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Inorganics, Volume 11, Issue 3 (March 2023) – 46 articles

Cover Story (view full-size image): Tetrylidyne complexes are compounds featuring a triple bond between a transition metal and the tetrels Si – Pb. They bear great synthetic potential in organoelement chemistry due to the highly reactive, polar M≡E bond. Following our earlier experimental work on cationic Group 10 tetrylidyne complexes, we provide in the present study a detailed insight into the electronic structure of the complex cations [(PMe3)3MER]+ (M = Ni, Pd, Pt; E = C, Si, Ge, Sn, Pb; R = ArMes, Tbb (Si)), utilizing a comprehensive quantum-chemical toolset that includes the Pipek–Mezey orbital localization method, the energy decomposition analysis (EDA), and the extended-transition state method with natural orbitals of chemical valence (ETS-NOCV). View this paper
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13 pages, 1777 KiB  
Article
A New 1D Ni (II) Coordination Polymer of s-Triazine Type Ligand and Thiocyanate as Linker via Unexpected Hydrolysis of 2,4-Bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine
by Kholood A. Dahlous, Saied M. Soliman, Matti Haukka, Ayman El-Faham and Raghdaa A. Massoud
Inorganics 2023, 11(3), 135; https://doi.org/10.3390/inorganics11030135 - 22 Mar 2023
Viewed by 1549
Abstract
A new 1D Ni(II) coordination polymer was synthesized by the reaction of NiSO4·6H2O with 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (BPT) and SCN as a linker in an acidic medium by heating under reflux conditions. Unusually, the BPT ligand [...] Read more.
A new 1D Ni(II) coordination polymer was synthesized by the reaction of NiSO4·6H2O with 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (BPT) and SCN as a linker in an acidic medium by heating under reflux conditions. Unusually, the BPT ligand underwent acid-mediated hydrolysis by losing one of the pyrazolyl arms afforded the polymeric [Ni(MPT)(H2O)(SCN)2]n complex (MPT: 4-(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazin-2-ol. The Ni(II) center is coordinated with one MPT as a bidentate NN-chelate, one water molecule, and two thiocyanate groups in cis positions to one another. One of the thiocyanate groups acts as a bridging ligand between metal centers, leading to a one-dimensional polymeric structure that extends along the c-direction. The other thiocyanate group is terminally N-coordinated. The [Ni(MPT)(H2O)(SCN)2]n complex has been screened in vitro against two pathogenic fungal strains: A. fumigatus, C. albican, and four pathogenic bacterial strains: S. aureus, B. subtilis as gram-positive bacteria, E. coli, P. vulgaris as gram-negative bacteria. The results showed that the complex has the potential to be used as both an antibacterial and an antifungal agent. Also, the [Ni(MPT)(H2O)(SCN)2]n complex showed cytotoxic activities against hepatocellular (HepG-2) and lung (A-549) cell lines, with IC50 values of 132.67 ± 5.14 and 146.97 ± 7.34 μM, respectively. Full article
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12 pages, 3198 KiB  
Article
Multiferroics Made via Chemical Co-Precipitation That Is Synthesized and Characterized as Bi(1−x)CdxFeO3
by Syed Zain Mehmood, Mubashar Arshad, Fahad M. Alharbi, Sayed M. Eldin and Ahmed M. Galal
Inorganics 2023, 11(3), 134; https://doi.org/10.3390/inorganics11030134 - 21 Mar 2023
Cited by 1 | Viewed by 1108
Abstract
Cd-doped BiFeO3 powders, with varying doping concentrations of Cd (Bi(1−x)CdxFeO3, where x = 0–0.3), were prepared through a facile chemical co-precipitation method and calcinated at 550 °C in the air. The BiFeO3 has a rhombohedral [...] Read more.
Cd-doped BiFeO3 powders, with varying doping concentrations of Cd (Bi(1−x)CdxFeO3, where x = 0–0.3), were prepared through a facile chemical co-precipitation method and calcinated at 550 °C in the air. The BiFeO3 has a rhombohedral crystal structure, which changes to an orthorhombic crystal structure with an increase in Cd doping. The presence of dopant has also altered the bandgap of material suppressing it from 2.95 eV to 2.51 eV, improving the visible light absorption. Vibrating sample magnetometry (VSM) confirmed stronger ferromagnetic character for Bi0.7Cd0.3FeO3 with a coercivity of 250 Oe, and remnant magnetization was 0.15 emu/g, which is because of the misalignment of the two sublattices of perovskite structure after doping resulting in the imbalanced magnetic moment giving rise to net nonzero magnetic behavior. The particle size reduction is observed with an increase in the doping concentration of Cd. Full article
(This article belongs to the Special Issue First-Row Transition Metal-Based Catalysts for Water Oxidation)
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17 pages, 5920 KiB  
Article
Photocatalytic Reduction of Cr(VI) to Cr(III) and Photocatalytic Degradation of Methylene Blue and Antifungal Activity of Ag/TiO2 Composites Synthesized via the Template Induced Route
by Zunaira Zahid, Abdul Rauf, Mohsin Javed, Ahmad Alhujaily, Shahid Iqbal, Adnan Amjad, Muhammad Arif, Sajjad Hussain, Ali Bahadur, Nasser S. Awwad, Hala A. Ibrahium, Foziah F. Al-Fawzan and Eslam B. Elkaeed
Inorganics 2023, 11(3), 133; https://doi.org/10.3390/inorganics11030133 - 21 Mar 2023
Cited by 7 | Viewed by 2707
Abstract
Water treatment through photocatalysts has become an important topic regarding environmental protection. In the present study, silver and TiO2 (Ag/TiO2) composites for photocatalysts were effectively synthesized by adopting the template induced method. The prepared samples were characterized using XRD, FTIR [...] Read more.
Water treatment through photocatalysts has become an important topic regarding environmental protection. In the present study, silver and TiO2 (Ag/TiO2) composites for photocatalysts were effectively synthesized by adopting the template induced method. The prepared samples were characterized using XRD, FTIR spectroscopy, SEM, and EDX. The constructed samples’ particle size and shape were evaluated using a SEM, and the XRD patterns showed anatase crystalline phases. Their morphologies were controllable with changing concentration of reactants and calcination temperature. The synthesized composites act as catalyst in the degradation of methylene blue (MB) and reduction of Cr(VI) to Cr(III) under solar irradiation. In both of these activities, the best result has been shown by the 0.01 Ag/TiO2 composite. Methanol is used as the hole scavenger in the reduction of Cr(VI) to Cr(III). While the pH factor is important in the photocatalytic reduction of Cr(VI) to Cr(III). According to observations, S. macrospora and S. maydis were each subject to 0.01 Ag/TiO2 nanocomposites maximum antifungal activity, which was 38.4 mm and 34.3 mm, respectively. The outcomes demonstrate that both photocatalytic and antifungal properties are effectively displayed by the constructed material. Full article
(This article belongs to the Special Issue Nanocomposites for Photocatalysis)
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21 pages, 3777 KiB  
Article
A Tridentate Cu(II) Complex with a 2-(4′-Aminophenyl)Benzothiazole Derivative: Crystal Structure and Biological Evaluation for Anticancer Activity
by Barbara Mavroidi, Marina Sagnou, Eleftherios Halevas, George Mitrikas, Fotis Kapiris, Penelope Bouziotis, Antonios G. Hatzidimitriou, Maria Pelecanou and Constantinos Methenitis
Inorganics 2023, 11(3), 132; https://doi.org/10.3390/inorganics11030132 - 20 Mar 2023
Viewed by 1304
Abstract
Herein, the synthesis, structural characterization and in vitro biological evaluation of a novel Cu(II) complex with the 2-(4-aminophenyl)benzothiazole pharmacophore conjugated with the (2-pyridinyl)methylamino chelating moiety is reported for the first time. A full characterization of the Cu(II) complex was conducted by X-ray crystallography, [...] Read more.
