents a simple and rapid synthesis method for improving ethylene selectivity in copper catalysts. Full article

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

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4 pages, 149 KiB

Open AccessEditorial

Carbon Nanomaterials for Advanced Technology

by Ben McLean and Alister J. Page

Inorganics 2025, 13(5), 129; https://doi.org/10.3390/inorganics13050129 - 23 Apr 2025

Abstract

Carbon nanomaterials are composed of extended networks of bonded carbon atoms [...] Full article

(This article belongs to the Special Issue Carbon Nanomaterials for Advanced Technology)

13 pages, 6465 KiB

Open AccessArticle

Prediction of Thermal Transport Properties of Pristine and BN-Substituted Holey Graphynes

by Qingchen Li, Yujie Zhang, Yanlong Liu, Yan Gao and Baoxia Deng

Inorganics 2025, 13(4), 128; https://doi.org/10.3390/inorganics13040128 - 21 Apr 2025

Abstract

The merging of pore designs is a potential strategy for achieving ultra-low lattice thermal conductivity (κ), for which phonon anharmonicity and size effect are indispensable for discovering novel functional materials in thermal applications. In this study, monolayer holey graphyne (HGY) and [...] Read more.

The merging of pore designs is a potential strategy for achieving ultra-low lattice thermal conductivity (κ), for which phonon anharmonicity and size effect are indispensable for discovering novel functional materials in thermal applications. In this study, monolayer holey graphyne (HGY) and boron nitride holey graphyne (BN-HGY) were examined for their phonon thermal transport properties through first-principles calculation and phonon Boltzmann function. HGY exhibits an intrinsic lattice thermal conductivity (κ) of 38.01 W/mK at room temperature, which exceeds BN-HGY’s 24.30 W/mK but is much lower than 3550 W/mK for BTE graphene. The phonon–phonon scattering behavior of BN-HGY is obviously increased compared to HGY due to the enhancement of anharmonicity, which leads to a shorter phonon lifetime and lower κ. Additionally, at room temperature, the representative mean free path (rMFP) of BN-HGY is substantially higher than that of HGY, and the κ of BN-HGY decreases faster at a larger rMFP (within a unit nm). This work will be constructive to further the application of HGY and BN-HGY as thermal management materials. Full article

(This article belongs to the Special Issue Boron-Based Low-Dimensional Nanoclusters and Nanomaterials)

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11 pages, 1801 KiB

Open AccessArticle

Lanthanide Exposure In Vitro Differentially Diminishes MTT Cell Viability in Axenic Neuronal or Glial Cell Model Systems

by David C. Platt, Linda M. Ferrence, Faith Breausche, Katelyn Terry, Gregory M. Ferrence and Marjorie A. Jones

Inorganics 2025, 13(4), 127; https://doi.org/10.3390/inorganics13040127 - 20 Apr 2025

Abstract

Applications of lanthanide chemistry have been successful in metallics and the petroleum industry. In the medical realm, lanthanides have shown utility in radiotherapy agents, photodynamic therapy agents, and magnetic resonance imaging (MRI) contrast agents. The lanthanide group elements have a few known biological [...] Read more.

Applications of lanthanide chemistry have been successful in metallics and the petroleum industry. In the medical realm, lanthanides have shown utility in radiotherapy agents, photodynamic therapy agents, and magnetic resonance imaging (MRI) contrast agents. The lanthanide group elements have a few known biological roles, notably among some bacteria and the yeast Saccharomyces cerevisiae, which have been used as models for changes in gene expression. However, the systematic effects of lanthanide nitrates on eukaryotic cell model systems have not yet been reported. This study presents the first documented effects on cell viability, after acute incubations of various lanthanide nitrate salts, using axenic C6 glial or PC12 neuronal cells in vitro. Cultures were exposed to a 1 mM concentration of lanthanide nitrate salts for 24 h. In comparison to the saline control, several cultures demonstrated significantly lower cell viability, as measured by the MTT viability assay. Data were analyzed as an average absorbance of n = 4 replicate samples, corrected for the average absorbance of cell-free blanks. The reported results were normalized to the average of the saline control cells. Among the 13 lanthanides tested, Praseodymium, Holmium, Erbium, Thulium, and Ytterbium nitrates exhibited the most pronounced inhibitory effects, resulting in over 40% reduction in cell viability at 1 mM for either or both cell types. Recovery after lanthanide exposure also was cell-type-dependent as well as lanthanide-type-dependent, with Lutetium having the greatest effect on both cell types. PC12 cells displayed greater sensitivity for inhibition than the C6 cells with some of the lanthanides but not all. Furthermore, the controls of sodium nitrate and calcium nitrate showed only modest discernible impacts on cell viability for PC12 and C6 cells, highlighting the role of the lanthanides in influencing cell viability. Full article

