Quantifying chemical short-range order in metallic alloys.

Metallic alloys often form phases-known as solid solutions-in which chemical elements are spread out on the same crystal lattice in an almost random manner. The tendency of certain chemical motifs to be more common than others is known as chemical short-range order (SRO), and it has received substantial consideration in alloys with multiple chemical elements present in large concentrations due to their extreme configurational complexity (e.g., high-entropy alloys). SRO renders solid solutions "slightly less random than completely random," which is a physically intuitive picture, but not easily quantifiable due to the sheer number of possible chemical motifs and their subtle spatial distribution on the lattice. Here, we present a multiscale method to predict and quantify the SRO state of an alloy with atomic resolution, incorporating machine learning techniques to bridge the gap between electronic-structure calculations and the characteristic length scale of SRO. The result is an approach capable of predicting SRO length scale in agreement with experimental measurements while comprehensively correlating SRO with fundamental quantities such as local lattice distortions. This work advances the quantitative understanding of solid-solution phases, paving the way for the rigorous incorporation of SRO length scales into predictive mechanical and thermodynamic models.

Exceptional enhancement of mechanical properties in high-entropy alloys via thermodynamically guided local chemical ordering.

Understanding the local chemical ordering propensity in random solid solutions, and tailoring its strength, can guide the design and discovery of complex, paradigm-shifting multicomponent alloys. First, we present a simple thermodynamic framework, based solely on binary enthalpies of mixing, to select optimal alloying elements to control the nature and extent of chemical ordering in high-entropy alloys (HEAs). Next, we couple high-resolution electron microscopy, atom probe tomography, hybrid Monte-Carlo, special quasirandom structures, and density functional theory calculations to demonstrate how controlled additions of Al and Ti and subsequent annealing drive chemical ordering in nearly random equiatomic face-centered cubic CoFeNi solid solution. We establish that short-range ordered domains, the precursors of long-range ordered precipitates, inform mechanical properties. Specifically, a progressively increasing local order boosts the tensile yield strengths of the parent CoFeNi alloy by a factor of four while also substantially improving ductility, which breaks the so-called strength-ductility paradox. Finally, we validate the generality of our approach by predicting and demonstrating that controlled additions of Al, which has large negative enthalpies of mixing with the constituent elements of another nearly random body-centered cubic refractory NbTaTi HEA, also introduces chemical ordering and enhances mechanical properties.

Fluctuations in local shear-fault energy produce unique and dominating strengthening in metastable complex concentrated alloys.

Local chemical short-range ordering (SRO) and spatial fluctuations of planar fault energy are important features of multi-element and metastable complex concentrated alloys (CCAs). Arising from them, dislocations in such alloys are distinctively wavy in both static and migrating conditions; yet, such effects on strength have remained unknown. In this work, molecular dynamics simulations are used to show that the wavy configurations of dislocations and their jumpy motion in a prototypic CCA of NiCoCr are due to the local fluctuations of the energy of SRO shear-faulting that accompanies dislocation motion, with the dislocation getting pinned at sites of hard atomic motifs (HAMs) associated with high local shear-fault energies. Unlike the global averaged shear-fault energy which in general will subdue on successive dislocation passes, the local fluctuations in the fault energy always remain in a CCA, thus offering a strength contribution that is unique in such alloys. Analysis of the magnitude of this form of dislocation resistance shows that this is dominating over contributions due to elastic misfit of alloying elements and is in good agreement with strengths predicted from molecular dynamics simulations and experiments. This work has unfolded the physical basis of strength in CCAs, which is important for the development of these alloys into useful structural materials.

Unlocking the Potential of High Entropy Alloys in Electrochemical Water Splitting: A Review.

The global pursuit of sustainable energy is focused on producing hydrogen through electrocatalysis driven by renewable energy. Recently, High entropy alloys (HEAs) have taken the spotlight in electrolysis due to their intriguing cocktail effect, broad design space, customizable electronic structure, and entropy stabilization effect. The tunability and complexity of HEAs allow a diverse range of active sites, optimizing adsorption strength and activity for electrochemical water splitting. This review comprehensively covers contemporary advancements in synthesis technique, design framework, and physio-chemical evaluation approaches for HEA-based electrocatalysts. Additionally, it explores design principles and strategies aimed at optimizing the catalytic activity, stability, and effectiveness of HEAs in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and overall water splitting. Through an in-depth investigation of these aspects, the complexity inherent in constituent element interactions, reaction processes, and active sites associated with HEAs is aimed to unravel. Eventually, an outlook regarding challenges and impending difficulties and an outline of the future direction of HEA in electrocatalysis is provided. The thorough knowledge offered in this review will assist in formulating and designing catalysts based on HEAs for the next generation of electrochemistry-related applications.