Herein, the synthesis, structural characterization and in vitro biological evaluation of a novel Cu(II) complex with the 2-(4-aminophenyl)benzothiazole pharmacophore conjugated with the (2-pyridinyl)methylamino chelating moiety is reported for the first time. A full characterization of the Cu(II) complex was conducted by X-ray crystallography, EPR, IR, elemental and MS analysis, and its binding to CT-DNA was investigated by UV-vis spectroscopy, ethidium bromide competition studies, circular dichroism, viscometry and thermal denaturation. The data clearly indicate that the Cu(II) complex interacts with CT-DNA via intercalation, registering a difference compared to previously reported Pt(II) and Pd(II) analogues. To evaluate the anticancer activity of the complex, a series of in vitro experiments against breast, glioblastoma, prostate and lung cancer cell lines along with healthy fibroblasts were implemented. Cytotoxicity, cellular uptake, intracellular ROS production, cell cycle and apoptosis analysis revealed an increased anticancer activity towards breast cancer cells that is accompanied by an induction in intracellular ROS levels and a significant G2/M arrest followed by apoptosis. Full article
(This article belongs to the Special Issue Bioactivity of Transition Metal-Based Complexes)
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13 pages, 319 KiB  
Article
Effectiveness of Artificially Synthesized Granitic Residual Soil-Supported Nano Zero-Valent Iron (Gr-nZVI) as Effective Heavy Metal Contaminant Adsorbent
by Nur ‘Aishah Zarime, Badariah Solemon, Wan Zuhairi Wan Yaacob, Habibah Jamil, Rohayu Che Omar and Adeleke Abdulrahman Oyekanmi
Inorganics 2023, 11(3), 131; https://doi.org/10.3390/inorganics11030131 - 20 Mar 2023
Cited by 1 | Viewed by 1255
Abstract
Supported nano zero-valent iron is receiving great attention nowadays due to its effectiveness in treating heavy metal pollutants. Therefore, this study aimed to investigate the effectiveness of granitic residual soil-supported nano zero-valent iron (Gr-nZVI) for the removal of the heavy metals Pb2+ [...] Read more.
Supported nano zero-valent iron is receiving great attention nowadays due to its effectiveness in treating heavy metal pollutants. Therefore, this study aimed to investigate the effectiveness of granitic residual soil-supported nano zero-valent iron (Gr-nZVI) for the removal of the heavy metals Pb2+, Cu2+, Co2+, Cd2+ Ni2+ and Zn2+ in mixture solutions under different experimental conditions of batch equilibrium tests. In this study, Gr-nZVI was successfully synthesized by using the chemical reduction of Ferric Chloride Hexahydrate (FeCl3.6H2O) and Sodium Borohydride (NaBH4). The physical and chemical properties, morphology and mineralogy of all adsorbents were characterized by the Braeuer–Emmett–Teller (BET) method, cation exchange capacity (CEC), X-ray fluorescence (XRF), scanning electron microscopy (SEM), field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Isotherm, kinetic and diffusion model analyses were conducted to fit the experimental data. The results show rapid adsorption within 5 min in the initial adsorption stage for Pb2+ on nZVI (qe.Pb = 17.89 mg/g) and Gr-nZVI (qe.Pb = 15.29 mg/g). nZVI and Gr-nZVI also showed no significant effects on pH and temperature, serving as a good example of an energy-efficient process. The isotherm data fitted better to the Langmuir model and the pseudo-second-order kinetic model for the adsorption of all of the heavy metals. The diffusion models revealed that adsorption was not the only rate-limiting step. In this study, nZVI compared to Gr-nZVI and Gr demonstrated superior adsorption capacity for the heavy metal adsorption selectivity. Hence, these materials can be utilized as alternative energy-efficient adsorbents for the adsorption of metal ions from wastewater. Full article
(This article belongs to the Section Inorganic Materials)
5 pages, 216 KiB  
Editorial
New Advances into Nanostructured Oxides
by Roberto Nisticò
Inorganics 2023, 11(3), 130; https://doi.org/10.3390/inorganics11030130 - 20 Mar 2023
Viewed by 1077
Abstract
Inorganic nanostructured (metal) oxides are a large class of inorganic materials extensively investigated for their unique and outstanding properties that allow for their use within a multitude of technological fields of emerging interest, such as (photo)catalysis, environmental remediation processes, energy storage, controlled transport [...] Read more.
Inorganic nanostructured (metal) oxides are a large class of inorganic materials extensively investigated for their unique and outstanding properties that allow for their use within a multitude of technological fields of emerging interest, such as (photo)catalysis, environmental remediation processes, energy storage, controlled transport and/or release of drugs and chemicals, biomedicine, sensing, development of smart materials, stimuli-responsive materials, and nanocomposites [...] Full article
(This article belongs to the Special Issue New Advances into Nanostructured Oxides)
30 pages, 10177 KiB  
Article
The Electronic Nature of Cationic Group 10 Ylidyne Complexes
by Leonard R. Maurer, Jens Rump and Alexander C. Filippou
Inorganics 2023, 11(3), 129; https://doi.org/10.3390/inorganics11030129 - 18 Mar 2023
Cited by 5 | Viewed by 1813
Abstract
We report a broad theoretical study on [(PMe3)3MER]+ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = ArMes, Tbb, (ArMes = 2,6-dimesitylphenyl; Tbb = C6H [...] Read more.
We report a broad theoretical study on [(PMe3)3MER]+ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = ArMes, Tbb, (ArMes = 2,6-dimesitylphenyl; Tbb = C6H2-2,6-[CH(SiMe3)2]2-4-tBu). A few years ago, our group succeeded in obtaining heavier homologues of cationic group 10 carbyne complexes via halide abstraction of the tetrylidene complexes [(PMe3)3M=E(X)R] (X = Cl, Br) using a halide scavenger. The electronic structure and the M-E bonds of the [(PMe3)3MER]+ complexes were analyzed utilizing quantum-chemical tools, such as the Pipek–Mezey orbital localization method, the energy decomposition analysis (EDA), and the extended-transition state method with natural orbitals of chemical valence (ETS-NOCV). The carbyne, silylidyne complexes, and the germylidyne complex [(PMe3)3NiGeArMes]+ are suggested to be tetrylidyne complexes featuring donor–acceptor metal tetrel triple bonds, which are composed of two strong π(M→E) and one weaker σ(E→M) interaction. In comparison, the complexes with M = Pd, Pt; E = Sn, Pb; and R = ArMes are best described as metallotetrylenes and exhibit considerable M−E−C bending, a strong σ(M→E) bond, weakened M−E π-components, and lone pair density at the tetrel atoms. Furthermore, bond cleavage energy (BCE) and bond dissociation energy (BDE) reveal preferred splitting into [M(PMe3)3]+ and [ER] fragments for most complex cations in the range of 293.3–618.3 kJ·mol−1 and 230.4–461.6 kJ·mol−1, respectively. Finally, an extensive study of the potential energy hypersurface varying the M−E−C angle indicates the presence of isomers with M−E−C bond angles of around 95°. Interestingly, these isomers are energetically favored for M = Pd, Pt; E = Sn, Pb; and R = ArMes over the less-bent structures by 13–29 kJ·mol−1. Full article
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15 pages, 3255 KiB  
Article
Destabilization of the LiBH4–NaBH4 Eutectic Mixture through Pore Confinement for Hydrogen Storage
by Filippo Peru, Seyedhosein Payandeh, Torben R. Jensen, Georgia Charalambopoulou and Theodore Steriotis
Inorganics 2023, 11(3), 128; https://doi.org/10.3390/inorganics11030128 - 18 Mar 2023
Cited by 3 | Viewed by 1480
Abstract
Both LiBH4 and NaBH4 are well known for having high hydrogen contents, but also high decomposition temperatures and slow hydrogen absorption–desorption kinetics, preventing their use for hydrogen storage applications. The low melting temperature (219 °C) of their eutectic mixture 0.71 LiBH [...] Read more.
