Adsorbate Resonance Induces Water-Metal Bonds in Electrochemical Interfaces.

This study delves into the intricate interactions between surface-near species, OH and H2O, on electrodes in electrochemical interfaces. These species are an inevitable part of many electrocatalytic energy conversion reactions such as the oxygen reduction reaction. In our modeling, we utilize high statistics on a dataset of complex solid solutions with high atomic variability to show the emergence of H2O-metal covalent bonds under specific conditions. Based on density functional theory (DFT) calculations of adsorption energies on many thousands of different surface compositions, we provide a quantifiable physical understanding of this induced water covalency, which is rooted in simple quantum mechanics. Directional hydrogen bonding between surface-near H2O and OH, enables surface bonding electrons to delocalize mediated by near-symmetrical adsorbate resonance structures. The different adsorbate resonance structures differ by surface coordination explaining the induced H2O-metal bonding.

The effect of changing constituents on tensile mechanical properties of HfNbTaTiZr high entropy alloy: A molecular dynamics study.

The recent trend of high-entropy alloys (HEAs) was studied extensively for their promising mechanical properties, but individual constituents' effects have remained unexplored. In this work, the effects of changing the percentage of elements of HfNbTaTiZr-HEA on the mechanical properties were analyzed during uniaxial tension using molecular dynamics simulation. The tensile strength and modulus of elastic properties of the samples were analyzed. It was found that adding Nb or Ta up to 10 % (i.e. Nb10/Ta10) in the high entropy alloys increased the ultimate tensile strength (UTS) from 2.9 GPa in the base alloy to 3.8/3.9 GPa (Nb10/Ta10) respectively, but further increment of these elements to 30 % resulted in a downgrade of UTS to 2.7 GPa. Similarly, the modulus of elasticity increased from 117.7 (±3) GPa in the base alloy to 137.7/129 (±3) GPa (Nb10/Ta10) respectively, but fell to 112-115 GPa upon further increment. The initial increase in strength could be due to the solid solution strengthening mechanism. However, further increases in these elements might hinder the development of a homogeneous solid solution because of differences in atomic size and crystal structure, which could ultimately reduce the alloy's strength. However, the effect of Ti and Zr follows an opposite trend as compared to Nb and Ta. Furthermore, the optimum composition of HEAs alloys was analyzed using a surface-contour plot and suggests minimizing the inclusion of Ta for maximizing the UTS, E, and %Elongation. Also, the high-temperature behavior of the optimized HEA's alloy was analyzed which showed a deterioration in properties at elevated temperature. The fracture evolution of the samples showed cup and cone-type fractures propagating under strain, the linear thermal expansion coefficient of HfNbTaTiZr-HEA was also calculated and found closer to the literature value.

Radiation Resistance of High-Entropy Alloys CoCrFeNi and CoCrFeMnNi, Sequentially Irradiated with Kr and He Ions.

This work studied the effect of sequential irradiation by krypton and helium ions at room temperature on the composition and structure of CoCrFeNi and CoCrFeMnNi high-entropy alloys (HEAs). Irradiation of the HEAs by 280 keV Kr14+ ions up to a fluence of 5 × 1015 cm-2 and 40 keV He2+ ions up to a fluence of 2 × 1017 cm-2 did not alter their elemental distribution and constituent phases. Blisters formed on the nickel surface after sequential irradiation, where large blisters had an average diameter of 3.8 µm. The lattice parameter of the (Co, Cr, Fe and Ni) and (Co, Cr, Fe, Mn and Ni) solid solutions increased by 0.17% and 0.37% after sequential irradiation, respectively. Irradiation by Kr ions led to a decrease in tensile macrostresses in the HEAs in the region of krypton ion implantation (Region I) and the formation of compressive macrostresses in the region behind the peak of implanted krypton (Region II). Sequential irradiation formed large compressive stresses in Ni and HEAs equal to -131.5 MPa, -300 MPa and -613.5 MPa in Ni, CoCrFeNi and CoCrFeMnNi, respectively, in the Region II. Irradiation by krypton ions decreased the dislocation density by 1.6-2.3 times, and irradiation with helium ions increased it by 11-15 times relative to unirradiated samples for CoCrFeNi and CoCrFeMnNi, respectively. Sequentially irradiated CoCrFeMnNi HEA had higher macrostresses and dislocation density than CoCrFeNi.

