欢迎访问《电化学(中英文)》期刊官方网站,今天是
论文

高效(Co,Ni,Mn,Cu,Zn)O高熵氧化物纳米管双功能电催化剂用于氧析出及肼氧化反应

  • 陈潘妍 ,
  • 武婉婉 ,
  • 边恒 ,
  • 李伟伟 ,
  • 赵新生 ,
  • 韦露
展开
  • 江苏师范大学物理与电子工程学院江苏 徐州 221116

收稿日期: 2025-11-27

  修回日期: 2026-02-14

  录用日期: 2026-03-11

  网络出版日期: 2026-03-11

(Co,Ni,Mn,Cu,Zn)O High-Entropy Oxide Nanotubes as Efficient Bifunctional Electrocatalyst for Oxygen Evolution and Hydrazine Oxidation Reactions

  • Pan-Yan Chen ,
  • Wan-Wan Wu ,
  • Heng Bian ,
  • Wei-Wei Li ,
  • Xin-Sheng Zhao ,
  • Lu Wei
Expand
  • School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou 221116, Jiangsu, China
Author contributions

Pan-Yan Chen: writing, experiment, data collection and analysis; Wan-Wan Wu: investigation, data analysis; Heng Bian: experiment, investigation; Wei-Wei Li: conceptualization, software; Xin-Sheng Zhao: funding acquisition, supervision; Lu Wei: experimental design, project administration, data analysis, supervision, investigation, funding acquisition, writing-review & editing. All authors read and approved the final manuscript.

Received date: 2025-11-27

  Revised date: 2026-02-14

  Accepted date: 2026-03-11

  Online published: 2026-03-11

摘要

高熵氧化物(HEOs)因其多元素和高熵特性,在设计与合成方面面临重大挑战。这主要源于其需将多种金属阳离子和氧阴离子以等摩尔比例进行复杂组合,以实现稳定的晶体结构。本文采用一种梯度静电纺丝策略,通过调控聚乙烯醇的分子量分布并结合可控热解工艺,成功制备了一维(Co,Ni,Mn,Cu,Zn)O高熵氧化物纳米管(HEO-NTs)。得益于高熵特性及多组分位点的协同效应,所合成的(Co,Ni,Mn,Cu,Zn)O HEO-NTs在氧析出反应(OER)与肼氧化反应(HzOR)中表现出卓越的双功能电催化活性。本研究为高熵氧化物纳米管的设计提供了新思路,并揭示了多组分协同效应增强高熵氧化物在OER与HzOR中电催化性能的作用机制。

本文引用格式

陈潘妍 , 武婉婉 , 边恒 , 李伟伟 , 赵新生 , 韦露 . 高效(Co,Ni,Mn,Cu,Zn)O高熵氧化物纳米管双功能电催化剂用于氧析出及肼氧化反应[J]. 电化学, 2026 , 32(5) : 2511271 . DOI: 10.61558/2993-074X.3608

Abstract

High-entropy oxides (HEOs) present significant scientific challenges in both design and synthesis due to their multielement and high-entropy nature, which involves complex combinations of multiple metal cations and oxygen anions, typically arranged in equimolar ratios to achieve structural stability. Herein, one-dimensional (Co,Ni,Mn,Cu,Zn)O high-entropy oxide nanotubes (HEO-NTs) are fabricated by means of a gradient electrospinning strategy with a tailored polyvinyl alcohol (PVA) molecular weight distribution and controlled pyrolysis. Benefiting from the HEO features and the synergistic effect of multicomponent sites, the as-synthesized (Co,Ni,Mn,Cu,Zn)O HEO-NTs exhibit exceptional bifunctional electrocatalytic activity for the oxygen evolution and hydrazine oxidation reactions (OER/HzOR). This study offers new insight into the design of HEO-NTs and unveiling the multicomponent synergy on HEOs for enhanced electrocatalytic activities of OER and HzOR.

