Skip to main content
SpringerLink
Log in

Semimetallic hydroxide materials for electrochemical water oxidation

半金属氢氧化物材料用于电化学水氧化

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Searching for catalyst materials with high intrinsic activity for water oxidation holds the key to numerous clean energy technologies. Hydroxide semiconductors are electrochemically active to drive oxygen evolution reaction (OER), but suffer from poor electronic conductivity, restricting their intrinsic electrocatalytic activity. Here, a semimetallic hydroxide material was designed as efficient OER catalyst with both improved electronic conductivity and intrinsic electrocatalytic activity. By cationic doping and anionic vacancy manipulation, the NiFe layered double hydroxide (LDH) semiconductor was turned into semi-metallic with two orders of magnitude lower resistivity. Consequently, the semi-metallic LDH (SM LDH) array electrode exhibited an intrinsically improved OER activity with a low overpotential of 195 mV at 10 mA cm−2 and a low Tafel slope of 40.9 mV dec−1 in alkaline medium, outperforming commercial RuO2 catalysts (316 mV, 99.6 mV dec−1) under the same test condition. In-depth Raman and first-principles calculations demonstrated that the enhanced OER intrinsic activity of SM LDH was associated with the high electronic conductivity, which promoted the formation and stabilization of high-valence metal sites in oxyhydroxide intermediates. These finding suggest semi-metallic hydroxides as an advanced electrode material with both fascinating electric and catalytic properties.

摘要

寻找具有高本征活性的水氧化催化剂材料对许多清洁能源技术 的发展至关重要. 氢氧化物半导体对析氧反应具有一定的电催化活性. 然而, 该材料导电性较差, 限制着其电催化本征活性的提升. 本文提出 一种兼具高导电性和高催化活性的半金属氢氧化物析氧电催化材料. 通过阳离子掺杂和阴离子空位协同作用, 镍铁水滑石半导体可转化为 半金属材料, 其电阻率降低了两个数量级. 相应半金属氢氧化物阵列电 极的电催化活性显著提升, 在10 mA cm−2电流密度下其析氧过电势仅 为195 mV, Tafel斜率仅为40.9 mV dec−1, 显著优于商用RuO2催化剂 (316 mV, 99.6 mV dec−1). 原位拉曼光谱和理论计算结果表明, 半金属 氢氧化物可在较低过电位下转化为羟基氧化物中间体, 有助于高价态 金属活性位点的形成与稳定, 从而提升材料的析氧本征活性. 本研究表 明, 兼具优异导电性和催化活性的半金属氢氧化物可作为先进的电极 材料.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Mefford JT, Akbashev AR, Kang M, et al. Correlative operando microscopy of oxygen evolution electrocatalysts. Nature, 2021, 593: 67–73

    Article  CAS  PubMed  Google Scholar 

  2. Kang J, Qiu X, Hu Q, et al. Valence oscillation and dynamic active sites in monolayer NiCo hydroxides for water oxidation. Nat Catal, 2021, 4: 1050–1058

    Article  CAS  Google Scholar 

  3. Shi H, Wang T, Liu J, et al. A sodium-ion-conducted asymmetric electrolyzer to lower the operation voltage for direct seawater electrolysis. Nat Commun, 2023, 14: 3934

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. Zhang Y, Cai Z, Zhao Y, et al. Superaerophilic copper nanowires for efficient and switchable CO2 electroreduction. Nanoscale Horiz, 2019, 4: 490–494

    Article  CAS  PubMed  Google Scholar 

  5. Xiong P, Tan J, Lee H, et al. Two-dimensional carbon-based heterostructures as bifunctional electrocatalysts for water splitting and metal-air batteries. Nano Mater Sci, 2022, doi: https://doi.org/10.1016/j.nanoms.2022.10.001

  6. Chen M, Kitiphatpiboon N, Feng C, et al. Recent progress in transition-metal-oxide-based electrocatalysts for the oxygen evolution reaction in natural seawater splitting: A critical review. eScience, 2023, 3: 100111

    Article  Google Scholar 

  7. Zhou Y, Li C, Zhang Y, et al. Controllable thermochemical generation of active defects in the horizontal/vertical MoS2 for enhanced hydrogen evolution. Adv Funct Mater, 2023, 33: 2304302

    Article  CAS  Google Scholar 

  8. Li G, Duan X, Liu X, et al. Locking active Li metal through localized redistribution of fluoride enabling stable Li-metal batteries. Adv Mater, 2023, 35: 2207310

