Incorporation Of Metal Ions Research Articles

The birth of zinc anode-based electrochromic devices

Since the discovery of electrochemical coloration phenomenon, electrochromic devices capable of monitoring transmittance, reflectance, and absorption at designated wavelengths have embraced great achievements. The marriage of electrochemistry and optical modulation has infused fascinating properties in electrochromic devices, which find applications in thermal management, display, smart windows, and camouflage. Inspired by the multipronged advancements in electrochemical devices, the incorporation of multivalent metal ions having rich electrochemistry into electrochromic devices is bloomed in recent years. Zinc, distinguished by its high crustal abundance, suitable standard redox potential, and inherent safety, has facilitated the assembly of highly efficient electrochromic devices. Zinc anode-based electrochromic devices with dual-band (visible and near-infrared) tunability, energy retrieval functions, multi-color options, multiple working modes (transmittance mode and reflectance mode), and scalability have been prominently showcased. Here in this review, the birth of zinc anode-based electrochromic devices will be systematically narrated, starting from the discovery of electrochromic phenomenon, to the evolution of electrochromic devices, and to the latest achievements in zinc anode-based electrochromic devices. Additionally, this review delves into the future development trends and perspectives of zinc anode-based electrochromic devices. This review serves as a handbook, which summarizes the history of electrochromism, introduces the physics behind it, highlights the development in zinc anode-based electrochromic devices, and aims to inspire future endeavors into this field, particularly those focused on developing energy-efficient electrochromic devices.

Streamlined synthesis of iron and cobalt loaded MCM-48: High-performance heterogeneous catalysts for selective liquid-phase oxidation of toluene to benzaldehyde

Hydrothermal synthesis of MCM-48 molecular sieves featuring the incorporation of both iron and cobalt with Si/M ratios of 20, 40 and 80 (where M represents either iron or cobalt) was performed using tetraethyl orthosilicate as the silica source and cetyltrimethylammonium bromide as a template. To gain a comprehensive understanding of the synthesized materials, these were thoroughly characterized using various techniques, including XRD, XPS, UV–Vis (DRS), FT-IR, N2 adsorption-desorption analysis, SEM with EDX, TEM, TGA and NH3-TPD analysis. XRD analysis revealed the presence of well-ordered MCM-48 structure in the metal-incorporated materials, while XPS and UV–Vis DRS confirmed the successful partial incorporation of metal ions precisely in their desired tetrahedral coordination within the framework. To assess their catalytic performance, we studied the activity and selectivity of these catalysts in liquid phase oxidation of toluene using tert-butyl hydroperoxide as the oxidant. Under optimized conditions, employing a 6% (w/w) Fe-MCM-48 (40) catalyst and maintaining a toluene to oxidant molar ratio of 1:3 at 353 K in a solvent-free environment for 8 h, the oxidation reaction resulted in the formation of benzaldehyde (88.1%) as the major product and benzyl alcohol (11.9%) as the minor product.

Advancements in incorporating metal ions onto the surface of biomedical titanium and its alloys via micro-arc oxidation: a research review.

The incorporation of biologically active metallic elements into nano/micron-scale coatings through micro-arc oxidation (MAO) shows significant potential in enhancing the biological characteristics and functionality of titanium-based materials. By introducing diverse metal ions onto titanium implant surfaces, not only can their antibacterial, anti-inflammatory and corrosion resistance properties be heightened, but it also promotes vascular growth and facilitates the formation of new bone tissue. This review provides a thorough examination of recent advancements in this field, covering the characteristics of commonly used metal ions and their associated preparation parameters. It also highlights the diverse applications of specific metal ions in enhancing osteogenesis, angiogenesis, antibacterial efficacy, anti-inflammatory and corrosion resistance properties of titanium implants. Furthermore, the review discusses challenges faced and future prospects in this promising area of research. In conclusion, the synergistic approach of micro-arc oxidation and metal ion doping demonstrates substantial promise in advancing the effectiveness of biomedical titanium and its alloys, promising improved outcomes in medical implant applications.

Exploring the Performance Improvement for CO2 Chemical Fixation in Zn/ZnMg-MOFs.