Both LiBH4 and NaBH4 are well known for having high hydrogen contents, but also high decomposition temperatures and slow hydrogen absorption–desorption kinetics, preventing their use for hydrogen storage applications. The low melting temperature (219 °C) of their eutectic mixture 0.71 LiBH4–0.29 NaBH4 allowed the synthesis of a new composite material through the melt infiltration of the hydrides into the ~5 nm diameter pores of a CMK-3 type carbon. A composite of 0.71 LiBH4–0.29 NaBH4 and non-porous graphitic carbon discs was also prepared by similar methods for comparison. Both composites showed improved kinetics and a partial reversibility of the dehydrogenation/rehydrogenation reactions. However, the best results were observed for the CMK-3 nanoconfined hydrides; a consistent uptake of about 3.5 wt.% H2 was recorded after five hydrogenation/dehydrogenation cycles for an otherwise non-reversible system. The improved hydrogen release kinetics are attributed to carbon–hydride surface interactions rather than nanoconfinement, while enhanced heat transfer due to the carbon support may also play a role. Likewise, the carbon–hydride contact proved beneficial in terms of reversibility, without, however, ruling out the potential positive effect of pore confinement. Full article
(This article belongs to the Special Issue State-of-the-Art and Progress in Metal-Hydrogen Systems)
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13 pages, 2081 KiB  
Article
Half-Sandwich Nickelacarboranes Derived from [7-(MeO(CH2)2S)-7,8-C2B9H11]
by Dmitriy K. Semyonov, Marina Yu. Stogniy, Kyrill Yu. Suponitsky and Igor B. Sivaev
Inorganics 2023, 11(3), 127; https://doi.org/10.3390/inorganics11030127 - 17 Mar 2023
Cited by 1 | Viewed by 1241
Abstract
New carboranyl thioethers 1-MeO(CH2)nS-1,2-C2B10H11 (n = 2, 3) were prepared by the alkylation of the trimethylammonium salt of 1-mercapto-ortho-carborane with 1-bromo- 2-methoxyethane and 1-bromo-3-methoxypropane, respectively. Their deboronation with cesium fluoride in ethanol [...] Read more.
New carboranyl thioethers 1-MeO(CH2)nS-1,2-C2B10H11 (n = 2, 3) were prepared by the alkylation of the trimethylammonium salt of 1-mercapto-ortho-carborane with 1-bromo- 2-methoxyethane and 1-bromo-3-methoxypropane, respectively. Their deboronation with cesium fluoride in ethanol gave the corresponding nido-carboranes Cs[7-MeO(CH2)nS-7,8-C2B9H11] (n = 2, 3). The reactions of Cs[7-MeO(CH2)2S-7,8-C2B9H11] with various nickel(II) phosphine complexes [(dppe)NiCl2] and [(R’R2P)2NiCl2] (R = R’ = Ph, Bu; R = Me, R’ = Ph; R = Ph, R’ = Me, Et) were studied and a series of nickelacarboranes 3,3-dppe-1-MeO(CH2)2S-closo-3,1,2-NiC2B9H10 and 3,3- (R’R2P)2-1-MeO(CH2)2S-closo-3,1,2-NiC2B9H10 (R = R’ = Bu; R = Me, R’ = Ph; R = Ph, R’ = Me, Et) was prepared. The molecular crystal structure of 3,3-dppe-1-MeO(CH2)2S-closo-3,1,2-NiC2B9H10 was determined by single-crystal X-ray diffraction. Full article
(This article belongs to the Special Issue Bioactivity of Transition Metal-Based Complexes)
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15 pages, 5834 KiB  
Article
Inorganic Sorbents for Wastewater Treatment from Radioactive Contaminants
by Natalya A. Nekrasova, Vitaly V. Milyutin, Victor O. Kaptakov and Evgeny A. Kozlitin
Inorganics 2023, 11(3), 126; https://doi.org/10.3390/inorganics11030126 - 16 Mar 2023
Cited by 4 | Viewed by 1775
Abstract
The article presents the distribution coefficient (Kd) values of 137Cs and 90Sr tracer radionuclides in solutions of sodium and calcium salts for a wide range of commercially available inorganic sorbents: natural and synthetic aluminosilicates, manganese, titanium and zirconium oxyhydrates, [...] Read more.
The article presents the distribution coefficient (Kd) values of 137Cs and 90Sr tracer radionuclides in solutions of sodium and calcium salts for a wide range of commercially available inorganic sorbents: natural and synthetic aluminosilicates, manganese, titanium and zirconium oxyhydrates, titanium and zirconium phosphates, titanosilicates of alkali metals, and ferrocyanides of transition metals. The results were obtained using a standard technique developed by the authors for evaluating the efficiency of various sorption materials towards cesium and strontium radionuclides. It was shown that bentonite clays and natural and synthetic zeolites are the best for decontaminating low-salt natural water from cesium radionuclides, and ferrocyanide sorbents are the choice for decontaminating high-salt-bearing solutions. The manganese (III, IV) oxyhydrate-based MDM sorbent is the most effective for removing strontium from natural water; for seawater, the barium silicate-based SRM-Sr sorbent is the first-in-class. Results of the study provide a possibility of making a reasonable choice of sorbents for the most effective treatment of natural water and technogenic aqueous waste contaminated with cesium and strontium radionuclides. Full article
(This article belongs to the Special Issue Inorganic Sorbents in Water Treatment)
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15 pages, 4386 KiB  
Article
Spectroscopic, Anti-Cancer Activity, and DFT Computational Studies of Pt(II) Complexes with 1-Benzyl-3-phenylthiourea and Phosphine/Diamine Ligands
by Dina Saadi Mohamed, Subhi A. Al-Jibori, Reza Behjatmanesh-Ardakani, Ahmed S. Faihan, Tarek A. Yousef, Abdulrahman G. Alhamzani, Mortaga M. Abou-Krisha, Ahmed S. M. Al-Janabi and Benjamin S. Hsiao
Inorganics 2023, 11(3), 125; https://doi.org/10.3390/inorganics11030125 - 16 Mar 2023
Cited by 5 | Viewed by 1641
Abstract
The reaction between [PtCl2(L-L)] (L-L = dppe, dppp, dppb, dppf, Phen and Bipy) or [PtCl2(PPh3)2] with 1-benzyl-3-phenylthiourea (H2BPT) in a basic medium (CHCl3/EtOH) created new coordinated square planner Pt(II) complexes with [...] Read more.
