Bimetallic Materials Research Articles

The Structure and Optical Properties of Luminescent Terbium Terephthalate Metal–Organic Frameworks Doped with Yttrium, Gadolinium, and Lanthanum Ions

The structural features and luminescent properties of heterometallic Tb–Gd, Tb–La, and Tb–Y terephthalate metal–organic frameworks, namely (TbxM1−x)2(1,4-bdc)3∙4H2O (M = Gd, La, Y), were studied in detail in a wide concentration range (x = 0.001–1). The crystalline phase of synthesized compounds corresponds to Ln2(1,4-bdc)3·4H2O. The lifetime of 5D4 decreased with increased Tb3+ concentration, but PLQY depends non-linearly on the Tb3+ concentration. The 50% substitution of Tb3+ for Y3+, Gd3+, or La3+ ions result in the significant enhancement of photoluminescence quantum yield, up to 1.6 times. The morphology, thermal stability, and vibrational structure of the selected homo- and bi-metallic materials is reported as well.

Study and Characterisation of Bimetallic Structure (316LSI and S275JR) Made by Hybrid CMT WAAM Process

The main objective of this research is to conduct an experimental investigation of the bimetallic material formed by 316LSI stainless steel and S275JR structural steel, produced via hybrid wire arc additive manufacturing technology with cool metal transfer welding and machining, and with the objective of being able to reduce the industrial cost of certain requirements for one of the materials. A methodological investigation has been carried out starting with welding beads of 316LSI on S275JR plates, followed by overlapping five beads and conducting final experiments with several vertical layers, with or without intermediate face milling. The results achieved optimal bead conditions for wire speeds of 4 m/min and 5 m/min at a travel speed of 400 mm/min. Overlap experiments show that the best deposition results are obtained with an overlap equal to or greater than 28%. Cooling time does not significantly influence the final geometry of the coatings. Regarding metallographic analysis, the filler material presents an austenitic columnar structure. In the base material, a bainitic structure with inferred grain refinement was detected in the heat-affected zone. An increase in hardness is observed in the heat-affected zone. In the results obtained from the tensile tests of the bimetallic material, an increase in mechanical strength and yield strength is observed in the tested specimens.

Altering preferential product selectivity in electrocatalytic CO2 reduction over fluorine-modified CuIn bimetallic materials

Integrating carbon dioxide (CO2)-derived renewable technologies into the petrochemical industry presents a promising avenue for carbon neutrality. The renewable-energy-powered electrochemical CO2 reduction (eCO2R) process, particularly over Cu-based electrocatalysts, is a valuable asset for our decarbonization efforts to avoid climate consequences. Intending to enhance process efficiency, this work is a distinctive case study emphasizing the need to develop electrocatalysts in conjunction with adjusting operating conditions. A representative case is presented using fluorine-modified CuIn bimetallic electrocatalysts with tunable In/Cu ratios, demonstrating how to alter selectivity preferences based on reactor configuration: Our optimized catalyst system led to the highest faradaic efficiency (FE) for C2+ products of 68 % and the highest C1 FE of 80 % using gas diffusion electrodes (GDE)- and H-cell-type based electrolyzer, respectively. Moreover, the controllable In/Cu ratio and the degree of fluoride doping played a pivotal role in governing the physicochemical properties of the bimetallic electrocatalysts and their eCO2R performance. Diverse characterization tools offered systematic insights into the relationships between catalyst structure and properties, reactor configuration, electrolyte, and performance, aiming to enhance the Technology Readiness Level of the eCO2R process.

Tracking the Early-life of PtNi/C Shape-Controlled Catalysts upon their Integration in PEMFC

