Mixed Metal Research Articles

Synthesis, Characterization, and Catalytic Performance of a New Heterobimetallic Y/Tb Metal-Organic Framework with High Catalytic Activity.

A three-dimensional heterobimetallic porous structure with the formula {[Y3.5Tb1.5L6(OH)3(H2O)1.5 (DMF)1.5] n ·1.5H2O·DMF} n (L = 3-amino-4-hydroxybenzoate) (Y/Tb-MOF) has been synthesized and characterized by single crystal and powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), inductively coupled plasma mass spectrometry (ICP-MS), electrophoretic mobility, and Fourier transform infrared (FTIR) spectroscopy. The structure presents two metal environments: a bioaugmented isosceles wedge (mm2) MO8 and a tricapped trigonal prism (-6m2) MN3O6. These configurations facilitate the creation of channels with a diameter of 10.7 Å, enabling its utilization as an active catalyst where the heterobimetallic nature of the assembly will be explored. This mixed-metal metal-organic framework has been tested in the cycloaddition of epoxides with carbon dioxide as well as in the cyanosilylation and hydroboration reactions of carbonylic substrates. Additionally, a monometallic Tb-MOF analogue has been synthesized for comparative evaluation of their catalytic performances. Both the mixed metal and monometallic variants exhibit outstanding activity in the cyanosilylation and hydroboration of carbonyls and in the synthesis of carbonates under CO2 pressure. However, only the latter exhibits high recyclability.

Biocompatible Cobalt Oxide Nanoparticles for X-ray Fluorescence Microscopy.

The synthesis of water-soluble nanoparticles is a well-developed field for ferrite-based nanoparticles with the majority consisting of iron oxide or mixed metal iron oxide nanoparticles. However, the synthesis of non-agglomerated non-ferrite metal/metal oxide NPs is not as well established. The synthesis and characterization of uniform 20 nm, biologically compatible cobalt oxide (CoO) nanoparticles (NPs) is described. These nanoparticles have two principle components: 1) a CoO core of suitable size to contain enough cobalt atoms to be visualized by X-ray fluorescence microscopy (XFM) and 2) a robust coating that inhibits NP aggregation as well as renders them water-soluble and biocompatible (i.e. stealth coatings). Stable cobalt oxide NPs are obtained with octadecyl amine coatings as reported by Bhattacharjee. Two strategies for solubilizing these NPs in water were investigated with varying degrees of success. Exchanging the octadecyl amine coating for a nitrodopamine anchored PEG coating yielded the desired water-soluble NPs but in very low yield. Alternately, leaving the octadecyl amine coating on the NP and interdigitating this with a maleic anhydride-vinyl copolymer with different hydrophobic sidechains followed by opening the maleic anhydride ring with amine substituted PEG polymers (the water solubilizing component), yielded the desired water soluble NPS were obtained in good yield. Characterization data for the nanoparticles and the components of the coatings required for bioorthogonal reactions to ligate them with biotargeting agents are also described.

Pourbaix Machine Learning Framework Identifies Acidic Water Oxidation Catalysts Exhibiting Suppressed Ruthenium Dissolution.

The demand for green hydrogen has raised concerns over the availability of iridium used in oxygen evolution reaction catalysts. We identify catalysts with the aid of a machine learning-aided computational pipeline trained on more than 36,000 mixed metal oxides. The pipeline accurately predicts Pourbaix decomposition energy (Gpbx) from unrelaxed structures with a mean absolute error of 77 meV per atom, enabling us to screen 2070 new metallic oxides with respect to their prospective stability under acidic conditions. The search identifies Ru0.6Cr0.2Ti0.2O2 as a candidate having the promise of increased durability: experimentally, we find that it provides an overpotential of 267 mV at 100 mA cm-2 and that it operates at this current density for over 200 h and exhibits a rate of overpotential increase of 25 μV h-1. Surface density functional theory calculations reveal that Ti increases metal-oxygen covalency, a potential route to increased stability, while Cr lowers the energy barrier of the HOO* formation rate-determining step, increasing activity compared to RuO2 and reducing overpotential by 40 mV at 100 mA cm-2 while maintaining stability. In situ X-ray absorption spectroscopy and ex situ ptychography-scanning transmission X-ray microscopy show the evolution of a metastable structure during the reaction, slowing Ru mass dissolution by 20× and suppressing lattice oxygen participation by >60% compared to RuO2.