    Article  CAS  Google Scholar 

  9. Zhang N, Hu Y, An L, et al. Surface activation and Ni-S stabilization in NiO/NiS2 for efficient oxygen evolution reaction. Angew Chem Int Ed, 2022, 61: e202207217

    Article  CAS  Google Scholar 

  10. Chen YF, Li JH, Liu TT, et al. Constructing robust NiFe LDHs–NiFe alloy gradient hybrid bifunctional catalyst for overall water splitting: one-step electrodeposition and surface reconstruction. Rare Met, 2023, 42: 2272–2283

    Article  CAS  Google Scholar 

  11. Xie R, Luo W, Zou L, et al. Low-temperature synthesis of colloidal few-layer WTe2 nanostructures for electrochemical hydrogen evolution. Discover Nano, 2023, 18: 44

    Article  PubMed  PubMed Central  Google Scholar 

  12. Jia B, Zhang B, Cai Z, et al. Construction of amorphous/crystalline heterointerfaces for enhanced electrochemical processes. eScience, 2023, 3: 100112

    Article  Google Scholar 

  13. Cai Z, Bi Y, Hu E, et al. Single-crystalline ultrathin Co3O4 nanosheets with massive vacancy defects for enhanced electrocatalysis. Adv Energy Mater, 2017, 8: 1701694

    Article  Google Scholar 

  14. Lee YJ, Park SK. Synergistically coupling of Ni–Fe LDH arrays with hollow Co–Mo sulfide nanotriangles for highly efficient overall water splitting. Rare Met, 2024, 43: 522–532

    Article  CAS  Google Scholar 

  15. Zhu H, Sun S, Hao J, et al. A high-entropy atomic environment converts inactive to active sites for electrocatalysis. Energy Environ Sci, 2023, 16: 619–628

    Article  CAS  Google Scholar 

  16. Xiao Z, Zhou W, Yang B, et al. Tuned d-band states over lanthanum doped nickel oxide for efficient oxygen evolution reaction. Nano Mater Sci, 2023, 5: 228–236

    Article  CAS  Google Scholar 

  17. Xu X, Wang S, Guo S, et al. Cobalt phosphosulfide nanoparticles encapsulated into heteroatom-doped carbon as bifunctional electrocatalyst for Zn-air battery. Adv Powder Mater, 2022, 1: 100027

    Article  Google Scholar 

  18. Lin R, Kang L, Zhao T, et al. Identification and manipulation of dynamic active site deficiency-induced competing reactions in electrocatalytic oxidation processes. Energy Environ Sci, 2022, 15: 2386–2396

    Article  CAS  Google Scholar 

  19. Duan X, Getaye Sendeku M, Zhang D, et al. Tungsten-doped NiFe-layered double hydroxides as efficient oxygen evolution catalysts. Acta Physico Chim Sin, 2023, 0: 2303055

    Article  Google Scholar 

  20. Han X, Li N, Baik JS, et al. Sulfur mismatch substitution in layered double hydroxides as efficient oxygen electrocatalysts for flexible zinc–air batteries. Adv Funct Mater, 2023, 33: 2212233

    Article  CAS  Google Scholar 

  21. Deng R, Guo M, Wang C, et al. Recent advances in cobalt phosphide-based materials for electrocatalytic water splitting: From catalytic mechanism and synthesis method to optimization design. Nano Mater Sci, 2022, doi: https://doi.org/10.1016/j.nanoms.2022.04.003

  22. Chen L, Wang H, Tan L, et al. PEO-PPO-PEO induced holey NiFe-LDH nanosheets on Ni foam for efficient overall water-splitting and urea electrolysis. J Colloid Interface Sci, 2022, 618: 141–148

    Article  CAS  PubMed  Google Scholar 

  23. Wang L, Zhang L, Ma W, et al. In situ anchoring massive isolated Pt atoms at cationic vacancies of α-NixFe1−x(OH)2 to regulate the electronic structure for overall water splitting. Adv Funct Mater, 2022, 32: 2203342

    Article  CAS  Google Scholar 

  24. Hu R, Wei L, Xian J, et al. Microwave shock process for rapid synthesis of 2D porous La0.2Sr0.8CoO3 perovskite as an efficient oxygen evolution reaction catalyst. Acta Physico Chim Sin, 2023, 0: 2212025