Enthralling Anodic Protection by Molybdate on High-Entropy Alloy-Based Electrocatalyst for Sustainable Seawater Oxidation.

Efficient and sustainable seawater electrolysis is still limited due to the interference of chloride corrosion at the anode. The designing of suitable electrocatalysts is one of the crucial ways to boost electrocatalytic activity. However, the approach may fall short as achieving high current density often occurs in chlorine evolution reaction (CER)-dominating potential regions. Thereby, apart from developing an OER-active high-entropy alloy-based electrocatalyst, the present study also offers a unique way to protect anode surface under high current density or potential by using MoO4 2- as an effective inhibitor during seawater oxidation. The wide variation of d-band center of high-entropy alloy-based electrocatalyst allows great oxygen evolution reaction (OER) proficiency exhibiting an overpotential of 230 mV at current density of 20 mA cm-2. Besides, the electrocatalyst demonstrates impressive stability over 500 h at high current density of 1 A cm-2 or at a high oxidation potential of 2.0 V versus RHE in the presence of a molybdate inhibitor. Theoretical and experimental studies reveal MoO4 2- electrostatically accumulated at anode surface due to higher adsorption ability, thereby creating a protective layer against chlorides without affecting OER.

Low-Frequency Evolution Mechanism of Customized HEAs-Based Electromagnetic Response Modes Manipulated by Carbothermal Shock.

An emerging carbothermal shock method is an ultra-convenient strategy for synthesizing high-entropy alloys (HEAs), in which the intelligent combination of carbon support and HEAs can be serve as a decisive factor for interpreting the trade-off relationship between conductive gene and dielectric gene. However, the feedback mechanism of HEAs ordering degree on electromagnetic (EM) response in 2-18 GHz has not been comprehensively demystified. Herein, while lignin-based carbon fiber paper (L-CFP) as carbon support, L-CFP/FeCoNiCuZn-X with is prepared by carbothermal shock method. The reflection loss of -82.6 dB with thickness of 1.31 mm is achieved by means of pointing electron enrichment within L-CFP/FeCoNiCuZn HEAs heterointerfaces verified by theoretical calculations. Simultaneously, low-frequency evolution with high-intensity and broadband EM response relies on a "sacrificing" strategy achieved by construction of polymorphic L-CFP/semi-disordered-HEAs heterointerfaces. The practicality of L-CFP/FeCoNiCuZn-X in complex environments is given prominence to thermal conductivity, hydrophobicity, and electrocatalytic property. This work is of great significance for insightful mechanism analysis of HEAs in the application of electromagnetic wave absorption.

Highly Dispersed Ultrasmall High-Entropy Alloys Nanoparticles as Efficient Electrocatalysts for Oxygen Reduction in Acidic Media.

High-entropy alloys nanoparticles (HEAs NPs) have gained considerable attention due to their extensive compositional tunability and intriguing catalytic properties. However, the synthesis of highly dispersed ultrasmall HEAs NPs remains a formidable challenge due to their inherent thermodynamic instability. In this study, highly dispersed ultrasmall (ca. 2 nm) PtCuGaFeCo HEAs NPs are synthesized using a one-pot solution-based method at 160 °C and atmospheric pressure. The PtCuGaFeCo NPs exhibit good catalytic activity for the oxygen reduction reaction (ORR). The half-wave potential relative to the reversible hydrogen electrode (RHE) reaches 0.88 V, and the mass activity and specific activity are approximately six times and four times higher than that of the commercial Pt/C catalyst. Based on X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analyses, the surface strain and optimized coordination environments of PtCuGaFeCo have led to high ORR activities in acidic media. Moreover, the ultrasmall size also plays an important role in enhancing catalytic performance. The work presents a facile and viable synthesis strategy for preparing the ultrasmall HEAs NPs, offering great potential in energy and electrocatalysis applications through entropy engineering.

Unique Hierarchically Structured High-Entropy Alloys with Multiple Adsorption Sites for Rechargeable Li-CO2 Batteries with High Capacity.