(This article belongs to the Section Bioinorganic Chemistry)

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13 pages, 4135 KiB

Open AccessArticle

Uncooled Microbolometers Based on Nitrogen-Doped Hydrogenated Amorphous Silicon-Germanium (a-SiGe:H,N)

by Oscar Velandia, Alfonso Torres, Alfredo Morales, Luis Hernández, Alberto Luna, Karim Monfil, Javier Flores, Gustavo M. Minquiz, Ricardo Jiménez and Mario Moreno

Inorganics 2025, 13(4), 126; https://doi.org/10.3390/inorganics13040126 - 20 Apr 2025

Abstract

An uncooled microbolometer is a thermal sensor consisting of a membrane suspended from the substrate to provide thermal insulation. Typically, the membrane is composed of a stack of three films integrated by a supporting film, an IR sensing film, and an IR absorbing [...] Read more.

An uncooled microbolometer is a thermal sensor consisting of a membrane suspended from the substrate to provide thermal insulation. Typically, the membrane is composed of a stack of three films integrated by a supporting film, an IR sensing film, and an IR absorbing film. However, the above increases the thickness of the device and affects its mechanical stability and thermal mass, thereby reducing its performance. One solution is to use a single film as a membrane with both IR sensing and IR absorbing properties. In this regard, this work presents the fabrication and evaluation of uncooled microbolometers using nitrogen-doped hydrogenated amorphous silicon-germanium (a-SiGe:H,N) as a single IR-absorber/IR sensing membrane. The films were deposited via low frequency Plasma Enhanced Chemical Vapor Deposition (PECVD) at 200 °C. Three microbolometer configurations were fabricated using a-SiGe:H,N films deposited from a SiH₄, GeH₄, N_2, and H₂ gas mixture with different SiH₄ and GeH₄ flow rates and, consequently, with different properties, such as temperature coefficient of resistance (TCR) and conductivity at room temperature. The microbolometer that exhibited the best performance achieved a voltage responsivity of 7.26 × 10⁵ V/W and a NETD of 22.35 mK at 140 Hz, which is comparable to state-of-the-art uncooled infrared (IR) sensors. These results confirm that the optimization of the deposition parameters of the a-SiGe:H,N films significantly affects the microbolometers final performance, enabling an optimal balance between thermal sensitivity (TCR) and conductivity. Full article

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

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29 pages, 6083 KiB

Open AccessReview

Carbon Nanomaterials for Electrochemical Hydrogen Storage: Mechanisms and Advancements

by Amir Reza Mashtizadeh, Shahab Khameneh Asl, Hossein Aghajani, Seyed Morteza Masoudpanah and Marek Wojnicki

Inorganics 2025, 13(4), 125; https://doi.org/10.3390/inorganics13040125 - 17 Apr 2025

Abstract

This review article investigates the rising global energy demand, which is primarily driven by population growth and industrialization, raising significant environmental concerns due to the extensive reliance on fossil fuels. In response, hydrogen is being explored as a potential eco-friendly energy solution to [...] Read more.