    Article  Google Scholar 

  25. Duan X, Li T, Jiang X, et al. Catalytic applications of single-atom metal-anchored hydroxides: Recent advances and perspective. Mater Rep-Energy, 2022, 2: 100146

    CAS  Google Scholar 

  26. Xie Q, Cai Z, Li P, et al. Layered double hydroxides with atomic-scale defects for superior electrocatalysis. Nano Res, 2018, 11: 4524–4534

    Article  CAS  Google Scholar 

  27. Wang H, Chen L, Tan L, et al. Electrodeposition of NiFe-layered double hydroxide layer on sulfur-modified nickel molybdate nanorods for highly efficient seawater splitting. J Colloid Interface Sci, 2022, 613: 349–358

    Article  CAS  PubMed  Google Scholar 

  28. Wang Z, Wang C, Ye L, et al. MnOx film-coated NiFe-LDH nanosheets on Ni foam as selective oxygen evolution electrocatalysts for alkaline seawater oxidation. Inorg Chem, 2022, 61: 15256–15265

    Article  CAS  PubMed  Google Scholar 

  29. Bi Y, Cai Z, Zhou D, et al. Understanding the incorporating effect of Co2+/Co3+ in NiFe-layered double hydroxide for electrocatalytic oxygen evolution reaction. J Catal, 2018, 358: 100–107

    Article  CAS  Google Scholar 

  30. Luo M, Cai Z, Wang C, et al. Phosphorus oxoanion-intercalated layered double hydroxides for high-performance oxygen evolution. Nano Res, 2017, 10: 1732–1739

    Article  CAS  Google Scholar 

  31. Cai Z, Zhou D, Wang M, et al. Introducing Fe2+ into nickel-iron layered double hydroxide: local structure modulated water oxidation activity. Angew Chem Int Ed, 2018, 57: 9392–9396

    Article  CAS  Google Scholar 

  32. Tan L, Yu J, Wang C, et al. Partial sulfidation strategy to NiFe-LDH@FeNi2S4 heterostructure enable high-performance water/sea-water oxidation. Adv Funct Mater, 2022, 32: 2200951

    Article  CAS  Google Scholar 

  33. Huang C, Zhou Q, Duan D, et al. The rapid self-reconstruction of Fe-modified Ni hydroxysulfide for efficient and stable large-current-density water/seawater oxidation. Energy Environ Sci, 2022, 15: 4647–4658

    Article  CAS  Google Scholar 

  34. Xiong X, Cai Z, Zhou D, et al. A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide. Sci China Mater, 2018, 61: 939–947

    Article  CAS  Google Scholar 

  35. Bao Y, Lian C, Huang K, et al. Generating high-valent iron-oxo ≡FeIV=O complexes in neutral microenvironments through peroxymonosulfate activation by Zn–Fe layered double hydroxides. Angew Chem Int Ed, 2022, 61: e202209542

    Article  CAS  Google Scholar 

  36. Yuan Z, Bak SM, Li P, et al. Activating layered double hydroxide with multivacancies by memory effect for energy-efficient hydrogen production at neutral pH. ACS Energy Lett, 2019, 4: 1412–1418

    Article  CAS  Google Scholar 

  37. Xin K, Yang W, Xia J, et al. Research progress of ultra-wide bandgap two-dimensional semiconductor materials and devices. Sci Sin-Phys Mech Astron, 2022, 52: 297302

    Google Scholar 

  38. Kumar N, Shekhar C, Wu SC, et al. Observation of pseudo-two-dimensional electron transport in the rock salt-type topological semi-metal LaBi. Phys Rev B, 2016, 93: 241106

    Article  Google Scholar 

  39. Zhao Y, Zhang X, Jia X, et al. Sub-3 nm ultrafine monolayer layered double hydroxide nanosheets for electrochemical water oxidation. Adv Energy Mater, 2018, 8: 1703585

    Article  Google Scholar 

  40. Faid AY, Barnett AO, Seland F, et al. Ni/NiO nanosheets for alkaline hydrogen evolution reaction: In situ electrochemical-Raman study. Electrochim Acta, 2020, 361: 137040

    Article  CAS  Google Scholar 

  41. Qiu Z, Tai CW, Niklasson GA, et al. Direct observation of active catalyst surface phases and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting. Energy Environ Sci, 2019, 12: 572–581

