Heterostructure Engineering in High-Entropy Alloy Catalysts

Wenhui Shi , Hanwen Liu , Shijin Liu , Jinli Chen , Fatang Tan , Jun Wan , Yonggang Yao

SusMat ›› 2025, Vol. 5 ›› Issue (2) : e261

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SusMat ›› 2025, Vol. 5 ›› Issue (2) : e261 DOI: 10.1002/sus2.261
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Heterostructure Engineering in High-Entropy Alloy Catalysts

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Abstract

Confronting the limitation of traditional homogeneous high-entropy alloys (HEAs) with randomly distributed elements and active sites, heterostructured HEAs were developed to further amplify catalytic activity and stability. This perspective dissects the genesis of heterogeneity within HEAs, highlighting how their expansive compositional space facilitates the customization of heterogeneity. By manipulating key factors, such as chemical affinity, standard redox potentials, and oxidation potential, researchers are tapping into heterostructured HEAs with unprecedented attributes. Strategies like acid leaching, galvanic replacement, and additive deposition are broadening the structural repertoire of HEAs, steering the development of heterostructured catalysts. This perspective synthesizes current discoveries, introduces provocative concepts, and provides a roadmap for structural engineering in HEA catalysts, particularly harnessing the heterogeneity of HEAs to elevate their catalytic efficiency. The confluence of theoretical and practical advancements is anticipated to lead the way in the evolution of HEA catalysts, endowing them with exceptional capabilities.

Keywords

compositional design / heterostructure / high-entropy alloy / processing technique

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Wenhui Shi, Hanwen Liu, Shijin Liu, Jinli Chen, Fatang Tan, Jun Wan, Yonggang Yao. Heterostructure Engineering in High-Entropy Alloy Catalysts. SusMat, 2025, 5(2): e261 DOI:10.1002/sus2.261

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References

[1]

Y. Yao, Z. Huang, L. A. Hughes, et al., “Extreme Mixing in Nanoscale Transition Metal Alloys,” Matter 4, no. 7 (2021): 2340-2353.

[2]

Y. Yao, Q. Dong, A. Brozena, et al., “High-Entropy Nanoparticles: Synthesis-Structure-Property Relationships and Data-Driven Discovery,” Science 376, no. 6589 (2022): eabn3103.

[3]

G. Cao, J. Liang, Z. Guo, et al., “Liquid Metal for High-Entropy Alloy Nanoparticles Synthesis,” Nature 619, no. 7968 (2023): 73-77.

[4]

Y. Yao, Z. Huang, P. Xie, et al., “Carbothermal Shock Synthesis of High-Entropy-Alloy Nanoparticles,” Science 359, no. 6383 (2018): 1489-1494.

[5]

J.-T. Ren, L. Chen, H.-Y. Wang, and Z.-Y. Yuan, “High-Entropy Alloys in Electrocatalysis: From Fundamentals to Applications,” Chemical Society Reviews 52, no. 23 (2023): 8319-8373.

[6]

N. Kumar Katiyar, K. Biswas, J.-W. Yeh, S. Sharma, and C. Sekhar Tiwary, “A Perspective on the Catalysis Using the High Entropy Alloys,” Nano Energy 88 (2021): 106261.

[7]

P. Xie, Y. Yao, Z. Huang, et al., “Highly Efficient Decomposition of Ammonia Using High-Entropy Alloy Catalysts,” Nature Communications 10, no. 1 (2019): 4011.

[8]

L. Yu, K. Zeng, C. Li, et al., “High-Entropy Alloy Catalysts: From Bulk to Nano toward Highly Efficient Carbon and Nitrogen Catalysis,” Carbon Energy 4, no. 5 (2022): 731-761.

[9]

E. P. George, D. Raabe, and R. O. Ritchie, “High-Entropy Alloys,” Nature Reviews Materials 4, no. 8 (2019): 515-534.

[10]

Z. W. Chen, J. Li, P. Ou, et al., “Unusual Sabatier Principle on High Entropy Alloy Catalysts for Hydrogen Evolution Reactions,” Nature Communications 15, no. 1 (2024): 359.