A new 3D zinc-based metal-organic framework {[Zn7L2(DMF)3(H2O)(OH)2]·5DMF}n (1) (H6L = 5,5',5″-(methylsilanetriyl) triisophthalic acid) was constructed with an organosilicon-based linker, where H6L is a tetrahedral structure furnished with rich -COO- chelating sites for Zn(II) immobilization. Compound 1 exhibited two types of irregular one-dimensional channels and a three-dimensional skeleton with large specific surface area, making it a promising catalytic platform. Moreover, by incorporation of the second metal ion into the inorganic node of framework 1, isomorphic bimetallic MOF ZnMg-1 was successfully synthesized. ZnMg-1 demonstrated enhanced catalytic activity compared to 1 under identical conditions. Contrast experiments and theoretical calculations indicate that bimetallic active sites play a facilitating role in the chemical fixation of epoxides and CO2. It indicated that efficient chemical fixation of CO2 to cyclic carbonates was obtained over isomorphic MOF catalysts 1 and ZnMg-1.

Unraveling the molecular mechanism for enhanced gas adsorption in mixed-metal MOFs via solid-state NMR spectroscopy

The incorporation of multiple metal ions in metal-organic frameworks (MOFs) through one-pot synthesis can induce unique properties originating from specific atomic-scale spatial apportionment, but the extraction of this crucial information poses challenges. Herein, nondestructive solid-state NMR spectroscopy was used to discern the atomic-scale metal apportionment in a series of bulk Mg1-xCox-MOF-74 samples via identification and quantification of eight distinct arrangements of Mg/Co ions labeled with a 13C-carboxylate, relative to Co content. Due to the structural characteristics of metal-oxygen chains, the number of metal permutations is infinite for Mg1-xCox-MOF-74, making the resolution of atomic-scale metal apportionment particularly challenging. The results were then employed in density functional theory calculations to unravel the molecular mechanism underlying the macroscopic adsorption properties of several industrially significant gases. It is found that the incorporation of weak adsorption sites (Mg2+ for CO and Co2+ for CO2 adsorption) into the MOF structure counterintuitively boosts the gas adsorption energy on strong sites (Co2+ for CO and Mg2+ for CO2 adsorption). Such effect is significant even for Co2+ remote from Mg2+ in the metal-oxygen chain, resulting in a greater enhancement of CO adsorption across a broad composition range, while the enhancement of CO2 adsorption is restricted to Mg2+ with adjacent Co2+. Dynamic breakthrough measurements unambiguously verified the trend in gas adsorption as a function of metal composition. This research thus illuminates the interplay between atomic-scale structures and macroscopic gas adsorption properties in mixed-metal MOFs and derived materials, paving the way for developing superior functional materials.

Significance of the Disulfide Bridge in the Structure and Stability of Metalloprotein Azurin.

Metalloproteins make up a class of proteins that incorporate metal ions into their structures, enabling them to perform essential functions in biological systems, such as catalysis and electron transport. Azurin is one such metalloprotein with copper cofactor, having a β-barrel structure with exceptional thermal stability. The copper metal ion is coordinated at one end of the β-barrel structure, and there is a disulfide bond at the opposite end. In this study, we explore the effect of this disulfide bond in the high thermal stability of azurin by analyzing both the native S-S bonded and S-S nonbonded (S-S open) forms using temperature replica exchange molecular dynamics (REMD). Similar to experimental observations, we find a 35 K decrease in denaturation temperature for S-S open azurin compared to that of the native holo form (420 K). As observed in the case of native holo azurin, the unfolding process of the S-S open form also started with disruptions of the α-helix. The free energy surfaces of the unfolding process revealed that the denaturation event of the S-S open form progresses through different sets of conformational ensembles. Subsequently, we compared the stabilities of individual β-sheet strands of both the S-S bonded and the S-S nonbonded forms of azurin. Further, we examined the contacts between individual residues for the central structures from the free energy surfaces of the S-S nonbonded form. The microscopic origin of the lowering in the denaturation temperature is further supplemented by thermodynamic analysis.