参考文献

[1] Yao Y G, Dong Q, Brozena A, Luo J, Miao J W, Chi M F, Wang C, Kevrekidis I G, Ren Z J, Greeley J, Wang G F, Anapolsky A, Hu L B. High-entropy nanoparticles: Synthesis-structure-property relationships and data-driven discovery[J]. Science, 2022, 376(6589): abn3103. https://dx.doi.org/10.1126/science.abn3103.
[2] Sun Y F, Dai S. High-entropy materials for catalysis: A new frontier[J]. Sci. Adv., 2021, 7(20): eabg1600. https://dx.doi.org/10.1126/sciadv.abg1600.
[3] Wang Z, Tan X J, Ye Z Y, Chen S Y, Li G J, Wang Q, Yuan S. High entropy materials: potential catalysts for electrochemical water splitting[J]. Green. Chem., 2024, 26(18): 9569-9598. https://dx.doi.org/10.1039/d4gc02329c.
[4] Kirsch A, B?jesen E D, Lefeld N, Larsen R, Mathiesen J K, Skj?rv? S L, Pittkowski R K, Sheptyakov D, Jensen K M ?. High-entropy oxides in the mullite-type structure[J]. Chem. Mater., 2023, 35(20): 8664-8674. https://dx.doi.org/10.1021/acs.chemmater.3c01830.
[5] Zhai Y Y, Ren X R, Wang B L, Liu S Z. High-entropy catalyst—A novel platform for electrochemical water splitting[J]. Adv. Funct. Mater., 2022, 32(47): 2207536. https://dx.doi.org/10.1002/adfm.202207536.
[6] Nandan R, Nam H N, Phung Q M, Nara H, Henzie J, Yamauchi Y. Mesoporous single-crystal high-entropy alloy[J]. JACS., 2025, 147(22): 18651-18661. https://dx.doi.org/10.1021/jacs.5c01260.
[7] Xin Y, Li S H, Qian Y Y, Zhu W K, Yuan H B, Jiang P Y, Guo R H, Wang L B. High-entropy alloys as a platform for catalysis: progress, challenges, and opportunities[J]. ACS Catal., 2020, 10(19): 11280-11306. DOI: 10.1021/acscatal.0c03617.
[8] Zhang Y Q, Wang D D, Wang S Y. High-entropy alloys for electrocatalysis: Design, characterization, and applications[J]. Small., 2021, 18(7): 2104339. https://dx.doi.org/10.1002/smll.202104339.
[9] George E P, Raabe D, Ritchie R O. High-entropy alloys[J]. Nat. Rev. Mater., 2019, 4(8): 515-534. https://doi.org/10.1038/s41578-019-0121-4.
[10] Miracle D B, Senkov O N. A critical review of high entropy alloys[J]. Adv. Mater., 2017, 122: 448-511. https://doi.org/10.1016/j.actamat.2016.08.081.
[11] Zhang W R, Liaw P K, Zhang Y. Science and technology in high-entropy alloys[J]. Sci. China. Mater., 2018, 61(1): 2-22. https://doi.org/10.1007/s40843-017-9195-8.
[12] Wang W, Song W J, Li Y S, Guo Y Q, Yang K Q, Yu L H, Xie F R, Ren Q Q, He K, Wang S, Yuan Y F. Mesocrystallinely stabilized lithium storage in high-entropy oxides[J]. Nano Energ., 2024, 124: 109482. https://doi.org/10.1016/j.nanoen.2024.109482.
[13] Gao H, Li J Y, Zhang F, Li C C, Xiao J, Nie X M, Zhang G L, Xiao Y, Zhang D Y, Guo X, Wang Y, Kang Y M, Wang G X, Liu H. Revealing the potential and challenges of high-entropy layered cathodes for sodium-based energy storage[J]. Adv. Energy. Mater., 2024, 14(20): 2304529. https://doi.org/10.1002/aenm.202304529.
[14] Shahbazi H, Seraji P, Farraj H, Yang T M, Kim A, Fattahpour S, Papailias I, Diamond M, Namvar S, Ahmadiparidari A, Wang S X, Liu Z X, Feng S H, Kumar K, Ahart M, Cabana J, Kadkhodaei S, Wang J L, Huang Z H, Hemley R J, Salehi-Khojin A. Resiliency, morphology, and entropic transformations in high-entropy oxide nanoribbons[J]. Science, 2025, 388(6750): 950-956. https://doi.org/10.1126/science.adr5604.
