Oxide Precursor Research Articles

High-Entropy Alloy Al0.2Co1.5CrFeNi1.5Ti0.5 Prepared from High-Entropy Oxide (Al0.2Co1.5CrFeNi1.5Ti0.5)3O4 by a Deoxidation Process via a CaH2-Assisted Molten Salt Method

High-entropy alloys (HEAs) have attracted a great deal of research interest these days because of their attractive properties. Low-temperature chemical synthesis methods are being developed to obtain nanoscale HEAs with low energy consumption. In this study, we prepared HEA Al0.2Co1.5CrFeNi1.5Ti0.5 nanoparticles from high-entropy oxide (HEO) (Al0.2Co1.5CrFeNi1.5Ti0.5)3O4 by a deoxidation process via a CaH2-assisted molten salt method at 600 °C. X-ray diffraction measurements demonstrated that the oxide precursor and the reduced product have single-phases of spinel structure and face-centered cubic structures, indicating the formation of HEO and HEA, respectively. The HEA nanoparticles exhibited superior catalytic performance in the liquid-phase hydrogenation of p-nitrophenol at room temperature with little leaching of the component elements. Scanning electron microscopy (SEM) with energy-dispersive X-ray spectrometry (EDX) exhibited a good distribution of constituent elements over the HEA nanoparticles in a micro-sized range. However, transmission electron microscopy (TEM) with EDX revealed a slight deviation of elemental distributions of Al and Ti from those of Co, Cr, Fe, and Ni in a nano-sized range, probably due to the incomplete reduction of aluminum and titanium oxides. The elemental homogeneity in the HEA nanoparticles could be improved by taking advantage of the HEO precursor with homogeneous elemental distributions, but the experimental results suggested the importance of the total reduction of oxide precursors to prepare homogeneous HEAs from HEOs.

Preventive effect of an ethanolic avocado on apoptosis induced via oxidative damage in albino rats tissues

Oxidative stress is the result of an imbalance between the production of oxidant precursors and the capacity of antioxidant defense. Oxygen free radicals play an important role in causing diseases. In this study, the protective effect of ethanolic avocado on apoptosis caused by oxidative damage in the tissue of albino rats was investigated. 24 male albino rats of the Faculty of Veterinary Medicine in Mosul, Iraq, which were kept in standard conditions for at least 10 days before and through the experimental work, were examined. Four groups of rats include the control group (healthy group), the group of male rats with ethanolic avocado consumption; The third group of male rats that were treated with 0.5% of hydrogen peroxide H2O2; and the fourth group of male rats that were treated with both 0.5% H2O2 and avocado ethanolic extract (50 mg kg-1 BW) for four weeks. After fixing the tissues of the liver, kidney, lung, spleen and testis in 10% buffered formalin, they were stained with hematoxylin. TUNEL assay was performed using the TUNEL cell death assay kit to detect apoptotic cells. In this investigation, the histology results in four groups of rats showed that in the rats that were treated with avocado, there were minor tissue changes in their liver, kidney, and intestine, and the tissues of these organs were healthy. In TUNEL staining, it was also shown that there are no apoptotic cells in the liver, kidney and testis cells in avocado-treated rats. The results showed that ethanolic Avocado is useful against oxidative stress damage and it may be used to protect tissues against oxidative stress.

Growth and characterization of physical properties of photovoltaic (K,Ba)(Ni,Nb)O3 single crystals

The substitution of fossil energy for green-energy sources is a world demand. Photovoltaic devices are a well-known safety solution to convert solar energy into electricity. Ferroelectric materials are one of the most promising candidates for substituting Si-based compounds in solar-energy conversion devices due to their relatively low cost and bulk photovoltaic effect instead of the classical p-n junction. In this work, (K,Ba)(Nb,Ni)O3 single crystal was grown by vertical Bridgman-Stockbarger method, and structural, chemical, and optical properties of the as-grown material were characterized. Growth parameters were chosen based on the thermal properties of the precursor oxide and on theoretical models.