Uncovering the influence of Ni-doping in CuBi2O4 photocatalyst on its visible-light-responsiveness for the efficient removal of toxic Alizarin yellow R dye from wastewater

In recent years, wastewater pollution has a significant huge impact on both human life and aquatic animals. Wastewater treatment has become a challenging task for researchers due to the presence of complex organic pollutants. In the present work, we report the investigation of the influence of Ni-doping on photocatalytic activity of CuBi2O4 to effectively removal of complex organic pollutants. For this, we synthesized the various photocatalysts, including CuBi2O4, Ni0.05Cu0.95Bi2O4, Ni0.10Cu0.90Bi2O4, and Ni0.15Cu0.85Bi2O4 using a facile hydrothermal method. The photocatalytic efficiency of the synthesized photocatalysts was evaluated for degradation of Alizarin yellow R (AYR) dye under visible-light illumination. The experimental results revealed an 85.78% degradation of AYR dye in the presence of a CuBi2O4 photocatalyst. In constrast, the degradation rate increased to 98.43% for Ni0.10Cu0.90Bi2O4 photocatalyst within 70 min. Similarly, the rate constant also increased from 0.0286 min−1 to 0.0633 min−1, affirming the photocatalytic efficacy of the Ni0.10Cu0.90Bi2O4 photocatalyst. The increased photocatalytic efficiency of the Ni0.10Cu0.90Bi2O4 photocatalyst was attributed to its increased surface area (98.27 m2 g−1) and reduced the optical bandgap energy due to the incorporation of Ni metal ions into the basic framework of CuBi2O4. Furthermore, the investigation into the effect of various reaction parameters revealed a significant influence on the removal of AYR dye. It can be perceived that the formation of •OH and O2•− radicals on the surface of the catalyst resulted in the degradation of AYR. Notably, the synthesized Ni0.10Cu0.90Bi2O4 photocatalyst displayed exceptional photostability. This work provides a cost-effective method of developing efficient photocatalyst for wastewater remediation.

A new mixed-ligand zinc(II) complex of 3-hydroxy and 4-chloro substituted pyridine-2-carboxylic acid: Synthesis, characterization, NLO properties and DFT calculation

Molecular engineering of metal-organic frameworks has recently attracted increasing attention due to their potential technological applications in the fields of optics and photonics. In addition to improved optical properties, the incorporation of metal ions into organic ligands makes it possible to control the intensity and polarization of the incident laser light. This makes organometallic complexes valuable and suitable candidates for nonlinear optical applications. In this study, a novel Zn(II) complex was synthesized by using 4-chloropyridine-2-carboxylic acid (4-Clpca) and 3-hydroxypyridine-2-carboxylic acid (3OHpca). The structural and spectroscopic properties of the Zn(II) complex were examined through XRD, FT-IR and UV-Vis techniques. The HOMO-LUMO energy range for the Zn(II) complex was found to be 4.7358 eV. Nonlinear optical parameters of Zn(II) complex were investigated as static and frequency-dependent (ω = 0.0856453887 au) methods. The dc-Kerr effect γ(-ω;ω,0,0) and EFSHG γ(−2ω;ω,ω,0) parameters were calculated as 13.04 × 10−36 esu and 2258.9 × 10−36 esu, respectively. The newly synthesized Zn(II) complex, which has weak second-order NLO properties due to the fully occupied electronic configuration of the Zn(II) ion, is quite promising in terms of its third-order optical properties.

Unrevealing the potential of multicomponent metal-ion incorporation and sulfide modification in cobalt oxide for efficient water oxidation

The design and development of highly efficient electrocatalysts from transition metals have shown a great potential for substituting precious metal-based electrocatalysts in water-splitting processes.