    Article  CAS  Google Scholar 

  42. Jing C, Yuan T, Li L, et al. Electrocatalyst with dynamic formation of the dual-active site from the dual pathway observed by in situ Raman spectroscopy. ACS Catal, 2022, 12: 10276–10284

    Article  CAS  Google Scholar 

  43. Lan L, Li Q, Gu G, et al. Hydrothermal synthesis of γ-MnOOH nanorods and their conversion to MnO2, Mn2O3, and Mn3O4 nanorods. J Alloys Compd, 2015, 644: 430–437

    Article  CAS  Google Scholar 

  44. Enkhtuvshin E, Yeo S, Choi H, et al. Surface reconstruction of Ni–Fe layered double hydroxide inducing chloride ion blocking materials for outstanding overall seawater splitting. Adv Funct Mater, 2023, 33: 2214069

    Article  CAS  Google Scholar 

  45. Trześniewski BJ, Diaz-Morales O, Vermaas DA, et al. In situ observation of active oxygen species in Fe-containing Ni-based oxygen evolution catalysts: the effect of pH on electrochemical activity. J Am Chem Soc, 2015, 137: 15112–15121

    Article  PubMed  Google Scholar 

  46. Friebel D, Louie MW, Bajdich M, et al. Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. J Am Chem Soc, 2015, 137: 1305–1313

    Article  CAS  PubMed  Google Scholar 

  47. Lu T, Chen F. Multiwfn: A multifunctional wavefunction analyzer. J Comput Chem, 2012, 33: 580–592

    Article  PubMed  Google Scholar 

  48. Zhou L, Zhang C, Zhang Y, et al. Host modification of layered double hydroxide electrocatalyst to boost the thermodynamic and kinetic activity of oxygen evolution reaction. Adv Funct Mater, 2021, 31: 2009743

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (22205068 and 22109144), the “CUG Scholar” Scientific Research Funds at China University of Geosciences (Wuhan) (2022118), and the Fundamental Research Funds for the Central Universities, China University of Geosciences (Wuhan) (162301202673). We appreciate eceshi (www.eceshi.com) and Shiyanjia Lab (www.shiyanjia.com) for the PPMS analyses. Thanks to the in-situ Raman electrochemical cell from Hefei In-situ Technology. Co., Ltd.

Author information

Authors and Affiliations

  1. Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, 430074, China

    Jing Wang  (王静), Qiang Gao  (高强), Bo Han  (韩波), Ruimin Sun  (孙睿敏), Chenggang Zhou  (周成冈) & Zhao Cai  (蔡钊)

  2. School of Energy and Environment, Department of Materials Science and Engineering, City University of Hong Kong, Kowloon Tong, Hong Kong, 999077, China

    Mohammed-Ibrahim Jamesh & Hsien-Yi Hsu

Authors
  1. Jing Wang  (王静)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mohammed-Ibrahim Jamesh
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qiang Gao  (高强)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bo Han  (韩波)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ruimin Sun  (孙睿敏)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Hsien-Yi Hsu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Chenggang Zhou  (周成冈)
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Zhao Cai  (蔡钊)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Author contributions Wang J, Zhou C and Cai Z conceived the project. Wang J, Gao Q, Han B, Sun R and Zhao C performed the experiments. Wang J, Jamesh MI, Hsu HY and Cai Z wrote the manuscript. Cai Z and Zhou C supervised the project. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Zhao Cai  (蔡钊).

Ethics declarations

Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Jing Wang received her Bachelor and Master’s degrees from China University of Geoscience (Wuhan) in 2019 and 2022, respectively. She is pursuing her doctoral degree under the supervision of Prof. Zhao Cai at China University of Geoscience (Wuhan). Her research interests mainly focus on transition metal-based nanomaterials for electrocatalysis.

Zhao Cai gained his BS degree and PhD in Chemistry from Beijing University of Chemical Technology in 2012 and 2018, respectively. After working as a visiting scholar at Yale University and postdoctoral researcher at Wuhan National Laboratory for Optoelectronics, he joined China University of Geosciences (Wuhan) as a professor of chemistry in 2022. His research focuses on developing novel transition metal nanostructures for key energy conversion and storage processes, such as electrocatalysis and aqueous batteries.

Supplementary Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, J., Jamesh, MI., Gao, Q. et al. Semimetallic hydroxide materials for electrochemical water oxidation. Sci. China Mater. 67, 1551–1558 (2024). https://doi.org/10.1007/s40843-023-2802-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-023-2802-8

Keywords

Search

Navigation