Effect of TiO2/Fe2O3 nanopowder synthesis method on visible light photocatalytic degradation of reactive blue dye

Water pollution and scarcity of clean water are major issues of concern globally. In this study, titanium dioxide (TiO2) photocatalyst doped with ferric oxide (Fe2O3) was used to degrade reactive blue dye (171) using sunlight irradiation. Two approaches were employed to synthesize the photocatalyst: synthesis of ferric oxide and titanium precursor through ultrasonic-assisted sol-gel method and using iron (III) nitrate nonahydrate with commercial titanium dioxide. The photocatalysts were characterized using FTIR Spectroscopy, SEM, XRD analyses, and UVDRS to determine their chemical composition, morphology, crystallinity, and light absorption, respectively. The effect of contaminant concentration (1–3 ppm), solution pH and photocatalyst type on the degradation efficiency was studied. Doping enabled visible light absorption as confirmed by the UVDRS analysis. Solar photocatalytic degradation resulted in complete (100 % removal) of the dye within 2 h under solar irradiation for all concentrations of the dye studied. Furthermore, the photocatalysts exhibited superior performance in both neutral and acidic solutions compared to basic ones. After four cycles, the dye removal efficiency has decreased by less than 15 % for all the photocatalysts confirming the significant activity and high stability of the nanocomposite. The increased dye photodegradation efficacy of Fe2O3 doped TiO2 under sunlight irradiation is attributed to the narrowing of the photocatalyst's bandgap from 3.76 eV (in pure TiO2) to 2.83 eV. This narrowing of the bandgap enhances the absorption of visible light from sunlight, thus making this photocatalyst effective under sunlight and eliminating the use of electricity which is a requirement for ultraviolet photocatalysis.

Acridine-Isoxazole and Acridine-Azirine Hybrids: Synthesis, Photochemical Transformations in the UV/Visible Radiation Boundary Region, and Anticancer Activity.

Easy-to-handle N-hydroxyacridinecarbimidoyl chloride hydrochlorides were synthesized as convenient nitrile oxide precursors in the preparation of 3-(acridin-9/2-yl)isoxazole derivatives via 1,3-dipolar cycloaddition with terminal alkynes, 1,1-dichloroethene, and acrylonitrile. Azirines with an acridin-9/2-yl substituent attached directly or via the 1,2,3-triazole linker to the azirine C2 were also synthesized. The three-membered rings of the acridine-azirine hybrids were found to be resistant to irradiation in the UV/visible boundary region, despite their long-wave absorption at 320-420 nm, indicating that the acridine moiety cannot be used as an antenna to transfer light energy to generate nitrile ylides from azirines for photoclick cycloaddition. The acridine-isoxazole hybrids linked at the C9-C3 or C2-C3 atoms under blue light irradiation underwent the addition of such hydrogen donor solvents, such as, toluene, o-xylene, mesitylene, 4-chlorotoluene, THF, 1,4-dioxane, or methyl tert-butyl ether (MTBE), to the acridine system to give the corresponding 9-substituted acridanes in good yields. The synthesized acridine-azirine, acridine-isoxazole, and acridane-isoxazole hybrids exhibited cytotoxicity toward both all tested cancer cell lines (HCT 116, MCF7, and A704) and normal cells (WI-26 VA4).

Boosting hydroxyl radical generation for highly efficient electrooxidation of sulfamethazine via facile doping strategy

