Fe-Ni Alloys Research Articles

An Angstrom‐Scale Protective Skin Grown In Situ on Perovskite Oxide to Enhance Stability in Water

AbstractThe utilization of perovskite oxide as a catalyst for aqueous reactions is promising but challenging in stability. Here, we propose an in situ growth strategy that constructs an ultrathin protective skin on the Sr0.9Fe0.81Ta0.09Ni0.1O3‐δ perovskite surface and thus effectively solves the stability issue. Using a spherical aberration‐corrected transmission electron microscope, we observe the coexistence of an angstrom‐scale (~7 Å) Fe2O3 protective skin and FeNi alloy nanoparticles. A number of alloy nanoparticles grow along with the skin and uniformly take root on the skin surface. Such a hierarchical structure can reconstruct the surface electronic structure and suppress the ion leaching of perovskite oxide in water. Benefiting from this unique structure, the catalyst has experienced a substantial increase (800 h, more than three orders of magnitude) in its stable operation time in water (for example, in a hydrogen evolution reaction). These results provide valuable insight into solid‐solid phase transitions and have substantial implications for using structural defects at surfaces to modulate mass transport and transformation kinetics. Our strategy is sufficiently simple and can be used to subtly manipulate the catalyst structures to improve the performance of perovskite‐based catalysts and potentially other oxide catalysts for a wide range of reactions.

In Situ Anodic Transition and Cathodic Contamination Affect the Overall Voltage of Alkaline Water Electrolysis

NiFe (oxy)hydroxide has been widely used as a benchmark anodic catalyst for oxygen evolution reactions (OERs) in alkaline water electrolysis devices; however, the energy saving actually takes contributions from both the anodic OER and cathodic hydrogen evolution reaction (HER). In this work, we observe the catalytic promotion upon the in situ-derived NiFe (oxy)hydroxide from the NiFe alloy monolithic electrode and also point out that the coupled nickel cathode is contaminated, leading to the loss of HER activity and a reduction in overall efficiency. It is found that Ni2+ and Fe3+ cations are inevitably detached from the anode into the electrolyte and electrodeposited on the nickel cathode after the three-month industrial simulation. This research presents the significant enhancement of the oxygen evolution catalysis using an in situ aging process and emphasizes that the catalytic application should not only be isolated on the half reaction, but a reasonable coupled electrode match to get rid of the contamination from the electrolyte is also of great significance to sufficiently present the intrinsic catalytic yielding for the real application.

Breaking the Limitations of Activity and Stability in Powdered Materials for Oxygen Evolution Reaction: The Critical Role of Catalyst-Inducing Seeds

Powdered catalysts are extensively employed in industrial-scale energy conversion devices but struggle with weak powder-substrate adhesion and inherent instability in gas-evolving and highly oxidative oxygen evolution reactions (OER). This work introduces an innovative strategy in which powdered materials serve a critical role as catalyst-inducing seeds to break these limitations. Specifically, powdered Ti2CTx MXene with anchored cobalt single atoms (Co-SAs) shows negligible catalytic activity on its own but serves as catalyst-inducing seeds, significantly enhancing the catalytic activity of the conductive FeNi substrate. Mechanistic studies demonstrate that Co-SAs accelerate the oxidation rate of Ti2CTx, leading to the micro-battery corrosion behavior between oxidized Co/Ti2CTx and FeNi alloy, which generates highly OER-active corrosion products tightly bonded to FeNi alloy, thereby enhancing catalytic activity and ensuring stability. The prepared porous electrode shows a low overpotential of 303mV to deliver an ultra-high current density of 1000mAcm-2 and maintains activity for 1200hours under high current density conditions, rivaling advanced self-supporting electrodes. Moreover, replacing Co in Co/Ti2CTx with metals like Fe, Ni or Mn, yields comparable effects, suggesting the scalability of catalyst-inducing seeds. This approach breaks traditional limitations of powdered materials in OER, offering an effective pathway to engineer advanced catalytic electrodes.