Production and Characterization of Fine-Grained Multielement AlCoxCrFeNi (x = 1, 0.75, 0.5) Alloys for High-Temperature Applications.

In the present work, three different AlCoxCrFeNi (x = 1, 0.75, 0.5) alloys were produced through the mechanical milling of powders and spark plasma sintering. These alloys were characterized in terms of their microstructural, mechanical, and oxidation behaviors. Mechanical milling and spark plasma sintering were chosen to achieve a fine and homogeneous microstructure. Pore-free samples were produced by properly setting the sintering parameters. The unavoidable uptake of oxygen from the powders when exposed to air after milling was advantageously used as a source of oxides, which acted as reinforcing particles in the alloy. Oxidation behavior, studied through TGA tests, showed that decreasing the Co content promotes better oxidation protection due to the formation of a dense, compact Al2O3 layer. The alloy containing the lowest amount of Co is considered a good candidate for high-temperature structural applications.

Ultra-High Strength in FCC+BCC High-Entropy Alloy via Different Gradual Morphology.

In this study, high-pressure torsion (HPT) processing is applied to the as-cast Al0.5CoCrFeNi high-entropy alloy (HEA) for 1, 3, and 5 turns. Microstructural observations reveal a significant refinement of the second phase after HPT processing. This refinement effect is influenced by the number of processing turns and the distance of the processing position from the center. As the number of processing turns or the distance of the processing position from the center increases, the fragmentation effect on the second phase becomes more pronounced. The hardness of the alloy is greatly enhanced after HPT processing, but there is an upper limit to this enhancement. After increasing the number of processing turns to 5, the increase in hardness at the edge becomes less significant, while the overall hardness becomes more uniform. Additionally, the strength of the processed alloy is significantly enhanced, while its ductility undergoes a noticeable decrease. With an increase in the number of processing turns, the second phase is further refined, resulting in improvement of strength and ductility.

High-Temperature Oxidation of NbTi-Bearing Refractory Medium- and High-Entropy Alloys.

The oxidation of six NbTi-i refractory medium- and high-entropy alloys (NbTi + Ta, NbTi + CrTa, NbTi + AlTa, NbTi + AlMo, NbTi + AlMoTa and NbTi + AlCrMo) were investigated at 1000 °C for 20 h. According to our observation, increased Cr content promoted the formation of protective CrNbO4 and Cr2O3 oxides in NbTi + CrTa and NbTi + AlCrMo, enhancing oxidation resistance. The addition of Al resulted in the formation of AlTi-rich oxide in NbTi + AlTa. Ta addition resulted in the formation of complex oxides (MoTiTa8O25 and TiTaO4) and decreased oxidation resistance. Meanwhile, Mo's low oxygen solubility could be beneficial for oxidation resistance while protective Cr2O3/CrNbO4 layers were formed. In NbTi + Ta, NbTi + AlTa and NbTi + CrTa, a considerable quantity of Ti-rich oxide was observed at the interdendritic region. In NbTi + AlCrMo, the enrichment of Cr and Ti at the interdendritic region could fasten the rate of oxidation. Compared to the recent research, NbTi + AlCrMo alloy is a light-weight oxidation-resistant alloy (weight gain of 1.29 mg/cm2 at 1000 °C for 20 h and low density (7.2 g/cm3)).

Structural Changes in High-Entropy Alloys CoCrFeNi and CoCrFeMnNi, Irradiated by He Ions at a Temperature of 700 °C.