Microstructure, hardness, electrical, and thermal conductivity of SZCN solder reinforced with TiO2 and ZrO2 nanoparticles fabricated by powder metallurgy method

The microstructure and characterization of Sn–Zn–Cu–Ni (SZCN) solder alloy reinforced with TiO2 and ZrO2 nanoparticles (NPs) synthesized by powder metallurgy were investigated. Sn, Zn, Cu and Ni metallic powders were mixed mechanical by 10:1 ball to powder ratio with 300 rpm speed for 2 h. Then 0.5 wt% from nano ZrO2 or TiO2 was mixed by the same parameters with the mixed metal powder. The morphologies and microstructures development during the fabrication process was investigated by X-ray diffractometer (XRD), optical microscope (OM), and scanning electron microscope (SEM) with energy dispersive X-ray spectrometry (EDX). The results reveal an improved distribution of TiO2 or ZrO2 NPs in the SZCN matrix solder, which resulted in an improvement in its density. The analyses of microstructural demonstrated that the addition of TiO2 or ZrO2 NPs to SZCN solder results in the grain refinement of the β-Sn phase, besides the formation of Ni3Sn IMC with small size and uniform distribution. The microhardness was enhanced as a result of the addition of TiO2 or ZrO2 NPs. The experimental results showed that the SZCN-ZrO2 composite solder had the greatest hardness and stress exponent values due to its effectiveness in suppressing the growth of β-Sn grains and the pile-up of dislocations. Both the electrical and thermal conductivities were improved by incorporating TiO2 NPs compared to other solders.

Valorization of palm oil refining by-product for organotin mercaptide as a polyvinyl chloride thermal stabilizer: Synthesis, efficacy and comparison to mixed metal stearate

Organotin mercaptide-based thermal stabilizer is recognized for its effectiveness in enhancing thermal stability of polyvinyl chloride (PVC). In this study, we synthesized an organotin mercaptide-based thermal stabilizer from palm fatty acid distillate, which is a by-product of palm oil refining process, and then evaluated its thermal stabilizing effects on PVC and compared its efficacy and economics to those of mixed metal stearate. The synthesized thermal stabilizer manifests as methyltin mercaptoethyl carboxylate sulfides. Both dehydrochlorination and two-roll mill discoloration tests have demonstrated the high efficacy of the resulting thermal stabilizer in stabilizing PVC, surpassing the performance of mixed metal stearate, as evidenced by the lower dosage required. The synthesized PVC thermal stabilizer not only provides effective stabilization but also presents a competitive viable alternative.

New Series of Ni(II), Cu(II), Zr(IV), Ag(I), and Cd(II) Complexes of Trimethoprim and Diamine Ligands: Synthesis, Characterization, and Biological Studies