The one-electron water oxidation reaction (WOR) to generates hydroxyl radicals (•OH) plays a pivotal role in electrochemical advanced oxidation processes (EAOPs). In this study, we present a novel and facile strategy involving Ho-doping to regulate the electronic configuration of the conventionally nonactive PbO2 electrode. Experimental findings demonstrate that PbO2 doped with 2.4% Ho achieves the highest degradation performance of sulfamethazine (SMZ) (∼100%; kobs = 0.093 min−1) and highest •OH generation efficiency with a relatively concentration of •OH = 1.9 × 107. The doped electrodes exhibit a notable enhancement compare to the undoped electrode, which elevating SMZ degradation efficiency and •OH generation by factors of 1.45 and 3.8, respectively. Electrochemical characterization and degradation results elucidate that the modulation of electron transfer rate and oxygen evolution potential are crucial factors governing the performance of the Ho-doped PbO2 anode. Specifically, maintaining a suitably high oxygen evolution potential (OEP) enables the thermodynamically feasible production of •OH, while a relatively fast electron transfer rate ensures the generation of H2O+ (the oxidation precursor of •OH) with kinetic feasibility. Furthermore, a degradation pathway for SMZ is proposed based on the identification of transformation mechanism using density functional calculation (DFT) and the detection of intermediates via LC-MS/MS. This study provides an universal strategy for simultaneously enhancing the OEP and optimizing the electron transfer rate of an EAOP anode through the modulation of anodic electronic configuration, thereby advancing the field of efficient water treatment applications.

Evaluation of cellular viability in chitosan/L-arginine hydrogels.

There is a lack of studies evaluating the toxicity of nitric oxide (NO) precursors in chitosan/L-arginine hydrogels and their topical administration. However, clarifying the characteristics of these elements is essential for their possible use in non-surgical techniques of tooth movement acceleration. Such characteristics include interaction with different cell types, metabolism and drug safety. This in vitro study aimed to assess the cytotoxicity of chitosan hydrogels on human HeLa cells using different concentrations of L-arginine. The hydrogels were synthesized in a materials engineering laboratory, with a controlled environment, using 4 different L-arginine concentrations of 0%, 10%, 15%, and 20%. Once the hydrogels were prepared, their physical and chemical properties were characterized, and viability analysis was performed using 2 different methods, including a 48-h assay with Artemia salina nauplii and a 24-h cell culture with human HeLa cells followed by a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) proliferation assay. Data analysis was performed using a Mann-Whitney U test to evaluate positive and negative controls in the cell culture, with a significance level of 0.01. A Wilcoxon paired test contrasted the 24-h compared to 48-h Artemia salina assays, with a Kruskal-Wallis and post hoc Dunn test used to compare groups using a significance level of 0.05. In the more viscous hydrogels, Artemia salina nauplii decreased drastically in 24 h, while the 15% and 20% hydrogels had no statistical differences from the negative control. The 10% and 20% hydrogels were statistically different from the negative control when comparing cell culture data. Our findings suggest that chitosan/L-arginine hydrogels could be used in humans without toxic effects. However, more trials and tests are needed to evaluate tooth movement rate during orthodontic treatment.

Copper-catalysed dehydrogenation or lactonization of C(sp3)-H bonds.

Cytochrome P450 enzymes are known to catalyse bimodal oxidation of aliphatic acids via radical intermediates, which partition between pathways of hydroxylation and desaturation1,2. Developing analogous catalytic systems for remote C-H functionalization remains a significant challenge3-5. Here, we report the development of Cu(I)-catalysed bimodal dehydrogenation/lactonization reactions of synthetically common N-methoxyamides through radical abstractions of the γ-aliphatic C-H bonds. The feasibility of switching from dehydrogenation to lactonization is also demonstrated by altering reaction conditions. The use of a readily available amide as both radical precursor and internal oxidant allows for the development of redox-neutral C-H functionalization reactions with methanol as the sole side product. These C-H functionalization reactions using a Cu(I) catalyst with loading as low as 0.5 mol.% is applied to the diversification of a wide range of aliphatic acids including drug molecules and natural products. The exceptional compatibility of this catalytic system with a wide range of oxidatively sensitive functionality demonstrates the unique advantage of using a simple amide substrate as a mild internal oxidant.

Integration of Ultrathin Hafnium Oxide with a Clean van der Waals Interface for Two-Dimensional Sandwich Heterostructure Electronics.