[11]

Y. Mei, Y. Feng, C. Zhang, Y. Zhang, Q. Qi, and J. Hu, “High-Entropy Alloy with Mo-Coordination as Efficient Electrocatalyst for Oxygen Evolution Reaction,” ACS Catalysis 12, no. 17 (2022): 10808-10817.

[12]

H. Li, Y. Han, H. Zhao, et al., “Fast Site-to-Site Electron Transfer of High-Entropy Alloy Nanocatalyst Driving Redox Electrocatalysis,” Nature Communications 11, no. 1 (2020): 5437.

[13]

T. A. A. Batchelor, J. K. Pedersen, S. H. Winther, I. E. Castelli, K. W. Jacobsen, and J. Rossmeisl, “High-Entropy Alloys as a Discovery Platform for Electrocatalysis,” Joule 3, no. 3 (2019): 834-845.

[14]

H. Li, J. Lai, Z. Li, and L. Wang, “Multi-Sites Electrocatalysis in High-Entropy Alloys,” Advanced Functional Materials 31, no. 47 (2021): 2106715.

[15]

Y. Xin, S. Li, Y. Qian, et al., “High-Entropy Alloys as a Platform for Catalysis: Progress, Challenges, and Opportunities,” ACS Catalysis 10, no. 19 (2020): 11280-11306.

[16]

Y. Zhai, X. Ren, B. Wang, and S. Liu, “High-Entropy Catalyst-A Novel Platform for Electrochemical Water Splitting,” Advanced Functional Materials 32, no. 47 (2022): 2207536.

[17]

J. Tian, Y. Rao, W. Shi, et al., “Sabatier Relations in Electrocatalysts Based on High-Entropy Alloys with Wide-Distributed D-Band Centers for Li-O2 Batteries,” Angewandte Chemie International Edition 62, no. 44 (2023): e202310894.

[18]

S. Schweidler, M. Botros, F. Strauss, et al., “High-Entropy Materials for Energy and Electronic Applications,” Nature Reviews Materials 9, no. 4 (2024): 266-281.

[19]

L. Liu and A. Corma, “Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles,” Chemical Reviews 123, no. 8 (2023): 4855-4933.

[20]

T. Löffler, A. Ludwig, J. Rossmeisl, and W. Schuhmann, “What Makes High-Entropy Alloys Exceptional Electrocatalysts?,” Angewandte Chemie International Edition 60, no. 52 (2021): 26894-26903.

[21]

L. Banko, O. A. Krysiak, J. K. Pedersen, et al., “Unravelling Composition-Activity-Stability Trends in High Entropy Alloy Electrocatalysts by Using a Data-Guided Combinatorial Synthesis Strategy and Computational Modeling,” Advanced Energy Materials 12, no. 8 (2022): 2103312.

[22]

A. Kormányos, Q. Dong, B. Xiao, et al., “Stability of High-Entropy Alloys under Electrocatalytic Conditions,” Iscience 26, no. 10 (2023): 107775.

[23]

T. Priamushko, A. Kormányos, and S. Cherevko, “What Do We Know about the Electrochemical Stability of High-Entropy Alloys?,” Current Opinion in Chemical Engineering 44 (2024): 101020.

[24]

W. A. Saidi, W. Shadid, and G. Veser, “Optimization of High-Entropy Alloy Catalyst for Ammonia Decomposition and Ammonia Synthesis,” Journal of Physical Chemistry Letters 12, no. 21 (2021): 5185-5192.

[25]

S. Tang, M. Xie, S. Yu, et al., “General Synthesis of High-Entropy Single-Atom Nanocages for Electrosynthesis of Ammonia from Nitrate,” Nature Communications 15, no. 1 (2024): 6932.

[26]

D. Zhang, H. Zhao, X. Wu, et al., “Multi-Site Electrocatalysts Boost pH-Universal Nitrogen Reduction by High-Entropy Alloys,” Advanced Functional Materials 31, no. 9 (2021): 2006939.

[27]

R. Zhang, Y. Zhang, B. Xiao, et al., “Phase Engineering of High-Entropy Alloy for Enhanced Electrocatalytic Nitrate Reduction to Ammonia,” Angewandte Chemie International Edition 63, no. 35 (2024): e202407589.