The reaction between [PtCl2(L-L)] (L-L = dppe, dppp, dppb, dppf, Phen and Bipy) or [PtCl2(PPh3)2] with 1-benzyl-3-phenylthiourea (H2BPT) in a basic medium (CHCl3/EtOH) created new coordinated square planner Pt(II) complexes with [Pt(BPT)(L-L)] (14,6,7) and [Pt(BPT)(PPh3)2] (5) types. These complexes were fully characterized by analytical and spectroscopic techniques (i.e., IR, UV. Vis., 1H, and 31P NMR). The results indicated that the thiourea derivative ligand act as a dianion ligand bonded through both S and N atoms in a chelating mode or as a mono-anion ligand coordinated through a sulfur atom with Pt(II) ion. Cytotoxicity activity was performed by the MTT assay to determine anti-cancer activities against MCF-7 breast cancer cells. The study indicated that IC50 values for MCF-7 cells were 10.96–78.90 µM. Additionally, the complexes [Pt(BPT)(dppe)] (1), [Pt(BPT)(PPh3)2] (5), and [Pt(BPT)2(Bipy)] (7) were investigated theoretically, where their quantum parameters were evaluated using the Gaussian 09 program using the theory of B3LYP/Def2TZVP//B3LYP/Lanl2dz. The calculation results confirmed the optimized structures of the complexes square planar geometry. However, the calculated bond lengths and angles showed a slightly distorted square planar geometry due to the trans influence of the sulfur atom. Additionally, complexes of [Pt(BPT)(dppe)] (1) and [Pt(BPT)(PPh3)2] (5) showed higher stability compared to [Pt(BPT)2(Bipy)] (7), which can be attributed to the higher back-donation of (1) and (5) complexes. Furthermore, among the three complexes, the [Pt(BPT)2(Bipy)] (7) complex possessed the lowest HOMO–LUMO gap, which may be a good candidate as the photo-catalyst material. Full article
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10 pages, 1758 KiB  
Article
Organometallic Iridium Complexes with Glucose Based Phosphite Ligands
by Maria R. Gonchar, Fedor S. Ninin, Dmitrii M. Mazur, Konstantin A. Lyssenko, Elena R. Milaeva and Alexey A. Nazarov
Inorganics 2023, 11(3), 124; https://doi.org/10.3390/inorganics11030124 - 15 Mar 2023
Viewed by 1140
Abstract
New organometallic iridium compounds with phosphorus modified glucose ligands containing isopropylidene protection group or bearing uracil, thymine, and 5-fluorouracil (3,5,6-bicyclophosphite-1,2-O-isopropylidene-α-d-glucofuranoside, 3,5,6-bicyclophosphite-1-β-D-glucofuranosyluracil, 3,5,6-bicyclophosphite-1-β-D-glucofuranosylthymine, 3,5,6-bicyclophosphite-1-β-D-glucofuranosyl-5-flurouracil) were prepared. The structure of the new complexes was confirmed by the spectroscopic technique (1H, 31 [...] Read more.
New organometallic iridium compounds with phosphorus modified glucose ligands containing isopropylidene protection group or bearing uracil, thymine, and 5-fluorouracil (3,5,6-bicyclophosphite-1,2-O-isopropylidene-α-d-glucofuranoside, 3,5,6-bicyclophosphite-1-β-D-glucofuranosyluracil, 3,5,6-bicyclophosphite-1-β-D-glucofuranosylthymine, 3,5,6-bicyclophosphite-1-β-D-glucofuranosyl-5-flurouracil) were prepared. The structure of the new complexes was confirmed by the spectroscopic technique (1H, 31P{1H} NMR) and mass spectrometry, and purity by elemental analysis. The molecular structure of the complex with the isopropylidene protection group was established by the X-ray analysis. The antiproliferative activity of the new iridium compounds was evaluated against several cancer cell lines of human origin, and all compounds showed low toxicity independent of the pyrimidine base nature, attached to the sugar unit. Full article
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9 pages, 2330 KiB  
Article
H2O·HF@C70: Encapsulation Energetics and Thermodynamics
by Zdeněk Slanina, Filip Uhlík, Xing Lu, Takeshi Akasaka and Ludwik Adamowicz
Inorganics 2023, 11(3), 123; https://doi.org/10.3390/inorganics11030123 - 15 Mar 2023
Viewed by 1048
Abstract
This report deals with the quantum-chemical evaluation of the energetics and thermodynamics of the simultaneous encapsulation of HF and H2O by the IPR (isolated pentagon rule) C70 fullerene cage, yielding H2O·HF@C70 species which [...] Read more.
This report deals with the quantum-chemical evaluation of the energetics and thermodynamics of the simultaneous encapsulation of HF and H2O by the IPR (isolated pentagon rule) C70 fullerene cage, yielding H2O·HF@C70 species which were synthesized and characterized recently, thus further expanding the family of fullerene endohedrals with non-metallic encapsulates. The structures were optimized at the DFT (density functional theory) M06-2X/6-31++G** level. The encapsulation energetics were further refined by the advanced B2PLYPD/6-31++G** and B2PLYPD/6-311++G** methods. After enhancement of the B2PLYPD/6-311++G** encapsulation energy for the BSSE and steric corrections, the encapsulation energy gain was obtained, as 26 kcal/mol. The equilibrium encapsulation thermodynamics were described using the M06-2X/6-31++G** partition functions. The results correspond to our previous evaluations for the water dimer encapsulation by C84 cages. Full article
(This article belongs to the Special Issue Advances in Fullerene Science)
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18 pages, 3849 KiB  
Article
Exploring the Emergent Redox Chemistry of Pd(II) Nodes with Pendant Ferrocenes: From Precursors, through Building Blocks, to Self-Assemblies
by Austin B. Gilbert, Matthew R. Crawley, Trevor J. Higgins, Yuguang C. Li, David F. Watson and Timothy R. Cook
Inorganics 2023, 11(3), 122; https://doi.org/10.3390/inorganics11030122 - 15 Mar 2023
Cited by 1 | Viewed by 2254
Abstract
Energy-relevant small molecule activations and related processes are often multi-electron in nature. Ferrocene is iconic for its well-behaved one-electron chemistry, and it is often used to impart redox activity to self-assembled architectures. When multiple ferrocenes are present as pendant groups in a single [...] Read more.
Energy-relevant small molecule activations and related processes are often multi-electron in nature. Ferrocene is iconic for its well-behaved one-electron chemistry, and it is often used to impart redox activity to self-assembled architectures. When multiple ferrocenes are present as pendant groups in a single structure, they often behave as isolated sites with no separation of their redox events. Herein, we study a suite of molecules culminating in a self-assembled palladium(II) truncated tetrahedron (TT) with six pendant ferrocene moieties using the iron(III/II) couple to inform about the electronic structure and, in some cases, subsequent reactivity. Notably, although known ferrocene-containing metallacycles and cages show simple reversible redox chemistry, this TT undergoes a complex multi-step electrochemical mechanism upon oxidation. The electrochemical behavior was observed by voltammetric and spectroelectrochemical techniques and suggests that the initial Fc-centered oxidation is coupled to a subsequent change in species solubility and deposition of a film onto the working electrode, which is followed by a second separable electrochemical oxidation event. The complicated electrochemical behavior of this self-assembly reveals emergent properties resulting from organizing multiple ferrocene subunits into a discrete structure. We anticipate that such structures may provide the basis for multiple charge separation events to drive important processes related to energy capture, storage, and use, especially as the electronic communication between sites is further tuned. Full article
(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)
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22 pages, 2994 KiB  
Review
Layered Double Hydroxide Materials: A Review on Their Preparation, Characterization, and Applications
by Jitendra Kameliya, Aazad Verma, Partha Dutta, Charu Arora, Shweta Vyas and Rajender S. Varma
Inorganics 2023, 11(3), 121; https://doi.org/10.3390/inorganics11030121 - 14 Mar 2023
Cited by 25 | Viewed by 6876
Abstract
Layered double hydroxides (LDHs), a type of synthetic clay with assorted potential applications, are deliberated upon in view of their specific properties, such as adsorbent-specific behavior, biocompatibility, fire-retardant capacity, and catalytic and anion exchange properties, among others. LDHs are materials with two-dimensional morphology, [...] Read more.