Integrating high-κ dielectrics with a small equivalent oxide thickness (EOT) with two-dimensional (2D) semiconductors for low-power consumption van der Waals (vdW) heterostructure electronics remains challenging in meeting both interface quality and dielectric property requirements. Here, we demonstrate the integration of ultrathin amorphous HfOx sandwiched within vdW heterostructures by the selective thermal oxidation of HfSe2 precursors. The self-cleaning process ensures a high-quality interface with a low interface state density of 1011-1012 cm-2 eV-1. The synthesized HfOx displays excellent dielectric properties with an EOT of ∼1.5 nm, i.e., a high κ of ∼16, an ultralow leakage current of 10-6 A/cm2, and an impressively high breakdown field of 9.5 MV/cm. This facilitates low-power consumption vdW heterostructure MoS2 transistors, demonstrating steep switching with a low subthreshold swing of 61 mV/decade. This one-step integration of high-κ dielectrics into vdW sandwich heterostructures holds immense potential for developing low-power consumption 2D electronics while meeting comprehensive dielectric requirements.

Ruddlesden-Popper Oxyfluorides La2Ni1-xCuxO3F2 (0 ≤ x ≤ 1): Impact of the Ni/Cu Ratio on the Structure.

Ruddlesden-Popper oxyfluorides La2Ni1-xCuxO3F2 (0 ≤ x ≤ 1) were obtained by topochemical reaction of oxide precursors La2Ni1-xCuxO4, prepared by citrate-based soft chemistry synthesis, with polyvinylidene fluoride (PVDF) as the fluorine source. Systematic changes of the crystal structure in the oxide as well as the oxyfluoride substitution series were investigated. For 0.2 ≤ x ≤ 0.9, the oxyfluorides adopt the monoclinic (C2/c) structural distortion previously solved for the x = 0.8 compound based on neutron powder diffraction data, whereas the sample with a lower Cu content of x = 0.1 crystallizes in the orthorhombic (Cccm) structure variant of La2NiO3F2. The orthorhombic-to-monoclinic structural transition was found to be the result of an additional tilt component of the Jahn-Teller elongated CuO4F2 octahedra. The structural transitions were additionally studied by DFT calculations, confirming the monoclinic space group symmetry. The "channel-like" anionic ordering of the endmembers La2NiO3F2 and La2CuO3F2 was checked by 19F MAS NMR experiments and was found to persist throughout the entire substitution series.

Perfectly dense ceramics of highly pure calcium manganese oxide

Immensely thermally stable and perfectly dense ceramics of highly pure calcium manganese oxide (CaMnO3) powders is realized at optimized minimal processing temperature and time using cost-effective ball-milling and hot-press techniques. The effect of ball milling time on the calcination time to prepare highly pure CaMnO3 powder and sintering time on the temperature adequate enough to achieve perfectly dense CaMnO3 ceramics is studied thoroughly and systematically. The as-synthesized single phase CaMnO3 is attained by mixing precursors of calcium carbonate and manganese oxide, using high energy ball milling for longer time followed by calcination for shorter time duration and vice-versa. A decrease in particle size in as-synthesized CaMnO3 is noticed for powders prepared with longer ball milling and shorter calcination times. The minimal time required for achieving highly pure and fine-grained powders containing sub-micrometer particles of CaMnO3 is accomplished by ball milling the precursor mixture for 12 h and calcining at 1273 K for 2 h. Relative density of 99.03% is achieved for the as-synthesized CaMnO3 powders hot pressed at 1073 K for 30 min.

ZIF-67-derived Co@NC as an efficient catalyst for magnesium sulfite oxidation in the flue gas desulfurization process

Magnesium desulfurization is a wet flue gas desulfurization (WFGD) technology widely used in China, however, the low oxidation rate of magnesium sulfite (MgSO3), a byproduct of WFGD, causes the subsequent oxidation and crystallization process to require amount energy. Here, we prepared a cobalt-based nitrogen-doped porous carbon catalyst (Co@NC) using ZIF-67 as a precursor for the efficient catalytic oxidation of MgSO3 generated during magnesium desulfurization. The performance of Co@NC catalysts obtained at an optimal calcination temperature of 650 °C showed that the catalysts with oxidation rates up to 0.1332 mmol·L−1·s−1 of MgSO3 were considerably better than those previously studied, which outperformed the catalysts described in earlier research by a considerable margin. Further studies revealed that the Co@NC’s exceptional catalytic activity was attributed to both its special porous structure and the exposed active Co sites in the organic skeleton. The uniformly dispersed Co species act as the active sites of the Co@NC that can be fully contacted with the reactant. The presence of 0.5 g·L−1 Co@NC increases the MgSO3 oxidation rate by about 14 times compared to the noncatalytic benchmark. A practical tactic is furnished by this research for energy saving and emission reduction in the WFGD process, especially for the efficient oxidation and resource conversion of the by-product MgSO3.