New compounds series of [M(TMP)(en)]X·nH2O and [M(TMP)(PD)]X·nH2O, where M = Ni2+, Cu2+, Zr4+, Ag+, Cd2+, TMP = trimethoprim, en = ethylenediamine, PD = o-phenylene and X= Cl− or NO3−, were prepared. The compounds were characterized using techniques including melting points, conductance, elemental analysis, FTIR, NMR, and mass spectroscopy. FTIR spectra indicated TMP acted like a bi-dentate ligand, combining via the nitrogen atoms of azomethine and pyrimidine amino groups. Diamine ligands (en or o-PD) are coordinated via two nitrogen atoms. Prepared compounds showed monomeric behavior and adopted a 6-coordinate octahedral geometry based on magnetic susceptibility and UV spectra. Conductivity measurements revealed Zr(IV) compounds were 1:2 conductive, while Ag+ and Cd2+ were 1:1 conductive; Ni2+ and Cu2+ compounds were non-conductive. Antibacterial tests on compounds and ligands against Bacillus subtilis and Staphylococcus aureus demonstrated broad-spectrum antibacterial activity. The mixed metal compounds revealed an observable tendency of antibacterial activity in the order Zr > Cd = Ag > Cu, making Zr(IV) compounds the most biologically active among them against S. aureus (Gram-positive) while the same compounds showed less antibacterial activity against B. subtilis (Gram-negative) than the free ligand.

Synergistic advancements in nanocomposite design: Harnessing the potential of mixed metal oxide/reduced graphene oxide nanocomposites for multifunctional applications

Reduced graphene oxide-based nanocomposites find applications in designing and fabrication of smart materials due to their unique optical, electrical, mechanical, sensing, photochemical, and energy-storing capacities. This comprehensive review article explores different synthetic pathways employed in fabricating reduced graphene oxide (rGO)/metal oxides based nanocomposites (NCs) with improved properties for multifaceted applications. The different applications of the mixed metal oxide/rGO NCs were explored in gas sensing, photocatalysis, energy storage, and biomedical applications. Through comparative assessments, this review focuses on the change in optical, physical, chemical, mechanical, electrical, photocatalytic, sensing, charge storing, and antibacterial properties as we move from mixed metal nanoparticles and pure rGO to NCs. This review article opens the door for the design and synthesis of rGO-based multifunctional composite materials by providing insightful information about the development and design of mixed metal oxide/rGO NCs. The findings presented herein hold the potential to revolutionize future endeavors in energy storage, sensing, photocatalysis, adsorption, catalytic processes, purification, separation, protective coatings, and beyond.

Model-based catalyst screening and optimal experimental design for the oxidative coupling of methane

The oxidative coupling of methane (OCM) to produce ethane and ethylene (C2 compounds) as platform chemicals involves complex chemistry with reactions both in the gas phase and on the catalyst surface, resulting in a distribution of products at the expense of C2 selectivity. This work uses experimental data from a variety of mixed metal oxides on supports at different reaction conditions (temperature, contact time, and reactant flow rates) to train a random forest regressor that predicts methane conversion and C2 selectivity (key performance indicators (KPIs)). The kinetically validated random forest models are deployed to locate optimal conditions that maximize C2 yield for each of the catalysts. Investigating the regressor interpretability via feature importance reveals that the choice of metals and support are crucial to C2 selectivity predictions in addition to the reaction conditions, while the predictions of methane conversion are largely governed by the reaction conditions. The machine learning (ML) regressor is used as a kinetic surrogate to find a locus of optimal reaction conditions that maximize both selectivity-conversion for each of the catalysts via a multi-objective optimization routine. The maximum C2 yields for catalysts are projected to be improved by 15% on average. Analyzing the catalysts with respect to a popular OCM catalyst, Mn-Na2WO4/SiO2, using the optimal locus eliminates variability in the process conditions to reveal distinct patterns based on intrinsic properties of metals and supports. Further, the decision space with catalyst descriptors and reaction conditions is optimized for high C2 yields using the ML surrogate, in a static multi-objective optimization routine, and an adaptive Bayesian routine, where the latter was found to have a wider field focus in proposing catalyst formulations and reaction conditions. Transition metal oxides on a variety of supports were proposed but not their lanthanide oxide counterparts. The framework has the potential to lend itself to materials acceleration platforms where it is crucial to consider multi-scale phenomena that impact downstream KPIs.

Mixed Metal Amide-Hydride Solid Solutions for Potential Energy Storage Applications.

