Transition Metal Elements Research Articles

Advanced mechanical properties obtained via transition metals doped in CrFeNi medium entropy alloy

Medium entropy alloys (MEAs) have attracted significant interest due to their exceptional mechanical characteristics. This study employs molecular dynamics simulations to investigate the impact of transition metal (TM) elements doping on the mechanical properties of face-centered cubic (FCC) (CrFeNi)100−xTMx(TM=Cu,Mo,Nb,Tiandx=0,4) MEAs. We have doped 4% TM elements with pure CrFeNi MEA and analyze several mechanical characteristics such as lattice distortion, Yield strength, elastic constants and moduli, Vickers hardness, machinability index, and Kleinman parameters. The correlation between elastic moduli and doping implies a decrement in the stiffness of (CrFeNi)100−xTMx alloys. To confirm the ductility, a thorough assessment involving Poisson's ratio, Cauchy's pressure, and Pugh's ratio are conducted. According to the anisotropy factor analysis, the presence of doping increases anisotropy in (CrFeNi)100−xTMx MEAs. The findings of our work suggest that the improved mechanical properties can be beneficial in the development of MEAs suitable for diverse applications.

Additive roles of antiferromagnetically coupled elements in the magnetic proximity effect in the GdFeCo/Pt system

Interfacial magnetic interactions between different elements are the origin of various spin-transport phenomena in multi-elemental magnetic systems. We investigate the coupling between the magnetic moments of the rare-earth, transition-metal, and heavy-metal elements across the interface in a GdFeCo/Pt thin film, an archetype system to investigate ferrimagnetic spintronics. The Pt magnetic moments induced by the antiferromagnetically aligned FeCo and Gd moments are measured using element-resolved x-ray measurements. It is revealed that the proximity-induced Pt magnetic moments are always aligned parallel to the FeCo magnetic moments, even below the ferrimagnetic compensation temperature where FeCo has a smaller moment than Gd. This is understood by a theoretical model showing distinct effects of the rare-earth Gd 4f and transition-metal FeCo 3d magnetic moments on the Pt electronic states. In particular, the Gd and FeCo work in-phase to align the Pt moment in the same direction, despite their antiferromagnetic configuration. The unexpected additive roles of the two antiferromagnetically coupled elements exemplify the importance of detailed interactions among the constituent elements in understanding magnetic and spintronic properties of thin film systems.

Design strategies for MOFs-derived Ce10-xZrxOy catalysts with polyhedral coordination to enhance soot combustion

Various cerium-based metal–organic frameworks (Ce-MOFs and Ce10-xZrx-MOFs) and their derivatives (Ce10-xZrxOy complex oxide catalysts) with different structures and properties by modulating the organic ligands (i.e., trimesic acid (BTC), 1,2,4,5-benzenetetracarboxylic acid (PMA), and terephthalic acid (BDC)) and transition metal elements via the solvothermal method. The performance of these catalysts was tested in the diesel soot oxidation reaction. In contrast, morphology engineering and the introduction of heteroatom zirconium to modify CeO2 can significantly improve the catalytic activity and stability of the catalyst. Among them, the best Ce5Zr5Oy-BDC shows remarkable catalytic performance for soot oxidation, converting 90% of soot particles into CO2 at about 410 °C. A series of characterization results demonstrate that the engineering of morphology provides a highly active polycrystalline surface for the adhesion of reactants, and the electron transfer system caused by Zr doping weakens the Ce-O bond. With the help of their combined action, the exposed polycrystal surfaces greatly enhance the oxygen vacancy content and the ability to generate reactive oxygen species. The DFT investigations shows that the presence of Zr can weaken the Ce-O link, result in favorable defect structures, and the reactive oxygen species of formation were promoted. This study provides an idea for the design of non-precious metal catalysts with high activity and stability.