High-entropy alloys (HEA) are promising structural materials that will successfully resist high-temperature irradiation with helium ions and radiation-induced swelling in new generations of nuclear reactors. In this paper, changes in the elemental and phase composition, surface morphology, and structure of CoCrFeNi and CoCrFeMnNi HEAs irradiated with He2+ ions at a temperature of 700 °C were studied. Structural studies were mainly conducted using the X-ray diffraction method. The formation of a porous surface structure with many microchannels (open blisters) was observed. The average diameter of the blisters in CoCrFeMnNi is around 1.3 times smaller than in CoCrFeNi. It was shown that HEAs' elemental and phase compositions are stable under high-temperature irradiation. It was revealed that, in the region of the peak of implanted helium, high-temperature irradiation leads to the growth of tensile macrostresses in CoCrFeNi by 3.6 times and the formation of compressive macrostresses (-143 MPa) in CoCrFeMnNi; microstresses in the HEAs increase by 2.4 times; and the dislocation density value increases by 4.3 and 7.5 times for CoCrFeNi and CoCrFeMnNi, respectively. The formation of compressive macrostresses and a higher value of dislocation density indicate that the CoCrFeMnNi HEA tends to have greater radiation resistance compared to CoCrFeNi.

Predicting Yield Strength and Plastic Elongation in Body-Centered Cubic High-Entropy Alloys.

We employ machine learning (ML) to predict the yield stress and plastic strain of body-centered cubic (BCC) high-entropy alloys (HEAs) in the compression test. Our machine learning model leverages currently available databases of BCC and BCC+B2 entropy alloys, using feature engineering to capture electronic factors, atomic ordering from mixing enthalpy, and the D parameter related to stacking fault energy. The model achieves low Root Mean Square Errors (RMSE). Utilizing Random Forest Regression (RFR) and Genetic Algorithms for feature selection, our model excels in both predictive accuracy and interpretability. Rigorous 10-fold cross-validation ensures robust generalization. Our discussion delves into feature importance, highlighting key predictors and their impact on mechanical properties. This work provides an important step toward designing high-performance structural high-entropy alloys, providing a powerful tool for predicting mechanical properties and identifying new alloys with superior strength and ductility.

Microstructure evolution and catalytic activity of AlCo1-xFeNiTiMox high entropy alloys fabricated by powder metallurgy route.

This investigation presents the synthesis of equiatomic and non-equiatomic AlCo1-xFeNiTiMox (x = 0, 0.1, 0.25 and 1.0) high entropy alloys fabricated by mechanical alloying. Mo partially replaced Co. Classic thermodynamic calculations, such as mixing enthalpy (ΔHmix), configurational entropy (ΔSmix), the atomic size difference (δ), entropy to enthalpy ratio (Ω), electronegativity difference (△χ), and valence electron concentration (VEC) were used. Considering δ, Ω and VEC parameters, a BCC solid solution and an intermetallic phase can be predicted due to the partial replacement of Co by Mo. X-ray and electron diffraction of equiatomic HEA without Mo content revealed that after 35 h of milling, a Fe-type BCC lattice phase was formed in the alloy and two L21 phases, in addition to a minimal amount of FCC phase. As the Mo content increased, the Fe-type BCC phase was steadily replaced by the Mo-type BCC phase and the Fe-type FCC phase, and two L21 phases were also developed. When the 5 at% Mo-containing (x = 0.25) alloy was further milled for 80 h, the amount of phases remained almost the same; only the grain size was strongly reduced. The influence of the Mo addition on the properties of studied alloys was also confirmed in the decolourisation of Rhodamine B using a modified photo-Fenton process. The decolourisation efficiency within 20 min was 72% for AlCoFeNiTi and 87% for AlCo0.75FeNiTiMo0.25 using UV light with 365 nm wavelength.

Spontaneous Orientation Polarization of Anisotropic Equivalent Dipoles Harnessed by Entropy Engineering for Ultra-Thin Electromagnetic Wave Absorber.