Lithium-carbon dioxide (Li-CO2) batteries offer the possibility of synchronous implementation of carbon neutrality and the development of advanced energy storage devices. The exploration of low-cost and efficient cathode catalysts is key to the improvement of Li-CO2 batteries. Herein, high-entropy alloys (HEAs)@C hierarchical nanosheet is synthesized from the simulation of the recycling solution of waste batteries to construct a cathode for the first time. Owing to the excellent electrical conductivity of the carbon material, the unique high-entropy effect of the HEAs, and the large number of catalytically active sites exposed by the hierarchical structure, the FeCoNiMnCuAl@C-based battery exhibits a superior discharge capability of 27664 mAh g-1 and outstanding durability of 134 cycles as well as low overpotential with 1.05 V at a discharge/recharge rate of 100 mA g-1. The adsorption capacity of different sites on the HEAs is deeply understood through density functional theory calculations combined with experiments. This work opens up the application of HEAs in Li-CO2 batteries catalytic cathodes and provides unique insights into the study of adsorption active sites in HEAs.

Ultra-Small High-Entropy Alloy as Multi-Functional Catalyst for Ammonia Based Fuel Cells.

Ammonia fuel cells using carbon-neutral ammonia as fuel are regarded as a fast, furious, and flexible next-generation carbon-free energy conversion technology, but it is limited by the kinetically sluggish ammonia oxidation reaction (AOR), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER). Platinum can efficiently drive these three types of reactions, but its scale-up application is limited by its susceptibility to poisoning and high cost. In order to reduce the cost and alleviate poisoning, incorporating Pt with various metals proves to be an efficient and feasible strategy. Herein, PtFeCoNiIr/C trifunctional high-entropy alloy (HEA) catalysts are prepared with uniform mixing and ultra-small size of 2 ± 0.5 nm by Joule heating method. PtFeCoNiIr/C exhibits efficient performance in AOR (Jpeak = 139.8 A g-1 PGM), ORR (E1/2 = 0.87 V), and HER (E10 = 20.3 mV), outperforming the benchmark Pt/C, and no loss in HER performance at 100 mA cm-2 for 200 h. The almost unchanged E1/2 in the anti-poisoning test indicates its promising application in real fuel cells powered by ammonia. This work opens up a new path for the development of multi-functional electrocatalysts and also makes a big leap toward the exploration of cost-effective device configurations for novel fuel cells.

Rational Design Strategy for High-Valence Metal-Driven Electronically Modulated High-Entropy Co-Ni-Fe-Cu-Mo (Oxy)Hydroxide as Superior Multifunctional Electrocatalysts.

Creating durable and efficient multifunctional electrocatalysts capable of high current densities at low applied potentials is crucial for widespread industrial use in hydrogen production. Herein, a Co-Ni-Fe-Cu-Mo (oxy)hydroxide electrocatalyst with abundant grain boundaries on nickel foam using a scalable coating method followed by chemical precipitation is synthesized. This technique efficiently organizes hierarchical Co-Ni-Fe-Cu-Mo (oxy)hydroxide nanoparticles within ultrafine crystalline regions (<4 nm), enriched with numerous grain boundaries, enhancing catalytic site density and facilitating charge and mass transfer. The resulting catalyst, structured into nanosheets enriched with grain boundaries, exhibits superior electrocatalytic activity. It achieves a reduced overpotential of 199 mV at 10 mA cm2 current density with a Tafel slope of 48.8 mV dec1 in a 1 m KOH solution, maintaining stability over 72 h. Advanced analytical techniques reveal that incorporating high-valency copper and molybdenum elements significantly enhances lattice oxygen activation, attributed to weakened metal-oxygen bonds facilitating the lattice oxygen mechanism (LOM). Synchrotron radiation studies confirm a synergistic interaction among constituent elements. Furthermore, the developed high-entropy electrode demonstrates exceptional long-term stability under high current density in alkaline environments, showcasing the effectiveness of high-entropy strategies in advancing electrocatalytic materials for energy-related applications.

Design and Development of Stable Nanocrystalline High-Entropy Alloy: Coupling Self-Stabilization and Solute Grain Boundary Segregation Effects.