This review article investigates the rising global energy demand, which is primarily driven by population growth and industrialization, raising significant environmental concerns due to the extensive reliance on fossil fuels. In response, hydrogen is being explored as a potential eco-friendly energy solution to meet the urgent need for sustainable energy. This review covers various hydrogen storage methods, including compressed gas, cryogenic liquids, solid materials, and electrochemical techniques. Among these, electrochemical technology is highly regarded as a leading experimental approach for hydrogen storage, and it is noted for its outstanding performance under normal conditions. The characteristics of a material’s surface play a crucial role in determining its electrochemical hydrogen storage capacity. Innovative materials, such as graphene oxide and 3D graphene oxide, are particularly significant in this regard, as they can significantly enhance hydrogen storage capacity; electrochemical hydrogen storage functions by incorporating atomic hydrogen into carbon materials following the reduction of water. This article underscores the significance of green energy and the need to ensure safety and precision at room temperature and ambient pressure using electrochemical hydrogen storage techniques and mechanisms. Furthermore, it offers a comprehensive review of developments in electrochemical hydrogen storage and its mechanisms, focusing on carbon, graphene oxide, and the contributions of 3D graphene foam. Full article

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17 pages, 3075 KiB

Open AccessReview

Application of Fluorescent Probes for the Detection of Zinc Ions in Cells and Oil Paintings

by Zhankun Wang, Zhixin Ren, Yanan Niu, Xi Cao and Yuguang Lv

Inorganics 2025, 13(4), 124; https://doi.org/10.3390/inorganics13040124 - 17 Apr 2025

Abstract

Zinc is an essential trace metal element in the human body, but it also constitutes a variety of proteins in the body of the important elements necessary; this element plays an important role in physiological metabolism. Disturbances in the metabolism of zinc ions [...] Read more.

Zinc is an essential trace metal element in the human body, but it also constitutes a variety of proteins in the body of the important elements necessary; this element plays an important role in physiological metabolism. Disturbances in the metabolism of zinc ions in the body can significantly threaten human health, especially neurological diseases. Therefore, developing a rapid and straightforward method for determining zinc ions is important. Fluorescent probe technology has been widely used for detecting and labeling zinc ions. Among many fluorescent probes, the rhodamine derivative LPDQ fluorescent probe has unique application scenarios, for example, it plays an important role in the detection of zinc white in oil colors, and its advantages are simplicity, rapidity, and real-time operation. This paper introduces the types of fluorescent probes for zinc ions and the three main mechanisms of fluorescent probe detection. The characteristics, design strategies, and application effects of the three fluorescent probes for zinc ions, as well as their advantages and limitations, are reviewed and summarized, which are intended to provide valuable references for the development of new probes for zinc ions detection in the future and for the future direction of research in this field. Full article

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21 pages, 11004 KiB

Open AccessReview

Mitigating Lead Toxicity in Halide Perovskite Solar Cells: Strategies for Sustainable Development

by Wenguang Li, Tianci Mi, Tian Tian, Meifang Yang and Huan Pang

Inorganics 2025, 13(4), 123; https://doi.org/10.3390/inorganics13040123 - 13 Apr 2025

Abstract

Halide perovskite solar cells (PSCs) exhibit remarkable potential for addressing global energy challenges due to their exceptional photovoltaic properties and cost-effectiveness. However, their widespread adoption is hindered by the presence of toxic lead in the perovskite materials, posing risks to both human health [...] Read more.

Halide perovskite solar cells (PSCs) exhibit remarkable potential for addressing global energy challenges due to their exceptional photovoltaic properties and cost-effectiveness. However, their widespread adoption is hindered by the presence of toxic lead in the perovskite materials, posing risks to both human health and the environment. This review comprehensively examines the environmental safety concerns associated with PSCs, focusing on the toxicity of lead and its potential for leakage during device operation and end-of-life disposal. Strategies to mitigate lead leakage are explored, including advanced external encapsulation methods, internal lead immobilization techniques, and innovative recycling approaches. These strategies are evaluated based on their effectiveness, feasibility, and potential challenges, highlighting the need for a multi-pronged approach to ensure the responsible and sustainable development of PSC technology. By addressing the toxicity issue and implementing robust prevention and recycling strategies, PSCs can become a driving force for the global transition towards clean and renewable energy while minimizing environmental and health risks. Full article

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

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25 pages, 8071 KiB

Open AccessArticle

The Interface Interaction of C₃N₄/Bi₂S₃ Promoted the Separation of Excitons and the Extraction of Free Photogenerated Carriers in the Broadband Light Spectrum Range

by Xingfa Ma, Xintao Zhang, Mingjun Gao, Ruifen Hu, You Wang and Guang Li

Inorganics 2025, 13(4), 122; https://doi.org/10.3390/inorganics13040122 - 12 Apr 2025

Abstract

Exciton generation and separation play an important role in the photoelectric properties and the luminescence performance of materials. In order to tailor the defects and grain boundaries and improve the exciton separation and light harvesting of the graphitic carbon nitride (g-C₃N [...] Read more.