The synthesis of carbon supporter/nanoscale high-entropy alloys (HEAs) electromagnetic response composites by carbothermal shock method has been identified as an advanced strategy for the collaborative competition engineering of conductive/dielectric genes. Electron migration modes within HEAs as manipulated by the electronegativity, valence electron configurations and molar proportions of constituent elements determine the steady state and efficiency of equivalent dipoles. Herein, enlightened by skin-like effect, a reformative carbothermal shock method using carbonized cellulose paper (CCP) as carbon supporter is used to preserve the oxygen-containing functional groups (O·) of carbonized cellulose fibers (CCF). Nucleation of HEAs and construction of emblematic shell-core CCF/HEAs heterointerfaces are inextricably linked to carbon metabolism induced by O·. Meanwhile, the electron migration mode of switchable electron-rich sites promotes the orientation polarization of anisotropic equivalent dipoles. By virtue of the reinforcement strategy, CCP/HEAs composite prepared by 35% molar ratio of Mn element (CCP/HEAs-Mn2.15) achieves efficient electromagnetic wave (EMW) absorption of - 51.35 dB at an ultra-thin thickness of 1.03 mm. The mechanisms of the resulting dielectric properties of HEAs-based EMW absorbing materials are elucidated by combining theoretical calculations with experimental characterizations, which provide theoretical bases and feasible strategies for the simulation and practical application of electromagnetic functional devices (e.g., ultra-wideband bandpass filter).

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.

Light-Driven Reverse Water Gas Shift Reaction with 1000-H Stability on High-Entropy Alloy Catalysts.

Highly stable and active catalysts are of significant importance and a longstanding challenge for a number of industrial chemical transformations. Here, motivated by the principle of the high entropy-stabilized structure, high-entropy alloy-loaded porous TiO2 as an efficient and sintering-resistant catalyst for the light-driven reverse water gas‒shift reaction without external heating is synthesized. The optimized CoNiCuPdRu/TiO2 catalyst exhibits a long-term stability of 1000 h (1.23 mol gmetal -1 h-1 CO production rate, >99% high selectivity). In situ characterizations confirm that the slow diffusion effect of high-entropy alloys endows the catalyst with excellent structural stability. The CO adsorption measurements and theoretical calculations consolidate that the hydrogen surface coverage weakens CO adsorption on the catalyst surface. Two major problems of catalyst deactivation - sintering and poisoning, are handled in one case, which synergistically enable unparalleled stability. This work provides new guidance for the rational design of ultradurable harsh-condition operation catalysts for industrial catalysis.

Study on the Properties of TiC Coating Deposited by Spark Discharge on the Surface of AlFeCoCrNiCu High-Entropy Alloy.

Titanium carbide (TiC) coatings were prepared on the surface of AlFeCoCrNiCu high-entropy alloy blocks using electro-spark deposition (ESD). The microhardness and corrosion resistance of the TiC coatings prepared under different voltage and capacitance process parameters were studied. The research shows that the maximum microhardness of the TiC coating on sample 4 (working voltage of 20 V, working capacitance of 1000 µF) is 844.98 HV, which is 81.5% higher than the microhardness of the substrate. This is because the deposition energy increases with the increase in voltage, and the adhesion and aggregation between the coating and the substrate are enhanced, increasing the hardness of the coating. It is worth noting that excessive deposition energy can increase surface defects and reduce the microhardness of the coating surface. Electrochemical testing analysis shows that the corrosion current density of the TiC coating is the lowest (9.475 × 10-7 ± 0.06 × 10-7), and the coating impedance is the highest (2.502 × 103 Ω·com2). The absolute phase angle value is the highest (about 72°). The above indicates that the TiC coating prepared with a working voltage of 20 V and a working capacitance of 1000 µF has better microhardness and corrosion resistance.

Study on cavitation erosion-corrosion behavior of CoCrFeNiMoCu0.1 high entropy alloy in 3.5 wt% NaCl solution.