Iron and nickel based alloy nanoparticles anchored on phosphorus-modified carbon-nitrogen plane enhances electrochemical nitrate reduction to ammonia

The catalysts of iron and nickel nanoparticles anchored on carbon–nitrogen plane (FeNi-CN) are considered as the potential candidates for promising electrochemical nitrate reduction to ammonia (ENO3RR). However, the high d-orbital energy levels of iron and nickel sites coordinated with nitrogen atoms often lead to overly strong adsorption of reaction intermediates on active sites, severely limiting the improvement of catalytic performance. Herein, a catalyst FeNi3@P-NC consisting FeNi3 alloy nanoparticles confined in phosphorus (P)-modified carbon–nitrogen plane is successfully fabricated, where the electron withdrawal effect induced by P on the carbon–nitrogen plane decreases the d-orbital energy, and optimizes the d-band center of FeNi alloy, thus weakening the overly strong adsorption of intermediates at the metal-N sites and thereby improving NO3RR activity. The prepared FeNi3@P-NC catalyst exhibits exceptional NO3RR performance with a 93 ± 4.5 % Faradaic efficiency of NH3 production (FENH3) and a high NH3 yield rate (YNH3) of 9633 ± 227.3 μg h−1 cm−2 at −0.7 V versus Reversible Hydrogen Electrode (vs. RHE) under alkaline medium. Importantly, FeNi3@P-NC also demonstrates superior catalytic stability and durability, which maintains stability over twenty-five successive electrochemical cycles and for 50 h of continuous electrolysis at 100 mA cm−2.

A new nanoindentation approach for determining both indentation size effect and continuous apparent activation volume during loading of nanocrystalline Ni and Ni-20 wt.% Fe alloy

A new nanoindentation approach is developed in this study to determine both indentation size effect (ISE) and continuous apparent activation volume () during loading of nanocrystalline nickel (NC Ni) and nanocrystalline nickel-20 wt.% iron alloy (NC Ni-Fe alloy). This approach involves conducting nanoindentation tests under loading modes controlled by both constant strain rate (CSR) and constant loading rate (CLR). Firstly, a new empirical expression for the parameter in the modified Nix-Gao model is established to study the strain rate dependence of the ISEs created in the CSR and CLR tests. Then, continuous data of each individual sample (indentation) during loading are obtained in the CLR test through the alternative use of continuous stiffness measurement technique. The stress dependence of is analyzed based on Duhamel et al.’s model, which considers the role of vacancies generated during inhomogeneous dislocation nucleation. Finally, based on the above experimental and theoretical work as well as transmission electron microscopy observation, the influences of loading mode, loading rate, and material properties (stacking fault energy) on resulting intrinsic hardness of NC Ni and NC Ni-Fe alloy are analyzed. The nanoindentation approach developed in this study provides profound insights into the mechanical behaviors during loading and underlying mechanisms of materials.

Decrypting Synergy of Alloy & Metal Nanoparticles Within Nitrogen-Doped Carbon Nanosheets for Zn-Air Batteries with Ultralong Cycling Stability.

The exploration of efficient, robust, and low-cost bifunctional electrocatalysts to drive the commercial application of Zn-air batteries (ZABs) is of great significance but still remains a challenge. Herein, a 1D coordination polymer (1D-CP) derived FeNi alloy & Co nanoparticles (NPs) co-implanted N-doped carbon nanosheets (FNC/NCS) is judiciously crafted and employed as a high-performance electrocatalyst for ultralong lifetime ZABs. The key to this strategy is the leveraging of metal-coordinated melamine to direct the pyrolysis of 1D-CP, enabling the in situ formation of well-dispersed FeNi alloy and Co NPs within the carbon matrix. The resulting FNC/NCS exhibits prominent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity with a small overall oxygen potential difference (ΔE = 0.68V). Density functional theory (DFT) simulation demonstrates that the synergistic effect between FeNi alloy and Co NPs can reduce energy barriers, promote electron transfer, and optimize the formation of crucial intermediates, thereby largely boost ORR/OER activity of FNC/NCS. The FNC/NCS-assembled ZABs possess high specific capacity, large power density, and ultralong cycling life in both aqueous (> 3300h) and solid-state (150h) electrolytes. This work provides a viable strategy for 1D-CP-derived bifunctional electrocatalysts and dissects the synergistic effect between different metal species, affording significant guidance for the development of renewable energy materials.

