Metal Incorporation Research Articles

Ultrasound Effect on the Hydrogen Peroxide Oxidation of Corn Starch, Molecular Structure, and Functional Properties of Obtained Starch Derivatives

AbstractThis study aims to determine the effect of ultrasound on the oxidation process of starch, molecular structure, and its functional properties. Corn starch is oxidized by hydrogen peroxide (with Cu(II) or Fe(II) ions as catalysts) in the ultrasound field. Changes in starch structure are identified based on determinations of the carboxyl, carbonyl groups, copper, iron content, molecular characterization by GPC, crystallinity, gelatinization characteristics, and surface area. Functional properties are determined based on analysis of color parameters, water binding capacity, solubility in water, and pasting characteristics. It is found that the effectiveness of the starch oxidation under ultrasound is affected by the presence and type of catalysts. The content of metal incorporated into starch during oxidation is approximately 15% lower when an ultrasound treatment is applied. When starch oxidation is assisted with ultrasound, the metal incorporation preferentially occurs in the pores and holes of the grain. Starches oxidized in the presence of Fe(II) and Cu(II) catalysts can be successfully used not only as thickeners in food industry but also as metal carriers in many industries.

Cr- and Ga-Modified ZSM-5 Catalyst for the Production of Renewable BTX from Bioethanol.

Light aromatics (benzene, toluene, and xylene, collectively known as BTX) are essential commodity chemicals in the petrochemical industry. The present study examines the aromatization of bioethanol with Cr- and Ga-modified ZSM-5. Both Cr and Ga were incorporated by the ion-exchange method. Cr-modified ZSM-5 outperforms the Ga-modified ZSM-5 and H-ZSM-5 catalysts. Cr-H-ZSM-5 almost doubled the carbon yield of aromatics compared to H-ZSM-5 at an optimum reaction temperature of 450 °C. Cr-H-ZSM-5 produced aromatics with a yield of ~40 %. The effect of dilution in feed on BTX production is also studied. Cr-H-ZSM-5 was found to be more active than H-ZSM-5. Complete ethanol conversion was obtained with both pure and dilute bioethanol. The Bronsted-Lewis acid (BLA) pair formed after metal incorporation is responsible for dehydrogenation followed by aromatization, leading to increased aromatic production.

Crystallization, microstructural evolution, heavy metals migration, and solidification mechanism of blast furnace slag glass-ceramics

In recent years, researchers have prepared glass-ceramics using a mixture of multiple solid waste materials, which is an effective and resourceful way to use and store solid waste. However, solid waste usually contains multiple heavy metals, which presents challenges during the mixing and co-solidification processes. In this study, high-performance glass-ceramics with low leaching were prepared from blast furnace slag (BFS). The synergistic curing mechanism of BFS glass-ceramics for heavy metals Cr, Mn, Cu, Zn, Ni, and Co was investigated in detail, as well as the migration pattern and storage state of heavy metals under different heat treatment stages and different Cr contents. The results show that the increases in temperature and Cr2O3 content contribute to the incorporation of heavy metals into the crystal lattice and promote crystal growth. Excessive crystallization of spinel causes aggregation, which further curtails the leaching of heavy metals. The leaching concentration of heavy metals mainly depends on the heavy metal content in the glass network and the degree of network polymerization. Thus, spinel acts as a crystal core for the solidification of heavy metals, while augite and glass phases act as a double barrier to physically encapsulate them, which is effective for the storage of a wide range of heavy metals. Furthermore, the physical and chemical properties of BFS glass-ceramics are consistent with the Chinese industry standard “Glass-ceramics plate for industrial application” (JC/T 2097-2011). This study provides important theoretical support for the synergistic solidification of multiple heavy metals in glass-ceramics, as well as insights into the preparation of glass-ceramics by mixing BFS with other solid wastes.