The challenge of cavitation erosion (CE) in flow-handling components of marine engineering has promoted the development of advanced materials due to safety incidents and economic costs. High entropy alloys (HEAs), known for high hardness and corrosion resistance, emerge as promising candidates. This paper delved into the CE characteristics of CoCrFeNiMoCu0.1 HEA when subjected to the 3.5 wt% NaCl solution, elucidating the synergistic effect of CE-corrosion. The quantitative analysis revealed that CE-corrosion synergy contributed 48.02% to total CE mass loss, primarily attributed to corrosion-induced CE damage. Meanwhile, electrochemical noise (EN) was utilized to reveal the corrosion behavior of CoCrFeNiMoCu0.1 HEA in 3.5 wt% NaCl solution combined with the morphologies observation and surface roughness. Extended CE time compromised the corrosion resistance of CoCrFeNiMoCu0.1 HEA and diminished the impact of selective phase corrosion on the surface. Eventually, the CE damage mechanism of CoCrFeNiMoCu0.1 HEA was revealed based on pertinent experimental findings. The results showed that with increased CE time, the CoCrFeNiMoCu0.1 HEA transitioned from predominantly extensive exfoliation of the initial FCC phase to further damage of the intermetallic σ and µ phases.

Advances in Nickel-Containing High-Entropy Alloys: From Fundamentals to Additive Manufacturing.

High-entropy alloys (HEAs) are recognized as a class of advanced materials with outstanding mechanical properties and corrosion resistance. Among these, nickel-based HEAs stand out for their impressive strength, ductility, and oxidation resistance. This review delves into the latest advancements in nickel-containing HEAs, covering their fundamental principles, alloy design strategies, and additive manufacturing techniques. We start by introducing HEAs and their unique properties, emphasizing the crucial role of nickel. This review examines the complex relationships between alloy composition, valence electron concentration (VEC), and the resulting crystal structures. This provides insights into design principles for achieving desired microstructures and mechanical properties. Additive manufacturing (AM) techniques like selective laser melting (SLM), electron beam melting (EBM), and laser metal deposition (LMD) are highlighted as powerful methods for fabricating intricate HEA components. The review addresses the challenges of AM processes, such as porosity, fusion defects, and anisotropic mechanical properties, and discusses strategies to mitigate these issues through process optimization and improved powder quality. The mechanical behavior of AM-processed nickel-based HEAs is thoroughly analyzed, focusing on compressive strength, hardness, and ductility. This review underscores the importance of microstructural features, including grain size, phase composition, and deformation mechanisms, in determining the mechanical performance of these alloys. Additionally, the influence of post-processing techniques, such as heat treatment and hot isostatic pressing (HIP) on enhancing mechanical properties is explored. This review also examines the oxidation behavior of nickel-containing HEAs, particularly the formation of protective oxide scales and their dependence on aluminum content. The interplay between composition, VEC, and oxidation resistance is discussed, offering valuable insights for designing corrosion resistant HEAs. Finally, this review outlines the potential applications of nickel-based HEAs in industries such as aerospace, automotive, and energy, and identifies future research directions to address challenges and fully realize the potential of these advanced materials.

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.

PdMoPtCoNi High Entropy Nanoalloy with d Electron Self-Complementation-Induced Multisite Synergistic Effect for Efficient Nanozyme Catalysis.

Engineering multimetallic nanocatalysts with the entropy-mediated strategy to reduce reaction activation energy is regarded as an innovative and effective approach to facilitate efficient heterogeneous catalysis. Accordingly, conformational entropy-driven high-entropy alloys (HEAs) are emerging as a promising candidate to settle the catalytic efficiency limitations of nanozymes, attributed to their versatile active site compositions and synergistic effects. As proof of the high-entropy nanozymes (HEzymes) concept, elaborate PdMoPtCoNi HEA nanowires (NWs) with abundant active sites and tuned electronic structures, exhibiting peroxidase-mimicking activity comparable to that of natural horseradish peroxidase are reported. Density functional theory calculations demonstrate that the enhanced electron abundance of HEA NWs near the Fermi level (EF) is facilitated via the self-complementation effect among the diverse transition metal sites, thereby boosting the electron transfer efficiency at the catalytic interface through the cocktail effect. Subsequently, the HEzymes are integrated with a portable electronic device that utilizes Internet of Things-driven signal conversion and wireless transmission functions for point-of-care diagnosis to validate their applicability in digital biosensing of urinary biomarkers. The proposed HEzymes underscore significant potential in enhancing nanozymes catalysis through tunable electronic structures and synergistic effects, paving the way for reformative advancements in nano-bio analysis.

