Scalable Dealloying Route to Mesoporous Ternary CoNiFe Layered Double Hydroxides for Efficient Oxygen Evolution

  • Chaoqun Dong
    Chaoqun Dong
    Key Laboratory for Liquid−Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jingshi Road 17923, Jinan 250061, P. R. China
    More by Chaoqun Dong
  • Lulu Han
    Lulu Han
    Key Laboratory for Liquid−Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jingshi Road 17923, Jinan 250061, P. R. China
    More by Lulu Han
  • Chi Zhang
    Chi Zhang
    School of Applied Physics and Materials, Wuyi University, 22 Dongcheng Village, Jiangmen 529020, P. R. China
    More by Chi Zhang
  • , and 
  • Zhonghua Zhang*
    Zhonghua Zhang
    School of Applied Physics and Materials, Wuyi University, 22 Dongcheng Village, Jiangmen 529020, P. R. China
    Key Laboratory for Liquid−Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jingshi Road 17923, Jinan 250061, P. R. China
    *E-mail: [email protected]
Cite this: ACS Sustainable Chem. Eng. 2018, 6, 12, 16096–16104
Publication Date (Web):October 29, 2018
Copyright © 2018 American Chemical Society
Article Views
Read OnlinePDF (5 MB)
Supporting Info (1)»


The mass production of clean hydrogen fuels via (photo)electrochemical water splitting calls for highly efficient, cost-effective, and eco-friendly catalysts. Herein, a facile and scalable strategy, namely, dealloying, is advanced to fabricate mesoporous ternary layered double hydroxides (LDHs) containing Co, Ni, and Fe for highly efficient oxygen evolution and overall water splitting, based upon elaborate design of precursors and accurate control of the dealloying process. The Co1Ni2Fe1-LDH exhibits remarkable catalytic properties toward oxygen evolution reaction in 1 M KOH, for instance low overpotentials (only requires 240.4 mV on glass carbon electrode, and 228.5 mV on Ni foam to drive 10 mA cm–2), a small Tafel slope (38.6 mV dec–1), as well as excellent stability (lasts 45 h for 10 mA cm–2 without deactivation). Surprisingly, a symmetric alkaline electrolyzer constructed with Co1Ni2Fe1-LDH serving as the catalyst for both cathode and anode requires only 1.65 V to drive 10 mA cm–2. The distinguished features of the catalysts lie in the combined effects of the unique LDH structure with large interlayer spaces, the 3D porous structure, and the synergistic interplay of the metal species, concurrently contributing to the fully exposed active sites, accelerated electrolyte penetration and charge/ion transfer, as well as the well-promoted reaction kinetics. The consolidation of the electrocatalytic merits and the facile, economical fabrication route endows the ternary CoNiFe-LDHs as promising catalysts for the generation of renewable energy resources.

Supporting Information

Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b02656.

  • Photographs, SEM images, EDX spectra, N2 adsorption–desorption isotherms and pore size distributions, XPS spectrum, XRD patterns, polarization curves, Nyquist diagrams, electrical equivalent circuit model, TEM images, OER performance comparison (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 38 publications.