Au-Based MOFs as Anodic Electrocatalysts for Direct Borohydride Fuel Cells

Researchers are exploring direct liquid fuel cells (DLFCs) as alternatives to proton-exchange membrane fuel cells because of their higher energy density and ease of storing and transporting the fuel. Direct borohydride fuel cells (DBFCs) are of particular interest as they offer a sustainable energy source with their high-power density output and the use of a highly alkaline NaBH4 medium [1]. Ensuring efficient and cost-effective catalysts for DBFCs is crucial for their commercial viability. Metal-organic frameworks (MOFs) have demonstrated significant potential as anodic electrocatalysts for BOR in DBFCs [2]. However, research should explore various modifications to MOFs, such as the incorporation of alternative metal ions or functional groups, to improve their catalytic efficiency and reduce cost. This study evaluated the performance of newly developed MOF-based electrocatalysts for DBFCs. Specifically, six MOF-based materials were synthesized and analyzed for their ability to facilitate borohydride oxidation (BOR) using cyclic voltammetry and chronoamperometry in alkaline media. MIL-101_Au@NH2 and MOF-808_Au@NH2 were found to be highly effective for BOR. The kinetic parameters for BOR with MOF-based electrocatalysts, including activation energy, reaction order, exchanged electrons, and anodic charge transfer coefficient, were determined. The activation energy for BOR was found to be 13.6 kJ mol−1 and 15.3 kJ mol−1 for MIL-101_Au@NH2 and MOF-808_Au@NH2, respectively. The number of transferred electrons, n, was found to be 7.0 and 3.1 for MIL-101_Au@NH2 and MOF-808_Au@NH2, respectively. This study demonstrates that MOF-based electrocatalysts can enhance DBFCs' performance, while offering insight into the potential usage of MOFs in other fuel cell technologies.[1] B. Šljukić, D.M.F. Santos, "Direct borohydride fuel cells", in: "Direct Liquid Fuel Cells: Fundamentals, Advances, and Future", 1st ed., R.G. Akay, A.B. Yurtcan (eds.), Academic Press, USA, 203-232 (2021)[2] G. Backovic, B. Šljukić, G.S. Kanberoglu, M. Yurderi, A. Bulut, M. Zahmakiran, D.M.F. Santos, Ruthenium (0) nanoparticles stabilized by the metal-organic framework as an efficient electrocatalyst for borohydride oxidation reaction, International Journal of Hydrogen Energy, 45, 27056-27066 (2020).

ZnO incorporated hybrid catalytic proton exchange membrane for H2 generation

Electrocatalytic proton exchange membranes (PEMs) represent a promising avenue for advancing the field of electrochemical energy conversion and storage by combining the proton-conducting function of PEMs with enhanced catalytic activity by incorporation of metal ions. Here, we systematically studied the ZnO-based metal-organic framework (MOF) and found the introduction of pegylated ZnO to the (diethyl methylamine)/(H2PO4) matrix to form the p-type conducting MOF membrane with a bandgap of 3.67 eV. This membrane not only has a high protonic conductivity of 0.027 S/cm at 300 K with a transference number >0.99 but also possesses high activity (Tafel slope ∼36 mV/decade). The high reaction kinetics supported by finite element modeling simulations shows its ability to produce efficient and sustainable hydrogen. Our results suggest high current density of 1.52 mA/cm2, a turn over frequency [H2 (s−1)] ∼0.474×1018s−1, and a stability of 168 h in neutral medium (pH = 7). This work will enhance new strategies for fabricating membranes with ionic liquid in order to get membranes with protonic conductivity along with high activity for large-scale water electrolysis.

Electroactive Prussian Blue Analogues/TiO2 Nanocomposites Obtained through SILAR Assembly in Mesoporous Nanoarchitectures

AbstractThe preparation of nanomaterials for energy applications such as intercalation batteries and materials that can act as substrates for water oxidation is a subject of major interest nowadays. In this work, we report the deposition of Prussian blue (PB) and its cobalt analogue (CoPBA) on mesoporous titania thin films (MTTF) using the successive ionic layer adsorption reaction (SILAR) technique under soft conditions. A bifunctional ligand, 1,10‐phenanthroline‐5,6‐dione (pd), was used to functionalize the titania surface and promote the growth of PB and CoPBA. The resulting PB@MTTF and CoPBA@MTTF nanocomposites were characterized using several techniques and it was determined that PB and CoPBA grow in a controlled and sequential manner, maintaining the mesoporous architecture. Both PB@MTTF and CoPBA@MTTF demonstrated very good electroactive properties, while CoPBA@MTTF exhibited water oxidation capabilities. The flexibility of this PBA@MTTF platform allows the incorporation of any labile transition metal ion or fragment into the structure of the coordination polymer embedded into a mesoporous matrix, opening the door for (photo)electrochemical devices and catalysts.