Hydrocracking Rubber Seeds Oil for Biofuel Production Using Bifunctional Sarulla‐Derived Natural Zeolite–Ni and Ni–Mo/SNZ Catalyst

Rubber seeds, due to their rich vegetable oil content, emerge as a promising substrate for biofuel production. Harnessing the progressive catalytic hydrocracking methodology, this research delves into the activation of Sarulla‐derived natural zeolite followed by Ni and Ni–Mo metal impregnation, subsequently subjecting rubber seed oil to hydrocracking at 400, 450, and 500 °C under atmospheric pressure at 0.1 MPa. Zeolite characteristics undergo notable transformations postmetal impregnation. Importantly, at 500 °C, gasoline fraction selectivity exhibits superior efficacy, with the Ni/SNZ‐A catalyst demonstrating consistently high selectivity (>85%) across varied temperatures. Posthydrocracking reveals an amplification in n‐paraffin, aromatic, olefin, and methyl ester profiles to 19.6%, 7.3%, 25.7%, and 17.7%, respectively, contrasting the diminution of cycloparaffin, carboxylic acid, and ketones to 3.6%, 0.2%, and 2.5%, respectively. The aforementioned discoveries hold significant importance in the realm of further investigation into the generation of gasoline fractions through the utilization of natural zeolite catalysts and the incorporation of metals with lower mass, all conducted under atmospheric pressure conditions with the ultimate objective of mitigating production expenses.

Superconductivity and stability of the novel electron-doped H3S system under high pressure

As promising candidate materials for high-temperature superconductors, hydrides have attracted much attention. In particular, the discovery of Im3¯m H3S with a high Tc of 203 K has set off an upsurge in hydride research. As an electron donor, the incorporation of metal in binary polyhydrides is believed to play an important role in stabilizing the crystal structure and improving superconductivity. The novel Pm3¯m H3SM (M = K, Rb, Sr, Tl, Cs, Ba) systems, which can be regarded as electron-doped Im3¯m H3S, are discovered to be dynamically and thermodynamically stable under pressure. Unfortunately, their superconductivity is not as good as that of the parent H3S. As the most promising superconductor among them, H3STl is predicted to be superconducting with a Tc of 111.7 K under 160 GPa. These findings reveal the intricacy of electron doping in modulating the superconductivity of hydrogen-based superconductors. Electron-phonon coupling (EPC) is found to have a negative correlation with the central frequency ωc of phonon, which opens new avenues for designing and optimizing novel high-Tc superconductors.

Biosynthesis of Zinc Nanoparticles From Actinobacterium Streptomyces Species and Their Biological Potential.

In today's world, antibiotic-resistant microorganisms are a major concern. There is solid evidence that metal nanoparticles (NPs) tend to have antimicrobial properties. The most effective substitute for antibiotic resistance is the incorporation of metal NPs.The antibacterial properties of NPs are currently being explored and shown to be successful.Zinc (Zn)NPsthat are biosynthesized frommarine Actinobacterium proved to be more biocompatible, bioactive, and affordable. Aim: This study aims to investigate the synthesis of ZnNPs from Actinobacterium Streptomyces species and their antimicrobial effects against gram-positive and gram-negative bacteria. The current study uses natural, considerably safer processes to synthesize ZnNPs from marine Actinobacteria with little to no negative side effects. It involves sample collection, identification, and isolation of Actinobacterium Streptomyces species. The isolated sample was air-dried, and extracts of ZnNPswere taken. Among the isolates from marine sediment, two Actinobacteria that generate bioactive secondary metabolites-Streptomyces species (MOSEL-ME28) and Rhodococcus rhodochrous (MOSEL-ME29)-were selected for extracellular synthesis of ZnNPs.The antimicrobial activity of the biosynthesized ZnNPs from marine Actinobacteria was analyzed againstStaphylococcus(MRSA), Klebsiella pneumoniae,and Streptococcus mutans. The results were statistically analyzed and graphs were created. ZnNPs obtained from Actinobacterium Streptomyces species exhibited antimicrobial effects against Staphylococcus (MRSA), Klebsiella, and Streptococcus mutans. At 280 nm wavelength, analysis of the UV spectrum showed anotable absorbance value of 1.8. The antibacterial efficacy against Staphylococcus MRSA, Klebsiella species, and Streptococcus mutans was assessed by measuring the zone of inhibition in diameter. The zones of inhibition were 8, 8, and 7 mm on the evaluation forStreptococcus mutans, S. aureus, and Klebsiella species, respectively, at a dose of 75 μg/mL. When the dosage was increased to 100 μg/mL, the inhibition zones were found to be 9.5, 9, and 7.5mm for the respective bacterial strains. ZnNPs are biosynthesized from marine Actinobacterium Streptomyces species in this research study. They have a significant antimicrobial activity against both gram-positive and negative bacteria. This indicates that ZnNPs have enormous antimicrobial potential and have an extensive spectrum of applications. However, clinical trials must be completed before it can be used safely on patients.