[15] Abdelhafiz A, Wang B, HarutyuAnyan A R, Li J. Carbothermal shock synthesis of high entropy oxide catalysts: dynamic structural and chemical reconstruction boosting the catalytic activity and stability toward oxygen evolution reaction[J]. Adv. Energy. Mater., 2022, 12(35): 2200742. https://doi.org/10.1002/aenm.202200742.
[16] Broge N L N., Bondesgaard M, S?ndergaard‐Pedersen F, Roelsgaard M, Iversen B B. Autocatalytic formation of high-entropy alloy nanoparticles[J]. Angew. Chem. Int. Ed., 2020, 59(49): 21920-21924. https://doi.org/10.1002/anie.202009002.
[17] Li X L, Chen T, Wang C X, Sun N, Zhang G J, Zhou Y C, Wang M, Zhu J, Xu L, Wang S R. An Active and stable high-entropy ruddlesden-popper type La1.4Sr0.6Co0.2Fe0.2Ni0.2Mn0.2Cu0.2O4±δ oxygen electrode for reversible solid oxide cells[J]. Adv. Funct. Mater., 2024, 34(52): 2411216. https://doi.org/10.1002/adfm.202411216.
[18] Iwase K Honma I. high-entropy spinel oxide nanoparticles synthesized via supercritical hydrothermal processing as oxygen evolution electrocatalysts[J]. ACS. Appl. Energy. Mater., 2022, 5(8): 9292-9296. https://doi.org/10.1021/acsaem.2c01751.
[19] Gao Y, Tian X C, Niu Q, Zhang P F. General synthesis of high-entropy oxides and carbon-supported high‐entropy oxides by mechanochemistry[J]. ChemSusChem., 2024, 18(2): 2401517. https://doi.org/10.1002/cssc.202401517.
[20] ?nci? E, Bi?lgi?n S, Sünbül S E, Alver ü, ?ztürk S ??i?n K. Designing ultra-thin high entropy oxide nanofibers with electrospinning method[J]. Ceramics Int., 2025, 51(25): 46277-46293. https://doi.org/10.1016/j.ceramint.2025.07.336.
[21] Wang C, Wang W, Qi H X, Dai Y Q, Jiang S H, Ding B, Wang X F, Li C J, Zeng J F, Wu T, Li H Y, Wang Y F, Zhao Y, Wang W L, Li Z Y, Mo X M, Hou H Q, Dong L J, Ma H Y, Liu Y, Su C L, Bai J, Wu W W, Guo G, Nie G D, Wang N, Zhu H, Bai J, Fang J, Liang D X, Ba Z C, Han G P, Lu X F, Wang K Z, Zhang X Y, Kang W M, Deng N P, Hu W, Chen W H, Zhang X L, Yang D Z, Wang F Y, Bian Y, Liu Z, Zhang L, Li X, Li L, Li Y X, Huang H, Jia X T, Li X F, Yang D X, Jin X C, Li S Y, Zhang X D, Tang N, Hao R N, Tian F, Mai L Q, Wei Y, Xue J J. Electrospinning and electrospun nanofibers: From academic research to industrial production[J]. Pro. Mater. Sci., 2025, 154: 101494. https://doi.org/10.1016/j.pmatsci.2025.101494.
[22] Zhao R. Multifunctional application of electrospun fiber[J]. Polymers., 2025, 17(18): 2519. https://doi.org/10.3390/polym17182519.
[23] Deng Q Y, Xue L Y, Ma M T, Du J M, Xin H Y, Chen H, Huang M Z, Yang F. A novel high-entropy (Y0.2La0.2Er0.2Ho0.2Tm0.2)6MoO12ceramic nanofibers with high near-infrared reflection and low thermal conductivity[J]. J. Eur. Ceram. Soc., 2025, 45(12): 117461. https://doi.org/10.1016/j.jeurceramsoc.2025.117461.
[24] Huang J H, Pang H L, Liu Z X, Wang X, Zhang C Y, Zhang W, Liu S, He W J. Electrospinning biohybrid technology for wastewater treatment: principle, applications and perspectives[J]. Chem. Eng. J., 2024, 491: 151971. https://doi.org/10.1016/j.cej.2024.151971.
[25] Zhang J, Yu M, Tao S H. Advanced electrospinning nanomaterials: From spinning fabrication techniques to electrochemical applications[J]. Nano Res., 2024, 17(8): 7077-7116. https://doi.org/10.1007/s12274-024-6753-8.