Abstract The integration of promising bimetallic electrocatalytic active materials for oxygen reduction reaction (ORR) into practical and functional proton-exchange membrane fuel cell (PEMFC) electrodes remains largely impeded by the poor performances that these exhibit at high current loads. The early life of PtNi/C catalysts presenting either structurally faceted/ordered or defective/disordered surface morphology is compared to that of both spherical PtNi/C and Pt/C catalysts. Different single-cell operating conditions were studied. At low current density, in the kinetically limited region, a good agreement between liquid electrolyte and single-cell configuration is reported and the kinetic benefit of PtNi/C catalysts compared to Pt/C is (at least partially) maintained. However, PtNi/C catalysts show severe limitations in the O2 mass transport limited region. Morphological and compositional changes were monitored at each stage showing that Ni atoms are leached at every step from ink formulation to the first PEMFC test. We show that Ni is already redistributed in the membrane in the fresh membrane electrode assembly (MEA) state. Ni2+ cationic contamination of the ionomer/membrane contributes to the disappointing results obtained in MEA configuration. In addition, for shaped-controlled PtNi/C, the surface faceting loss combined with restructuring via coalescence and crystallite growth further compromise their transfer in technological devices.

MOF-derived three-dimensional porous dodecahedral structured bimetallic Mn/Co-C-N composite for high-performance durable oxygen reduction reaction electrocatalysts

Investigating high-efficiency oxygen reduction reaction (ORR) catalysts is one of the most effective methods for addressing the sluggish kinetics at the fuel cell cathode. Bimetallic three-dimensional porous materials have garnered significant attention due to their diverse structures, large specific surface area and synergistic catalytic effects. Herein, we synthesized a bimetallic three-dimensional porous dodecahedral structure, Mn/Co-C-N, derived from MOF using a straightforward approach. Experimental reults confirm that the strategic incorporation of Mn enhances the electrocatalytic activity for ORR. Meanwhile, the synergistic effects of Mn and Co, as well as the advantages of the dodecahedral structure for expediting electron transfer, all contribute to the exceptional ORR performance. Arc testing in an alkaline electrolyte reveals that the initial potential (Eonset) and the half-wave potential (E1/2) are 0.89 V and 0.80 V, closely approximating those of commercial Pt/C (20 wt%). Following 10 000 stability test cycles, the half-wave potential exhibits a mere 8 mV change, confirming its remarkable stability.

Removal of tetracycline antibiotic from aqueous solution using bimetallic CuCo-ZIFs as an efficient catalyst in the presence of hydrogen peroxide

Antibiotics play an important role in disease treatment; however, they are also a threat to public health and the ecosystem. Therefore, a bimetallic CuCo-ZIFs catalyst was manufactured through the ultrasonic-assisted solvothermal method to activate H2O2 towards the removal of tetracycline (TC) in an aqueous environment, a polluting broad-spectrum antibiotic model. PXRD, SEM, TEM, EDX, TGA, FT-IR, and BET analyses indicated that CuCo-ZIFs cubic crystals were successfully synthesized with high crystallinity, large specific surface area, and ideal thermal stability. Factors affecting the TC removal were investigated, including CuCo-ZIFs dosage, H2O2 concentration, treatment time, initial TC concentration, and reaction temperature. The results showed that the CuCo-ZIFs/H2O2 catalytic system was capable of effectively handling TC, with about 93.9% of TC removed in the presence of 0.3 g.L-1 CuCo-ZIFs, 0.01 mol.L-1 H2O2 at room temperature within 30 min. Conclusively, this study contributes to expanding the application potential of bimetallic CuCo-ZIFs materials to eliminate antibiotic residues in an aqueous environment and inspire research on environmental improvement.

Microstructure and Mechanical Properties of Bimetallic Materials Containing Ceramic Particles Made Using Directed Energy Deposition

Microstructure and Mechanical Properties of Bimetallic Materials Containing Ceramic Particles Made Using Directed Energy Deposition

Phosphidation‐Free Synthesis of NixCoyP on Nanostructured N,S,P‐Doped Carbon Networks as Self‐Supported Multifunctional Electrocatalysts