A database of multi-principal element alloy phase-specific mechanical properties measured with nano-indentation.

Multi-principal element alloys (MPEAs) have been the focus of study and computationally-guided design for two reasons. MPEAs have shown high strengths and, the vast potential compositional space is more efficiently navigated with machine learning. In this article, we present data from 7385 indentation tests performed on 19 different MPEAs. Samples were arc melted, a thermodynamically complex process forming many distinct phases within a sample. The database was generated by performing hundreds of nanoindentation tests on a given sample and registering the location of those indents with local phase compositions measured with energy dispersive spectroscopy (EDS). The database contains the phases formed in the MPEA, the composition at the location of each indent, and the associated hardness (HV) and modulus for each indent. This data allows researchers targeting data-driven design of high strength systems to extract meaningful correlations between alloying composition, the resulting phases, and mechanical properties for future study.

Toluene-Poisoning-Resistant High-Entropy Non-Noble Metal Anode for Direct One-Step Hydrogenation of Toluene to Methylcyclohexane.

The direct one-step hydrogenation of toluene to methylcyclohexane facilitated by a proton-exchange membrane water electrolyzer driven by renewable energy has garnered considerable attention for stable hydrogen storage and safe hydrogen transportation. However, a persistent challenge lies in the crossover of toluene from the cathode to the anode chamber, which deteriorates the anode and decreases its energy efficiency and lifetime. To address this challenge, the catalyst-poisoning mechanism is systematically investigated using IrO2 and high-entropic non-noble-metal alloys as anodes in acidic electrolytes saturated with toluene and toluene-oxidized derivatives, such as benzaldehyde, benzyl alcohol, and benzoic acid. Benzoic acid plays an important role in polymer-like carbon-film formation by blocking the catalytically active sites on the anode surface. Moreover, Nb and the highly entropic state on the surface of the multi-element alloy lower the adsorbing ability of toluene and prevent polymer-like carbon film formation. This study contributes to the design of catalyst-poisoning-resistant anodes for organic hydride technology, advanced fuel cells, and batteries.

Tailored Design of Mesoporous Nanospheres with High Entropic Alloy Sites for Efficient Redox Electrocatalysis.

High Entropy Alloys (HEAs) are a versatile material with unique properties, tailored for various applications. They enable pH-sensitive electrocatalytic transformations like hydrogen evolution reaction (HER) and hydrogen oxidation reactions (HOR) in alkaline media. Mesoporous nanostructures with high surface area are preferred for these electrochemical reactions, but designing mesoporous HEA sis challenging. To overcome this challenge, a low-temperature triblock copolymer-assisted wet-chemical approach is developed to produce mesoporous HEA nanospheres composed of PtPdRuMoNi systems with sufficient entropic mixing. Owing to active sites with inherent entropic effect, mesoporous features, and increased accessibility, optimized HEA nanospheres promote strong HER/HOR performance in alkaline medium. At 30 mV nominal overpotential, it exhibits a mass activity of ≈167 (HER) and 151 A gPt -1 (HOR), far exceeding commercial Pt-C electrocatalysts (34 and 48 A gPt -1) and many recently reported various alloys. The Mott-Schottky analysis reveals HEA nanospheres inherit high charge carrier density, positive flat band potential, and smaller charge transfer barrier, resulting in better activity and faster kinetics. This micelle-assisted synthetic enable the exploration of the compositional and configurational spaces of HEAs at relatively low temperature, while simultaneously facilitating the introduction of mesoporous nanostructures for a wide range of catalytic applications.