Mixed solid solutions have played an important role in improving the kinetics and performance of hydrogen storage materials, as reported for the Li-Mg-N-H, K-Mg-N-H, and Rb-Mg-N-H systems. Besides, the formation of a homogeneous solid solution, mostly due to partial ionic substitution, is known to be an effective approach to improve the ionic conductivity of a material, which is an important property in electrochemical applications. We have reported a series of solid solutions based on mixed amide-hydride materials of the Group 1 elements, e.g., K(NH2)xH1-x, Rb(NH2)xH1-x, and Cs(NH2)xH1-x, via the exchange of NH2-/H- anions with the change of the lattice cell of the solid solution. Extending the research in this direction, we study the M-N-H solid solution in the MNH2-MH systems (M = K, Rb, Cs, and their combinations), i.e., KNH2-RbH, RbNH2-KH, RbNH2-CsH, and CsNH2-RbH via ex situ/in situ XRD, IR, and 1H 2D solid-state NMR. The results obtained confirm the formation of mixed metal amide-hydride solid solutions associated with an exchange between both anionic (NH2- and H-) and cationic species (K+, Rb+, and Cs+). With this study, we aim to create an accessible library of M-N-H solid solutions for further studies as additives for hydrogen storage materials or ionic conductors.

Mixed Fe-Mo carbide prepared by a sonochemical synthesis as highly efficient nitrate reduction electrocatalyst

Ammonia, a versatile compound that can be used as a fertilizer, chemical or fuel, has since long been produced through the energy-intensive Haber-Bosch process. Recently, the electrochemical nitrate reduction reaction (NO3RR) using electricity generated from renewable sources has attracted widespread attention. However, the complex reaction pathway of NO3RR leads to the formation of many undesirable by-products. Herein we successfully prepared a mixed (FeMo)2C catalyst with good electrocatalytic NO3RR, having a NH3 yield of 14.66 mg h-1 cm-2 and an FE of 94.35% at low potential -0.3 V vs RHE. DFT calculations show that the presence of Fe in Mo2C lattice changes the reaction mechanism, decreasing the potential barrier to be overcome from 1.36 to 0.89 eV. In addition, mixed Fe-Mo carbide facilitates the adsorption of intermediates and promotes NH3 desorption, facilitating NO3− reduction to NH3. In addition, (FeMo)2C was used as cathode for Zn-NO3 battery to generate electricity, producing ammonia at the same time, with a power density of 3.8 mWcm-2 and an NH3 FE of 88%. This work describes a new synthesis method for mixed metal carbides and provides a promising strategy for NH3 production.

Synergistic Effect of Co and Ni Co-Existence on Catalytic Decomposition of Ammonia to Hydrogen—Effect of Catalytic Support and Mg-Al Oxide Matrix

Hydrotalcite-derived mixed metal oxides containing Co and Ni and containing these metals supported on MgO and Al2O3 were prepared and tested as catalysts for the decomposition of ammonia to hydrogen and nitrogen. The obtained samples were characterised in terms of chemical composition (ICP-OES), structure (XRD), textural parameters (low-temperature N2 adsorption–desorption, SEM), form and aggregation of transition-metal species (UV-Vis DRS), reducibility (H2-TPR) and surface acidity (NH3-TPD). The catalytic efficiency of the tested systems strongly depends on the support used. Generally, the alumina-based catalyst operated at lower temperatures compared to transition metals deposited on MgO. For both series of catalysts, a synergistic effect of the co-existence of cobalt and nickel on the catalytic efficiency was observed. The best catalytic results were obtained for hydrotalcite-derived catalysts; however, in the case of these catalysts, an increase in the Al/Mg ratio resulted in a further increase in catalytic activity in the decomposition of ammonia.