The synthesis of supported multielement transition metal phosphides (TMPs) to exploit the synergistic interplay between electronic and geometric effects resulting from the presence of different metals in the material and the arrangement of heterogeneous atoms is pivotal for reducing metal content while offering multiple active sites. However, the integration of Ni, Co, and P, for example, into a nanostructured carbon network to develop self‐supporting NixCoyP bimetallic phosphides is limited by several factors, including the synthesis and the discrepancy between the crystal structure of the respective monometallic phosphides. Moreover, conventional synthesis of supported TMPs often separates nanoparticles, support and phosphidation steps, which do not allow tailoring of physical and catalytic properties via particle support, electronic and geometric interactions. Herein, an innovative solid‐state, ex situ phosphidation‐free approach tailored to synthesize a library of self‐supporting NixCoyP TMPs in N,S,P‐modified nanostructured carbon networks generated together with NixCoyP particles is presented. Extensive multivariate characterization validates the unique properties of NixCoyP bimetallic materials with enhanced electrocatalytic performance for the hydrogen evolution reaction and the selective electroconversion of biomass‐derived 5‐hydroxymethylfurfural (5‐HMF) to value‐added 2,5‐furandicarboxylic acid (FDCA) with 90–100% Faradaic efficiency. Overall, the synthesis expands the possibilities for tailoring the microstructure of supported TMPs for improved physical/catalytic properties.

Damage mechanics coupled with a transfer learning approach for the fatigue life prediction of bronze/steel diffusion welded bimetallic material

The bronze/steel diffusion welded (BSDW) bimetallic material is often applied in the rotors of piston pumps to withstand complex alternating loads under high-speed operating conditions. Although diffusion welding is a type of solid-phase welding method to achieve high-quality material connections, the fatigue problems still deserve our attention, especially the very high cycle fatigue (VHCF) and high cycle fatigue (HCF) problems. However, due to the high cost of obtaining data, it is necessary to find an efficient and high-precision fatigue life prediction method for diffusion welded materials with a small sample size. In this study, a novel method continuum damage mechanics − transfer learning method (CDM-TLM) for fatigue life prediction of BSDW material is proposed based on the transfer learning (TL) and continuum damage mechanics − finite element method (CDM-FEM). In comparison with the test results, the predicted values of BSDW material fatigue life all fall within the twice error band of the median values of the test life. The influence of frozen layers during TL and training samples in source and target models on the prediction performance is further discussed. CDM-TLM is an effective life prediction method for high-precision life prediction of BSDW material with a small sample size.

Tuning the morphology and surface structure of MnOx@GF through Ce for high-efficiency degradation of Rhodamine B by electro-Fenton

Widespread and ineffective dye treatment in aquatic environment leads to serious pollution problems, threatening ecology and human health. Herein, manganese cerium bimetallic oxide cathode material (MnCeOx@GF) was prepared by hydrothermal method combined with calcination, and the electrochemical Fenton degradation performance of a typical dye Rhodamine B (Rh B) was investigated. The results show that the degradation of Rh B by MnCeOx@GF can reach 96.5 % within 2 h in acidic environment and continue to perform effectively after 4 repeated experiments. Combined with SEM and electrochemical test results, it can be seen that the bimetallic composite oxides formed by manganese and cerium on the surface of the support can effectively enhance the catalytic activity of the material, the addition of cerium changes the morphology of manganese oxides and promotes the generation of multiple valence composite oxides of transition metals, and improves the degradation of Rh B. Based on the free radical masking experiments, hydroxyl radical (·OH) is the main active substance in the electro-Fenton degradation process. This work not only provides a way to design and manufacture cathode materials for in situ electrosynthesis of H2O2, but also provides an important reference for improving the reusability of cathodes for sustainable dye wastewater treatment.

Mechanistic insight into the simultaneous removal of Cr(VI) and phosphate by a novel versatile bimetallic material

Industrial wastewater containing hexavalent chromium Cr(VI) and phosphate poses a great threat to human health and the aquatic ecological environment. In this study, a novel La(OH)3- and CaO2-fabricated CNT (La-Ca-CNT) material was developed for the simultaneous and highly effective removal of aqueous Cr(VI) and phosphate. Characterization results showed that synergistic effects existed between the CNT support and La and Ca species. La-Ca-CNT showed high phosphate and Cr(VI) removal rates in acidic conditions with high stability. Kinetic study suggested that the fast adsorption of phosphate on La-Ca-CNT was controlled by intraparticle diffusion. The removal of Cr(VI) and phosphate interacted with each other, and the removal of Cr(VI) went through a slow-fast-slow reaction, reaching a Cr(VI) removal rate of over 97% within 180min. La-Ca-CNT had a high phosphate adsorption capacity (174.3mg/g), and over 70% of the adsorbed phosphate could be recovered. The presence of co-existing anions showed negative effects on phosphate adsorption but negligible effects on Cr(VI) reduction, while organic carbon in natural water showed no effect on phosphate and Cr(VI) removal. A mechanistic study revealed that phosphate was removed by physical-chemical adsorption (outer-sphere complexation and ligand exchange) over La-Ca-CNT, while Cr(VI) was reduced by H2O2 generated from CaO2 or directly by surface CaO2.