Layered double hydroxides (LDHs), a type of synthetic clay with assorted potential applications, are deliberated upon in view of their specific properties, such as adsorbent-specific behavior, biocompatibility, fire-retardant capacity, and catalytic and anion exchange properties, among others. LDHs are materials with two-dimensional morphology, high porosity, and exceptionally tunable and exchangeable anionic particles with sensible interlayer spaces. The remarkable feature of LDHs is their flexibility in maintaining the interlayer spaces endowing them with the capacity to accommodate a variety of ionic species, suitable for many applications. Herein, some synthetic methodologies, general characterizations, and applications of LDHs are summarized, encompassing their broader appliances as a remarkable material to serve society and address several problems viz. removal of pollutants and fabrication of sensors and materials with multifaceted useful applications in the medical, electrochemical, catalytic, and agricultural fields, among others. Full article
(This article belongs to the Special Issue Inorganics for Catalysts: Design, Synthesis and Applications)
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10 pages, 1293 KiB  
Article
Nickel(II) N-Heterocyclic Carbene Complex for the Hydrogenation of 2-Acetylpyridine under Mild Conditions
by Mitu Sharma, Amanda M. Perkins, Alison K. Duckworth, Emily J. Rouse, Bruno Donnadieu, Bhupendra Adhikari, Sean L. Stokes and Joseph P. Emerson
Inorganics 2023, 11(3), 120; https://doi.org/10.3390/inorganics11030120 - 14 Mar 2023
Cited by 3 | Viewed by 1534
Abstract
Catalyst-mediated hydrogenation of ketones via hydride transfer can be directly used in the synthesis of alcohols which can exhibit great potential in the practical synthesis of pharmaceuticals. The application of Ni-NHC complexes in the hydrogenation of ketones is still limited. In a pursuit [...] Read more.
Catalyst-mediated hydrogenation of ketones via hydride transfer can be directly used in the synthesis of alcohols which can exhibit great potential in the practical synthesis of pharmaceuticals. The application of Ni-NHC complexes in the hydrogenation of ketones is still limited. In a pursuit to study the effect of Ni-NHC-based complexes in the reactivity towards hydrogenation, we have studied the catalytic efficiency of a pendent-type nickel complex [Ni(NHC)2](PF6)2 constructed from a benzimidazole moiety. The hydrogenation of 2-acetylpyridine was studied with respect to catalyst loading, reaction temperature, reaction time, and solvent medium. The complex was broadly characterized by X-ray crystallography, ESI-MS, NMR, UV-Vis, and IR spectral studies. Full article
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13 pages, 3616 KiB  
Article
Direct Z-Scheme CoFe2O4-Loaded g-C3N4 Photocatalyst with High Degradation Efficiency of Methylene Blue under Visible-Light Irradiation
by Gebrehiwot Gebreslassie, Mamo Gebrezgiabher, Bin Lin, Madhu Thomas and Wolfgang Linert
Inorganics 2023, 11(3), 119; https://doi.org/10.3390/inorganics11030119 - 13 Mar 2023
Cited by 7 | Viewed by 1631
Abstract
Magnetically recyclable direct Z-scheme CoFe2O4-loaded g-C3N4 photocatalyst material was fabricated using a facile hydrothermal technique and subsequently characterized by XRD, VSM, PL, FT-IR, EDX, DRS, SEM, and BET techniques. The characterization results confirmed that nanoparticles of [...] Read more.
Magnetically recyclable direct Z-scheme CoFe2O4-loaded g-C3N4 photocatalyst material was fabricated using a facile hydrothermal technique and subsequently characterized by XRD, VSM, PL, FT-IR, EDX, DRS, SEM, and BET techniques. The characterization results confirmed that nanoparticles of CoFe2O4 are loaded on the surface of g-C3N4 sheets. The optical band gap of g-C3N4 has been decreased from 2.65 eV to 1.30 eV by means of the loading of CoFe2O4 nanoparticles onto the nanosheets of g-C3N4. This has enhanced the separation process of electron-hole. Under visible light irradiation, the photocatalytic activity of the developed direct Z-scheme CoFe2O4-loaded g-C3N4 photocatalyst was evaluated for the photodegradation of methylene blue (MB); during this process the MB decomposed by up to 98.86% in 140 min. Meanwhile, under the same irradiation and time conditions, the g-C3N4 and CoFe2O4 themselves degraded MB up to 74.92% and 51.53%, respectively. The direct Z-scheme CoFe2O4-loaded g-C3N4 material was recovered from the solution after the photocatalytic activity using an external magnet and studied to determine its stability. It was shown that the photoactivity did not change significantly after five consecutive cycles. Full article
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20 pages, 5185 KiB  
Review
Vanadium Oxide-Based Cathode Materials for Aqueous Zinc-Ion Batteries: Energy Storage Mechanism and Design Strategy
by Yu Qiu, Zhaoqian Yan, Zhihao Sun, Zihao Guo, Hongshou Liu, Benli Du, Shaoyao Tian, Peng Wang, Han Ding and Lei Qian
Inorganics 2023, 11(3), 118; https://doi.org/10.3390/inorganics11030118 - 12 Mar 2023
Cited by 1 | Viewed by 2634
Abstract
Aqueous zinc ion batteries (AZIBs) are an ideal choice for a new generation of large energy storage devices because of their high safety and low cost. Vanadium oxide-based materials have attracted great attention in the field of AZIB cathode materials due to their [...] Read more.
Aqueous zinc ion batteries (AZIBs) are an ideal choice for a new generation of large energy storage devices because of their high safety and low cost. Vanadium oxide-based materials have attracted great attention in the field of AZIB cathode materials due to their high theoretical capacity resulting from their rich oxidation states. However, the serious structural collapse and low intrinsic conductivity of vanadium oxide-based materials cause rapid capacity fading, which hinders their further applications in AZIB cathode materials. Here, the structural characteristics and energy storage mechanisms of vanadium oxide-based materials are reviewed, and the optimization strategies of vanadium oxide-based cathode materials are summarized, including substitutional doping, vacancy engineering, interlayer engineering, and structural composite. Finally, the future research and development direction of vanadium oxide-based AZIBs are prospected in terms of cathode, anode, electrolyte, non-electrode components, and recovery technology. Full article
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12 pages, 1937 KiB  
Article
Machine-Guided Design of Oxidation-Resistant Superconductors for Quantum Information Applications
by Carson Koppel, Brandon Wilfong, Allana Iwanicki, Elizabeth Hedrick, Tanya Berry and Tyrel M. McQueen
Inorganics 2023, 11(3), 117; https://doi.org/10.3390/inorganics11030117 - 11 Mar 2023
Viewed by 1403
Abstract
Decoherence in superconducting qubits has long been attributed to two-level systems arising from the surfaces and interfaces present in real devices. A recent significant step in reducing decoherence was the replacement of superconducting niobium by superconducting tantalum, resulting in a tripling of transmon [...] Read more.
