Nano-Engineered High-Entropy Intermetallic Compounds for Catalysis: From Designs to Catalytic Applications

Tao Chen; Yang Wang; Weifang Liu; Kaiyu Liu; Dingguo Xia

doi:10.1007/s41918-025-00263-y

Electrochemical Energy Reviews ›› 2025, Vol. 8 ›› Issue (1) :30 DOI: 10.1007/s41918-025-00263-y

Review Article

review-article

Nano-Engineered High-Entropy Intermetallic Compounds for Catalysis: From Designs to Catalytic Applications

Author information +

¹Hunan Provincial Key Laboratory of Chemical Power Sources, College of Chemistry and Chemical Engineering, Central South University, 410083, Changsha, Hunan, China

²Beijing Key Laboratory of Theory and Technology for Advanced Batteries Materials, School of Materials Science and Engineering, Peking University, 100871, Beijing, China

³College of Chemistry and Chemical Engineering, Hunan University of Science and Technology, 411201, Xiangtan, Hunan, China

^a taochen4486@163.com

^b kaiyuliu309@163.com

^c dgxia@pku.edu.cn

Tao Chen

Tao Chen received his bachelor degree and master degree from Central South University, China. He is pursuing his Ph.D. degree in Materials Science at Peking University. His current research interest includes high-efficiency catalysts. He obtained his Ph.D. degree in the department of energy and resources engineering at Peking University in 2020 under the guidance of Prof. Xia. Since July 2024, he has been serving as a Lecturer at Central South University.

Yang Wang

Yang Wang received her bachelor degree in engineering from Hunan University of Science and Technology, China. She is pursuing a master’s degree at Central South University. Her current research interest includes high-entropy alloy catalysts.

Weifang Liu

Weifang Liu received her bachelor’s degree in Central South University, China. She received her master’s degree in Polymer Physics and Chemistry and Ph.D. degree in Chemical Engineering Technology at Central South University. She is carrying out her postdoctoral research in Hunan University under the supervision of Prof. Shuangyin Wang. Currently, she is focusing on the synthesis and characterization of energy storage materials for transition‐metal oxides.

Kaiyu Liu

Kaiyu Liu is a professor of Chemistry and Chemical Engineering at Central South University, Changsha, China. He graduated from the Department of Mineral processing in 1988 and obtained his Ph.D. degree in 2003 from Central South University. He joined Central South University in 1998. His primary scientific interests cover the fields of new energy storage devices and related materials, including sodium‐ion batteries, zinc‐ion batteries, lithium‐ion batteries, and supercapacitors.

Dingguo Xia

Dingguo Xia obtained his Master degree in physical chemistry from the Harbin Institute of Technology and his Ph.D. degree in metallurgical physical chemistry from the University of Beijing Science and Technology. He worked as a professor in the College of Environmental and Energy Engineering at Beijing University of Technology from 1995 to 2010. He has worked at Peking University since May 2010 and supervises researchers working on lithium-ion battery materials, low-temperature fuel cell catalysis, and DFT investigation of energy materials.

Show less

History +

PDF

Abstract

The exploration of nanoscale high-entropy intermetallic compounds (HEICs) represents a transformative frontier in materials science, particularly in catalysis. The unique combination of multi-element composition, long-range atomic ordering, and nanoscale dimensions endows HEICs with superior electronic, structural, and catalytic properties that surpass those of traditional metal catalysts. However, achieving both uniform multi-element mixing and long-range ordered structures at the nanoscale is challenging. Building on this, this review highlights the key role of configurational entropy, mixing enthalpy, elemental composition, and size effects in the stable formation of nanoscale HEICs through thermodynamic and kinetic analysis. The latest advancements and existing challenges in the design, synthesis, structure, and applications of HEIC catalysts are discussed, with a focus on exploring their synthesis–structure–performance relationships from multiple perspectives. We hope that this review will offer valuable insights for further exploration and development of HEICs in catalytic applications.

