Three factors make bulk high-entropy alloys as effective electrocatalysts for oxygen evolution

Tao Zhang; Huifeng Zhao; Keyan Wang; Zhenjie Chen; Li Li; Jing Peng; Xu Peng; Yongjiang Huang; Haibin Yu

doi:10.1088/2752-5724/aceef3

Volume 2 Issue 4

December 2023

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Tao Zhang, Huifeng Zhao, Keyan Wang, Zhenjie Chen, Li Li, Jing Peng, Xu Peng, Yongjiang Huang, Haibin Yu. Three factors make bulk high-entropy alloys as effective electrocatalysts for oxygen evolution[J]. Materials Futures, 2023, 2(4): 045101. doi: 10.1088/2752-5724/aceef3

Citation:

Tao Zhang, Huifeng Zhao, Keyan Wang, Zhenjie Chen, Li Li, Jing Peng, Xu Peng, Yongjiang Huang, Haibin Yu. Three factors make bulk high-entropy alloys as effective electrocatalysts for oxygen evolution[J]. Materials Futures, 2023, 2(4): 045101. doi: 10.1088/2752-5724/aceef3

Citation:

Tao Zhang, Huifeng Zhao, Keyan Wang, Zhenjie Chen, Li Li, Jing Peng, Xu Peng, Yongjiang Huang, Haibin Yu. Three factors make bulk high-entropy alloys as effective electrocatalysts for oxygen evolution[J]. Materials Futures, 2023, 2(4): 045101. doi: 10.1088/2752-5724/aceef3

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Three factors make bulk high-entropy alloys as effective electrocatalysts for oxygen evolution

Materials Futures, Volume 2, Number 4

Received Date: 2023-07-06
Accepted Date: 2023-08-07
Publish Date: 2023-08-25

Article information

doi: 10.1088/2752-5724/aceef3

1 Wuhan National High Magnetic Field Center & School of Physics, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
2 College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, People’s Republic of China
3 School of Materials Science and Engineering, Center of Analysis Measurement and Computing, Harbin Institute of Technology, Harbin 150001, People’s Republic of China
4 Faculty of Materials Science and Energy Engineering/Institute of Technology for Carbon Neutrality, Shenzhen 518055, People’s Republic of China
5 Shenzhen Key Laboratory of Energy Materials for Carbon Neutrality, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, People’s Republic of China

Funds:

This work was supported by the National Thousand a Young Talents Program of China, the Fundamental Research Funds for the Central Universities (2018KFYXKJC009), the National Natural Science Foundation of China (51871076), the NSFC of Hubei (Grant 2021CFB420).The computational work was carried out on the public computing service platform provided by the Network and Computing Center of HUST.

Abstract

Abstract

Even in their bulk forms, complex alloys like high-entropy alloys (HEAs) exhibit favorable activity and stability as electrocatalysts for the oxygen evolution reaction (OER). However, the underlying reasons are not yet fully understood. In a family of Mo-doped CrFeCoNi-based HEAs, we have identified three crucial factors that govern their performance: (i) homogeneous solid solution phase of HEAs helps to maintain high-valence states of metals; (ii) surface reconstruction results in a hybrid material comprising amorphous domains and percolated crystalline structures; (iii) diversity of active intermediate species (M–O, M–OOH, and, notably, the abundance of superoxide μ–OO), which display stronger adsorption capacity on the reconstructed surface. These results are revealing due to their resemblance to findings in other families of electrocatalysts for OER, as well as their unique features specific to HEAs. In line with these factors, a CrFeCoNiMo0.2 bulk integrated electrode displays a low overpotential of 215 mV, rapid kinetics, and long-term stability of over 90 d. Bulk HEAs hold great potential for industrial applications.
- high-entropy alloy,
- solid solution,
- electrocatalysis,
- DFT calculation,
- oxygen evolution reaction

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References(57)