Heavy metal poisoning caused by Chinese folk remedies in psoriasis patients: a retrospective analysis

Psoriasis, characterized as a chronic relapsing disease with a protracted course, often drives patients to seek relief through Chinese folk remedies (CFR). Nonetheless, the complex compositions of these remedies frequently result in unintended adverse effects, notably various types of heavy metal poisoning. Our study involved an exhaustive collection and analysis of clinical data from psoriasis patients who developed heavy metal poisoning due to CFR usage, admitted to Beijing Chao-Yang Hospital from January 2011 to October 2023. Our analysis identified 44 cases of mercury poisoning, 17 of lead poisoning, 21 of arsenic poisoning, and 4 instances of mixed heavy metal poisoning. The folk remedies used ranged from fumigation and inhalation to skin application and oral administration. Distinct pathogenic characteristics were observed in each poisoning type. After treatment with metal chelating agents, all patients experienced a reduction in heavy metal levels in their bodies, accompanied by varying degrees of symptom alleviation. This study underscores the vital necessity of opting for formal, medically approved treatments for psoriasis, thereby avoiding the hazardous consequences of unregulated folk remedies that may lead to severe heavy metal poisoning.

Enhanced heavy metal adsorption capacity of surface-functionalized Philippine natural zeolite in simulated wastewater

The adsorption efficiency of surface-functionalized Philippine natural zeolite (PNZ) for heavy metal uptake from single and mixed metal ion-simulated wastewater solution is reported in this work. Atomic adsorption spectroscopy (AAS) findings revealed that NaCl-modified PNZ (MPNZ) exhibited the highest zinc ion adsorption of 99.96 % while PNZ yielded an adsorption of 95.61 %. The adsorption isotherms of raw PNZ and MPNZ both show similar shapes that reflect Type IV adsorption-desorption isotherms with Type H2 hysteresis loop which can be observed for micro-mesoporous materials (pore containing 2–50 nm). An increase in PNZ pore size from 10.11 nm to 13.36 nm for NaCl-PNZ and 15.59 for NaOH-PNZ is observed after alkaline treatment. EDS confirmed the decrease in Si/Al ratio from 4.02 to 3.76, indicative of possible higher negative charge in the PNZ framework which is favorable for an enhanced Coulombic or electrostatic interaction with the cationic heavy metals being detected in this study. MPNZ demonstrated an adsorption capacity of 99.96 % for copper in mixed-ion solution while 88.49 % and 86.67 % were obtained for zinc and nickel, respectively. These values are higher compared to PNZ having only 32.21 % uptake for zinc and 38.00 % for nickel. A hierarchy of the average metal adsorption capacity showed the order: copper > nickel > zinc. Rapid adsorption at the first hour of the adsorption reaction was attained in all solutions while samples with pH 9 exhibited the highest Ni2+ and Zn2+ percent removal. Moreover, the increase in initial solution concentration led to lower adsorption efficiency and the maximum uptake was attained at 100 ppm. The equilibrium data of adsorption and mechanism were suitably described by Langmuir isotherm model. With these, surface functionalization of PNZ has further enhanced its cationic adsorption capacity on heavy metals in both single and mixed-ion solution having promising potential for wastewater remediation.

Ciprofloxacin Electrochemical Sensor Using Copper-Iron Mixed Metal Oxides Nanoparticles/Reduced Graphene Oxide Composite.

The harmful effects of antibiotic proliferation on the environment and its persistent nature are urgent global problems. Ciprofloxacin (CIP) is a fluoroquinolone-class antibiotic agent used widely to treat pathogen-related diseases in humans and animals. Its excretion into surface water causes antibiotic resistance in microbes, resulting in difficult-to-treat or untreatable infectious diseases. This study developed a simple and efficient electrochemical sensor to detect CIP. Hydrothermal chemistry was utilized to synthesize an electrophotocatalytic composite of copper-iron mixed metal oxides (CIMMO) on reduced graphene oxide (rGO) (CIMMO/rGO). The composite was employed in an electrochemical sensor and exhibited outstanding performance in detecting CIP. The sensor was operated in differential pulse voltammetry (DPV) mode under light source illumination. The sensor yielded a linear response in the concentration range of 0.75 × 10-9-1.0 × 10-7 mol L-1 CIP and showed a limit of detection (LOD) of 4.74 × 10-10 mol L-1. The excellent sensing performance of the composite is attributable to the synergic effects between CIMMO nanoparticles and rGO, which facilitate photoinduced electron-hole separation and assist in the indirect electrochemical reactions/interactions with CIP.