Cobalt and chlorine co-doped Bi5O7I catalysts for LED-induced photocatalytic or PMS-activation antibiotics degradation

Multifunctional semiconductor catalysts can meet the urgent needs for the removal of antibiotic pollutants in water. Bifunctional catalysts, cobalt and chlorine co-doped Bi5O7I (signed as Co-BIC) catalysts, were purposefully designed through a two-step aqueous strategy. The preformed Bi5O7I precursor provided one-dimensional structure and Bi-rich character for the construction of Co-BIC catalysts. Co and Cl co-doping in Bi5O7I crystals can form a doping energy level and improve the internal electric field, which led to enlarged visible-light absorption and charge separation efficiency during the photocatalytic reaction process. These advantages made Co-BIC crystals exhibit good photocatalytic activities for the removal of antibiotic levofloxacin (LEV), ciprofloxacin (CIP) and tetracycline (TC) under visible LED (100 W) light irradiation. The degradation efficiency of LEV, CIP and TC over the typical Co-BIC-60 catalyst can reach more than 80 % under 60 min of LED irradiation. In the system of Co-BIC activated peroxymonosulfate (PMS), ∼ 90 % of LEV, CIP and TC degraded within 20 min over 20 mg of Co-BIC-60 catalyst. The mechanism of photocatalytic degradation and PMS oxidation degradation over Co-BIC catalysts was proposed on band structures of Co-BIC catalysts and the active species in the capture experiments. This work could provide new ideas for the preparation of bismuth oxyhalide catalysts coupled with transition metal elements.

Synergistic Ni-W Dimer Sites Induced Stable Compressive Strain for Boosting the Performance of Pt as Electrocatalyst for the Oxygen Reduction Reaction.

Alloying Pt catalysts with transition metal elements is an effective pathway to enhance the performance of oxygen reduction reaction (ORR), but often accompanied with severe metal dissolution issue, resulting in poor stability of alloy catalysts. Here, instead of forming traditional alloy structure, we modify Pt surface with a novel Ni-W dimer structure by the atomic layer deposition (ALD) technique. The obtained NiW@PtC catalyst exhibits superior ORR performance both in liquid half-cell and practical fuel cell compared with initial Pt/C. It is discovered that strong synergistic Ni-W dimer structure arising from short atomic distance induced a stable compressive strain on the Pt surface, thus boosting Pt catalytic performance. This surface modification by synergistic dimer sites offers an effective strategy in tailoring Pt with excellent activity and stability, which provides a significant perspective in boosting the performance of commercial Pt catalyst modified with polymetallic atom sites.

Synergistic Ni−W Dimer Sites Induced Stable Compressive Strain for Boosting the Performance of Pt as Electrocatalyst for the Oxygen Reduction Reaction

AbstractAlloying Pt catalysts with transition metal elements is an effective pathway to enhance the performance of oxygen reduction reaction (ORR), but often accompanied with severe metal dissolution issue, resulting in poor stability of alloy catalysts. Here, instead of forming traditional alloy structure, we modify Pt surface with a novel Ni−W dimer structure by the atomic layer deposition (ALD) technique. The obtained NiW@PtC catalyst exhibits superior ORR performance both in liquid half‐cell and practical fuel cell compared with initial Pt/C. It is discovered that strong synergistic Ni−W dimer structure arising from short atomic distance induced a stable compressive strain on the Pt surface, thus boosting Pt catalytic performance. This surface modification by synergistic dimer sites offers an effective strategy in tailoring Pt with excellent activity and stability, which provides a significant perspective in boosting the performance of commercial Pt catalyst modified with polymetallic atom sites.

Crystal Structure Regulation of CoSe2 Induced by Fe Dopant for Promoted Surface Reconstitution toward Energetic Oxygen Evolution Reaction.

Most nonoxide catalysts based on transition metal elements will inevitably change their primitive phases under anodic oxidation conditions in alkaline media. Establishing a relationship between the bulk phase and surface evolution is imperative to reveal the intrinsic catalytic active sites. In this work, it is demonstrated that the introduction of Fe facilitates the phase transition of orthorhombic CoSe2 into its cubic counterpart and then accelerates the Co-Fe hydroxide layer generation on the surface during electrocatalytic oxygen evolution reaction (OER). As a result, the Fe-doped cubic CoSe2 catalyst exhibits a significantly enhanced activity with a considerable overpotential decrease of 79.9 and 66.9 mV to deliver 10 mA·cm-2 accompanied by a Tafel slope of 48.0 mV·dec-1 toward OER when compared to orthorhombic CoSe2 and Fe-doped orthorhombic CoSe2, respectively. Density functional theory (DFT) calculations reveal that the introduction of Fe on the surface hydroxide layers will tune electron density around Co atoms and raise the d-band center. These findings will provide deep insights into the surface reconstitution of the OER electrocatalysts based on transition metal elements.