Degradation of organic dyes by Peroxymonosulfate activated with Zn/Co-ZIF

In this study, we successfully synthesized a bimetallic metal-organic framework material Zn/Co-ZIF to start Peroxymonosulfate (PMS) for organic dye degradation in the water body. Material characterization was evaluated by advanced methods, such as XRD, FT-IR, SEM, EDX, and BET. The influence of different factors on methylene blue (MB) decomposition rate was investigated. The results show that Zn/Co-ZIF has a porous structure, a high specific surface area and decomposes 98.22% MB (20 mg/L) in 4 minutes under reaction conditions of 40 mg/L catalyst, 0.814mM PMS, pH = 7. The decomposition efficiency of dyes increases in the order CR (79.85%) <RhB (90.81 %) < DB71 (96.07%) < MO (97.63%) < MB (98.22%). The main ROS for the degradation MB in this study were SO4—-, O2—- and 1O2. This shows that Zn/Co-ZIF materials are potential heterogeneous catalysts to activate PMS to decompose organic pollutants in water.

Longevous Protic Hybrid Supercapacitors Using Bimetallic Prussian Blue Analogue/rGO-Based Nanocomposite Against MXene Anode.

MXenes exhibit a unique combination of properties-2D structure, high conductivity, exceptional capacity, and chemical resistance-making them promising candidates for hybrid supercapacitors (HSCs). However, the development of MXene-based HSCs is often hindered by the limited availability of cathode materials that deliver comparable electrochemical performance, especially in protic electrolytes. In this study, this challenge is addressed by introducing a durable protic HSC utilizing a bimetallic Prussian Blue Analogue (PBA) decorated on reduced graphene oxide (rGO) as a nanocomposite cathode paired with a single-layered Ti3C2Tx MXene (SL-MXene) anode. The bimetallic PBA, specifically nickel hexacyanocobaltate (NiHCC), is utilized by virtue of its open and stable structure that facilitates efficient charge storage, leading to enhanced stability and energy storage capabilities. The resulting NiHCC/rGO//SL-MXene cell demonstrates impressive performance, achieving a maximum specific energy of 38.03Wh kg-1 and a power density of 20666.67W kg-1. Remarkably, the NiHCC/rGO//SL-MXene HSC cell also exhibits excellent cycling stability without any loss even after 15000 cycles while retaining ≈100% coulombic efficiency. This work underscores the potential of bimetallic PBA materials with conductive rGO backbone for overcoming the limitations of current MXene-based protic HSCs, highlighting the significance of this work.

Effect of Ni interlayer on microstructure and mechanical properties of Sn-based alloy/steel bimetallic materials via liquid-solid compound casting

Tin-based alloys have been widely used as an excellent bearing material. However, preparing of Tin/steel bimetallic materials with sound metallurgical interfaces has proven challenging. Importantly, a large number of brittle intermetallic compounds inevitably form at the interface, affecting the material's bonding properties. In this study, an electroplated Ni layer was used for the first time as an intermediate layer in Tin/steel bimetallic composites. It solves the problems of steel surface oxidation and poor wettability. Additionally, the introduction of the electroplated Ni layer impedes the formation of brittle phases, thereby improving interfacial bond strength. The results show that the Tin/steel interface of the Ni interlayer consists mainly of a large number of Ni3Sn4 phases rather than the commonly known FeSn2 phase. A thin layer of residual Ni plating also exists between the steel and the diffusion layer. Furthermore, the properties of Ni3Sn4 and FeSn2 phases were calculated using first-principles calculations. A Tin/steel bimetallic interface achieved a maximum shear strength of 58.63 MPa in the presence of the Ni intermediate layer. At that time, the residual thickness of the Ni layer was 1.5 μm, and the thickness of the diffusion layer was 4.8 μm.