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Boosting Urea-Assisted Natural Seawater Electrolysis in 3D Leaf-Like Metal-Organic Framework Nanosheet Arrays Using Metal Node Engineering.

Metal node engineering, which can optimize the electronic structure and modulate the composition of poor electrically conductive metal-organic frameworks, is of great interest for electrochemical natural seawater splitting. However, the mechanism underlying the influence of mixed-metal nodes on electrocatalytic activities is still ambiguous. Herein, a strategic design is comprehensively demonstrated in which mixed Ni and Co metal redox-active centers are uniformly distributed within NH2-Fe-MIL-101 to obtain a synergistic effect for the overall enhancement of electrocatalytic activities. Three-dimensional mixed metallic MOF nanosheet arrays, consisting of three different metal nodes, were in situ grown on Ni foam as a highly active and stable bifunctional catalyst for urea-assisted natural seawater splitting. A well-defined NH2-NiCoFe-MIL-101 reaches 1.5 A cm-2 at 360 mV for the oxygen evolution reaction (OER) and 0.6 A cm-2 at 295 mV for the hydrogen evolution reaction (HER) in freshwater, substantially higher than its bimetallic and monometallic counterparts. Moreover, the bifunctional NH2-NiCoFe-MIL-101 electrode exhibits eminent catalytic activity and stability in natural seawater-based electrolytes. Impressively, the two-electrode urea-assisted alkaline natural seawater electrolysis cell based on NH2-NiCoFe-MIL-101 needs only 1.56 mV to yield 100 mA cm-2, much lower than 1.78 V for alkaline natural seawater electrolysis cells and exhibits superior long-term stability at a current density of 80 mA cm-2 for 80 h.

Unraveling the link between heavy metals, perfluoroalkyl substances and depression: Insights from epidemiological and bioinformatics strategies

Heavy metals and per- and polyfluoroalkyl substances (PFASs) have become particularly important when studying the development of depression, a common illness that severely restricts psychosocial functioning and diminishes quality of life. Therefore, the potential joint effects of heavy metal and PFAS exposure on depression, as well as the underlying mechanisms involved, were investigated by using integrated epidemiological and bioinformatic approaches in the present study. A thorough analysis of 7301 samples from the National Health and Nutrition Examination Survey (NHANES) cycles that occurred between 2005 and 2018 was performed. Single-exposure studies have shown that cadmium exposure is positively associated with depression, whereas perfluorooctanesulfonic acid (PFOS) exposure and perfluorodecanoic acid (PFDE) exposure are negatively associated with depression. Furthermore, the Bayesian kernel machine regression (BKMR) and quantile g-computation (QGcomp) models were employed to investigate the collective impact of exposure to mixed metals on depression. Cadmium emerged as the principal contributor to depression. Moreover, the addition of PFAS to the metal mixture had an antagonistic effect on depression, with PFOS having the most prominent influence. Analysis of the effects of co-exposure to cadmium and PFOS confirmed the presence of an antagonistic effect. The inflection points of cadmium and PFOS were determined to be −1.11 and 2.27, respectively. Additionally, exposure to cadmium and PFOS had the opposite effects on two crucial pathways, namely, the rap1 and calcium signaling pathways, which involve core genes related to depression such as ADORA2A, FGF2, and FGFR1. These findings have significant implications for future studies and provide new strategies for exploring the mechanisms underlying co-exposure effects.