[28]

J.-H. Cha, S.-H. Cho, D.-H. Kim, et al., “Flash-Thermal Shock Synthesis of High-Entropy Alloys Toward High-Performance Water Splitting,” Advanced Materials 35, no. 46 (2023): 2305222.

[29]

K. Huang, X. Cao, Y. Lu, et al., “Lattice-Disordered High-Entropy Alloy Engineered by Thermal Dezincification for Improved Catalytic Hydrogen Evolution Reaction,” Advanced Materials 36, no. 32 (2024): 2304867.

[30]

J. Kwon, S. Sun, S. Choi, et al., “Tailored Electronic Structure of Ir in High Entropy Alloy for Highly Active and Durable Bifunctional Electrocatalyst for Water Splitting Under an Acidic Environment,” Advanced Materials 35, no. 26 (2023): 2300091.

[31]

A. Sivanantham, H. Lee, S. W. Hwang, et al., “Complementary Functions of Vanadium in Boosting Electrocatalytic Activity of CuCoNiFeMn High-Entropy Alloy for Water Splitting,” Advanced Functional Materials 33, no. 34 (2023): 2301153.

[32]

M. Wei, Y. Sun, J. Zhang, F. Ai, S. Xi, and J. Wang, “High-Entropy Alloy Nanocrystal Assembled by Nanosheets with d-d Electron Interaction for Hydrogen Evolution Reaction,” Energy & Environmental Science 16 (2023): 4009-4019.

[33]

Y. Mei, J. Chen, Q. Wang, et al., “MoZn-Based High Entropy Alloy Catalysts Enabled Dual-Activation and Stabilization in Alkaline Oxygen Evolution,” Science Advances 10, no. 47 (2024): eadq6758.

[34]

H. Huang, J. Zhao, H. Guo, et al., “Noble-Metal-Free High-Entropy Alloy Nanoparticles for Efficient Solar-Driven Photocatalytic CO2 Reduction,” Advanced Materials 36, no. 26 (2024): 2313209.

[35]

H. Li, H. Huang, Y. Chen, et al., “High-Entropy Alloy Aerogels: A New Platform for Carbon Dioxide Reduction,” Advanced Materials 35, no. 2 (2023): 2209242.

[36]

K. Mori, N. Hashimoto, N. Kamiuchi, H. Yoshida, H. Kobayashi, and H. Yamashita, “Hydrogen Spillover-Driven Synthesis of High-Entropy Alloy Nanoparticles as a Robust Catalyst for CO2 Hydrogenation,” Nature Communications 12, no. 1 (2021): 3884.

[37]

S. Nellaiappan, N. K. Katiyar, R. Kumar, et al., “High-Entropy Alloys as Catalysts for the CO2 and CO Reduction Reactions: Experimental Realization,” ACS Catalysis 10, no. 6 (2020): 3658-3663.

[38]

J. K. Pedersen, T. A. A. Batchelor, A. Bagger, and J. Rossmeisl, “High-Entropy Alloys as Catalysts for the CO2 and CO Reduction Reactions,” ACS Catalysis 10, no. 3 (2020): 2169-2176.

[39]

W. Chen, S. Luo, M. Sun, et al., “High-Entropy Intermetallic PtRhBiSnSb Nanoplates for Highly Efficient Alcohol Oxidation Electrocatalysis,” Advanced Materials 34, no. 43 (2022): 2206276.

[40]

X. Lao, X. Liao, C. Chen, et al., “Pd-Enriched-Core/Pt-Enriched-Shell High-Entropy Alloy with Face-Centred Cubic Structure for C1 and C2 Alcohol Oxidation,” Angewandte Chemie International Edition 62, no. 31 (2023): e202304510.

[41]

Y. Lv, P. Liu, R. Xue, et al., “Cascaded p-d Orbital Hybridization Interaction in Ultrathin High-Entropy Alloy Nanowires Boosts Complete Non-CO Pathway of Methanol Oxidation Reaction,” Advanced Science 11, no. 19 (2024): 2309813.