Effect of silica addition on the photocatalytic activity of MO2@SiO2 (M=Ti, Zr, Sn, Ce) nanocomposites prepared by sol-gel

AbstractPhotocatalysis uses wide band gap ceramic semiconductors (anatase, zirconia, ceria, cassiterite…) that have the ability to promote electron-hole pairs by UV light irradiation producing both reducing and oxidants ions and radicals. In general, oxidizing species are more efficient, using photocatalysis as an advanced oxidation process (AOP) for the biodegradation of organic substances refractory to conventional treatments, such as azo dyes, or atmospheric pollutants as NOx. In this communication, the photocatalytic activity of xSiO2@(1-x)MO2 (M = TiO2, ZrO2, SnO2, CeO2, x = 0, 0.1, 0.3 and 0.5) composites on the Orange II azo dye in solution, as well as on NOx in air, was analysed. The composites were obtained by Sol-Gel methods based on the hydrolysis-condensation of alcoholic solutions of silicon tetraethoxide (TEOS) and titanium n-butoxide, zirconium iso-propoxide, SnCl2.2H2O and Ce(NO3)3.6H2O as precursors of MO2 oxides. The resulting xerogels were studied by XRD, bandgap measurements from UV-Vis-NIR diffuse reflectance spectroscopy, photocatalytic activity against Orange II in dissolution and NOx in air (efficiency in nitrate abatement), and SEM-EDX microstructural analysis. In the case of non-stabilized samples, charring samples at 300 °C/1 h and fired samples at 500 °C/1 h were also studied. The cassiterite-silica composite stands out for its photocatalytic activity against Orange II in solution and the cerianite-silica composite against NOx in air. Silica increases the photocatalytic activity on NOx in zirconia, tin oxide and ceria composites and also on Orange II in zirconia and tin oxide. Graphical Abstract

Preparation of Ce-Doped Gd3(Al, Ga)5O12 Nanopowders via Microwave-Assisted Homogenization Precipitation for Transparent Ceramic Scintillators.

Ce-doped gadolinium gallium aluminum oxide (Ce: GGAG) precursors were first prepared by the microwave-assisted homogeneous precipitation method (MAHP). Thermal gravity-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), specific surface area analysis (BET) and field emission scanning electron microscopy (FE-SEM) were employed to investigate the crystal structure, phase evolution and morphologies of the Ce: GGAG precursors and powders. The influence of Ga ion concentration in the salt solution on the properties of Ce: GGAG powders was investigated. All the precursors were transformed into single-phase GGAG after being calcined at 950 °C in a furnace for 3 h. Monodispersed Ce: GGAG powders were obtained as the Ga ion concentration was lower than 0.06 mol/L. Single-phase and dense Ce: GGAG ceramics were obtained after sintering at 1600 °C in a flowing oxygen atmosphere for 10 h. Specifically, the Ce: GGAG ceramic reached its maximum density of ~6.68 g/cm3, which was close to its theoretical density of 6.70 g/cm3, and exhibited the highest optical transmittance of 65.2% at 800 nm after hot isostatic pressing sintering (HIP) as the Ga ion concentration was 0.02 mol/L. The decay time and light yield of the GGAG ceramic were 35 ns and 35,000 ± 1250 ph/MeV, respectively, suggesting that Ce: GGAG ceramics prepared using MAHP-synthesized nanopowders are promising for scintillation applications.