Grain growth is prevalent in nanocrystalline (NC) materials at low homologous temperatures. Solute element addition is used to offset excess energy that drives coarsening at grain boundaries (GBs), albeit mostly for simple binary alloys. This thermodynamic approach is considered complicated in multi-component alloy systems due to complex pairwise interactions among alloying elements. Guided by empirical and GB-segregation enthalpy considerations for binary-alloy systems, a novel alloy design strategy, the "pseudo-binary thermodynamic" approach, for stabilizing NC-high entropy alloys (HEAs) and other multi-component-alloy variants is proposed. Using Al25Co25Cr25Fe25 as a model-HEA to validate this approach, Zr, Sc, and Hf, are identified as the preferred solutes that would segregate to HEA-GBs to stabilize it against growth. Using Zr, NC-Al25Co25Cr25Fe25 HEAs with minor additions of Zr are synthesized, followed by annealing up to 1123 K. Using advanced characterization techniques- in situ X-ray diffraction (XRD), scanning/transmission electron microscopy (S/TEM), and atom probe tomography, nanograin stability due to coupling self-stabilization and solute-GB segregation effects is reported in HEAs up to substantially high temperatures. The self-stabilization effect originates from the preferential GB-segregation of constituent HEA-elements that stabilizes NC-Al25Co25Cr25Fe25 up to 0.5Tm (Tm-melting temperature). Meanwhile, solute-GB segregation originates from Zr segregation to NC-Al25Co25Cr25Fe25 GBs; this results in further stabilization of the phase and grain-size (≈14 nm) up to ≈0.58 and ≈0.64Tm, respectively.

Magnetically driven short-range order can explain anomalous measurements in CrCoNi.

The presence, nature, and impact of chemical short-range order in the multi-principal element alloy CrCoNi are all topics of current interest and debate. First-principles calculations reveal that its origins are fundamentally magnetic, involving repulsion between like-spin Co-Cr and Cr-Cr pairs that is complemented by the formation of a magnetically aligned sublattice of second-nearest-neighbor Cr atoms. Ordering models following these principles are found to predict otherwise anomalous experimental measurements concerning both magnetization and atomic volumes across a range of compositions. In addition to demonstrating the impact of magnetic interactions and resulting chemical rearrangement, the possible explanation of experiments would imply that short-range order of this type is far more prevalent than previously realized.

Microstructure and wear behaviour of AlCoCrFeNi-coated SS316L by atmospheric plasma spray process.

The capacity to endure harsh wear in demanding conditions in stainless steel drops under extreme nature and applications. Protecting the surface by providing a coating layer supports the usage in harsh conditions. In this work, SS316L is coated with AlCoCrFeNi high-entropy alloy (HEA) by atmospheric plasma spray process and annealed at 600°C for 2 hours. The AlCoCrFeNi HEA exhibited spherical particles with bcc phase and 20 µm particle size. The coating morphology revealed a uniform coating with a homogeneous distribution of HEA particles over a thickness of 150 µm. The coating post-annealing offered improved microhardness by 12% than the coated sample before annealing. The wear test was executed by varying load, sliding distance, and sliding velocity at normal temperature, 400°C and 600°C and the corresponding worn surface was analysed. The coated samples after annealing showed 57.6%, 87.5%, and 65.4% improved wear resistance at normal temperature than the coated sample before annealing at minimum levels of load, sliding velocity and distance. The wear rate of coated and annealed samples revealed 5.2%, 4.5%, and 4.4% better wear resistance at 400°C than the coated samples before annealing. The worn surface morphology showcased wear mechanisms to be delamination, abrasive wear, and oxide layer formation under all conditions.

The present work reports a novel study of plasma spraying of SS316L substrate using AlCoCrFeNi High-Entropy Alloy that marks the first attempt in analysing its hot wear performance.

Analysis of the temperature-dependent plastic deformation of single crystals of quinary, quaternary and ternary equiatomic high- and medium-entropy alloys of the Cr-Mn-Fe-Co-Ni system.

Temperature-dependent plastic deformation behaviors of single crystals of quaternary and ternary equiatomic medium-entropy alloys (MEAs) belonging to the Cr-Mn-Fe-Co-Ni system were investigated in compression at temperatures in the range 9 K to 1373 K. Their critical resolved shear stresses (CRSSs) increase with decreasing temperature below room temperature. There is also a dulling of the temperature dependence of CRSS below 77 K due to dislocation inertial effects that we attribute to a decrease in the phonon drag coefficient. These behaviors were compared with those of previously investigated single crystals of the equiatomic Cr-Co-Ni and Cr-Fe-Co-Ni MEAs, and the equiatomic Cr-Mn-Fe-Co-Ni high-entropy alloy (HEA). The temperature dependence of CRSS and the apparent activation volumes below room temperature can be well described by conventional thermal activation theories of face-centered cubic (FCC) alloys. Above 673 K, there is a small increase in CRSS, which we believe is due to elastic interactions between solutes and mobile dislocations, the so-called Portevin-Le Chatelier (PL) effect. The CRSS at 0 K was obtained by extrapolation of fitted CRSS vs. temperature curves and compared with predictions from solid solution strengthening models of HEA and MEAs.