An efficient novel NiCu@INA/rGO MOF hollow microsphere Z-scheme heterojunction catalyst for the photocatalytic degradation of tetracycline and simultaneous degradation of cationic and anionic Dyes

Bimetallic metal-organic framework materials have captivated considerable attention in photocatalysis because of their colossal properties like semiconducting, large surface area, and potent visible light harnessing ability. Self-aggregation and rapid recombination rates have greatly hindered their applications in photocatalysis. A novel reduced graphene oxide-incorporated bimetallic nickel copper metal-organic framework (NiCu@INA/rGO MOF) is fabricated using isonicotinic acid as an organic linker. A synergistic effect between the two metals increased the photocatalytic performance. Introducing reduced graphene oxide to nickel-copper MOF increased charge carrier retention transfer and enhanced the catalyst’s water dispersibility. The efficiency of the photocatalyst for the removal of tetracycline (TCn) and a mixture of Rhodamine B (RhB) and Orange G (OrG) dyes was investigated under visible light. A degradation efficiency of up to 89 % for TCn and close to ∼97.8 % and 93.5 % degradation in the case of RhB and OrG dyes was observed. The studies on the photocatalytic degradation mechanism were explored by conducting radical scavenger experiments, Electron spin resonance (ESR) studies, and Mott-Schottky analysis. TCn and RhB degradation pathways were explored by mass spectral analysis of the intermediates during the photocatalytic degradation of TCn and RhB. This work provides new paradigms for the functional modification of MOF for designing efficient photocatalysis.

Enhanced antibacterial activity of starch-alginate beads by a synergistic effect between Cu2+ and Zn2+ ions with a potential wound dressing application

The synthesis and characterization of starch/alginate composite beads, crosslinked with Cu2+, Zn2+, and Cu:Zn mixtures were investigated, focusing on their potential application in exudative wound dressings. Hydrogel beads were prepared using the external gelation method and then dried via freeze-drying to create cryogels and air-drying to create xerogels. Microstructural characterization was performed using SEM and EDS, showing the typical porous structure with a homogeneous distribution of cations across the beads. Unimetallic beads exhibited higher equilibrium water uptake compared to Cu:Zn bimetallic beads (500 % vs. 300 %). After the swelling study, the total amount of Cu2+ released was significantly below the maximum allowed level as a safeguard against copper toxicity. All beads demonstrated excellent antimicrobial activity against E. coli, S. aureus, and P. aeruginosa. Bimetallic materials, particularly cryogels with equal or greater amount of zinc relative to copper, were particularly effective against P. aeruginosa. Hence, the synthesized bimetallic starch-alginate materials presented superior water absorption capacity and significantly enhanced antibacterial response compared to unimetallic beads, due to the synergistic effect between Cu2+ and Zn2+ ions, making then suitable for use in exudative wound dressings.

The Influence of the Parameters of the Skew Rolling Process for Bimetallic Elements on the Mechanical Properties and Structure of Materials.

This paper presents selected results of theoretical and experimental research into the manufacture of axisymmetric bimetallic components using three-tool skew rolling technology. In the tests, it was assumed that the outer layer would be a material intended for heat treatment. However, low-carbon steel was used for the core. Experimental investigations were carried out in an innovative CNC skew rolling mill. Tests were carried out at different technological parameters of the process. In addition, the geometric parameters of the billet and the way it was heated were analyzed in relation to the quality of the resulting weld between the two materials. The quality of the weld was assessed based on metallographic observation and on strength tests (shear method). On the other hand, theoretical studies were based on numerical modeling (FEM). The numerical analysis made it possible to determine the distribution of temperature, deformation and stress in the rolling bimetallic component. The results obtained indicated that it is possible to produce bimetallic materials from the proposed steel grades. In addition, a significant effect of the method of heating the billet in the chamber furnace on the microstructure in the joining zone and the shear strength was found. There was an increase in Rc strength of about 35% when using oxidation protection. The results indicated better strength when the billet is rolling with a smaller outer layer thickness (about 50 MPa). This was confirmed by the results obtained from the FEM analysis, which indicated higher values of plastic strain and the occurrence of higher compressive stresses in the near-surface zones of the rolled bimetallic forging, both of which facilitate the welding process. From the temperature distribution (in the range of (600-1200) °C) obtained during the rolling of the bimetal forging, it can be seen that contact with cold tools does not affect the temperature in the welding zone.