Simultaneous Electrochemical Detection of Dopamine and Uric Acid via Au@Cu-Metal Organic Framework.

The incorporation of noble metals with metal-organic frameworks (MOFs) are conducive to the simultaneous electrochemical detection of analytes owing to multiple accessible reaction sites. Herein, Au@Cu-metal organic framework (Au@Cu-MOF) is successfully synthesized and modified as a screen-printed carbon electrode (SPCE), which serves as an excellent electrocatalyst for the oxidation of dopamine (DA) and uric acid (UA). The sensor shows a linear range from 10 μM to 1000 μM, with sensitivity and detection limit of 0.231 μA μM-1 cm-2 and 3.40 μM for DA, and 0.275 μA μM-1 cm-2 and 10.36 μM for UA. Au@Cu-MOF could realize the individual and simultaneous electrochemical sensing of DA and UA, with distinguishable oxidation peak potentials. Moreover, it exhibits reproducibility, repeatability, and stability. Ultimately, the sensor provides an avenue for an ultrasensitive label-free electrochemical detection of DA and UA.

Stabilizing Highly Active Ru Sites by Electron Reservoir in Acidic Oxygen Evolution.

Proton exchange membrane water electrolysis is hindered by the sluggish kinetics of the anodic oxygen evolution reaction. RuO2 is regarded as a promising alternative to IrO2 for the anode catalyst of proton exchange membrane water electrolyzers due to its superior activity and relatively lower cost compared to IrO2. However, the dissolution of Ru induced by its overoxidation under acidic oxygen evolution reaction (OER) conditions greatly hinders its durability. Herein, we developed a strategy for stabilizing RuO2 in acidic OER by the incorporation of high-valence metals with suitable ionic electronegativity. A molten salt method was employed to synthesize a series of high-valence metal-substituted RuO2 with large specific surface areas. The experimental results revealed that a high content of surface Ru4+ species promoted the OER intrinsic activity of high-valence doped RuO2. It was found that there was a linear relationship between the ratio of surface Ru4+/Ru3+ species and the ionic electronegativity of the dopant metals. By regulating the ratio of surface Ru4+/Ru3+ species, incorporating Re, with the highest ionic electronegativity, endowed Re0.1Ru0.9O2 with exceptional OER activity, exhibiting a low overpotential of 199 mV to reach 10 mA cm-2. More importantly, Re0.1Ru0.9O2 demonstrated outstanding stability at both 10 mA cm-2 (over 300 h) and 100 mA cm-2 (over 25 h). The characterization of post-stability Re0.1Ru0.9O2 revealed that Re promoted electron transfer to Ru, serving as an electron reservoir to mitigate excessive oxidation of Ru sites during the OER process and thus enhancing OER stability. We conclude that Re, with the highest ionic electronegativity, attracted a mass of electrons from Ru in the pre-catalyst and replenished electrons to Ru under the operating potential. This work spotlights an effective strategy for stabilizing cost-effective Ru-based catalysts for acidic OER.

Framework confinement of multi-metals within silica hollow spheres by one-pot synthesis process

ABSTRACT The control incorporation of metals in silica hollow spheres (SHSs) may bring new functions to silica mesoporous structures for applications including catalysis, sensing, molecular delivery, adsorption filtration, and storage. However, the strategies for incorporating metals, whether through pre-loading in the hollow interior or post-encapsulation in the mesoporous shell, still face challenges in achieving quantitative doping of various metals and preventing metal aggregation or channel blockage during usage. In this study, we explored the doping of different metals into silica hollow spheres based on the dissolution-regrowth process of silica. The process may promote the formation of more structural defects and functional silanol groups, which could facilitate the fixation of metals in the silica networks. With this simple and efficient approach, we successfully achieved the integration of ten diverse metal species into silica hollow sphere (SHS). Various single-metal, dual-metal, triple-metal, and quadruple-metal doped SHSs have been prepared, with the doped metals being stable and homogeneously dispersed in the structure. Based on the structural characterizations, we analyzed the influence of metal types on the morphology features of SHSs. The synergistic effects of multi-metals on the catalysis applications were also studied and compared.