Incorporation of Transition Metal Ions into Li2O + LiF + ZnF2 + B2O3 + P2O5-MnO Glasses: Effects on Elastic, Mechanical, and Radiation Effectiveness Behaviors

Incorporation of Transition Metal Ions into Li2O + LiF + ZnF2 + B2O3 + P2O5-MnO Glasses: Effects on Elastic, Mechanical, and Radiation Effectiveness Behaviors

Enhanced dielectric properties of zinc doped bentonite composites: an effect of cobalt doping concentrations and tight binding calculation

In this study we have successfully synthesized undoped and Zn and Co incorporated bentonite samples. The amount of Zn was kept constant while as Co amount was varied. All the synthesized samples were characterized using x-ray diffraction analysis which confirms the predominant presence of montmorillonite in all the samples thus confirming successful formation of bentonite. Similarly, EDX analysis confirms successful incorporation of Zn and Co in Ben sample. The analysis of the dielectric properties of the produced samples was successfully carried out, and the frequency dependence of the dielectric constant and dielectric loss was explored. According to the results, all the samples exhibit considerable dielectric dispersion at lower frequencies, whereas steady dielectric constant and modest dielectric loss are shown at higher frequencies. The effect of Zn, Co incorporation and temperature dependence of dielectric behaviour of all the samples was also analysed and it was observed that at low temperatures undoped Ben samples showed high dielectric constant while as at higher temperatures the incorporation of Zn and Co enhances the dielectric constant of as prepared sample. Similarly, the variation of conductivity of as prepared samples with frequency and temperature was analysed and it was observed that all the samples show similar conduction behaviour and follows correlated barrier hopping type of conduction. The real and imaginary part of electric modulus as a function of frequency was also analysed. Further, theoretical analysis showed considerable change in HUMO and LUMO which is considered as a main reason responsible for change in dielectric characteristics of Ben and Zn/Co incorporated samples. From this study it was observed that the incorporation of metal ions into the layered bentonite improved the dielectric properties at high temperature thus this study provides a new insight into the development of new dielectric materials which could be used under high temperature operation conditions.

Direct incorporation of metal ion into β-substituted porphyrinogen skelton

Direct incorporation of metal ion into β-substituted porphyrinogen skelton

Location of Carbonate Ions in Metal-Doped Carbonated Hydroxylapatites

The environment model for the description of the location of carbonate ions in apatites predicts that approximately half of the carbonate occupies the apatite channel. This model relies on the influence of entities surrounding the carbonate on its IR spectrum and can be used to determine how various substituents affect the location and structure of that ion. Careful deconvolution (peak-fitting) of the asymmetric carbonate IR region was used to determine the percentage of A-type (channel) ions, A′-type (channel with either a Ca2+ vacancy or substitution of Na+ for Ca2+) ions, and B-type (substitution for phosphate) ions. In our previous applications of this model, we have looked at the effect of alkali metal ions, such as sodium, lithium, and potassium, the ammonium ion, and the rare earth europium ion. In the present work, we explore the incorporation of the first-row transition metal ions and find that they have little effect on the location of the carbonate ion. Like the un-substituted carbonated apatite, these apatites contain about half of the carbonate in the channel, at least in derivatives that contain up to half a mole of the metal ion per mole of apatite. Attempts to incorporate greater amounts of metal ions by aqueous ion-combination reactions generally lead to lower-resolution XRD patterns and IR spectra that produce greater uncertainties in the peak-fitting modeling.