Self-Adaptive Layering Structure of Nanoconfined Fe-Ni Liquids: Origin of the Liquid-Liquid Phase Transition.

Metallic liquids under confinement exhibit different properties compared to those of their corresponding bulk phases, such as miscibility, diffusion, and phase transitions. Unfortunately, the challenges in experimentally characterizing Fe-Ni liquids at the nanoscale and the high cost of first-principles simulations hindered the atom-level understanding that is necessary for controlling Fe-Ni liquids. Here, we report a comprehensive molecular dynamics study of the liquid Fe-Ni alloy confined within nanoslits. Driven by the slit size, the confined Fe-Ni liquid experiences the liquid-liquid phase transition (LLPT) that is characterized by layering transitions. Interestingly, during the LLPT, a transition liquid phase appears, separating two layering phases, which is accompanied by abnormal variations in density, potential energy, and pressure perpendicular to the wall. The Voronoi cluster analysis reveals a self-adaptive local structural evolution in confined Fe-Ni liquids during the LLPT. The effect of temperature, pressure, and composition on the LLPT is investigated. Based on the pressure-confinement phase diagram, the LLPT is mainly induced by confinement under high pressure, while under low pressure, the LLPT is mainly pressure-driven. Our research will stimulate more interest in the phase transition under confinement in a metallic system.

On the Strengthening Mechanism in Lath Martensite of As-Quenched Fe–Ni Alloys

On the Strengthening Mechanism in Lath Martensite of As-Quenched Fe–Ni Alloys

Exploring multimetal interactions between FeNi3 alloy and Lu3Ga5O12 metal oxide for improved water splitting performance

The production of energy from fossil fuels generates greenhouse gases, leading to global warming and various environmental impacts. Extensive research into sustainable alternative fuels has identified hydrogen (H2) as a viable option. With net zero carbon emissions, hydrogen presents a promising solution for sustainable and renewable energy. This study employs a simple gel-matrix method to fabricate Ni-Fe alloy-based nanocomposites in alkaline media (1 M KOH). Achieving outstanding performance in hydrogen generation through the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with impressive turn-over frequencies (TOF) of 2.98 s−1 at 177 mV and 1.48 s−1 at 219 mV. Nanocomposite’s unique structure enhances electroactive surface area (347.5 cm2/gram), extending electrocatalytic active sites and durability to 60 h. It shows excellent performance, characterized by low Tafel slopes of 50 mV/dec and 37 mV/dec, and minimal overpotentials of 219 mV for the oxygen evolution reaction (OER) and 177 mV for the hydrogen evolution reaction (HER), reaching a current density of 10 mA cm−2. This study presents a method for synthesizing high-performance, sustainable metal-alloy/garnet hybrid electrocatalysts, offering a new frontier in design of next-generation materials for advanced energy conversion technologies.

Substrate and potential-driven surface morphology of bifunctional Ni-Fe electrode for efficient alkaline water electrolysis

Nickel-iron (Ni-Fe) alloy electrodes are synthesized using chronoamperometry. The influence of substrate type (copper, stainless steel, and nickel) and deposition potential on the structural, morphological, and electrocatalytic characteristics are systematically investigated. X-ray diffraction (XRD) analysis revealed the formation of a face-centered cubic (FCC) Ni-Fe alloy. Electrodeposition at higher potential (−1.45 V) forms well-defined nanoflakes, whereas electrodeposition at lower potential (−1.00 V) results aggregated Ni-Fe particles. The Ni-Fe alloy electrodes having well-defined nanoflakes demonstrated superior electrocatalytic performance, exhibiting a overpotential of −168 mV vs. RHE for the hydrogen evolution reaction (HER) and 236 mV vs. RHE for the oxygen evolution reaction (OER), at current density of 10 mA/cm2. The enhanced electrocatalytic activity of the nanoflakes based Ni-Fe alloy is attributed due to their larger catalytic surface area, porous morphology and higher Fe concentration. The Ni-Fe alloy electrodes displayed bifunctional electrocatalytic behavior, making them highly suitable for both HER and OER processes.