Effect of Al2O3 thickness and oxidant precursors on the interface composition and contamination in Al2O3/GaN structures

In this paper, we investigate the Al2O3/GaN critical buried interface of the next generation of gallium nitride (GaN)‐based transistors using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and hard X‐ray photoelectron spectroscopy (HAXPES). Results highlight that gallium oxidation at this interface is enhanced when increasing the Al2O3 thickness from 3 up to 20 nm. Gallium oxidation is reduced when using both O3 and H2O as oxidant precursors, compared with only H2O during the growth of Al2O3. In addition, the O3/H2O‐based Al2O3 favors a reduction of contaminants such as hydrogen and carbon but enhances the presence of halides (Cl− and F−) at this Al2O3/GaN interface.

Thermal atomic layer deposition of aluminum oxide, nitride, and oxynitride: A mechanistic investigation

Atomic layer deposition (ALD) has been proven to be a versatile method for the deposition of thin films of various materials. It yields films with exceptional conformality and allows tunable film compositions with control of film thickness at the atomic level. Thin films of Al oxide, nitride, and oxynitride are deposited via ALD using Al(CH3)3 (TMA)/AlCl3 with H2O/NH3. Herein, surface chemical reactions are examined using density functional theory calculations to elucidate the adsorption, oxidation, and nitridation of precursors [TMA and AlCl3] as well as the mechanism controlling the composition of Al oxynitride thin films obtained through ALD. The hydrogen-terminated substrate surface is transformed into a CH3/Cl-terminated surface after the reaction with the TMA/AlCl3 precursors. The molecular adsorption of TMA occurs through a spontaneous reaction, whereas that of AlCl3 requires a slight energy input. Although the adsorption energy of AlCl3 is higher than that of TMA, the activation energy and energy change of AlCl3 adsorption are higher and lower than those of TMA, respectively; furthermore, the use of AlCl3 results in the generation of a corrosive by-product (HCl). A similar tendency is observed in the second ALD half reaction, which is oxidation. Nitride formation is endothermic for molecularly adsorbed AlCl3 but exothermic for TMA. Furthermore, the investigation of the exchange reactions between surface moieties and excess gaseous reactants reveals a preference for the substitution of N by O, which is attributed to differences in bond energies between the surface moieties and the surface metal atom, as well as between H2O and NH3.

Synthesis of rGO-reinforced MgAl2O4 spinel composites by solid-state powder route mechanism: A comparative analysis between non-reinforced and rGO-reinforced spinel composites

Reduced Graphene Oxide (rGO)-reinforced MgAl2O4 spinel composite was successfully synthesized by a solid-state powder route mechanism via high-energy planetary ball milling of corresponding metal oxide precursors followed by a high-temperature single-stage sintering process. The effect of rGO on the homogeneity, phase development, morphology, chemical composition, rate of formation of spinel, and cation anti-site formation of the composites was methodically investigated. For comparison, a stoichiometric non-reinforced MgAl2O4 spinel was also synthesized. The addition of 0.2 wt% and 0.4 wt% of rGO as reinforcement increased the homogeneity of the ball-milled composite powder, with Polydispersity Index (PDI) values of 0.19 and 0.15 respectively, as compared to 0.24 obtained in non-reinforced spinel composite. The X-ray diffraction pattern and IR spectrum of 1650 °C sintered composites confirmed the formation of highly crystalline phases with spinel structure. The microstructural analysis revealed that the addition of rGO led to a reduction in porosity and improved the process of sintering. Calorimetric studies showed that spinelization started to occur at 858 °C and 880 °C for 0.2 wt% and 0.4 wt% rGO-reinforced composites respectively, which was faster than non-reinforced composite. 27Al solid-sate nuclear magnetic resonance (SS-NMR) analysis depicted that ceramic composite reinforced with rGO exhibited lesser inversion parameter of 0.09 (for 0.2 wt% rGO) and 0.055 (for 0.4 wt% rGO), as compared to 0.145 obtained in non-reinforced composite, indicating lesser cation anti-sites formation in rGO-reinforced spinel composite.