The novelty of our work entitled 'Analysis of the temperature-dependent plastic deformation of single crystals of quinary, quaternary and ternary equiatomic high- and medium-entropy alloys of the Cr-Mn-Fe-Co-Ni system' can be summarized as follows: The temperature dependences of CRSS were experimentally deduced from bulk single crystals of the six MEAs for the first time, so that fair comparison among the FCC HEA/MEAs is made.

Enhanced Magnetocaloric Properties of the (MnNi)0.6Si0.62(FeCo)0.4Ge0.38 High-Entropy Alloy Obtained by Co Substitution.

In order to improve the magnetocaloric properties of MnNiSi-based alloys, a new type of high-entropy magnetocaloric alloy was constructed. In this work, Mn0.6Ni1-xSi0.62Fe0.4CoxGe0.38 (x = 0.4, 0.45, and 0.5) are found to exhibit magnetostructural first-order phase transitions from high-temperature Ni2In-type phases to low-temperature TiNiSi-type phases so that the alloys can achieve giant magnetocaloric effects. We investigate why chexagonal/ahexagonal (chexa/ahexa) gradually increases upon Co substitution, while phase transition temperature (Ttr) and isothermal magnetic entropy change (ΔSM) tend to gradually decrease. In particular, the x = 0.4 alloy with remarkable magnetocaloric properties is obtained by tuning Co/Ni, which shows a giant entropy change of 48.5 J∙kg-1K-1 at 309 K for 5 T and an adiabatic temperature change (ΔTad) of 8.6 K at 306.5 K. Moreover, the x = 0.55 HEA shows great hardness and compressive strength with values of 552 HV2 and 267 MPa, respectively, indicating that the mechanical properties undergo an effective enhancement. The large ΔSM and ΔTad may enable the MnNiSi-based HEAs to become a potential commercialized magnetocaloric material.

Effect of Al Content on Microstructure and Properties of AlxCr0.2NbTiV Refractory High-Entropy Alloys.

High-temperature creep refers to the slow and continuous plastic deformation of materials under the effects of high temperatures and mechanical stress over extended periods, which can lead to the degradation or even failure of the components' functionality. AlxCr0.2NbTiV (x = 0.2, 0.5, or 0.8) refractory high-entropy alloys were fabricated by arc melting. The effects of Al content on the microstructure of AlxCr0.2NbTiV alloys were studied using X-ray diffraction, scanning electron microscopy, and electron backscatter diffraction. The microhardness, compression properties, and nanoindentation creep properties of AlxCr0.2NbTiV alloys were also tested. The results show that the AlxCr0.2NbTiV series exhibits a BCC single-phase structure. As the Al content increases, the lattice constant of the alloys gradually decreases, and the intensity of the (110) crystal plane diffraction peak increases. Adding aluminum enhances the effect of solution strengthening; however, due to grain coarsening, the microhardness and room temperature compressive strength of the alloy are only slightly improved. Additionally, because the effect of solution strengthening is diminished at high temperatures, the compressive strength of the alloy at 1000 °C is significantly reduced. The creep mechanism of the alloys is predominantly governed by dislocation creep. Moreover, increasing the Al content helps to reduce the sensitivity of the alloy to the loading rate during the creep process. At a loading rate of 2.5 mN/s, the Al0.8Cr0.2NbTiV alloy exhibits the lowest creep strain rate sensitivity index (m), which is 0.0758.

Irradiation-Hardening Model of TiZrHfNbMo0.1 Refractory High-Entropy Alloys.

In order to find more excellent structural materials resistant to radiation damage, high-entropy alloys (HEAs) have been developed due to their characteristics of limited point defect diffusion such as lattice distortion and slow diffusion. Specially, refractory high-entropy alloys (RHEAs) that can adapt to a high-temperature environment are badly needed. In this study, TiZrHfNbMo0.1 RHEAs are selected for irradiation and nanoindentation experiments. We combined the mechanistic model for the depth-dependent hardness of ion-irradiated metals and the introduction of the scale factor f to modify the irradiation-hardening model in order to better describe the nanoindentation indentation process in the irradiated layer. Finally, it can be found that, with the increase in irradiation dose, a more serious lattice distortion caused by a higher defect density limits the expansion of the plastic zone.

Effect of Reduced Graphene Oxide on Microwave Absorbing Properties of Al1.5Co4Fe2Cr High-Entropy Alloys.