Mesoporous RE0.5Ce0.5O2-x Fluorite Electrocatalysts for the Oxygen Evolution Reaction.

Developing highly active and stable electrocatalysts for the oxygen evolution reaction (OER) is key to improving the efficiency and practical application of various sustainable energy technologies including water electrolysis, CO2 reduction, and metal air batteries. Here, we use evaporation-induced self-assembly (EISA) to synthesize highly porous fluorite nanocatalysts with a high surface area. In this study, we demonstrate that a 50% rare-earth cation substitution for Ce in the CeO2 fluorite lattice improves the OER activity and stability by introducing oxygen vacancies into the host lattice, which results in a decrease in the adsorption energy of the OH* intermediate in the OER. Among the binary fluorite compositions investigated, Nd2Ce2O7 is shown to display the lowest OER overpotential of 243 mV, achieved at a current density of 10 mA cm-2, and excellent cycling stability in an alkaline medium. Importantly, we demonstrate that rare-earth oxide OER electrocatalysts with high activity and stability can be achieved using the EISA synthesis route without the incorporation of transition and noble metals.

Polymer‐Derived Ceramic Coatings with Excellent Thermal Cycling Stability

In the present work, transition metal‐containing preceramic silicon polymers were synthesized via chemical modification of a commercially available organopolysilazane with Hf and Ta amido complexes as well as with borane dimethyl sulfide complex. The incorporation of transition metals into the polymer structure, their influence on ceramization and processability were thoroughly investigated. Moreover, the prepared preceramics were coated onto silicon wafers via spin coating and converted into crack‐free, amorphous SiHfTa(B)CN‐based ceramic coatings with excellent adhesion to the substrate. The composition of the ceramic coatings was investigated via X‐ray photoelectron spectroscopy (XPS) and their high‐temperature behavior was studied via oxidation tests performed at 1100 °C. Moreover, a thermal cycling procedure to temperatures above 1250 °C with rapid heating and cooling rates (i.e., in the range of 100–120 K s−1) was applied to the ceramic coating, which showed no damage even after ten thermal cycles, indicating their outstanding performance and their potential for use as environmental barrier coatings at high temperatures.

Surficial engineering of active hydroxyls for ambient formaldehyde oxidation via enhanced Lewis acidity over Zr-doped cryptomelane materials

Lewis acids of solid catalysts have been featured for a pivotal role in promoting various reactions. Regarding the oxidation protocol to remove formaldehyde, the inherent drawback of the best-studied MnO2 materials in acidic sites has eventually caused deficiency of active hydroxyls to sustain low-temperature activity. Herein, the cryptomelane-type MnO2 was targeted and it was tuned via incorporation of Zr metal, exhibiting great advances in not only the complete HCHO-to-CO2 degradation but also cycling performance. Zr species were existent in doping state in the MnO2 lattice, rendering lower crystallinity and breaking the regular growth of MnO2 crystallites, which thereby tripled surface area and created larger volume of smaller mesopores. Meantime, the local electronic properties of Mn atoms were also changed by Zr doping, i.e., more low-valence Mn species were formed due to the electron transfer from Zr to Mn. The results of infrared studies demonstrate the higher possession of Lewis acid sites on ZrMn, and this high degree of electrophilic agents favored the production of hydroxyl species. Furthermore, the reactivity of surface hydroxyls, as investigated by CO temperature programmed reduction and temperature programmed desorption of adsorbed O2, was obviously improved as well after Zr modification. It is speculated jointly with the characterizations of the post-reaction catalysts that the accelerated production of active hydroxyls helped rapidly convert formaldehyde into key intermediate—formate, which was then degraded into CO2, avoiding the side reaction path with undesired intermediate—hydrocarbonate—over the pristine MnO2, where active sites were blocked and formaldehyde oxidation was inhibited. Additionally, Zr decoration could stabilize Lewis acidity to be more resistant to heat degeneration, and this merit brought about advantageous thermal recyclability for cycled application.

Redox Processes Involving Oxygen: The Surprising Influence of Redox-Inactive Lewis Acids.