Antimony removal using zero-valent iron-manganese bimetallic nanomaterial: Adsorption behavior and mechanism

Although the effectiveness of zero-valent iron (ZVI) and zero-valent manganese (ZVMn) in heavy metal removal is well-established, their combined synergistic potential for antimony (Sb) remediation from wastewater has remained largely unexplored. Addressing this gap, this study introduced a magnetic zero-valent iron-manganese bimetallic material (ZVIM), synthesized via the borohydride reduction method, to investigate its capabilities and underlying mechanisms for Sb reduction and adsorption. The ZVIM, characterized by a high specific surface area of 220 m²/g, exhibited a high adsorption capacity (614.6 mg/g for Sb(III) and 241.7 mg/g for Sb(V)), facilitating over 96.7 % removal for both Sb(III) and Sb(V). The adsorption conformed to the pseudo-second-order kinetic model, and the isotherm data aligned with the Freundlich model, indicative of a heterogeneous adsorption process. The removal of Sb(III) predominantly occurred via surface complexation and electrostatic adsorption to the positively charged ZVIM surface, accompanied by a partial oxidation of Sb(III) to Sb(V). In contrast, the elimination of Sb(V) was primarily facilitated through surface complexation mechanism, encompassing both reduction and electrostatic adsorption. The outcomes of this study shed light on the intricate interactions between Sb species and the ZVIM, revealing the material as a promising candidate for the efficacious removal of Sb from wastewater.

Engineering (FeSn)/S nanocubes heterojunctions for improved sodium ion battery performance

Transition metal sulfides have emerged as compelling anode materials for sodium-ion batteries (SIBs), leveraging their abundant elemental reserves and high theoretical capacities. However, the reaction of sulfur with Na ions is usually accompanied by significant volume dilation, which hinders their further development and application. Hence, constructing bimetallic sulfide (FeSn)/S for SIBs anode material greatly alleviates the circulation attenuation caused by volume expansion. Through constructing bimetallic heterojunction materials from nanocube precursors, the (FeSn)/S anode material retains a high specific capacity of 578 mAh/g at an intense current density of 2 A/g after 1000 cycles, and exhibits an great rate capability, delivering 796 mAh/g at 100 mA/g. The excellent electrochemical performance of the heterojunction material presents a promising solution to the enduring quest for enhanced anode material for SIBs.

“Enhancing electrochemical performance of Fe@Ir/GQDs electrodes with MoS₂ for advanced energy storage and hydrogen evolution Reaction”

Metal-organic frameworks (MOFs) have unique properties that make them important in energy storage systems. The layered structure, edge locations, wide surface area, and closeness impact of MoS2/GQDs nanostructures enhance their ability for energy storage. We are effectively utilizing the hydrothermal technique to synthesize Fe@Ir-MOF/MoS2/GQDs, a new composite electrode material for supercapattery energy storage devices. Using a three-electrode setup, we are assessing the electrochemical performance of Fe@Ir-MOF, Fe@Ir-MOF/MoS2, and Fe@Ir-MOF/MoS2/GQDs. Fe@Ir-MOF/MoS2/GQDs is showing exceptional electrochemical qualities, demonstrating an excellent specific capacity of 1104C/g in an electrolyte solution containing 1 M KOH. The Ir@Fe-MOF/MoS2/GQDs is exhibiting energy and power density of around 53 W h kg−1 and 2652 W kg−1, respectively. A Coulombic efficiency of 92.23 % and 96.14 % of capacity are being maintained by the Fe@Ir-MOF/MoS2/GQDs//AC material after 5000 cycles of alternative GCD measurements. The results of this work are showing that supercapattery applications can benefit from the new electrode material Fe@Ir-MOF/MoS2/GQDs. The HER is having a lower potential barrier of 32.12 mV dec-1 with a 130 mV overpotential at −10 mA cm−2 due to the Fe@Ir-MOF/MoS2/GQDs composite. This work is providing a way to develop effective bimetallic MOFs nanocomposite materials for use in biomedical and future energy storage systems.