[42]

W. Peng, Y.-R. Lu, H. Lin, et al., “Sulfur-Stabilizing Ultrafine High-Entropy Alloy Nanoparticles on MXene for Highly Efficient Ethanol Electrooxidation,” ACS Nano 17, no. 22 (2023): 22691-22700.

[43]

X. Han, G. Wu, S. Zhao, et al., “Nanoscale High-Entropy Alloy for Electrocatalysis,” Matter 6, no. 6 (2023): 1717-1751.

[44]

K. Zeng, J. Zhang, W. Gao, et al., “Surface-Decorated High-Entropy Alloy Catalysts with Significantly Boosted Activity and Stability,” Advanced Functional Materials 32, no. 33 (2022): 2204643.

[45]

W. Shi, H. Liu, Z. Li, et al., “High-Entropy Alloy Stabilized and Activated Pt Clusters for Highly Efficient Electrocatalysis,” SusMat 2, no. 2 (2022): 186-196.

[46]

L. An, Z. Zhang, J. Feng, et al., “Heterostructure-Promoted Oxygen Electrocatalysis Enables Rechargeable Zinc-Air Battery With Neutral Aqueous Electrolyte,” Journal of the American Chemical Society 140, no. 50 (2018): 17624-17631.

[47]

Y. Li, J. Zhang, Q. Chen, X. Xia, and M. Chen, “Emerging of Heterostructure Materials in Energy Storage: A Review,” Advanced Materials 33, no. 27 (2021): 2100855.

[48]

M. Luo and S. Guo, “Strain-Controlled Electrocatalysis on Multimetallic Nanomaterials,” Nature Reviews Materials 2, no. 11 (2017): 1-13.

[49]

J. Chen, H. Li, C. Fan, et al., “Dual Single-Atomic Ni-N4 and Fe-N4 Sites Constructing Janus Hollow Graphene for Selective Oxygen Electrocatalysis,” Advanced Materials 32, no. 30 (2020): 2003134.

[50]

G. Zhao, P. Li, N. Cheng, S. X. Dou, and W. Sun, “An Ir/Ni(OH)2 Heterostructured Electrocatalyst for the Oxygen Evolution Reaction: Breaking the Scaling Relation, Stabilizing Iridium (V), and Beyond,” Advanced Materials 32, no. 24 (2020): 2000872.

[51]

J. W. Yeh, Y. L. Chen, S. J. Lin, and S. K. Chen, “High-Entropy Alloy-a New Era of Exploitaion,” Trans Tech Publications Ltd 560, (2007): 1-9.

[52]

A. L. Maulana, P.-C. Chen, Z. Shi, et al., “Understanding the Structural Evolution of IrFeCoNiCu High-Entropy Alloy Nanoparticles under the Acidic Oxygen Evolution Reaction,” Nano Letters 23, no. 14 (2023): 6637-6644.

[53]

Y. Geng, H. Tan, L. Wang, et al., “Nano-Coupled Heterostructure Induced Excellent Mechanical and Tribological Properties in AlCoCrFeNi High Entropy Alloy,” Tribology International 154 (2021): 106662.

[54]

W. Jiang, Y. Zhu, and Y. Zhao, “Mechanical Properties and Deformation Mechanisms of Heterostructured High-Entropy and Medium-Entropy Alloys: A Review,” Frontiers in Materials 8 (2022): 792359.

[55]

D. Xu, X. Wang, and Y. Lu, “Heterogeneous-Structured Refractory High-Entropy Alloys: A Review of State-of-the-Art Developments and Trends,” Advanced Functional Materials (2024): 2408941.

[56]

G. Chen, J. W. Qiao, Z. M. Jiao, et al., “Strength-Ductility Synergy of Al0.1CoCrFeNi High-Entropy Alloys with Gradient Hierarchical Structures,” Scripta Materialia 167 (2019): 95-100.

[57]

Q. Mao, X. Chen, J. Li, and Y. Zhao, “Nano-Gradient Materials Prepared by Rotary Swaging,” Nanomaterials 11, no. 9 (2021): 2223.