Decoherence in superconducting qubits has long been attributed to two-level systems arising from the surfaces and interfaces present in real devices. A recent significant step in reducing decoherence was the replacement of superconducting niobium by superconducting tantalum, resulting in a tripling of transmon qubit lifetimes (T1). The identity, thickness, and quality of the native surface oxide, is thought to play a major role, as tantalum only has one oxide whereas niobium has several. Here we report the development of a thermodynamic metric to rank materials based on their potential to form a well-defined, thin, surface oxide. We first computed this metric for known binary and ternary metal alloys using data available from the Materials Project and experimentally validated the strengths and limits of this metric through the preparation and controlled oxidation of eight known metal alloys. Then we trained a convolutional neural network to predict the value of this metric from atomic composition and atomic properties. This allowed us to compute the metric for materials that are not present in the Materials Project, including a large selection of known superconductors, and, when combined with Tc, allowed us to identify new candidate superconductors for quantum information science and engineering (QISE) applications. We tested the oxidation resistance of a pair of these predictions experimentally. Our results are expected to lay the foundation for the tailored and rapid selection of improved superconductors for QISE. Full article
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22 pages, 4776 KiB  
Article
Synthesis and Characterization of Pt(II) and Pd(II) Complexes with Planar Aromatic Oximes
by Mikala Meadows, Lei Yang, Cody Turner, Mikhail Berezin, Sergiy Tyukhtenko and Nikolay Gerasimchuk
Inorganics 2023, 11(3), 116; https://doi.org/10.3390/inorganics11030116 - 10 Mar 2023
Viewed by 1575
Abstract
A series of four Werner-type complexes of Pd(II) and Pt(II) with planar, isomeric conjugated aromatic naphtoquinone oximes were synthesized for the first time. These ligands were 1-oxime-2-naphtoquinone (HL1) and 2-oxime-1-napthoquinone (HL2). Compounds were characterized using thermal analysis, [...] Read more.
A series of four Werner-type complexes of Pd(II) and Pt(II) with planar, isomeric conjugated aromatic naphtoquinone oximes were synthesized for the first time. These ligands were 1-oxime-2-naphtoquinone (HL1) and 2-oxime-1-napthoquinone (HL2). Compounds were characterized using thermal analysis, spectroscopic methods, and X-ray analysis. TG/DSC data were collected for pure starting organic ligands, their complexes, and indicated vigorous exothermic decomposition with at ~155 °C for starting HL and ~350 °C for transition metal complexes. Crystal structures for two Pt compounds with 2-oxime-1-quinone were determined and revealed the formation of the cis-geometry complexes and incorporation of molecules of stoichiometric solvents in the lattice: acetonitrile and nitrobenzene. Both solvents of crystallization displayed attractive interactions between their C-H groups and the oxygen atoms of the nitroso groups in complexes, leading to short distances in those fragments. Despite the presence of solvents of inclusion, the overall structure motifs in both compounds represent 1D columnar coordination polymer, in which the PtL2 units are held together via metallophilic interactions, thereby forming ‘Pt-wires’. The Hirshfield surface analysis was performed for both crystallographically characterized complexes. The results showed intermolecular ππ stacking and Pt–Pt interactions among the planar units of both complexes. In addition, the analysis also verified the presence of hydrogen bonding interactions between the platinum unit and solvent molecules. Solid bulk powdery samples of both PtL12 and PtL22 demonstrated pronounced photoluminescence in the near infrared region of spectrum at ~980 nm, being excited in the range of 750–800 nm. The NIR emission was observed only for Pt-complexes and not for pure starting organic ligands or Pd-complexes. Additionally, synthesized Pt-naphtoquinone oximes do not show luminescence in solutions, which suggests the importance of a 1D ‘metal wire’ structure for this process. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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11 pages, 2763 KiB  
Communication
Investigation on the Formation of Rare-Earth Metal Phenoxides via Metathesis
by Jintao Wang, Qijun Pei, Yang Yu, Jirong Cui, Shangshang Wang, Khai Chen Tan, Jiaquan Guo, Teng He and Ping Chen
Inorganics 2023, 11(3), 115; https://doi.org/10.3390/inorganics11030115 - 10 Mar 2023
Viewed by 1228
Abstract
A number of alkali organometallic complexes with suitable thermodynamic properties and high capacity for hydrogen storage have been synthesized; however, few transition metal–organic complexes have been reported for hydrogen storage. Moreover, the synthetic processes of these transition metal–organic complexes via metathesis were not [...] Read more.
A number of alkali organometallic complexes with suitable thermodynamic properties and high capacity for hydrogen storage have been synthesized; however, few transition metal–organic complexes have been reported for hydrogen storage. Moreover, the synthetic processes of these transition metal–organic complexes via metathesis were not well characterized previously, leading to a lack of understanding of the metathesis reaction. In the present study, yttrium phenoxide and lanthanum phenoxide were synthesized via metathesis of sodium phenoxide with YCl3 and LaCl3, respectively. Quasi in situ NMR, UV-vis, and theoretical calculations were employed to characterize the synthetic processes and the final products. It is revealed that the electron densities of phenoxides in rare-earth phenoxides are lower than in sodium phenoxide due to the stronger Lewis acidity of Y3+ and La3+. The synthetic process may follow a pathway of stepwise formation of dichloride, monochloride, and chloride-free species. Significant decreases in K-band and R-band absorption were observed in UV-vis, which may be due to the weakened conjugation effect between O and the aromatic ring after rare-earth metal substitution. Two molecular structures, i.e., planar and nonplanar, are identified by theoretical calculations for each rare-earth phenoxide. Since these two structures have very close single-point energies, they may coexist in the materials. Full article
(This article belongs to the Special Issue State-of-the-Art and Progress in Metal-Hydrogen Systems)
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11 pages, 3302 KiB  
Article
Neutral W(V) Complexes Featuring the W2O2(µ-O)2 Core and Amino Acids or EDTA Derivatives as Ligands: Synthesis and Structural Characterization
by Hristo P. Varbanov, Ferdinand Belaj, Toma Glasnov, Simon Herbert, Thomas Brumby and Nadia C. Mösch-Zanetti
Inorganics 2023, 11(3), 114; https://doi.org/10.3390/inorganics11030114 - 9 Mar 2023
Viewed by 1378
Abstract
Multinuclear complexes of heavy metals, such as tungsten, have demonstrated considerable potential as candidates for advanced radiocontrast agents. Of particular interest is the development of stable non-ionic compounds with high metal content and reasonably low osmolality in solution. Accordingly, we have synthesized a [...] Read more.