Enhanced diffusion kinetics in Y-doped SnO2 anodes for low-temperature lithium-ion batteries: A combined theoretical and experimental study

In recent years, there has been an increasing demand for lithium-ion batteries suitable for low temperatures in various fields. SnO2, with its high theoretical specific capacity, has emerged as an ideal candidate for low-temperature lithium-ion batteries. However, tin oxide exhibits inherent issues such as poor conductivity and limited cycle reversibility. Enhancing the diffusion rate of lithium ions in tin oxide is crucial for improving its low-temperature performance. We use first-principles calculations based on Density Functional Theory (DFT) to investigate the doping models of various transition metal elements (Sc, Y, Ti, Zr, V, Nb, Gr, Mo, Mn, Fe, Co, Ni) with a rational ratio of 4 % in SnO2. The results indicate that Y doping decreases the band gap of SnO2 by 0.253 eV, leading to a significant reduction in the Li-ion diffusion barrier of α-Sn. Furthermore, the synthesized SnO2 doped with Y (Y-SnO2) electrode exhibited excellent cyclic stability as an anode and achieved a high reversible capacity of 672 mAh g−1 at −10°C, surpassing that of the pure SnO2 (450 mAh g−1). Moreover, it demonstrated a higher diffusion coefficient of lithium ions and lower charge transfer impedance at both low and room temperatures.

Doping effects on magnesium hydroxide: Enhancing dehydration and hydration performance for thermochemical energy storage applications

Thermochemical energy storage (TCES) holds significant promise owing to its remarkable energy storage density and extended storage capabilities. One of the most extensively studied systems in TCES involves the reversible hydration/dehydration reaction of magnesium hydroxide (Mg(OH)2) to magnesium oxide (MgO). This system suffers from several challenges such as the dehydration temperature of 360 °C, which is considered higher for some applications, low kinetics, and conversion fraction, in addition to the conversion decay after cycles. Nonetheless, it is essential to recognize that each material within thermochemical systems has distinct operational requirements, including temperature and pressure conditions, making them suitable for specific applications. Consequently, the development of materials is a pivotal factor in expanding the effectiveness of sustainable technologies. This research addresses challenges associated with the reversible reaction by partially substituting Mg with transition metal elements like Zn, Ni, Mn, Co, and Cu, leading to the development of new materials Mg1-xMx(OH)2 with x = 0.05. The results indicate successful synthesis of hydroxide systems through coprecipitation. Morphological analysis reveals that material morphology plays a significant role in the performance of thermochemical systems. Additionally, the developed materials demonstrate a reduction in dehydration temperature, reaching 295 °C with cobalt doping. There is also an increase in the conversion reaction, with a 10 % improvement in energy density recorded for the material doped with 5 % Zn. Lastly, the developed materials exhibit good cyclability performance for up to 6 cycles.

Fe/Cu doped black ceramic coating on magnesium alloy by plasma electrolytic oxidation method based on first principles

The absorption of visible light by a solid material can correspond to its color. If all visible light is absorbed, the material is black, and the band width of the material defines the wave limit of visible light absorption. Based on this, the transition metal elements Fe and Cu were chosen to dope MgO, and the transition metal elements Fe or Cu were substituted to dope MgO using first-principles simulation. The doped elements' 3d and 4 s levels were introduced to shift the locations of MgO's valence and conduction bands, respectively, lowering the band gap width of MgO. The MgO ceramic coating may respond to light wave wavelength redshifting to 780 nm and entirely absorb visible light; The black MgO ceramic coating was prepared on the surface of AZ31 magnesium alloy utilizing Fe salt and Cu salt as plasma electrolytic oxidation (PEO) electrolyte additions, and the visible light absorption rates were 94.2 % and 94.1 %, respectively. The test findings show that the band gap of the MgO ceramic coating has been lowered from 4.97 eV to 1.58 eV and 1.60 eV, respectively, which is the primary reason for the achievement of strong absorption in all visible light bands. The first principle calculation of the influence of doping elements on the band gap of MgO ceramic coating can serve as a theoretical guidance for selecting coloring elements for the fabrication of black ceramic coating.