Graphical Abstract

Keywords

High-entropy intermetallic compounds / Nanoscale synthesis / Thermodynamic‒kinetic control / Catalytic applications / Structure‒property relationships

Cite this article

Download citation ▾

Tao Chen, Yang Wang, Weifang Liu, Kaiyu Liu, Dingguo Xia. Nano-Engineered High-Entropy Intermetallic Compounds for Catalysis: From Designs to Catalytic Applications. Electrochemical Energy Reviews, 2025, 8(1): 30 DOI:10.1007/s41918-025-00263-y

登录浏览全文

4963

注册一个新账户忘记密码

References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Shenvi N, Roy S, Tully JC. Dynamical steering and electronic excitation in NO scattering from a gold surface. Science. 2009, 326: 829-832.

[2]	Crawford SE, Andolina CM, Smith AMet al. . Ligand-Mediated “Turn On”, high quantum yield near-infrared emission in small gold nanoparticles. J. Am. Chem. Soc.. 2015, 137: 14423-14429.

[3]	Scholl JA, Koh AL, Dionne JA. Quantum plasmon resonances of individual metallic nanoparticles. Nature. 2012, 483: 421-427.

[4]	Dreaden EC, Alkilany AM, Huang Xet al. . The golden age: gold nanoparticles for biomedicine. Chem. Soc. Rev.. 2012, 41: 2740-2779.

[5]	Wu L, Mendoza-Garcia A, Li Qet al. . Organic phase syntheses of magnetic nanoparticles and their applications. Chem. Rev.. 2016, 116: 10473-10512.

[6]	Yan Y, Du JS, Gilroy KDet al. . Intermetallic nanocrystals: syntheses and catalytic applications. Adv. Mater.. 2017, 29: 1605997-1606026.

[7]	Hunt ST, Milina M, Alba-Rubio ACet al. . Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts. Science. 2016, 352: 974-978.

[8]	Yang X, Yang M, Pang Bet al. . Gold nanomaterials at work in biomedicine. Chem. Rev.. 2015, 115: 10410-10488.

[9]	Jones MR, Osberg KD, Macfarlane RJet al. . Templated techniques for the synthesis and assembly of plasmonic nanostructures. Chem. Rev.. 2011, 111: 3736-3827.

[10]	Ahmadi TS, Wang ZL, Green TCet al. . Shape-Con trolled Synthesis of Colloidal Platinum Nanoparticles. Science. 1996, 272: 1924-1926.

[11]	Tokarev A, Yatvin J, Trotsenko Oet al. . Nanostructured soft matter with magnetic nanoparticles. Adv. Funct. Mater.. 2016, 26: 3761-3782.

[12]	Lu AH, Salabas EL, Schüth F. Magnetic nanoparticles: synthesis, protection, functionalization, and application. Angew. Chem. -Int. Edit.. 2007, 46: 1222-1244.

[13]	Choi SI, Xie S, Shao Met al. . Synthesis and characterization of 9 nm Pt–Ni octahedra with a record high activity of 3.3 A/mgPt for the oxygen reduction reaction. Nano Lett.. 2013, 13: 3420-3425.

[14]	Bratlie KM, Lee H, Komvopoulos Ket al. . Platinum nanoparticle shape effects on benzene hydrogenation selectivity. Nano Lett.. 2007, 7: 3097-3101.

[15]	Chen M, Wu B, Yang Jet al. . Small adsorbate-assisted shape control of Pd and Pt nanocrystals. Adv. Mater.. 2012, 24: 862-879.

[16]	You H, Yang S, Ding Bet al. . Synthesis of colloidal metal and metal alloy nanoparticles for electrochemical energy applications. Chem. Soc. Rev.. 2013, 42: 2880-2904.

[17]	Cademartiri L, Ozin GA. Ultrathin nanowires—a materials chemistry perspective. Adv. Mater.. 2009, 21: 1013-1020.