Physicochemical characterization and anticancer activity of the new imipramine based Co(II), Pd(II) and Mn(II) compounds

Three new imipramine-based compounds, namely: (HIMP)2CoCl4, (HIMP)2Pd2Cl6 and (HIMP)2MnCl4 (HIMP = protonated imipramine) were synthesized in a single-step reaction between imipramine hydrochloride and metal(II) chlorides. The physicochemical properties of all three compounds were thoroughly investigated using appropriate analytical techniques: single crystal and powder X-Ray diffraction analysis, elemental analysis, UV–Vis and FTIR spectroscopies, fluorescence measurements, quantum mechanical calculations, TG-DTG thermogravimetric analysis and magnetic studies. The investigations proved the high purity of the compounds and the isostructurality of (HIMP)2CoCl4 and (HIMP)2MnCl4 compounds. Of all compounds, only (HIMP)2MnCl4 exhibited fluorescent properties. When heated, all three compounds decompose, yielding the appropriate metal(II) oxides in the case of (HIMP)2CoCl4 and (HIMP)2MnCl4 compounds or metallic palladium in the case of (HIMP)2Pd2Cl6. In the last step, the anticancer activity of all three compounds was evaluated against MKN-74, PANC-1, SCOV-3, MDA-MB-231, MDA-MB-468, A-375 and SK-MEL-28 cell lines. Cytotoxicity evaluation revealed that the incorporation of the active metal ions significantly increased the imipramine activity against all tested cancer cell lines without significant toxicity against normal fibroblasts.

Enhanced Photoluminescence Quantum Yield of Metal Halide Perovskite Microcrystals for Multiple Optoelectronic Applications.

Recently, metal 1halide perovskites have shown compelling optoelectronic properties for both light-emitting devices and scintillation of ionizing radiation. However, conventional lead-based metal halide perovskites are still suffering from poor material stability and relatively low X-ray light yield. This work reports cadmium-based all-inorganic metal halides and systematically investigates the influence of the metal ion incorporation on the optoelectronic properties. This work introduces the bi-metal ion incorporation strategy and successfully enhances the photoluminescence quantum yield (98.9%), improves thermal stability, and extends the photoluminescence spectra, which show great potential for white light emission. In addition, the photoluminescent decay is also modulated with single metal ion incorporation, the charge carrier lifetime is successfully reduced to less than 1 µs, and the high luminescent efficiency and X-ray light yield (41000 photons MeV-1 ) are maintained. Then, these fast scintillators are demonstrated for high-speed light communication and sensitive X-ray detection and imaging.

Ambient Pressure Drying of Freeze-Cast Ceramics from Aqueous Suspension.

Freeze-casting has been wildly exploited to construct porous ceramics but usually requires costly and demanding freeze-drying (high vacuum, size limit, and supercooled chamber), which can be avoided by the ambient pressure drying (APD) technique. However, applying APD to freeze-cast ceramic based on an aqueous suspension is still challenging due to inert surface chemistry. Herein, a modified APD strategy is developed to improve the drying process of freeze-cast ceramics by exploiting the simultaneous ice etching, ionic cross-linking, and solvent exchange under mild conditions (-10-0 °C, ambient pressure). This versatile strategy is applicable to various ceramic species, metal ions, and freezing techniques. The incorporated metal ions not only enhance liquid-phase sintering, producing ceramics with higher density and mechanical properties than freeze-cast counterparts, but also render customizable coloration and antibacterial property. The cost-/time-efficient APD is promising for mass production and even successive production of large-size freeze-cast ceramics that exceed the size of commercial freeze-dryers.

Manufacture and extraction of PLLA films with incorporated metal ions

Abstract For the in vitro examination of the effects on cells and tissues of metal ions derived from implants by wear and corrosion, a system is needed to release metal ions in a controlled and sustained manner. As small concentrations may have an impact on biological systems, a corresponding slow release over a defined period of time is necessary. Here, a manufacturing method of polymeric Poly(L-lactic acid) (PLLA) films with incorporated cobalt ions via dip coating is reported. The establishment of two analytical methods for the detection and quantification of cobalt ions is shown. High performance liquid chromatography enables cobalt quantification over a concentration range of 0.33 μg/mL up to 33 μg/mL in sample solutions. Extraction and detection of cobalt ions from solvent cast PLLA-cobalt-films shows the feasibility of the manufacturing method. Initial biocompatibility tests with manufactured PLLA-cobaltfilms showed no effects on adipose derived primary mesenchymal stem cells (adMSCs).