Fe–Ni-doped metal-organic framework derived CoSe2 as an efficient and stable electrocatalyst for hydrogen evolution reaction

The development of efficient, stable and low-cost catalysts for hydrogen evolution reaction (HER) is one of the major difficulties in water electrolysis. It is also the key to realizing the large-scale production of hydrogen energy, a renewable and clean energy source. In recent years, metal-organic frameworks (MOFs) have attracted much attention as novel precursors for preparing water electrolysis catalysts due to their high porosity and large specific surface area. In this paper, we use ZIF-67 as a precursor and modify it by doping transition metal elements Fe and Ni. Afterwards, Fe–Ni–CoSe2@NC is synthesized by a thermal selenization process. The results show that the HER overpotential of the catalyst after modification is reduced by 50%, and the efficiency of water electrolysis is significantly improved. Moreover, the catalyst has good stability under alkaline condition and is more economical than the expensive Pt-based catalysts, which provides more possibilities for industrial applications.

Catalytic oxidation of formaldehyde by MnOx-decorated anatase TiO2{001}: Investigation of the effect of calcination temperature on catalytic activity and reaction mechanism

The removal of indoor formaldehyde (HCHO) is crucial for human health. The design of highly catalytically active nonprecious metal catalysts has major challenges, and the use of transition metal element modification to improve the catalytic performance is an effective strategy. In this study, the active component Mn was loaded on highly active crystalline anatase TiO2{001}, and the effect of the calcination temperature on the catalytic activity was investigated. The important influence of temperature on the catalyst valence distribution, surface active oxygen species, and content was thoroughly determined by characterization techniques, such as XPS, H2-TPR, and O2-TPD. The catalytic reaction process was further analyzed by in situ infrared technology to determine the reaction intermediates and to clarify the catalyst reaction poisoning mechanism; additionally, a reasonable HCHO catalytic reaction pathway was proposed with the combination of density function theory calculations. In addition, oxygen defects on the catalyst surface were determined by EPR, and based on theoretical calculations, the oxygen defects could further reduce the reaction energy barrier through the Langmuir-Hinshelwood mechanism. By exposing specific crystal surfaces and increasing the number of oxygen defects, the catalytic activity could be effectively improved; based on these results, our study provides a concept for the subsequent development of nonprecious metal catalysts.

Chemical Bonding and the Role of Node-Induced Electron Confinement.

The chemical bond is the cornerstone of chemistry, providing a conceptual framework to understand and predict the behavior of molecules in complex systems. However, the fundamental origin of chemical bonding remains controversial and has been responsible for fierce debate over the past century. Here, we present a unified theory of bonding, using a separation of electron delocalization effects from orbital relaxation to identify three mechanisms [node-induced confinement (typically associated with Pauli repulsion, though more general), orbital contraction, and polarization] that each modulate kinetic energy during bond formation. Through analysis of a series of archetypal bonds, we show that an exquisite balance of energy-lowering delocalizing and localizing effects are dictated simply by atomic electron configurations, nodal structure, and electronegativities. The utility of this unified bonding theory is demonstrated by its application to explain observed trends in bond strengths throughout the periodic table, including main group and transition metal elements.