[18]	van der Vliet DF, Wang C, Tripkovic Det al. . Mesostructured thin films as electrocatalysts with tunable composition and surface morphology. Nat. Mater.. 2012, 11: 1051-1058.

[19]	Strmcnik D, Uchimura M, Wang Cet al. . Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nat. Chem.. 2013, 5: 300-306.

[20]	Stamenkovic VR, Fowler B, Mun BSet al. . Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science. 2007, 315: 493-497.

[21]	Wang D, Li Y. Bimetallic nanocrystals: liquid-phase synthesis and catalytic applications. Adv. Mater.. 2011, 23: 1044-1060.

[22]	Cuenya BR. Metal nanoparticle catalysts beginning to shape-up. Acc. Chem. Res.. 2013, 46: 1682-1691.

[23]	Yang H. Platinum-based electrocatalysts with core-shell nanostructures. Angew. Chem. -Int. Edit.. 2011, 50: 2674-2676.

[24]	Chen Q, Jia Y, Xie Set al. . Well-faceted noble-metal nanocrystals with nonconvex polyhedral shapes. Chem. Soc. Rev.. 2016, 45: 3207-3220.

[25]	Yao Y, Huang Z, Xie Pet al. . Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science. 2018, 359: 1489-1494.

[26]	Luo M, Guo S. Strain-controlled electrocatalysis on multimetallic nanomaterials. Nat. Rev. Mater.. 2017, 2: 17059-17072.

[27]	Rost CM, Sachet E, Borman Tet al. . Entropy-stabilized oxides. Nat. Commun.. 2015, 6: 8485-8493.

[28]	Yao Y, Dong Q, Brozena Aet al. . High-entropy nanoparticles: Synthesis-structure-property relationships and data-driven discovery. Science. 2022, 376: 151-163.

[29]	Yeh JW. Recent progress in high-entropy alloys. Ann. Chim.-Sci. Mat.. 2006, 31: 633-648.

[30]	Yeh JW. Physical metallurgy of high-entropy alloys. JOM. 2015, 67: 2254-2261.

[31]	He QF, Tang PH, Chen HAet al. . Understanding chemical short-range ordering/demixing coupled with lattice distortion in solid solution high entropy alloys. Acta Mater.. 2021, 216: 117140-117152.

[32]	Zhou N, Jiang S, Huang Tet al. . Single-phase high-entropy intermetallic compounds (HEICs): bridging high-entropy alloys and ceramics. Sci. Bull.. 2019, 64: 856-864.

[33]	Wang JJ, Kou ZD, Fu Set al. . Microstructure and magnetic properties evolution of Al/CoCrFeNi nanocrystalline high-entropy alloy composite. Rare Met.. 2022, 41: 2038-2046.

[34]	Yao K, Liu L, Ren Jet al. . High-entropy intermetallic compound with ultra-high strength and thermal stability. Scr. Mater.. 2021, 194. 113674–113680

[35]	Wang H, He QF, Yang Y. High-entropy intermetallics: from alloy design to structural and functional properties. Rare Met.. 2022, 41: 1989-2001.

[36]	Liu J, Lee C, Hu Yet al. . Recent progress in intermetallic nanocrystals for electrocatalysis: from binary to ternary to high-entropy intermetallics. SmartMat. 2023, 4: 1210-1243.

[37]	Li C, Li JC, Zhao Met al. . Effect of aluminum contents on microstructure and properties of Al_xCoCrFeNi alloys. J. Alloys Compd.. 2010, 504: S515-S518.

[38]	Tsai MH. Three strategies for the design of advanced high-entropy alloys. Entropy. 2016, 18: 252-266.

[39]	Fan AC, Li JH, Tsai MH. On the phase constituents of three CoCrFeNiX (X =V, Nb, Ta) high-entropy alloys after prolonged annealin. J. Alloys Compd.. 2020, 823: 153524-153534.