Exciton generation and separation play an important role in the photoelectric properties and the luminescence performance of materials. In order to tailor the defects and grain boundaries and improve the exciton separation and light harvesting of the graphitic carbon nitride (g-C₃N₄) nanosheets, a C₃N₄/bismuth sulfide (Bi₂S₃) nanocomposite was synthesized. The photoelectric properties of the 405, 532, 650, 780, 808, 980 and 1064 nm light sources were studied using Au electrodes and graphite electrodes with 4B and 5B pencil drawings. The results indicate that the C₃N₄/Bi₂S₃ nanocomposite exhibited photocurrent switching behavior in the broadband light spectrum range. It is noted that even with zero bias applied, a good photoelectric signal was still measured. The resulting nanocomposite exhibited good photophysical stability. Physical mechanisms are discussed herein. It is suggested that the interfacial interaction of C₃N₄ and Bi₂S₃ in the nanocomposite creates a strong built-in electric field, which accelerates the separation of excitons. Therefore, as a dynamic process of photoexcitation, fluorescence, the photoelectric effect, and scattering are three main competing processes; the separation of excitons and the extraction of free photogenerated charge can be used as a reference for the fluorescent materials or other photoelectric materials studies as photophysical properties. This study also serves as an important reference for the design, defect and grain boundary modulation or interdisciplinary application of functional nanocomposites, especially for the bandgap modulation and suppression of photogenerated carrier recombination. Full article

(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials, 2nd Edition)

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21 pages, 2681 KiB

Open AccessReview

Exploring Metal- and Porphyrin-Modified TiO₂-Based Photocatalysts for Efficient and Sustainable Hydrogen Production

by Dimitrios Rafail Bitsos, Apostolos Salepis, Emmanouil Orfanos, Athanassios G. Coutsolelos, Ramonna I. Kosheleva, Athanassios C. Mitropoulos and Kalliopi Ladomenou

Inorganics 2025, 13(4), 121; https://doi.org/10.3390/inorganics13040121 - 11 Apr 2025

Abstract

Photocatalytic H₂ production is one of the most promising approaches for sustainable energy. The literature presents a plethora of carefully designed systems aimed at harnessing solar energy and converting it into chemical energy. However, the main drawback of the reported photocatalysts is [...] Read more.

Photocatalytic H₂ production is one of the most promising approaches for sustainable energy. The literature presents a plethora of carefully designed systems aimed at harnessing solar energy and converting it into chemical energy. However, the main drawback of the reported photocatalysts is their stability. Thus, the development of a cost-effective and stable photocatalyst, suitable for real-world applications remains a challenge. An ideal photocatalyst for H₂ production must possess appropriate band-edge energy positions, an effective sacrificial agent, and a suitable cocatalyst. Among the various photocatalysts studied, TiO₂ stands out due to its stability, abundance, and non-toxicity. However, its efficiency in the visible spectrum is limited by its wide bandgap. Metal doping is an effective strategy to enhance electron–hole separation and improve light absorption efficiency, thereby boosting H₂ synthesis. Common metal cocatalysts used as TiO₂ dopants include platinum (Pt), gold (Au), copper (Cu), nickel (Ni), cobalt (Co), ruthenium (Ru), iron (Fe), and silver (Ag), as well as bimetallic combinations such as Ni-Fe, Ni-Cu, Nb-Ta, and Ni-Pt. In all cases, doped TiO₂ exhibits higher H₂ production performance compared to undoped TiO₂, as metals provide additional reaction sites and enhance charge separation. The use of bimetallic dopants further optimizes the hydrogen evolution reaction. Additionally, porphyrins, with their strong visible light absorption and efficient electron transfer properties, have demonstrated potential in TiO₂ photocatalysis. Their incorporation expands the photocatalyst’s light absorption range into the visible spectrum, enhancing H₂ production efficiency. This review paper explores the principles and advancements in metal- and porphyrin-doped TiO₂ photocatalysts, highlighting their potential for sustainable hydrogen production. Full article