FeNi3 alloy doped carbon spheres for improving hydrogen storage performance of MgH2

MgH2 is one of the ideal hydrogen storage materials because of its high hydrogen storage density, but the thermodynamic stability and slow kinetics of Mg/MgH2 system hinder its practical application. Transition metal catalyst doping has become an important strategy to improve the hydrogen storage kinetics of MgH2. In this work, FeNi3@CS was prepared by solvothermal method with carbon spheres (CS) as the support, and introduced into Mg/MgH2 system to prepare MgH2–FeNi3@CS composite. The initial dehydrogenation temperature of MgH2–FeNi3@CS composite is 565 K, which is 100 K lower than additive-free MgH2. At 423 K, MgH2–FeNi3@CS composite could absorb 4.5 wt% H2, while the hydrogen absorption capacity of MgH2 without additives is only 2.0 wt%. After 10 cycles, the hydrogenation and dehydrogenation capacity could be maintained at 5.6 wt% and 4.5 wt%, respectively. In addition, the activation energy of MgH2–FeNi3@CS composite decreased by 52 kJ/mol compared with MgH2. FeNi3 was in situ converted to Mg2NiH4 and Fe after hydrogenation-ball milling, which were considered as the catalytic active substances in Mg/MgH2 system. The synergistic catalysis of Mg2Ni/Mg2NiH4, Fe and carbon materials has a positive effect on improving the hydrogen storage performance of Mg/MgH2 system.

An Angstrom-Scale Protective Skin Grown In Situ on Perovskite Oxide to Enhance Stability in Water.

The utilization of perovskite oxide as a catalyst for aqueous reactions is promising but challenging in stability. Here, we propose an in situ growth strategy that constructs an ultrathin protective skin on the Sr0.9Fe0.81Ta0.09Ni0.1O3-δ perovskite surface and thus effectively solves the stability issue. Using a spherical aberration-corrected transmission electron microscope, we observe the coexistence of an angstrom-scale (~7 Å) Fe2O3 protective skin and FeNi alloy nanoparticles. A number of alloy nanoparticles grow along with the skin and uniformly take root on the skin surface. Such a hierarchical structure can reconstruct the surface electronic structure and suppress the ion leaching of perovskite oxide in water. Benefiting from this unique structure, the catalyst has experienced a substantial increase (800 h, more than three orders of magnitude) in its stable operation time in water (for example, in a hydrogen evolution reaction). These results provide valuable insight into solid-solid phase transitions and have substantial implications for using structural defects at surfaces to modulate mass transport and transformation kinetics. Our strategy is sufficiently simple and can be used to subtly manipulate the catalyst structures to improve the performance of perovskite-based catalysts and potentially other oxide catalysts for a wide range of reactions.

Oxidation behavior of Fe-Ni Invar alloy under high pressure: A ReaxFF molecular dynamics study

The Fe-Ni Invar alloy is often employed under extreme conditions such as high temperatures, high pressures, and corrosive environments, making it susceptible to oxidation and subsequent failure. Hence, a thorough understanding of its oxidation behavior is crucial. We performed ReaxFF-based molecular dynamics (MD) simulations to study the oxidation behaviour of Fe-Ni Invar alloy at the atomic scale under extreme conditions. The initial stage of oxidation involves the preferential adsorption and dissociation of O2, demonstrating its surface-site selectivity. The initial oxidation kinetics follows a logarithmic law, and the whole oxidation process results in dominant low-coordinated clusters configurations in the oxide film. Simultaneously, Fe atoms tend to donate more electrons to O atoms than Ni atoms. Moreover, the O2 consumption rate were found to increase with pressure and amorphous oxides formed more readily under high pressure. Our results indicate that adjusting the pressure may enhance the oxidation resistance of the Fe-Ni alloy, which is significant for the design and application of alloys in extreme conditions.