[40]	Soto AO, Salgado AS, Niño EB. Thermodynamic analysis of high entropy alloys and their mechanical behavior in high and low-temperature conditions with a microstructural approach - a review. Intermetallics. 2020, 124: 106850-106872.

[41]	Yadav TP, Mukhopadhyay S, Mishra SSet al. . Synthesis of a single phase of high-entropy Laves intermetallics in the Ti–Zr–V–Cr–Ni equiatomic alloy. Philos. Mag. Lett.. 2018, 97: 494-503.

[42]	Yang CL, Wang LN, Yin Pet al. . Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells. Science. 2021, 374: 459-464.

[43]	Wang D, Chen Z, Wu Yet al. . Structurally ordered high-entropy intermetallic nanoparticles with enhanced C-C bond cleavage for ethanol oxidation. SmartMat. 2022, 4: e1117-e1127.

[44]	Zhang Q, Song M, Luo Get al. . Recent advances of high-entropy intermetallics for electrocatalysis. Chem. Mater.. 2024, 36: 10967-10985.

[45]	Chen T, Zhang X, Wang Het al. . Antisite defect unleashes catalytic potential in high-entropy intermetallics for oxygen reduction reaction. Nat. Commun.. 2025, 16: 3308-3319.

[46]	Rößner L, Armbrüster M. Electrochemical energy conversion on intermetallic compounds: a review. ACS Catal.. 2019, 9: 2018-2062.

[47]	Yang Y, Wei M. Intermetallic compound catalysts: synthetic scheme, structure characterization and catalytic application. J. Mater. Chem. A. 2020, 8: 2207-2221.

[48]	Song TW, Xu C, Sheng ZTet al. . Small molecule-assisted synthesis of carbon supported platinum intermetallic fuel cell catalysts. Nat. Comm.. 2022, 13: 6521-6531.

[49]	Chen T, Ning F, Qi Jet al. . PtFeCoNiCu high-entropy solid solution alloy as highly efficient electrocatalyst for the oxygen reduction reaction. iScience. 2023, 26: 105890-105903.

[50]	Chen T, Ouyang B, Fan Xet al. . Oxide cathodes for sodium-ion batteries: designs, challenges, and perspectives. Carbon Energy. 2022, 4: 170-199.

[51]	Chen T, Cai J, Wang Het al. . Symbiotic reactions over a high-entropy alloy catalyst enable ultrahigh-voltage Li–CO₂ batteries. Energy Environ. Sci.. 2025, 18: 853-861.

[52]	Tripathy B, Ojha PK, Bhattacharjee PP. Effect of warm-rolling on microstructure and superior mechanical properties of a cost-effective AlCrFe2Ni2 high entropy alloy. J. Alloys Compd.. 2023, 948: 169783-169794.

[53]	Ji X, Lee KT, Holden Ret al. . Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat. Chem.. 2010, 2: 286-293.

[54]	Zhang J, Zhang L, Cui Z. Strategies to enhance the electrochemical performances of Pt-based intermetallic catalysts. Chem. Commun.. 2021, 57: 11-26.

[55]	Avrami M. Kinetics of phase change. I general theory. J. Chem. Phys.. 1939, 7: 1103-1112.

[56]	Avrami M. Kinetics of phase change. II transformation-time relations for random distribution of nuclei. J. Chem. Phys.. 1940, 8: 212-224.

[57]	Avrami M. Granulation, phase change, and microstructure kinetics of phase change. Part III. J. Chem. Phys.. 1941, 9: 177-184.

[58]	Ngai KL, Magill JH, Plazek DJ. Flow, diffusion and crystallization of supercooled liquids: revisited. J. Chem. Phys.. 2000, 112: 1887-1892.

[59]	Laves F. Crystal structure and atomic size. Theory of Alloy Phases. 1956American Society for Metals

[60]	Qi W, Li Y, Xiong Set al. . Modeling size and shape effects on the order-disorder phase-transition temperature of CoPt nanoparticles. Small. 2010, 6: 1996-1999.