References

[1]	Chu S and Majumdar A 2012 Opportunities and challenges for a sustainable energy future Nature 488 294–303
[2]	Kulkarni A, Siahrostami S, Patel A and Norskov J K 2018 Understanding catalytic activity trends in the oxygen reduction reaction Chem. Rev. 118 2302–12
[3]	Seh Z W, Kibsgaard J, Dickens C F, Chorkendorff I, Norskov J K and Jaramillo T F 2017 Combining theory and experiment in electrocatalysis: insights into materials design Science 355 eaad4998
[4]	Suen N T, Hung S F, Quan Q, Zhang N, Xu Y J and Chen H M 2017 Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives Chem. Soc. Rev. 46 337–65
[5]	Li Y J, Sun Y J, Qin Y N, Zhang W Y, Wang L, Luo M C, Yang H and Guo S J 2020 Recent advances on water-splitting electrocatalysis mediated by noble-metal-based nanostructured materials Adv. Energy Mater. 10 1903120
[6]	Yao Y C et al 2019 Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis Nat. Catal. 2 304–13
[7]	Song J, Wei C, Huang Z F, Liu C, Zeng L, Wang X and Xu Z J 2020 A review on fundamentals for designing oxygen evolution electrocatalysts Chem. Soc. Rev. 49 2196–214
[8]	Kang Y et al 2021 Heterostructuring mesoporous 2D iridium nanosheets with amorphous nickel boron oxide layers to improve electrolytic water splitting Small Methods 5 e2100679
[9]	Yan X, Zou Y and Zhang Y 2022 Properties and processing technologies of high-entropy alloys Mater. Futures 1 022002
[10]	George E P, Raabe D and Ritchie R O 2019 High-entropy alloys Nat. Rev. Mater. 4 515–34
[11]	Löffler T, Savan A, Garzón-Manjón A, Meischein M, Scheu C, Ludwig A and Schuhmann W 2019 Toward a paradigm shift in electrocatalysis using complex solid solution nanoparticles ACS Energy Lett. 4 1206–14
[12]	Batchelor T A A, Pedersen J K, Winther S H, Castelli I E, Jacobsen K W and Rossmeisl J 2019 High-entropy alloys as a discovery platform for electrocatalysis Joule 3 834–45
[13]	Cavin J et al 2021 2D high-entropy transition metal dichalcogenides for carbon dioxide electrocatalysis Adv. Mater. 33 2100347
[14]	Wang T, Chen H, Yang Z, Liang J and Dai S 2020 High-entropy perovskite fluorides: a new platform for oxygen evolution catalysis J. Am. Chem. Soc. 142 4550–4
[15]	Zhang L, Cai W and Bao N 2021 Top-level design strategy to construct an advanced high-entropy Co-Cu-Fe-Mo (Oxy)hydroxide electrocatalyst for the oxygen evolution reaction Adv. Mater. 33 2100745
[16]	Chen Z J et al 2021 Engineering microdomains of oxides in high-entropy alloy electrodes toward efficient oxygen evolution Adv. Mater. 33 2101845
[17]	Ruiz Esquius J and Liu L 2023 High entropy materials as emerging electrocatalysts for hydrogen production through low-temperature water electrolysis Mater. Futures 2 022102
[18]	Kang Y et al 2023 Mesoporous multimetallic nanospheres with exposed highly entropic alloy sites Nat. Commun. 14 4182
[19]	Zhang N, Feng X, Rao D, Deng X, Cai L, Qiu B, Long R, Xiong Y, Lu Y and Chai Y 2020 Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation Nat. Commun. 11 4066
[20]	Ding Z Y, Bian J, Shuang S, Liu X D, Hu Y C, Sun C W and Yang Y 2020 High entropy intermetallic-oxide core-shell nanostructure as superb oxygen evolution reaction catalyst Adv. Sustain. Syst. 4 1900105