Metalloenzymes with heteromultimetallic active sites perform chemical reactions that control several biogeochemical cycles. Transformations catalyzed by such enzymes include dioxygen generation and reduction, dinitrogen reduction, and carbon dioxide reduction-instrumental transformations for progress in the context of artificial photosynthesis and sustainable fertilizer production. While the roles of the respective metals are of interest in all these enzymatic transformations, they share a common factor in the transfer of one or multiple redox equivalents. In light of this feature, it is surprising to find that incorporation of redox-inactive metals into the active site of such an enzyme is critical to its function. To illustrate, the presence of a redox-inactive Ca2+ center is crucial in the Oxygen Evolving Complex, and yet particularly intriguing given that the transformation catalyzed by this cluster is a redox process involving four electrons. Therefore, the effects of redox inactive metals on redox processes-electron transfer, oxygen- and hydrogen-atom transfer, and O-O bond cleavage and formation reactions-mediated by transition metals have been studied extensively. Significant effects of redox inactive metals have been observed on these redox transformations; linear free energy correlations between Lewis acidity and the redox properties of synthetic model complexes are observed for several reactions. In this Perspective, these effects and their relevance to multielectron processes will be discussed.

Leveraging a reduced polyoxomolybdate-alkoxide cluster for the formation of a stable U(v) sandwich complex.

The synthesis and characterization of a series of (TBA)2[M{Mo5O13(OMe)4NO}2] (M = Zr, Hf, Th, and U) sandwich complexes is reported. A preformed lacunary, Lindqvist-type, polyoxomolybdate-alkoxide cluster provides access to first examples of actinide-polyoxomolybdate sandwich complexes isolated under non-aqueous conditions. Incorporation of metal(iv) cations into this framework was found to "switch on" reversible redox chemistry at the {Mo5} ligands, with the Zr and Hf containing complexes accepting up to two electrons, while the Th and U derivates accommodate as many as four additional electrons. The enhancement of the redox properties of the cluster upon actinide incorporation is an exciting observation, presenting actinide "doping" as a novel approach for accessing functional redox-active materials. Oxidation of the uranium containing sandwich complex (TBA)2[U{Mo5O13(OMe)4NO}2], chemically or electrochemically, allows access to the U(v) centered species, which was characterized both spectroscopically and by single crystal X-ray diffraction. This represents the first example of a U(v)-polyoxometalate sandwich complex to be isolated and structurally characterized.

Optimizing post-synthetic metal incorporation in mixed-linker MOFs: insights from metalation studies on bipyridine-containing UiO-67 single crystals.

The postsynthetic metalation (PSM) of metal-organic frameworks (MOFs) with intrinsic metal binding sites is an intriguing strategy to introduce catalytic function into MOFs. The spatial distribution of the catalytic sites within the MOF crystal will affect the efficiency of the material, but the factors that govern depth distribution of the introduced metal sites are often not well understood. Herein, we employ Rutherford backscattering spectrometry (RBS) to investigate the metal distribution in a series of post-synthetically metalated mixed linker bpdc/BPY UiO-67 (UiO = Universitet i Oslo, bpdc = biphenyl-dicarboxylate, BPY = 2,2'-bipyridine-5,5'-dicarboxylate) single crystals as a function of linker ratio and metalation time. The RBS spectra reveal large differences in the depth distribution of inserted Ni2+ ions, and core/shell architectures are observed in high BPY materials at shorter incubation times. The incubation times to achieve uniform metal incorporation increases with increasing BPY ratios in the materials, suggesting that the presence of the BPY linkers slow down metal uptake. We propose a combination of ionic interactions and pore clogging, where coordinated ions reduce the available pore space for further ions to diffuse deeper into the framework as reasons for the observed trends. The observations are likely relevant for other mixed-linker MOF systems, and understanding the effect that linker ratios have on PSM and cation distribution will aid in future optimizations of catalytic MOFs.

Transition metal incorporation: electrochemical, structure, and chemical composition effects on nickel oxyhydroxide oxygen-evolution electrocatalysts

Trace metal cations dissolved in alkaline electrolytes incorporate into nickel hydroxide/oxyhydroxide through in situ cation exchange, creating an interstratified structure near the surface of the material that impacts the electrochemical performance.

Discarding metal incorporation in pyrazole macrocycles and the role of the substrate on single-layer assemblies.