[58]

P. Shi, W. Ren, T. Zheng, et al., “Enhanced Strength-ductility Synergy in Ultrafine-Grained Eutectic High-Entropy Alloys by Inheriting Microstructural Lamellae,” Nature Communications 10, no. 1 (2019): 489.

[59]

S. W. Wu, G. Wang, Q. Wang, et al., “Enhancement of Strength-Ductility Trade-off in a High-Entropy Alloy through a Heterogeneous Structure,” Acta Materialia 165 (2019): 444-458.

[60]

P. Zhang, X. Hui, Y. Nie, et al., “New Conceptual Catalyst on Spatial High-Entropy Alloy Heterostructures for High-Performance Li-O2 Batteries,” Small 19, no. 15 (2023): 2206742.

[61]

F. Lyu, C. Liu, S. Zeng, et al., “Boosting Hydrogen Evolution Activity: Next-Nearest Oxygen Coordination in Dual-Phase Supra-Nanostructured Multiprincipal Element Alloy Catalysts,” Energy & Environmental Science 17 (2024): 7908-7918.

[62]

L. Yao, F. Zhang, S. Yang, et al., “Sub-2 Nm IrRuNiMoCo High-Entropy Alloy With Iridium-Rich Medium-Entropy Oxide Shell to Boost Acidic Oxygen Evolution,” Advanced Materials 36, no. 25 (2024): 2314049.

[63]

Z. Huang, T. Li, B. Li, et al., “Tailoring Local Chemical Ordering via Elemental Tuning in High-Entropy Alloys,” Journal of the American Chemical Society 146, no. 3 (2024): 2167-2173.

[64]

J. Chang, G. Wang, C. Li, et al., “Rational Design of Septenary High-Entropy Alloy for Direct Ethanol Fuel Cells,” Joule 7, no. 3 (2023): 587-602.

[65]

M. Wu, M. Cui, L. Wu, et al., “Hierarchical Polyelemental Nanoparticles as Bifunctional Catalysts for Oxygen Evolution and Reduction Reactions,” Advanced Energy Materials 10, no. 25 (2020): 2001119.

[66]

S. Moniri, Y. Yang, J. Ding, et al., “Three-Dimensional Atomic Structure and Local Chemical Order of Medium- and High-Entropy Nanoalloys,” Nature 624, no. 7992 (2023): 564-569.

[67]

Q. Ding, Y. Zhang, X. Chen, et al., “Tuning Element Distribution, Structure and Properties by Composition in High-Entropy Alloys,” Nature 574, no. 7777 (2019): 223-227.

[68]

J. Ding, Q. Yu, M. Asta, and R. O. Ritchie, “Tunable Stacking Fault Energies by Tailoring Local Chemical Order in CrCoNi Medium-Entropy Alloys,” Proceedings of the National Academy of Sciences 115, no. 36 (2018): 8919-8924.

[69]

Y. Yang, Z. Jia, X. Zhang, et al., “Chemical Short-Range Order in Multi-Principal Element Alloy with Ordering Effects on Water Electrolysis Performance,” Materials Today 72 (2024): 97-108.

[70]

C. Zhan, L. Bu, H. Sun, et al., “Medium/High-Entropy Amalgamated Core/Shell Nanoplate Achieves Efficient Formic Acid Catalysis for Direct Formic Acid Fuel Cell,” Angewandte Chemie International Edition 62, no. 3 (2023): e202213783.

[71]

J. Hu, T. Guo, X. Zhong, et al., “In Situ Reconstruction of High-Entropy Heterostructure Catalysts for Stable Oxygen Evolution Electrocatalysis under Industrial Conditions,” Advanced Materials 36, no. 14 (2024): 2310918.

[72]

S. Chen, Z. H. Aitken, S. Pattamatta, et al., “Chemical-Affinity Disparity and Exclusivity Drive Atomic Segregation, Short-Range Ordering, and Cluster Formation in High-Entropy Alloys,” Acta Materialia 206 (2021): 116638.

[73]

Z. An, A. Li, S. Mao, et al., “Negative Mixing Enthalpy Solid Solutions Deliver High Strength and Ductility,” Nature 625, no. 7996 (2024): 697-702.