(This article belongs to the Special Issue Featured Papers in Inorganic Materials 2025)

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26 pages, 7099 KiB

Open AccessArticle

Straightforward Synthesis and Characterization of Analcime@Nickel Orthosilicate Novel Nanocomposite for Efficient Removal of Rhodamine B Dye from Aqueous Media

by Ehab A. Abdelrahman, Fawaz A. Saad, Mortaga M. Abou-Krisha, Abdalla M. Khedr and Zahrah Alqahtani

Inorganics 2025, 13(4), 120; https://doi.org/10.3390/inorganics13040120 - 10 Apr 2025

Abstract

Rhodamine B dye is a hazardous pollutant that poses significant risks to human health and aquatic ecosystems due to its toxic, carcinogenic nature and high chemical stability. To address this issue, analcime@nickel orthosilicate nanocomposites were synthesized via the hydrothermal method for efficient rhodamine [...] Read more.

Rhodamine B dye is a hazardous pollutant that poses significant risks to human health and aquatic ecosystems due to its toxic, carcinogenic nature and high chemical stability. To address this issue, analcime@nickel orthosilicate nanocomposites were synthesized via the hydrothermal method for efficient rhodamine B dye removal. Two nanocomposites were synthesized: EW (without a template) and ET (with polyethylene glycol 400 as a template, followed by calcination at 600 °C for 5 h). X-ray diffraction (XRD) confirmed the formation of analcime (NaAlSi₂O₆) and nickel orthosilicate (Ni₂SiO₄), with crystallite sizes of 72.93 nm (EW) and 63.60 nm (ET). Energy-dispersive X-ray spectroscopy (EDX) showed distinct distributions of oxygen, sodium, aluminum, silicon, and nickel. Field-emission scanning electron microscopy (FE-SEM) revealed irregular morphology for EW and uniform spherical nanoparticles for ET. The maximum adsorption capacities (Q_max) were 174.83 mg/g for EW and 210.53 mg/g for ET. Adsorption followed the pseudo-second-order kinetic model and was best described by the Langmuir isotherm, indicating monolayer chemisorption. Thermodynamic studies showed that adsorption was exothermic (ΔH = −45.62 to −50.92 kJ/mol) and spontaneous (ΔG < 0) and involved an entropy increase (ΔS = +0.1441 to +0.1569 kJ/mol·K). These findings demonstrate the superior adsorption efficiency of the ET composite and its potential application in dye-contaminated wastewater treatment. Full article

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18 pages, 5879 KiB

Open AccessArticle

Experimental Study on Van der Waals Interactions Between Organic Groups of Quaternary Ammonium Salt Surfactants and Montmorillonite in Aqueous Solutions

by Yongzheng Fu, Ming Chang, Yuhao Pan, Wennan Xu, Rui Li, Wenzhao Zhu and Hongliang Li

Inorganics 2025, 13(4), 119; https://doi.org/10.3390/inorganics13040119 - 8 Apr 2025

Abstract

Obtaining the dielectric constant and refractive index of the siloxane surface of montmorillonite (Mnt) and organic groups is difficult, limiting the study of Van der Waals (VDW) interactions between the hydrophilic end of quaternary ammonium surfactants (QASs) and Mnt. In this study, the [...] Read more.

Obtaining the dielectric constant and refractive index of the siloxane surface of montmorillonite (Mnt) and organic groups is difficult, limiting the study of Van der Waals (VDW) interactions between the hydrophilic end of quaternary ammonium surfactants (QASs) and Mnt. In this study, the average adsorption distance, VDW adsorption energy, and VDW constant of QASs and their groups adsorbed on the montmorillonite surface are obtained by microcalorimeter. Herein, the VDW interactions between five QASs and a Mnt surface are compared. Interactions between QASs with different hydrophilic ends and Mnt in aqueous solution were positively correlated with the dipole moment of the hydrophilic end groups, and the VDW interaction energies differed depending on the superposition of CH₂ adsorption at the hydrophobic ends. The electrostatic and VDW adsorption capacities were studied through zeta potential and adsorption capacity experiments. Physical adsorption was determined using Fourier-transform infrared spectroscopy, and the hydrophobic floc morphology was characterized using environmental scanning electron microscopy. Focused beam reflectance measurements, thermogravimetric-differential scanning calorimetry, and light transmittance were used to quantitatively analyze the hydrophobic effect of the QASs. Full article