Multinuclear complexes of heavy metals, such as tungsten, have demonstrated considerable potential as candidates for advanced radiocontrast agents. Of particular interest is the development of stable non-ionic compounds with high metal content and reasonably low osmolality in solution. Accordingly, we have synthesized a series of neutral W(V) complexes that contain the W2O2(µ-O)2 core and amino acids or disubstituted EDTA derivatives as ligands. The compounds were prepared from the oxalatotungstate(V) complex via a convenient procedure utilizing microwave heating. Their detailed characterization was accomplished by electrospray ionization high-resolution mass spectrometry (ESI-HRMS), 1H and 13C NMR spectroscopy, elemental analysis, and X-ray crystallography. Further experiments to evaluate the utility of the complexes as radiocontrast media were precluded by their poor aqueous solubility. Full article
(This article belongs to the Special Issue Metal-Based Compounds: Relevance for the Biomedical Field)
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10 pages, 2628 KiB  
Perspective
Bis(benzimidazole) Complexes, Synthesis and Their Biological Properties: A Perspective
by Zdeněk Šindelář and Pavel Kopel
Inorganics 2023, 11(3), 113; https://doi.org/10.3390/inorganics11030113 - 9 Mar 2023
Cited by 7 | Viewed by 2178
Abstract
Benzimidazoles are a very well-known, broad group of compounds containing nitrogen atoms in their structure that can mimic properties of DNA bases. The compounds show not only biological activities but also are used for spectral and catalytic properties. Biological activity of benzimidazoles can [...] Read more.
Benzimidazoles are a very well-known, broad group of compounds containing nitrogen atoms in their structure that can mimic properties of DNA bases. The compounds show not only biological activities but also are used for spectral and catalytic properties. Biological activity of benzimidazoles can be tuned and accelerated in coordination compounds. This minireview is focused on preparation of bis(benzimidazoles), their complexes, and biological properties that can be found from 2015. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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14 pages, 9132 KiB  
Article
Diester Chlorogenoborate Complex: A New Naturally Occurring Boron-Containing Compound
by Andrei Biţă, Ion Romulus Scorei, Nagendra Rangavajla, Ludovic Everard Bejenaru, Gabriela Rău, Cornelia Bejenaru, Maria Viorica Ciocîlteu, Laura Dincă, Johny Neamţu, Andrei Bunaciu, Otilia Constantina Rogoveanu, Mihai Ioan Pop and George Dan Mogoşanu
Inorganics 2023, 11(3), 112; https://doi.org/10.3390/inorganics11030112 - 9 Mar 2023
Cited by 7 | Viewed by 1488
Abstract
The natural compounds of boron have many applications, primarily as a dietary supplement. The research is based on the discovery that the diester chlorogenoborate complex can be detected and quantified from green coffee beans. The study reports that such a diester molecule can [...] Read more.
The natural compounds of boron have many applications, primarily as a dietary supplement. The research is based on the discovery that the diester chlorogenoborate complex can be detected and quantified from green coffee beans. The study reports that such a diester molecule can also be synthesized in a stable form via the direct reaction of boric acid and chlorogenic acid in a mixture of acetonitrile–water (1:1, v/v) and left to evaporate over a period of 48 h at room temperature, resulting in a spirocyclic form (diester complex). The diester complex, with its molecular structure and digestibility attributes, has potential application as a prebiotic in gut health and oral health, and as a micronutrient essential for microbiota in humans and animals. Full article
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8 pages, 1543 KiB  
Communication
Collectable Single Pure-Pd Metal Membrane with High Strength and Flexibility Prepared through Electroplating for Hydrogen Purification
by Naruki Endo, Yumi Kaneko, Norikazu Dezawa, Yasuhiro Komo and Masanobu Higuchi
Inorganics 2023, 11(3), 111; https://doi.org/10.3390/inorganics11030111 - 9 Mar 2023
Viewed by 1511
Abstract
Among the various film preparation methods, electroplating is one of the simplest and most economical methods. However, it is challenging to collect a dense single Pd film through plating, owing to the accumulation of stress in the film during the process. Therefore, the [...] Read more.
Among the various film preparation methods, electroplating is one of the simplest and most economical methods. However, it is challenging to collect a dense single Pd film through plating, owing to the accumulation of stress in the film during the process. Therefore, the characteristics of a single plated film have not been clearly identified, although pure Pd is widely used in metallic-hydrogen-purification membranes. In this study, stress concentration in film during preparation was reduced by optimizing the plating process, and a dense single flat film was successfully collected. No impurities were detected. Thus, a high-purity Pd film was prepared. Its surface texture was found to be significantly different from that of the rolled film, and several approximately 5 μm sized aggregates were observed on the surface. The plated film is reported to have mechanical properties superior to those of the rolled film, with twice the displacement and four times the breaking point strength. The hydrogen permeabilities of the plated film (5.4 × 10−9–1.1 × 10−8 mol·m−1·s−1·Pa−1/2 at 250–450 °C) were comparable to those of the rolled and reported films, indicating that the surface texture does not have a strong effect on hydrogen permeability. The results of this study promote the practical use of Pd-based membranes through electroplating. Full article
(This article belongs to the Special Issue State-of-the-Art and Progress in Metal-Hydrogen Systems)
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18 pages, 2703 KiB  
Article
Development of Aldehyde Functionalized Iridium(III) Complexes Photosensitizers with Strong Visible-Light Absorption for Photocatalytic Hydrogen Generation from Water
by Xiao Yao, Qian Zhang, Po-Yu Ho, Sze-Chun Yiu, Songwut Suramitr, Supa Hannongbua and Cheuk-Lam Ho
Inorganics 2023, 11(3), 110; https://doi.org/10.3390/inorganics11030110 - 8 Mar 2023
Viewed by 1926
Abstract
Four iridium(III) dyes functionalized with aldehyde functional group in the cyclometalating (C^N) ligands, bearing either diethyl [2,2′-bipyridine]-4,4′-dicarboxylate or tetraethyl [2,2′-bipyridine]-4,4′-diylbis(phosphonate) anchoring groups, coded as Ir1Ir4, are synthesized and explored as photosensitizers. The synthetic route is described and all of the [...] Read more.
Four iridium(III) dyes functionalized with aldehyde functional group in the cyclometalating (C^N) ligands, bearing either diethyl [2,2′-bipyridine]-4,4′-dicarboxylate or tetraethyl [2,2′-bipyridine]-4,4′-diylbis(phosphonate) anchoring groups, coded as Ir1Ir4, are synthesized and explored as photosensitizers. The synthetic route is described and all of the complexes are characterized with respect to their electrochemical and photophysical properties. Density functional theory (DFT) calculation was used to gain insight into the factors responsible for the photocatalytic properties of Ir1Ir4 as effective photosensitizers for photocatalytic hydrogen generation. Relative to common iridium(III) dyes, such as [Ir(ppy)2(dcbpy)]+ (ppy = 2-phenylpyridine), the absorption spectra of our dyes are broader, which is attributed to the extended π-conjugation in their C^N ligands. All of the new iridium(III) dyes were used as photosensitizers for visible-light driven hydrogen production by attaching to platinized TiO2 nanoparticles (Pt–TiO2) in the presence of sacrificial electron donor (SED) of ascorbic acid (AA) in a purely aqueous solution. A H2 turnover number (TON) up to 5809 was demonstrated for 280 h irradiation. Complexes with tetraethyl [2,2′-bipyridine]-4,4′-diylbis(phosphonate) anchoring groups were found to outperform those with classical diethyl [2,2′-bipyridine]-4,4′-dicarboxylate, which may be one of the important steps in developing high-efficiency iridium(III) photosensitizers in water splitting hydrogen generation. Full article
(This article belongs to the Special Issue Transition Metal Complex-Based Luminescent Probes)
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16 pages, 3563 KiB  
Article
Electrochemical Performance of Potassium Bromate Active Electrolyte for Laser-Induced KBr-Graphene Supercapacitor Electrodes
by Nagih M. Shaalan, Faheem Ahmed, Shalendra Kumar, Mohamad M. Ahmad, Abdullah F. Al-Naim and D. Hamad
Inorganics 2023, 11(3), 109; https://doi.org/10.3390/inorganics11030109 - 8 Mar 2023
Cited by 1 | Viewed by 1517
Abstract
In this paper, we have reported a low-concentration active electrolyte of KBrO3 for the supercapacitor’s application. The electrochemical processes were carried out in two concentrations of KBrO3 with 0.2 and 0.4 M. Additionally, we have reported a novel strategy for doping [...] Read more.