Design, synthesis, olfactory evaluation and molecular docking study of Isoxazoline carboxylate derivatives as fragrance molecules

AbstractIn this research, a wide range of aldoxime derivatives with aromatic and aliphatic substituents were synthesized as precursors to nitrile oxide in cycloaddition reactions. The aldoximes were synthesized with good to high yields and showed a lack of diastereoselectivity, as confirmed by 1H NMR measurements. These aldoximes were then utilized as precursors of nitrile oxide in 1,3‐dipolar cycloaddition reactions and were treated with dipolarophilic reagents, namely methyl methacrylate (MMA) and glycidyl methacrylate (GMA), to produce isoxazoline carboxylate derivatives with high regioselectivity. The obtained compounds were characterized using various techniques, including NMR, FT‐IR, GC–MS and TOF‐LCMS analyses. The study also targets the molecular docking analysis, using Autodock 4.2.6 software, targeting the OR51E2 protein. This protein has drawn recent attention, with the hypothesis that propionic acid activates OR51E2, making it a suitable candidate for the carboxylate group within the obtained isoxazoline skeleton. Through these multifaceted investigations, this research contributes to the design and development of fragrant molecules with potential applications in the fragrance industry, offering a promising avenue for future olfactory innovations.

Enhancing copper recycling through synergistic valence conversions in MnOx-modified capacitive deionization electrodes

The copper present in industrial waste has significant value for environmental resource recovery. Nonetheless, in electrosorption employed for ion separation, electrode materials commonly exhibit limited adsorption capacities, inadequate cycling stabilities, and insufficient selectivities toward specific ions for their single adsorption mechanism. In this study, a strategy was developed for optimizing the design of electrode materials to substitute zirconium atoms in organometallic frameworks (UiO-66, abbreviated as ZO) for manganese atoms from manganese oxide precursors to form a robust three-dimensional conductive structure (MZO). MZO has a stable and sizable adsorption region for electric adsorption, and manganese atoms with a dot-like dispersion provide Faraday active sites. Notably, in an external power supply circuit, Mn3+ fluently transforms to Mn2+ and then facilitates the deposition of copper ions by capturing electrons from Mn2+. Manganese regains electrons by utilizing the power source, which facilitates the continuous transfer of electrons to copper ions, enhancing the pseudocapacitance process. The combined effects of electrodeposition, a double-layer reaction, and a pseudocapacitive reaction improve the adsorption performance of MZO for copper ions, with an adsorption capacity of 249.5 mg·g−1 (at 1.2 V, 40 mg·L−1 Cu2+). Meanwhile, MZO based on ZO has acceptable cyclic stability, with a capacity retention rate of over 75 % after 32 cycles and 3 times of performance recovery experiments. Moreover, the MZO electrode exhibits positive selectivity for copper ions in mixed multiple salt solutions (separation factor α = 0.68). Density functional theory (DFT) calculations confirmed the selectivity of the MZO electrode for Cu2+ by providing the lowest binding energy (−2.4065 eV) for Cu2+.

Metallo-organic complexes as precursors for nanostructured metal oxides and their studies on protein interactions and drug loading characteristics

In the current study, we have synthesized and characterized Schiff base copper and zinc complexes based on (E)-2,4-dichloro-6-(((2-hydroxy-4-methyl-phenyl)-imino) methyl) phenol ligand obtained from 3,5-dichloro salicylaldehyde and 2-amino,4-methyl phenol. The interactions of these complexes with the protein, Bovine Serum Albumin (BSA) were monitored through the fluorescence spectral technique. The quenching of fluorescence with the incremental addition of the ligand and the complexes provides important information regarding the binding propensity of the tested compounds with the protein. Furthermore, these metal complexes are used as precursors to obtain the pure phases of copper oxide and zinc oxide nanostructures by the thermal decomposition method. The phase formation of the metal oxides was confirmed by powder X-ray diffraction (p-XRD) technique. The metal oxides prepared from their respective metal complexes have unique characteristics in terms of particle size, morphology, and band gap and are compared with the literature reports based on conventional solid-state methods. The studies on the interaction of the prepared metal oxide and curcumin with and without BSA, the drug carrier, have been investigated and the drug loading capacity is assessed.