Supergene formation of sulfur-rich, tochilinite-bearing serpentinites in the Oman ophiolite

Mass transfer processes between fluids and ultramafic rocks produce subsurface environments encompassing a wide range of redox conditions. A notable locality where an extensive range of redox conditions is observed in one location is Hole BA1B, a ∼ 400 m borehole drilled by the Oman Drilling Project. A sulfur-enriched serpentinite zone, containing up to 0.6 wt% S, occurs between shallow oxidized serpentinites (<30 m) and deep partially serpentinized harzburgite (>150 m). All three alteration zones are predominantly composed of serpentine. However, microanalysis of samples from the sulfur-enriched zone shows that mesh textures after olivine are composed of serpentine, brucite, and tochilinite mixtures, yielding optically black thin-section samples that characterize this sulfidic zone. It is proposed that sulfur accumulates in this zone via a process similar to those found in supergene ore deposits. Reaction-path models show that at shallow conditions open to atmospheric input, sulfur is mobilized via oxidative weathering of serpentinized dunite and harzburgite. Sulfate-bearing fluids percolate deeper and react with host rocks in a system closed to atmospheric input. As fluids become more reduced, dissolved sulfate is precipitated as sulfide minerals yielding rocks with ∼0.4 wt% S, like those observed in Hole BA1B. Despite enrichment of S in the sulfidic zone in Hole BA1B, Ni and Co contents are uniform throughout all three layers in the borehole. This is consistent with model results which show that Ni (and, by analogy, Co) is less mobile than S, and can be hosted in serpentine and NiFe alloys in addition to sulfides. The sulfur enrichment process may occur abiotically. However, sulfide enrichment via microbial reduction of sulfate and other sulfur species can also facilitate the formation of the sulfidic zone. Bioenergetic calculations show that abundant energy is available for sulfur reducing microbes, consistent with previous work demonstrating the presence of active, sulfate-reducing microorganisms in Hole BA1B and other nearby boreholes. This suggests that the observed sulfur enrichment is an ongoing process. Overall, this work shows that variable redox conditions are attained as fluids percolate and react with serpentinized ultramafic rocks at variable extents of interaction between aquifer fluids, host ultramafic rocks, and the atmosphere.

CeO2 enhanced performance of NiFe2O4-CaO for carbon capture and in-situ hydrogenation conversion to CO

NiFe2O4 exhibits excellent redox properties and is widely applied in CaO-NiFe2O4 chemical looping processes. However, rapid sintering of Ni-Fe alloy under reaction conditions limited its industrial applications. The CeO2-NiFe-CaO were synthesized through a physical mixing method with NiFe2O4 as a precursor, and its CO2 capture capacity and in-situ hydrogenation performance were conducted on ICCC-RWGS reaction under different conditions. 20CeO2-NiFe-CaO exhibited a CO yielding of 9.35 mmol/g at 650 °C. During the carbon capture stage, CO2 was adsorbed by CaO, leading to the formation of CaCO3. In the hydrogenation conversion stage, hydroxyl groups were generated on the surface, combining with CaCO3 to produce formate species, further generating H2O and CO. 15CNF-CaO exhibited superior cyclic ICCC-RWGS reaction performance compared to 15NF-CaO, with a CO yield of 1.88 mmol/g after 40 cycles. CeO2 inhibited the sintering of catalytic components, preserving a higher specific surface area and smaller particle size. Furthermore, CeO2 in 15CNF-CaO inhibited carbon deposition and enhanced in-situ hydrogenation performance, exhibiting better CaO regeneration capability and better cyclic stability. These results could provide insight for designing the DFMs for the ICCC-RWGS process.