The microwave absorption performance of high-entropy alloys (HEAs) can be improved by reducing the reflection coefficient of electromagnetic waves and broadening the absorption frequency band. The present work prepared flaky irregular-shaped Al1.5Co4Fe2Cr and Al1.5Co4Fe2Cr@rGO alloy powders by mechanical alloying (MA) at different rotational speeds. It was found that the addition of trace amounts of reduced graphene oxide (rGO) had a favorable effect on the impedance matching, reflection loss (RL), and effective absorbing bandwidth (EAB) of the Al1.5Co4Fe2Cr@rGO HEA composite powders. The EAB of the alloy powders prepared at 300 rpm increased from 2.58 GHz to 4.62 GHz with the additive, and the RL increased by 2.56 dB. The results showed that the presence of rGO modified the complex dielectric constant of HEA powders, thereby enhancing their dielectric loss capability. Additionally, the presence of lamellar rGO intensified the interfacial reflections within the absorber, facilitating the dissipation of electromagnetic waves. The effect of the ball milling speed on the defect concentration of the alloy powders also affected its wave absorption performance. The samples prepared at 350 rpm had the best wave absorption performance, with an RL of -16.23 and -17.28 dB for a thickness of 1.6 mm and EAB of 5.77 GHz and 5.43 GHz, respectively.

Study on Microstructure and High Temperature Stability of WTaVTiZrx Refractory High Entropy Alloy Prepared by Laser Cladding.

The extremely harsh environment of the high temperature plasma imposes strict requirements on the construction materials of the first wall in a fusion reactor. In this work, a refractory alloy system, WTaVTiZrx, with low activation and high entropy, was theoretically designed based on semi-empirical formula and produced using a laser cladding method. The effects of Zr proportions on the metallographic microstructure, phase composition, and alloy chemistry of a high-entropy alloy cladding layer were investigated using a metallographic microscope, XRD (X-ray diffraction), SEM (scanning electron microscope), and EDS (energy dispersive spectrometer), respectively. The high-entropy alloys have a single-phase BCC structure, and the cladding layers exhibit a typical dendritic microstructure feature. The evolution of microstructure and mechanical properties of the high-entropy alloys, with respect to annealing temperature, was studied to reveal the performance stability of the alloy at a high temperature. The microstructure of the annealed samples at 900 °C for 5-10 h did not show significant changes compared to the as-cast samples, and the microhardness increased to 988.52 HV, which was higher than that of the as-cast samples (725.08 HV). When annealed at 1100 °C for 5 h, the microstructure remained unchanged, and the microhardness increased. However, after annealing for 10 h, black substances appeared in the microstructure, and the microhardness decreased, but it was still higher than the matrix. When annealed at 1200 °C for 5-10 h, the microhardness did not increase significantly compared to the as-cast samples, and after annealing for 10 h, the microhardness was even lower than that of the as-cast samples. The phase of the high entropy alloy did not change significantly after high-temperature annealing, indicating good phase stability at high temperatures. After annealing for 10 h, the microhardness was lower than that of the as-cast samples. The phase of the high entropy alloy remained unchanged after high-temperature annealing, demonstrating good phase stability at high temperatures.

Independent Multiple-Atom-Site Functionality in Composition Adjustable Immiscible Ru-Rh-Pd-Pt Solid-Solution High-Entropy Alloys for NOx Reduction Outperforming Rh.

The high-entropy-alloy (HEA) nanoparticles with four, five or more metals significantly can yield the developments of functional materials with excellent performances in various reactions. However, the underlying reaction mechanisms of heterogeneous catalysis for HEA have been rarely investigated, due to their diverse elements and complex compositions. In this study, we successfully synthesized the homogeneously dispersed Ru-Rh-Pd-Pt HEA with adjustable compositions, as the multiple-atom-site catalysts (MASC). In the NOx reduction performance tests, Ru0.4 (Rh0.33Pd0.33Pt0.33)0.6 MASC showed the highest activity, which was significantly improved compared to that of the best monometal Rh, with the light-off temperature decreasing by ca. 50 °C. The Fourier transform infrared measurements revealed that the outstanding activity of Ru-Rh-Pd-Pt MASC was attributable to the well-coupled elementary steps of the CO adsorption, NO adsorption, NO dissociation and O spillover on the Ru, Rh, Rh-Pd and Pt sites, respectively, which explained the first clear reaction mechanism in heterogeneous catalysis for HEA.