Effect of different metal element substitution on microstructural and comprehensive hydrogen storage performance of Ti0·9Zr0·1Mn0·95Cr0·7V0.2M0.15 (M = Fe, Co, Ni, Cu, Mo) alloy

Hydrogen is now being used as a renewable clean energy carrier. One of the main issues with the application of hydrogen energy is a shortage of security and efficient hydrogen storage technology. TiMn-based alloys are considered promising hydrogen storage materials, but their comprehensive hydrogen storage properties and cyclic stable performance limit their further practical application. The hydrogen storage properties of alloys can be enhanced by substituting transition metal elements. Therefore, the comprehensive hydrogen storage performance of the Ti0·9Zr0·1Mn0·95Cr0·7V0.2M0.15 (M ​= ​Fe, Co, Ni, Cu, Mo) alloys was systematically investigated according to the Mn element on the B side is partially replaced by variety of transition metal elements. The M ​= ​Ni alloy, which showed the highest hydrogen storage capacity among the group of alloys, was used to explore cycle stability. The plateau pressures of the series alloys decreased in order, Fe ​> ​Co ​> ​Ni ​> ​Cu ​> ​Mo. Aspects of hydrogen absorption kinetics, all of the alloys can reach full hydrogen absorption saturation within 400 ​s at 303 ​K. The Ti0·9Zr0·1Mn0·95Cr0·7V0·2Mo0.15 alloy possessed the fastest hydrogen absorption kinetic rate (t0.9 ​= ​65 ​s) and the smallest hysteresis factor. This suggests that the substitution of Mo elements is effective in improving the hysteresis of the Laves phase alloys. Among the series of alloys, the M ​= ​Ni alloy exhibited the best overall hydrogen storage performance, which hydrogen storage capacity can reach 1.81 ​wt% and 97% of its capacity is kept after 100 cycles.

Mn Cluster-Embedded N/F Co-Doped Carbon toward Mild Aqueous Supercapacitors.

Aqueous supercapacitors have occupied a significant position among various types of stationary energy storage equipment, while their widespread application is hindered by the relatively low energy density. Herein, N/F co-doped carbon materials activated by manganese clusters (NCM) are constructed by the straightforward experimental routine. Benefiting from the elevated conductivity structure at the microscopic level, the optimized NCM-0.5 electrodes exhibited a remarkable specific capacitance of 653 F g-1 at 0.4 A g-1 and exceptional cycling stability (97.39% capacity retention even after 40,000 cycles at the scanning rate of 100 mV s-1) in a neutral 5 M LiCl electrolyte. Moreover, we assembled an asymmetric device pairing with a VOx anode (NCM-0.5//VOx), which delivered a durable life span of 95% capacity retention over 30,000 cycles and an impressive energy density of 77.9 Wh kg-1. This study provides inspiration for transition metal element doping engineering in high-energy storage equipment.

Tribological Properties of Polyimide Composites Modified with Diamondoid Metal-Organic Frameworks.

In this work, diamondoid metal-organic frameworks (MOFs) were efficiently prepared by sonochemical synthesis and grown on polyimide (PI), aiming to improve the anti-wear performance of the PI matrix. By introducing MOFs into the PI matrix, the free movement of PI molecular chains were restricted, and its hardness and elastic modulus were improved. It was found that the wear rate of the 3 wt.% MOFs/PI composites was reduced by 72.6% compared to pure PI at a load of 4 N after tribological testing by using a ball-on-disk tribometer. This can be attributed to the excellent load-bearing and shear resistance of the fourfold-interpenetrated diamondoid networks, in which the transition metal elements can favor the formation of transfer films. It is worth noting that the 3 wt.% MOFs/PI composites still exhibited great tribological properties under high loads or high speeds. The findings of the present study indicate that diamondoid metal-organic frameworks can be used as efficient modifiers to enhance the tribological properties of PI.

Strong electron-phonon coupling and high lattice thermal conductivity in half-Heusler thermoelectric materials.