Characterization and modulation of the unimolecular conformation of integrins with nanopore sensors

Integrins are a large family of heterodimeric mammalian transmembrane receptors that connect extracellular matrix (ECM) and the cytoskeleton. Integrin-mediated adhesion governs the cellular adhesion, mobility, and cell mechanobiology. Investigations on different integrins in cellular and the conformation change regulated by divalent metal ions and oligopeptides have been documented, they mainly adopted the cellular assays or surface manipulation to achieve the information of ensemble integrins with proteins and small molecules. This work presents the nanopore approach for the characterization of unimolecular integrin via resistive pulse sensing. The orientation selection in distinct nanopore in size and pH condition discloses the tiny disparity of the conformation and the local surface charge distribution. The divalent metal ions could efficiently modulate the conformation alteration of integrin, in which Ca2+ and Mn2+ could activate integrin αLβ2 to take larger physical dimension than Mg2+, and Ca2+ is superior to Mn2+ in the activation when integrin αLβ2 is treated in the mixed metal ions. The oligopeptide cRGD (cyclic Arg-Gly-Asp) and its derivatives cRGDfk and cRGDyk show specific binding with integrin αVβ3 and the complex of αVβ3-cRGD exhibits largest geometry upon Ca2+-mediation with characteristic nanopore translocation feature. This work provides a platform for unimolecular integrin sensing and the modulation of the local conformation transition regulated by divalent metal ions and oligopeptides, which will be valuable for the representation of integrin-related cellular behavior and bio-function.

Mesoporous Mn-substituted MnxZn1-xCo2O4 ternary spinel microspheres with enhanced electrochemical performance for supercapacitor applications.

Extensive investigations have been carried out on spinel mixed transition metal oxide-based materials for high-performance electrochemical energy storage applications. In this study, mesoporous Mn-substituted MnxZn1-xCo2O4 (ZMC) ternary oxide microspheres (x = 0, 0.3, 0.5, 0.7, and 1) were fabricated as electrode materials for supercapacitors through a facile coprecipitation method. Electron microscopy analysis revealed the formation of microspheres comprising interconnected aggregates of nanoparticles. Furthermore, the substitution of Mn into ZnCo2O4 significantly improved the surface area of the synthesized samples. The electrochemical test results demonstrate that the ZMC3 oxide microspheres with an optimal Mn substitution exhibited enhanced performance, displaying the largest specific capacitance of 589.9Fg-1 at 1Ag-1. Additionally, the ZMC3 electrode maintained a capacitance retention of 92.1% after 1000 cycles and exhibited a significant rate capability at a current density of 10Ag-1. This improved performance can be ascribed to the synergistic effects of multiple metals resulting from Mn substitution, along with an increase in the surface area, which tailors the redox behavior of ZnCo2O4 (ZC) and facilitates charge transfer. These findings indicate that the incorporation of Mn into mixed transition metal oxides holds promise as an effective strategy for designing high-performance electrodes for energy storage applications.

3D printing of poly(ethyleneimine)-functionalized Mg-Al mixed metal oxide monoliths for direct air capture of CO2

Direct air capture (DAC) of CO2 plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies. Since large air flows are required to capture the ultradilute CO2 from the air, lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies. A structured adsorbent is essential for the implementation of gas-solid contactors for cost- and energy-efficient DAC systems. In this study, efficient adsorbent poly(ethyleneimine) (PEI)-functionalized Mg-Al-CO3 layered double hydroxide (LDH)-derived mixed metal oxides (MMOs) are three-dimensional (3D) printed into monoliths for the first time with more than 90% adsorbent loadings. The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths. This structure exhibits a 32.7% higher specific surface area and a 46.1% higher pore volume, as compared to the direct printing of the MMO powder into a monolith. After impregnation of PEI, the monolith demonstrates a large adsorption capacity (1.82 mmol/g) and fast kinetics (0.7 mmol/g/h) using a CO2 feed gas at 400 ppm at 25 °C, one of the highest values among the shaped DAC adsorbents. Smearing of the amino-polymers during the post-printing process affects the diffusion of CO2, resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths. The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.