[21]	Jin Z et al 2019 Nanoporous Al-Ni-Co-Ir-Mo high-entropy alloy for record-high water splitting activity in acidic environments Small 15 1904180
[22]	Liu Y, Liang X, Gu L, Zhang Y, Li G D, Zou X and Chen J S 2018 Corrosion engineering towards efficient oxygen evolution electrodes with stable catalytic activity for over 6000 hours Nat. Commun. 9 2609
[23]	Masa J and Schuhmann W 2020 Breaking scaling relations in electrocatalysis J. Solid State Electr. 24 2181–2
[24]	Sarkar A, Wang Q, Schiele A, Chellali M R, Bhattacharya S S, Wang D, Brezesinski T, Hahn H, Velasco L and Breitung B 2019 High-entropy oxides: fundamental aspects and electrochemical properties Adv. Mater. 31 1806236
[25]	Li H D, Lai J P, Li Z J and Wang L 2021 Multi-sites electrocatalysis in high-entropy alloys Adv. Funct. Mater. 31 2106715
[26]	Ding H, Liu H, Chu W, Wu C and Xie Y 2021 Structural transformation of heterogeneous materials for electrocatalytic oxygen evolution reaction Chem. Rev. 121 13174–212
[27]	Roy C et al 2018 Impact of nanoparticle size and lattice oxygen on water oxidation on NiFeO_xH_y Nat. Catal. 1 820–9
[28]	Li D, Qin Y, Liu J, Zhao H Y, Sun Z J, Chen G B, Wu D Y, Su Y Q, Ding S J and Xiao C H 2021 Dense crystalline-amorphous interfacial sites for enhanced electrocatalytic oxygen evolution Adv. Funct. Mater. 32 2107056
[29]	Chen Y, Lai Z C, Zhang X, Fan Z X, He Q Y, Tan C L and Zhang H 2020 Phase engineering of nanomaterials Nat. Rev. Chem. 4 243–56
[30]	Zhang L, Jang H, Liu H, Kim M G, Yang D, Liu S, Liu X and Cho J 2021 Sodium-decorated amorphous/crystalline RuO₂ with rich oxygen vacancies: a robust pH-universal oxygen evolution electrocatalyst Angew. Chem., Int. Ed. 60 18821–9
[31]	Wang H Y, Hung S F, Hsu Y Y, Zhang L, Miao J, Chan T S, Xiong Q and Liu B 2016 In situ spectroscopic identification of µ–OO bridging on spinel Co₃O₄ water oxidation electrocatalyst J. Phys. Chem. Lett. 7 4847–53
[32]	Garcia A C, Touzalin T, Nieuwland C, Perini N and Koper M T M 2019 Enhancement of oxygen evolution activity of nickel oxyhydroxide by electrolyte alkali cations Angew. Chem., Int. Ed. 58 12999–3003
[33]	Zhang B et al 2020 High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics Nat. Catal. 3 985–92
[34]	Liu P F, Yang S, Zheng L R, Zhang B and Yang H G 2017 Mo⁶⁺ activated multimetal oxygen-evolving catalysts Chem. Sci. 8 3484–8
[35]	Martin-Sabi M, Soriano-Lopez J, Winter R S, Chen J J, Vila-Nadal L, Long D L, Galan-Mascaros J R and Cronin L 2018 Redox tuning the Weakley-type polyoxometalate archetype for the oxygen evolution reaction Nat. Catal. 1 208–13
[36]	Bajdich M, Garcia-Mota M, Vojvodic A, Norskov J K and Bell A T 2013 Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water J. Am. Chem. Soc. 135 13521–30
[37]	Kresse G and Hafner J 1993 Ab initio molecular dynamics for open-shell transition metals Phys. Rev. B 48 13115–8
[38]	Wang V, Xu N, Liu J C, Tang G and Geng W T 2021 VASPKIT: a user-friendly interface facilitating high-throughput computing and analysis using VASP code Comput. Phys. Commun. 267 108033
[39]	Krukau A V, Vydrov O A, Izmaylov A F and Scuseria G E 2006 Influence of the exchange screening parameter on the performance of screened hybrid functionals J. Chem. Phys. 125 224106