Traditional half-Heusler thermoelectric materials, identified as 18-electron compounds, are characterized by the high power factor and the high lattice thermal conductivity. Interestingly, the emerging 19-electron half-Heusler compounds were also found to be promising thermoelectric materials, but with a 5-10 times lower lattice thermal conductivity. Since the two kinds of compounds have similar chemical and physical structures, such as TiCoSb and VCoSb, the large difference in lattice thermal conductivity is a puzzling question. Here, we present a theoretical study to clarify the lattice thermal transport in half-Heusler thermoelectric materials. Based on electronic band structure analysis, we show that the two transition-metal elements in half-Heusler compounds form the strong and direct d-d interaction that is responsible for the high lattice thermal conductivity of 18-electron compounds. In 19-electron half-Heusler compounds, however, the extra valence electron enters the d-d antibonding states, which significantly weakens the atomic bond strength, leading to a large decrease in the cohesive energy. The resulting softened acoustic phonons enhance the phonon-phonon scattering, and thus reduce the lattice thermal conductivity significantly. By constructing an artificial 18-e compound V0.5Sc0.5CoSb, it is proved that the one less electron relative to VCoSb increases the lattice thermal conductivity significantly.

P/s-orbital hybridization induced by Mg-doping to active Na sites in Na2FePO4F cathode for long-life and high-rate sodium-ion batteries

The iron-based fluorophosphate Na2FePO4F (NFPF) is considered as a potential cathode for sodium-ion batteries due to the low-cost, non-toxicity and appropriate working voltage. However, the inferior intrinsic electronic conductivity and the restrained active Na sites bring the limits for full realization of electrochemical properties. Herein, Mg2+ with d0 orbital was introduced in FeO4F2 structure, aimed at activating the Na+ at Na1 site and enhancing the electronic conductivity. Different from the 3d transition metal (TM) elements that form 3d-O2p orbital interactions in the FeO4F2 structure, the Mg with d° contributes p and s orbitals mainly in Mg-O bonds, which corresponds to more stable orbital interaction and lattice structure. The electron distribution of bridge O due to the Mg-doping leads to the wooden barrel effect near the Mg site, thus activating Na+ at Na1 site by lowering the energy barrier of Na+ migration from Na1 to Na2 site. Hence, the obtained NFMPF electrode delivers high specific capacity (121.4 vs. 108.7 mAh g−1 at 0.1 C) and better cycling stability (73.8% vs. 54.2 % after 1000 cycles at 20 C). Overall, regulating the electronic structure and activating Na+ at inactive site is the key to break the bottleneck of low activity, which can be an effective strategy to design cathode materials with excellent electrochemical performance.

Epitaxial Tantalum‐Doped β‐Ga2O3 Thin Films Grown on Mgo (001) Substrate by Pulsed Laser Deposition

Epitaxial thin films of tantalum‐doped β‐Ga2O3 (Ta‐Ga2O3) are grown on MgO (001) substrates to study the effect of Ta doping on the electrical properties of β‐Ga2O3 films. X‐Ray diffraction (XRD) measurements show that the films with different Ta doping concentrations are (00l)‐oriented single‐crystalline β‐Ga2O3 without impurity phases. The incorporation of the Ta element modifies the electrical properties of Ta‐Ga2O3 films significantly. At a very low doping ratio of 0.05 mol%, the Ta‐Ga2O3 film showed a minimum resistivity of 2.32 Ω cm and a carrier concentration of 2.48 × 1017 cm−3. The corresponding activation energy of Ta element in the film is 16.8 meV, suggesting that the Ta element is a promising shallow donor dopant. The X‐ray photoelectron spectroscopy (XPS) analysis confirms that the Fermi level of the Ga2O3 films shifts toward the conduction band minimum after the introduction of Ta ions. These results indicate that the transition metal element Ta could be an effective n‐type dopant for modulating the carrier transport behavior of β‐Ga2O3 films.

Simple derivation of L-absorption spectra of 3d transition metal elements by the self-absorption effect observed in soft X-ray emission spectra.

This study proposes a simple evaluation method for deriving L-absorption information from two L-emission spectra of 3d transition metal (TM) elements obtained at two different accelerating voltages. This method realizes a spatial identity for X-ray emission and absorption spectroscopies. This method was evaluated for the Fe L-emission spectra of Fe and its oxides and was applied to the TM L-emission spectra of MnO, Co, CoO and NiO. The derived absorption peak positions were consistent with those obtained previously at synchrotron orbital radiation facilities, which considered the core-hole effect. This simple derivation method could be useful for obtaining X-ray absorption spectroscopy distribution images from X-ray emission spectroscopy mapping data obtained by scanning electron microscopy.