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15 pages, 2766 KiB

Open AccessArticle

Microwave-Assisted Synthesis of Pd/g-C₃N₄ for Enhanced Photocatalytic Degradation of Sulfamethoxazole

by Lan-Anh T. Hoang, Trinh Duy Nguyen and Taeyoon Lee

Inorganics 2025, 13(4), 118; https://doi.org/10.3390/inorganics13040118 - 8 Apr 2025

Abstract

Sulfamethoxazole (SMX) is a widely used antibiotic for bacterial infections and is frequently found in surface waters and wastewater treatment plant effluents, where it is commonly co-administered with trimethoprim. Because of its emerging ecological and health risks, the development of effective elimination strategies [...] Read more.

Sulfamethoxazole (SMX) is a widely used antibiotic for bacterial infections and is frequently found in surface waters and wastewater treatment plant effluents, where it is commonly co-administered with trimethoprim. Because of its emerging ecological and health risks, the development of effective elimination strategies is urgently required. In this study, a rapid microwave-assisted technique was employed to synthesize a Pd/g-C₃N₄ photocatalyst for the elimination of SMX in aqueous solution. The structure and optical properties of all samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL), and UV–visible diffuse reflectance spectroscopy. The photocatalytic performance of Pd/g-C₃N₄ was systematically evaluated under visible-light irradiation. The results demonstrated that Pd/g-C₃N₄ achieved a 97% removal efficiency, significantly outperforming pure g-C₃N₄, which reached only 57% removal. The degradation rate constant for Pd/g-C₃N₄ was calculated to be 0.0139 min⁻¹, approximately 6.6 times higher than that of bare g-C₃N₄. This enhanced performance is attributed to the incorporation of Pd nanoparticles, which effectively suppressed the recombination of photogenerated electron–hole pairs and promoted charge separation. The influence of key operational parameters, including pH, SMX concentration, and catalyst dose, were systematically examined. Furthermore, the photocatalytic mechanism of the Pd/g-C₃N₄ photocatalyst was explored to elucidate its degradation pathways. Full article

(This article belongs to the Special Issue Advanced Inorganic Nanomaterials for Energy Conversion and Catalysis Applications)

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12 pages, 3371 KiB

Open AccessArticle

The Effect of Localized Magnetic Fields on the Spatially Controlled Crystallization of Transition Metal Complexes

by Ian R. Butler, Rhodri M. Williams, Alice Heeroma, Peter N. Horton, Simon J. Coles and Leigh F. Jones

Inorganics 2025, 13(4), 117; https://doi.org/10.3390/inorganics13040117 - 7 Apr 2025

Abstract

A series of nickel (II) bis-phosphine organometallic complexes along with two pseudo [M₇] (M = Ni(II), Zn(II)) metallocalix[6]arene complexes and a dysprosium acetate coordination polymer have each been crystallised in the presence of localized magnetic fields set up using neodymium magnets, [...] Read more.

A series of nickel (II) bis-phosphine organometallic complexes along with two pseudo [M₇] (M = Ni(II), Zn(II)) metallocalix[6]arene complexes and a dysprosium acetate coordination polymer have each been crystallised in the presence of localized magnetic fields set up using neodymium magnets, using custom made Magnetic Crystallization Towers (MCTs). In all cases, whether the product complex is diamagnetic or paramagnetic, a complex spatial patterning of the crystals occurs based on the orientation of the magnetic field lines. When using magnetic block towers, the crystallization generally occurs adjacent to the magnet face. The effects of nucleation and solution concentration gradients on the crystallization process are also explored. These observations show how the crystallization process is affected by magnetic fields and thus these results have far-reaching effects which most certainly will include crystallization and ion migrations in biology. Full article

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

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