CeO2-confined Ni-Fe alloy enhanced high-temperature CO2 hydrogenation to CO

NiFe2O4 exhibits excellent redox properties and is widely applied in catalytic reactions. However, rapid inactivation under reaction conditions limited its industrial applications. In this study, CeO2-NiFe2O4 composite catalysts were synthesized, and the Reverse Water Gas Shift (RWGS) reaction was measured to reveal its CO2 hydrogenation performance under a high-temperature condition. NiFe2O4 catalysts got deactivated after being reduced to Fe-Ni alloy at 700 °C, decreasing the CO2 conversion rate. CeO2 addition can significantly improve its high-temperature activity, and 20CeO2-NiFe2O4 exhibited the best catalytic activity (80.85 %, 700 °C). The CeO2-confined maintained Ni-Fe alloy with a relatively small crystal size and larger specific surface area, supporting more active sites for CO2 hydrogenation. CeO2 addition induced higher oxygen vacancy concentration, enhancing CO2 activation and formates species formed on 20CeO2-NiFe2O4, resulting in higher CO2 conversion activity. In addition, 20CeO2-NiFe2O4 maintained its catalytic stability for 50 h at 700 °C. The CeO2 confined enhanced the high-temperature stability of Fe-Ni alloy. CeO2 and formed CeFeO3 dispersed in 20CeO2-NiFe2O4 inhibited excessive aggregation of Fe-Ni alloy, and CeO2 inhibited carbon deposition on Fe-Ni alloy, improving Fe-Ni alloy’s reaction stability under RWGS reaction conditions. CeO2 confined may give insight into improving metal stability under high-temperature and reductive conditions in heterogeneous catalysis.

Influence of hydrogen on the elastic properties and dislocation behavior in Fe–Cr and Fe–Ni alloys by DFT calculations

The effect of interstitial hydrogen on the elastic properties of bcc Fe, bcc Fe–Cr, and bcc Fe–Ni was investigated using density functional theory calculations. Our results indicate that the elastic moduli decrease linearly with increasing hydrogen concentration. The consequences of hydrogen for the mechanical properties of bcc Fe, bcc Fe–Cr, and bcc Fe–Ni were analyzed, considering various factors such as the ideal shear stress, Peierls stress, number of dislocation pile-ups, and critical crack growth lengths. At the same hydrogen concentration, compared to the bcc Fe and bcc Fe–Ni systems, fewer dislocation pile-ups and shorter critical crack growth lengths can facilitate the nucleation and propagation of cracks in the bcc Fe–Cr system. Finally, we propose a mechanism to explain the influence of Cr and Ni on hydrogen embrittlement.

Boosting the Performance and Stability of Perovskites by Construction of NiFe Alloy and PrOx Heterogeneously Structured Composites for High‐Performance Solid Oxide Fuel Cell Anode

Boosting the Performance and Stability of Perovskites by Construction of NiFe Alloy and PrO_x Heterogeneously Structured Composites for High‐Performance Solid Oxide Fuel Cell Anode

Computational Investigation on the Structural, Electronic and Magnetic Properties of Si-Doped L10 FeNi Alloy for Clean Energy

For the first time, this study conducts a computational analysis by employing density functional theory (DFT) to investigate the effects of silicon doping as substitutional defects on the structural, electronic, and magnetic characteristics of the L10-FeNi alloy. The aim of this study was to explore the potential applications of Si-doped FeNi compounds as alternatives to rare-earth permanent magnets. For this, we have performed full potential calculations of L10-FeNi with substitutional Si-doping within a generalized gradient approximation. Two types of substitutional Si-doping (ONi/OFe) in the Ni/Fe site of the parent alloy have been investigated. The computed formation energy (Ef) indicates that the incorporation of silicon defects increases the structural stability of tetragonally distorted L10-FeNi. Moreover, our findings demonstrate that the FeNi:Si(ONi) in the L10-structure has a stable saturation magnetization (Ms), whereas the FeNi:Si (OFe) has a small reduction in Ms. Therefore, Si-substituted FeNi alloys can be tuned to become a good candidate for permanents magnets.

Plasma Spheroidization of Al–Zn–Mg–Fe–Ni Alloy Powders for Selective Laser Melting

Plasma Spheroidization of Al–Zn–Mg–Fe–Ni Alloy Powders for Selective Laser Melting