Pyrazole derivatives are key in crystal engineering and liquid crystal fields and thrive in agriculture, pharmaceutical, or biomedicine industries. Such versatility relies in their supramolecular bond adaptability when forming hydrogen bonds or metal-pyrazole complexes. Interestingly, the precise structure of pyrazole-based macrocycles forming widespread porous structures is still unsolved. We bring insight into such fundamental question by studying the self-assembled structures of a bis-pyrazole derivative sublimed in ultra-high-vacuum conditions (without solvents) onto the three (111) noble metal surfaces. By means of high-resolution scanning tunneling microscopy that is validated by gas phase density functional theory calculations, we find a common hexagonal nanoporous network condensed by triple hydrogen bonds at the molecule-metal interface. Such assembly is disrupted and divergent after annealing: (i) on copper, the molecular integrity is compromised leading to structural chaos, (ii) on silver, an incommensurate new oblique structure requiring molecular deprotonation is found and, (iii) on gold, metal-organic complexes are promoted yielding irregular chain structures. Our findings confirm the critical role of these metals on the different pyrazole nanoporous structure formation, discarding their preference for metal incorporation into the connecting nodes whenever there is no solvent involved.

Degradation of amoxicillin residue under visible light over TiO2 doped with Cr prepared from tannery wastewater

The degradation of amoxicillin residue has been performed using TiO2 photocatalyst doped with Cr prepared from tannery wastewater under visible light exposure. The incorporation of Cr metal into TiO2 structure was conducted via hydrothermal method. From the characterization results, it is found that doping Cr from the tannery wastewater into TiO2 structure has been successfully shifted the light absorption into visible region. Among the various Cr content in the TiO2-Cr photocatalyst, TiO2-0.33Cr (medium level) shows the highest ability in the visible light absorption, suggesting it to be the best photocatalyst. It is also clearly proven that in the presence of TiO2-0.33Cr photocatalyst, the degradation of amoxicillin can reach almost 100 % after the third cycles. Furthermore, this study also investigated the optimum condition for photodegradation of amoxicillin as the prevalent antibiotic residue in batch technique. The concentration of amoxicillin after the photodegradation process was determined using a UV–visible spectrophotometer. The result identifies the optimal condition for the amoxicillin photodegradation is reached at pH 6, with 10 mg of the photocatalyst mass per 30 mL of the sample solution, and an irradiation time at 90 min. The photodegradation of amoxicillin using TiO2-0.33Cr follows the pseudo-first order kinetic model with kinetic constant (k) is high as 0.004 min−1.

High ratios of Ni3+ and Co3+ facilitated by Mn-addition for enhanced oxygen evolution reaction and ethanol oxidation reaction

The design of dual-functional catalyst for oxygen evolution reaction and ethanol oxidation reaction is essential for improving H2 production efficiency, and one strategy to improve catalytic performance is the incorporation of high-valence metal.

Dual-nodes bridged cobalt-modified Keggin-type polyoxometalate-based chains for highly efficient CO2 photoconversion.

The design of efficient catalysts for photocatalytic CO2 conversion is of great importance for the sustainable development of society. Herein, three polyoxometalate (POM)-based crystalline materials were formulated prepared by substituting transition metals and adjusting solvent acidity with 2-(2-pyridyl) benzimidazole (pyim) as the light-trapping ligand, namely {[SiW12O40][Co(pyim)2]2}·2C2H5OH (SiW12Co2), {[SiW12O40][Ni(pyim)2]2}·2C2H5OH (SiW12Ni2), and {[SiW12O40][Mn(pyim)2]2}·2C2H5OH (SiW12Mn2). X-ray crystallography diffraction analysis indicates that the three complexes exhibit isostructural properties, and form a stable one-dimensional chain structure stabilized by two [M(pyim)2]22+ (M = Co, Ni, and Mn) fragments serving as dual-nodes to the adjacent SiW12 units. A comprehensive analysis of the structural characterization and photocatalytic CO2 reduction properties is presented. Under light irradiation, SiW12Co2 exhibited a remarkable CO generation rate of 10 733 μmol g-1 h-1 with a turnover number of 328, outperforming most of the reported heterogeneous POM-based photocatalysts. Besides, cycling tests revealed that SiW12Co2 is an efficient and stable photocatalyst with great recyclability for at least four successive runs. This study proves that the successful incorporation of diverse transition metals into the POM anion could facilitate the development of highly efficient photocatalysts for the CO2RR.