[61]	Jacobs K, Zaziski D, Scher ECet al. . Activation volumes for solid-solid transformations in nanocrystals. Science. 2001, 293: 1803-1806.

[62]	Qi W. Nanoscopic thermodynamics. Acc. Chem. Res.. 2016, 49: 1587-1595.

[63]	Zhang Y, Wang Y, Xi Let al. . Electronic structure of antifluorite Cu₂X (X = S, Se, Te) within the modified Becke-Johnson potential plus an on-site Coulomb U. J. Chem. Phys.. 2014, 140: 074702-074711.

[64]	Yang B, Asta M, Mryasov ONet al. . The nature of A1–L10 ordering transitions in alloy nanoparticles: a Monte Carlo study. Acta Mater.. 2006, 54: 4201-4211.

[65]	Li X, Zhao J, Su D. Structural changes of intermetallic catalysts under reaction conditions. Small Struct.. 2021, 2: 2100011.

[66]	Zhao X, Cheng H, Chen Xet al. . Multiple metal-nitrogen bonds synergistically boosting the activity and durability of high-entropy alloy electrocatalysts. J. Am. Chem. Soc.. 2024, 1463010-3022.

[67]	Zhao Z, Liu Z, Zhang Aet al. . Graphene-nanopocket-encaged PtCo nanocatalysts for highly durable fuel cell operation under demanding ultralow-Pt-loading conditions. Nat. Nanotechnol.. 2022, 17: 968-975.

[68]	Feng Q, Wang X, Klingenhof Met al. . Low-Pt NiNC-supported PtNi nanoalloy oxygen reduction reaction electrocatalysts—in situ tracking of the atomic alloying process. Angew. Chem. -Int. Edit.. 2022, 61. e202203728–e202203738

[69]	Xiao F, Wang Q, Xu GLet al. . Atomically dispersed Pt and Fe sites and Pt–Fe nanoparticles for durable proton exchange membrane fuel cells. Nat. Catal.. 2022, 5: 503-512.

[70]	Gao R, Wang J, Huang ZFet al. . Pt/Fe₂O₃ with Pt–Fe pair sites as a catalyst for oxygen reduction with ultralow Pt loading. Nat. Energy. 2021, 6: 614-623.

[71]	Arif ZU, Khalid MY, ur Rehman Eet al. . A review on laser cladding of high-entropy alloys, their recent trends and potential applications. J. Manuf. Process.. 2021, 68: 225-273.

[72]	Guan J, Yang S, Liu Tet al. . Intermetallic FePt@PtBi core-shell nanoparticles for oxygen reduction electrocatalysis. Angew. Chem. -Int. Edit.. 2021, 60: 21899-21904.

[73]	Zeng Q, Liu D, Liu Het al. . Electronic and lattice strain dual tailoring for boosting Pd electrocatalysis in oxygen reduction reaction. iScience. 2021, 24: 103332-103348.

[74]	Shen T, Xiao D, Deng Zet al. . Stabilizing diluted active sites of ultrasmall high-entropy intermetallics for efficient formic acid electrooxidation. Angew. Chem. -Int. Edit.. 2024, 63. e202403260

[75]	Wang Y, Gong N, Liu Het al. . Ordering-dependent hydrogen evolution and oxygen reduction electrocatalysis of high-entropy intermetallic Pt₄FeCoCuNi. Adv. Mater.. 2023, 35: 2302067-2302083.

[76]	Cui M, Yang C, Hwang Set al. . Multi-principal elemental intermetallic nanoparticlessynthesized via a disorder-to-order transition. Sic. Adv.. 2022, 8: eabm4322.

[77]	Mingjin C, Yang YC, Hwang HSet al. . Multi-principal elemental intermetallic nanoparticles synthesized via a disorder-to-order transition. Sci. Adv.. 2022, 8eabm4322.