[40]	Perdew J P, Burke K and Ernzerhof M 1996 Generalized gradient approximation made simple Phys. Rev. Lett. 77 3865
[41]	Ren C, Lu S, Wu Y, Ouyang Y, Zhang Y, Li Q, Ling C and Wang J 2022 A universal descriptor for complicated interfacial effects on electrochemical reduction reactions J. Am. Chem. Soc. 144 12874–83
[42]	Choudhary K and Tavazza F 2019 Convergence and machine learning predictions of Monkhorst-Pack k-points and plane-wave cut-off in high-throughput DFT calculations Comput. Mater. Sci. 161 300–8
[43]	Liu X L, Zhang J X, Yin J Q, Bi S R, Eisenbach M and Wang Y 2021 Monte Carlo simulation of order-disorder transition in refractory high entropy alloys: a data-driven approach Comput. Mater. Sci. 187 110135
[44]	Liu W H, Lu Z P, He J Y, Luan J H, Wang Z J, Liu B, Liu Y, Chen M W and Liu C T 2016 Ductile CoCrFeNiMo_x high entropy alloys strengthened by hard intermetallic phases Acta Mater. 116 332–42
[45]	Zhang B et al 2016 Homogeneously dispersed multimetal oxygen-evolving catalysts Science 352 333–7
[46]	Zheng X et al 2018 Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft x-ray absorption Nat. Chem. 10 149–54
[47]	Huang K, Peng D, Yao Z X, Xia J Y, Zhang B W, Liu H, Chen Z B, Wu F, Wu J S and Huang Y Z 2021 Cathodic plasma driven self-assembly of HEAs dendrites by pure single FCC FeCoNiMnCu nanoparticles as high efficient electrocatalysts for OER Chem. Eng. J. 425 131533
[48]	Kang Y, Tang Y, Zhu L, Jiang B, Xu X, Guselnikova O, Li H, Asahi T and Yamauchi Y 2022 Porous nanoarchitectures of nonprecious metal borides: from controlled synthesis to heterogeneous catalyst applications ACS Catal. 12 14773–93
[49]	Jiang B et al 2023 Noble-metal-metalloid alloy architectures: mesoporous amorphous iridium-tellurium alloy for electrochemical N₂ reduction J. Am. Chem. Soc. 145 6079–86
[50]	Hu Y C, Sun C and Sun C 2019 Functional applications of metallic glasses in electrocatalysis ChemCatChem 11 2401–14
[51]	Hu Y C et al 2016 A highly efficient and self-stabilizing metallic-glass catalyst for electrochemical hydrogen generation Adv. Mater. 28 10293–7
[52]	Tao H B, Xu Y, Huang X, Chen J, Pei L, Zhang J, Chen J G and Liu B 2019 A general method to probe oxygen evolution intermediates at operating conditions Joule 3 1498–509
[53]	Mei Y J, Feng Y B, Zhang C X, Zhang Y, Qi Q L and Hu J 2022 High-entropy alloy with Mo-coordination as efficient electrocatalyst for oxygen evolution reaction ACS Catal. 12 10808–17
[54]	Hu C, Hu Y, Fan C, Yang L, Zhang Y, Li H and Xie W 2021 Surface-enhanced Raman spectroscopic evidence of key intermediate species and role of NiFe dualcatalytic center in water oxidation Angew. Chem., Int. Ed. 60 19774–8
[55]	Duan Y et al 2019 Scaled-up synthesis of amorphous NiFeMo oxides and their rapid surface reconstruction for superior oxygen evolution catalysis Angew. Chem., Int. Ed. 58 15772–7
[56]	Chen Y Y, Zhang Y, Zhang X, Tang T, Luo H, Niu S, Dai Z H, Wan L J and Hu J S 2017 Self-templated fabrication of MoNi₄/MoO_3-x nanorod arrays with dual active components for highly efficient hydrogen evolution Adv. Mater. 29 1703311
[57]	Cui X J, Ren P J, Deng D H, Deng J and Bao X H 2016 Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation Energy Environ. Sci. 9 123–9