In this paper, we have reported a low-concentration active electrolyte of KBrO3 for the supercapacitor’s application. The electrochemical processes were carried out in two concentrations of KBrO3 with 0.2 and 0.4 M. Additionally, we have reported a novel strategy for doping graphene during its fabrication process with a potassium bromide (KBr) solution. The chemical doping of graphene with KBr improved the electrochemical properties of graphene used as supercapacitors. HRTEM images confirmed the multi-layer graphene obtained by CO2 laser based on polyimide. The effect of KBr on the graphene lattice has been studied using Raman spectroscopy. The two electrodes of graphene and KBr-doped graphene were subjected to the electrochemical properties study as a supercapacitor by electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge techniques. The results exhibited the successful method of graphene doping and the stability of using KBrO3 as a suitable electrolyte for electrochemical processes with this lower molarity. The specific capacitance of the pristine graphene capacitor in 0.2 M of KBrO3 was 33 Fg−1, while this value increased up to 70 Fg−1 for KBr-doped graphene in 0.4 M of KBrO3. The specific capacity in mAhg−1 has also increased twofold. The results exhibited the possibility of using KBrO3 as an electrolyte. The supercapacitor performance almost showed good stability in the life cycle. Full article
(This article belongs to the Special Issue Electrochemical Study of Nanocarbon Based Materials)
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29 pages, 8462 KiB  
Article
Structural and Biological Properties of Heteroligand Copper Complexes with Diethylnicotinamide and Various Fenamates: Preparation, Structure, Spectral Properties and Hirshfeld Surface Analysis
by Milan Piroš, Martin Schoeller, Katarína Koňariková, Jindra Valentová, Ľubomír Švorc, Ján Moncoľ, Marian Valko and Jozef Švorec
Inorganics 2023, 11(3), 108; https://doi.org/10.3390/inorganics11030108 - 6 Mar 2023
Cited by 9 | Viewed by 1849
Abstract
Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of [...] Read more.
Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of composition: [Cu(fluf)2(dena)2(H2O)2] (1), [Cu(nifl)2(dena)2] (2), [Cu(tolf)2(dena)2(H2O)2] (3), [Cu(clon)2(dena)2] (4) and [Cu(mef)2(dena)2(H2O)2] (5), were synthesized, structurally (single-crystal X-ray diffraction) and spectroscopically characterized (IR, EA, UV-Vis and EPR). The studied complexes are monomeric, forming a distorted tetragonal bipyramidal stereochemistry around the central copper ion. The crystal structures of all five complexes were determined and refined with an aspheric model using the Hirshfeld atom refinement method. Hirshfeld surface analysis and fingerprint plots were used to investigate the intermolecular interactions in the crystalline state. The redox properties of the complexes were studied and evaluated via cyclic voltammetry. The complexes exhibited good superoxide scavenging activity as determined by an NBT assay along with a copper-based redox-cycling mechanism, resulting in the formation of ROS, which, in turn, predisposed the studied complexes for their anticancer activity. The ability of complexes 1–4 to interact with calf thymus DNA was investigated using absorption titrations, viscosity measurements and an ethidium-bromide-displacement-fluorescence-based method, suggesting mainly the intercalative binding of the complexes to DNA. The affinity of complexes 1–4 for bovine serum albumin was determined via fluorescence emission spectroscopy and was quantitatively characterized with the corresponding binding constants. The cytotoxic properties of complexes 1–4 were studied using the cancer cell lines A549, MCF-7 and U-118MG, as well as healthy MRC-5 cells. Complex 4 exhibited moderate anticancer activity on the MCF-7 cancer cells with IC50 = 57 μM. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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12 pages, 2256 KiB  
Article
Simulation of Sorption-Enhanced Steam Methane Reforming over Ni-Based Catalyst in a Pressurized Dual Fluidized Bed Reactor
by Linbo Yan, Kexin Li, Hongyang Sui, Boshu He, Cong Geng and Baizeng Fang
Inorganics 2023, 11(3), 107; https://doi.org/10.3390/inorganics11030107 - 5 Mar 2023
Viewed by 1445
Abstract
Steam methane reforming is a major method of hydrogen production. However, this method usually suffers from low energy efficiency and high carbon-emission intensity. To solve this issue, a novel steam-methane-reforming process over a Ni-based catalyst in a pressurized dual fluidized bed reactor is [...] Read more.
Steam methane reforming is a major method of hydrogen production. However, this method usually suffers from low energy efficiency and high carbon-emission intensity. To solve this issue, a novel steam-methane-reforming process over a Ni-based catalyst in a pressurized dual fluidized bed reactor is proposed in this work. A three-dimensional computational fluid dynamics (CFD) model for the complex physicochemical process was built to study the reforming characteristics. The model was first validated against the reported data in terms of hydrodynamics and reaction kinetics. Next, the performance of the proposed methane-steam-reforming process was predicted. It was found that the methane-conversion ratio was close to 100%. The mole fraction of H2 in the dry-yield syngas reached 98.8%, the cold gas efficiency reached 98.5%, and the carbon-capture rate reached 96.4%. It is believed that the proposed method can be used for methane reforming with high efficiency and low carbon intensity. Full article
(This article belongs to the Special Issue Inorganics for Catalysts: Design, Synthesis and Applications)
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11 pages, 3695 KiB  
Article
Effects of Al2O3 Thickness in Silicon Heterojunction Solar Cells
by Doowon Lee, Myoungsu Chae, Jong-Ryeol Kim and Hee-Dong Kim
Inorganics 2023, 11(3), 106; https://doi.org/10.3390/inorganics11030106 - 4 Mar 2023
Cited by 1 | Viewed by 1419
Abstract
In this paper, we investigate the effects of aluminum oxide (Al2O3) antireflection coating (ARC) on silicon heterojunction (SHJ) solar cells. Comprehensive ARCs simulation with Al2O3/ITO/c-Si structure is carried out and the feasibility to improve the [...] Read more.
In this paper, we investigate the effects of aluminum oxide (Al2O3) antireflection coating (ARC) on silicon heterojunction (SHJ) solar cells. Comprehensive ARCs simulation with Al2O3/ITO/c-Si structure is carried out and the feasibility to improve the short circuit current density (JSC) is demonstrated. Based on the simulation results, we apply Al2O3 ARC on SHJ solar cells, and the increasement in JSC to 1.5 mA/cm2 is observed with an Al2O3 layer thickness of 20 nm. It is because the total reflectance of SHJ solar cells is decreased by the shifting of the wavelength range on constructive and destructive light interference. As a result, we believe that the proposed Al2O3 ARC can support an effective engineering technic to increase JSC and efficiency of SHJ solar cells. Full article
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