[78]	Feng G, Ning F, Pan Yet al. . Engineering structurally ordered high-entropy intermetallic nanoparticles with high-activity facets for oxygen reduction in practical fuel cells. J. Am. Chem. Soc.. 2023, 14511140-11150.

[79]	Chen T, Qiu C, Zhang Xet al. . An ultrasmall ordered high-entropy intermetallic with multiple active sites for the oxygen reduction reaction. J. Am. Chem. Soc.. 2023, 146: 1174-1184.

[80]	Zhu G, Bao W, Xie Met al. . Accelerating tandem electroreduction of nitrate to ammonia via multi-site synergy in mesoporous carbon-supported high-entropy intermetallics. Adv. Mater.. 2024, 37: 2413560-2413572.

[81]	Chen T, Qiu C, Zhang Xet al. . An ultrasmall ordered high-entropy intermetallic with multiple active sites for the oxygen reduction reaction. J. Am. Chem. Soc.. 2024, 146: 1174-1184.

[82]	Zhu G, Bao W, Xie Met al. . Accelerating tandem electroreduction of nitrate to ammonia via multi-site synergy in mesoporous carbon-supported high-entropy intermetallics. Adv. Mater.. 2024.

[83]	Zhang L, Zhang X, Chen Cet al. . Machine learning-aided discovery of low-Pt high entropy intermetallic compounds for electrochemical oxygen reduction reaction. Angew. Chem. -Int. Ed.. 2024, 63. e202411123

[84]	Wang Y, Zhang XY, He Het al. . Ordered mesoporous high-entropy intermetallics for efficient oxygen reduction electrocatalysis. Adv. Energy Mater.. 2023, 14: 2303923-2303933.

[85]	Zhang Q, Shen T, Song Met al. . High-entropy L1₂-Pt(FeCoNiCuZn)₃ intermetallics for ultrastable oxygen reduction reaction. J. Energy Chem.. 2023, 86: 158-166.

[86]	Hu Y, Xu Z, Guo Xet al. . Hollow-carbon confinement annealing: a new synthetic approach to make high-entropy solid-solution and intermetallic nanoparticles. Nano Lett.. 2023, 23: 10765-10771.

[87]	Jia Z, Yang T, Sun Let al. . A novel multinary intermetallic as an active electrocatalyst for hydrogen evolution. Adv. Mater.. 2020, 32: 2000385-2000394.

[88]	Hao J, Wang T, Cai Jet al. . Suppression of structural heterogeneity in high-entropy intermetallics for electrocatalytic upgrading of waste plastics. Angew. Chem. -Int. Edit.. 2024, 64: e202419369-e202419381.

[89]	Chen W, Luo S, Sun Met al. . High-entropy intermetallic PtRhBiSnSb nanoplates for highly efficient alcohol oxidation electrocatalysis. Adv. Mater.. 2022, 34: 2206276-2206285.

[90]	Xing F, Ma J, Shimizu KIet al. . High-entropy intermetallics on ceria as efficient catalysts for the oxidative dehydrogenation of propane using CO₂. Nat. Comm.. 2022, 13: 5065-5075.

[91]	Nakaya Y, Hayashida E, Asakura Het al. . High-entropy intermetallics serve ultrastable single-atom Pt for propane dehydrogenation. J. Am. Chem. Soc.. 2022, 144: 15944-15953.

[92]	Ma J, Xing F, Nakaya Yet al. . Nickel-based high-entropy intermetallic as a highly active and selective catalyst for acetylene semihydrogenation. Angew. Chem. -Int. Edit.. 2022, 61. e202200889

[93]	Xing F, Ma J, Shimizu Kiet al. . High-entropy intermetallics on ceria as efficient catalysts for the oxidative dehydrogenation of propane using CO₂. Nat. Commun.. 2022, 13. 5065