[26] Lei Y P, Wang Q C, Peng S J, Ramakrishna S, Zhang D, Zhou K C. Electrospun inorganic nanofibers for oxygen electrocatalysis: Design, fabrication, and progress[J]. Adv. Energy. Mater., 2020, 10(45): 1902115. https://doi.org/10.1002/aenm.201902115.
[27] Niu C J, Meng J S, Wang X P, Han C H, Yan M Y, Zhao K N, Xu X M, Ren W H, Zhao Y L, Xu L, Zhang Q J, Zhao D Y, Mai L Q. General synthesis of complex nanotubes by gradient electrospinning and controlled pyrolysis[J]. Nat. Commun., 2015, 6(1): 7402. https://doi.org/10.1038/ncomms8402.
[28] Hao S M, Qu J, Zhu Z S, Zhang X Y, Wang Q Q, Yu Z Z. Hollow manganese silicate nanotubes with tunable secondary nanostructures as excellent Fenton‐type catalysts for dye decomposition at ambient temperature[J]. Adv. Funct. Mater., 2016, 26(40): 7334-7342.https://doi.org/10.1002/adfm.201603315.
[29] Zhang Y, Qi K, Lyu P, Petit E, Wu H L, Wang W S, Ma J Y, Wang Y, Salameh C, Voiry D. Grain-boundary engineering boosted undercoordinated active sites for scalable conversion of CO2 to Ethylene[J]. ACS. Nano., 2024, 18(27), 17483-17491. https://doi.org/10.1021/acsnano.3c12662.
[30] Liu R A, Yan Y T, Dun L, Yang T L, Qin B, Wang P J, Cai W, Liu S D, Zheng X H. Oxygen vacancy-mediated high-entropy oxide electrocatalysts for efficient oxygen evolution reaction[J]. Catal. Today., 2025, 8: 100086. https://doi.org/10.1016/j.mtcata.2024.100086.
[31] Aroyo M I. International tables for crystallography volume A: Space-group symmetry[M]. Wiley: Chichester, UK, 2016.
[32] Du K, Liu Y J, Yang Y F, Cui F Y, Wang J S, Han M S, Su J W, Wang J J, Han X P, Hu Y X. High entropy oxides modulate atomic-level interactions for high-performance aqueous zinc-ion batteries[J]. Adv. Mater., 2023, 35(51): 2301538. https://doi.org/10.1002/adma.202301538.
[33] Lee M Y, Ha H, Cho K H, Seo H, Park S, Lee Y H, Kwon S J, Lee T W, Nam K T. Importance of interfacial band structure between the substrate and Mn3O4 nanocatalysts during electrochemical water oxidation[J]. ACS. Catal., 2019, 10(2): 1237-1245. https://doi.org/10.1021/acscatal.9b03831.
[34] Wang L, Zhang L T, Lu X, Wu F Y, Sun X, Zhao H, Li Q. Surprising cocktail effect in high entropy alloys on catalyzing magnesium hydride for solid-state hydrogen storage[J]. Chem. Eng. J., 2023, 465: 142766. https://doi.org/10.1016/j.cej.2023.142766.
[35] Zhou Q, Shi L S, Yang T H, Xing W L, Dong Z F. Interfacial synergy in Co Ce bimetallic catalysts supported on gasification slag-derived porous silica: enhanced reaction dynamic for coal gangue-RDF co-gasification[J]. Chem. Eng. J., 2025, 520: 165997. https://doi.org/10.1016/j.cej.2025.165997.
[36] van der Heijden O, Park S, Vos R E, Eggebeen J J J, Koper M T M. Tafel slope plot as a tool to analyze electrocatalytic reactions[J]. ACS. Energy. Lett., 2024, 9(4): 1871-1879. https://doi.org/10.1021/acsenergylett.4c00266.
[37] Wang S, Zhang J, Gharbi O, Vivier V, Gao M, Orazem M E. Electrochemical impedance spectroscopy[J]. Nat. Rev. Methods. Primers., 2023: 301-350. https://doi.org/10.1115/1.860243_ch3.
[38] Rost C M, Sachet E, Borman T, Moballegh A, Dickey E C, Hou D, Jones J L, Curtarolo S, Maria J P. Entropy-stabilized oxides[J]. Nat. Commun., 2015, 6(1): 8485. https://doi.org/10.1038/ncomms9485.
文章导航

/