[74]

Z. An, T. Yang, C. Shi, et al., “Negative Enthalpy Alloys and Local Chemical Ordering: A Concept and Route Leading to Synergy of Strength and Ductility,” National Science Review 11, no. 4 (2024): nwae026.

[75]

Y. Wang, N. Gong, H. Liu, et al., “Ordering-Dependent Hydrogen Evolution and Oxygen Reduction Electrocatalysis of High-Entropy Intermetallic Pt4FeCoCuNi,” Advanced Materials 35, no. 28 (2023): 2302067.

[76]

M. Cui, C. Yang, S. Hwang, et al., “Multi-Principal Elemental Intermetallic Nanoparticles Synthesized Via a Disorder-to-Order Transition,” Science Advances 8, no. 4 (2022): eabm4322.

[77]

W. Yan, X. Wang, M. Liu, et al., “PCTS-Controlled Synthesis of L10/L12-Typed Pt-Mn Intermetallics for Electrocatalytic Oxygen Reduction,” Advanced Functional Materials 34, no. 6 (2024): 2310487.

[78]

Y. Kang, O. Cretu, J. Kikkawa, et al., “Mesoporous Multimetallic Nanospheres with Exposed Highly Entropic Alloy Sites,” Nature Communications 14, no. 1 (2023): 4182.

[79]

B. Jiang, C. Li, M. Imura, J. Tang, and Y. Yamauchi, “Multimetallic Mesoporous Spheres through Surfactant-Directed Synthesis,” Advanced Science 2, no. 8 (2015): 1500112.

[80]

N.-F. Yu, N. Tian, Z.-Y. Zhou, et al., “Electrochemical Synthesis of Tetrahexahedral Rhodium Nanocrystals with Extraordinarily High Surface Energy and High Electrocatalytic Activity,” Angewandte Chemie International Edition 53, no. 20 (2014): 5097-5101.

[81]

M. L. De Marco, W. Baaziz, S. Sharna, et al., “High-Entropy-Alloy Nanocrystal Based Macro-and Mesoporous Materials,” ACS Nano 16, no. 10 (2022): 15837-15849.

[82]

T. Li, Y. Yao, Z. Huang, et al., “Denary Oxide Nanoparticles as Highly Stable Catalysts for Methane Combustion,” Nature Catalysis 4, no. 1 (2021): 62-70.

[83]

T. B. Reed. “Free Energy of Formation of Binary Compouds” (MIT Press, 1971).

[84]

S. Hou, X. Ma, Y. Shu, et al., “Self-Regeneration of Supported Transition Metals by a High Entropy-Driven Principle,” Nature Communications 12, no. 1 (2021): 5917.

[85]

B. Song, Y. Yang, M. Rabbani, et al., “In Situ Oxidation Studies of High-Entropy Alloy Nanoparticles,” ACS Nano 14, no. 11 (2020): 15131-15143.

[86]

Y. Sun, K. Liang, R. Tu, et al., “Selective Hydrodeoxygenation of Lignin-Derived Vanillin via Hetero-Structured High-Entropy Alloy/Oxide Catalysts,” Energy & Environmental Materials 7 (2024): e12638.

[87]

A. A. H. Tajuddin, M. Wakisaka, T. Ohto, et al., “Corrosion-Resistant and High-Entropic Non-Noble-Metal Electrodes for Oxygen Evolution in Acidic Media,” Advanced Materials 35, no. 3 (2023): 2207466.

[88]

X. Zhao, H. Cheng, X. Chen, et al., “Multiple Metal-Nitrogen Bonds Synergistically Boosting the Activity and Durability of High-Entropy Alloy Electrocatalysts,” Journal of the American Chemical Society 146, no. 5 (2024): 3010-3022.

[89]

J. M. Veglak, A. Tsai, S. S. Soliman, G. R. Dey, and R. E. Schaak, “Disentangling Competitive and Synergistic Chemical Reactivities During the Seeded Growth of High-Entropy Alloys on High-Entropy Metal Sulfide Nanoparticles,” Journal of the American Chemical Society 146, no. 28 (2024): 19521-19536.

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