  1. Qiang Liu, Fang Zhou, Yuying Bai, Weikang Hu. Evaluating Properties of Carbon-Free Nano-NiCoFe-LDHs with Molybdate as Oxygen Evolution Catalysts and Their Applications in Rechargeable Air Electrodes. Energy & Fuels 2021, Article ASAP.
  2. Raina A. Krivina, Yingqing Ou, Qiucheng Xu, Liam P. Twight, T. Nathan Stovall, Shannon W. Boettcher. Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology. Accounts of Materials Research 2021, 2 (7) , 548-558.
  3. Anil Ashok Kashale, Chia-Hui Yi, Kum-Yi Cheng, Jhao-Sian Guo, Yu-Han Pan, I-Wen Peter Chen. Binder-Free Heterostructured NiFe2O4/NiFe LDH Nanosheet Composite Electrocatalysts for Oxygen Evolution Reactions. ACS Applied Energy Materials 2020, 3 (11) , 10831-10840.
  4. Qixin Xu, Weiwei Qin, Jin-Feng Chu. Novel Co3(1–x)Fe3xV2O8 Nanoparticles as Highly Active and Noble-Metal-Free Electrocatalysts for Oxygen Evolution Reaction. Energy & Fuels 2020, 34 (11) , 15019-15025.
  5. Fuzhi Li, Zhiqin Sun, He Jiang, Ziqian Ma, Qian Wang, Fengyu Qu. Ion-Exchange Synthesis of Ternary FeCoNi-Layered Double Hydroxide Nanocage Toward Enhanced Oxygen Evolution Reaction and Supercapacitor. Energy & Fuels 2020, 34 (9) , 11628-11636.
  6. Chao Feng, M. Bilal Faheem, Jie Fu, Yequan Xiao, Changli Li, Yanbo Li. Fe-Based Electrocatalysts for Oxygen Evolution Reaction: Progress and Perspectives. ACS Catalysis 2020, 10 (7) , 4019-4047.
  7. Hua-Jun Qiu, Gang Fang, Jiaojiao Gao, Yuren Wen, Juan Lv, Huanglong Li, Guoqiang Xie, Xingjun Liu, Shuhui Sun. Noble Metal-Free Nanoporous High-Entropy Alloys as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction. ACS Materials Letters 2019, 1 (5) , 526-533.
  8. Shipra Raj, Sengeni Anantharaj, Subrata Kundu, Poulomi Roy. In Situ Mn-Doping-Promoted Conversion of Co(OH)2 to Co3O4 as an Active Electrocatalyst for Oxygen Evolution Reaction. ACS Sustainable Chemistry & Engineering 2019, 7 (10) , 9690-9698.
  9. Junchao Ma, Sha Wang, Wenxiu He, Huan Chen, Xu Zhai, Fanbao Meng, Yu Fu. Synthesis of FeNiCo Ternary Hydroxides through Green Grinding Method with Metal‐Organic Frameworks as Precursors for Oxygen Evolution Reaction. ChemSusChem 2021, 14 (22) , 5042-5048.
  10. Mohammad Shaad Ansari, Haekyoung Kim. Enhanced electrocatalytic oxygen evolution reaction kinetics using dual-phase engineering of self-supported hierarchical NiCoV(OH)x nanowire arrays. Fuel 2021, 304 , 121309.
  11. Zheyin Yu, Ying Bai, George Tsekouras, Zhenxiang Cheng. Recent advances in Ni‐Fe (Oxy)hydroxide electrocatalysts for the oxygen evolution reaction in alkaline electrolyte targeting industrial applications. Nano Select 2021, 54
  12. Shuangshuang Jiang, Li Zhu, Zhanzhan Yang, Yingang Wang. Self-supported hierarchical porous FeNiCo-based amorphous alloys as high-efficiency bifunctional electrocatalysts toward overall water splitting. International Journal of Hydrogen Energy 2021, 46 (74) , 36731-36741.
  13. Xiaowei Xu, Tianyu Wang, Mingfang Zheng, Ying Li, Jichao Shi, Tian Tian, Runping Jia, Ying Liu. Metal-organic framework assisted formation of Ni-Fe-based porous nanoflowers for enhanced water splitting. Journal of Alloys and Compounds 2021, 875 , 159970.
  14. Shuangshuang Jiang, Li Zhu, Zhanzhan Yang, Yingang Wang. Morphological-modulated FeNi-based amorphous alloys as efficient alkaline water splitting electrocatalysts. Electrochimica Acta 2021, 389 , 138756.
  15. Ziqiang Wang, Wenjing Tian, Hongjie Yu, Tongqing Zhou, Peng Wang, You Xu, Xiaonian Li, Liang Wang, Hongjing Wang. Phosphorus modulation of a mesoporous rhodium film for enhanced nitrogen electroreduction. Nanoscale 2021, 13 (32) , 13809-13815.
  16. L. Lu, Y. Zheng, R. Yang, A. Kakimov, X. Li. Recent advances of layered double hydroxides–based bifunctional electrocatalysts for ORR and OER. Materials Today Chemistry 2021, 21 , 100488.
  17. Chunyan Li, Xin Li, Huiqin Wang, MengLing Zheng, Fang Tian, RuYong Tan, Pengwei Huo, Yan Yan, Xinkun Wang. Fabricated Ga (III) heterovalent substituted NiCo layered double hydroxides (NiCoGa-LDHs) electrode material for designed hybrid supercapacitor. Journal of Alloys and Compounds 2021, 871 , 159487.
  18. R.C. Rohit, Ajay D. Jagadale, Surendra K. Shinde, D.-Y. Kim, Vijay S. Kumbhar, Masaharu Nakayama. Hierarchical nanosheets of ternary CoNiFe layered double hydroxide for supercapacitors and oxygen evolution reaction. Journal of Alloys and Compounds 2021, 863 , 158081.
  19. Boya Hao, Zhiguo Ye, Jilin Xu, Liangliang Li, Juntong Huang, Xinyuan Peng, Duosheng Li, Zhong Jin, Guang Ma. A high-performance oxygen evolution electrode of nanoporous Ni-based solid solution by simulating natural meteorites. Chemical Engineering Journal 2021, 410 , 128340.
  20. Gracita M. Tomboc, Jun Kim, Yunting Wang, Yunchang Son, Jinghong Li, Jin Young Kim, Kwangyeol Lee. Hybrid layered double hydroxides as multifunctional nanomaterials for overall water splitting and supercapacitor applications. Journal of Materials Chemistry A 2021, 9 (8) , 4528-4557.
  21. Qian Ren, Jin-Qi Wu, Cheng-Fei Li, Lin-Fei Gu, Ling-Jie Xie, Yu Wang, Gao-Ren Li. Hierarchical porous Ni, Fe-codoped Co-hydroxide arrays derived from metal–organic-frameworks for enhanced oxygen evolution. Chemical Communications 2021, 57 (12) , 1522-1525.
  22. Chunyan Li, Yaju Zhou, Xin Li, Huiqin Wang, Pengwei Huo, Xinkun Wang. Ni dopping Co2Al ternary layered double hydroxides for improving electrochemical performance of high-performance hybrid supercapacitors. Applied Surface Science 2021, 536 , 147780.
  23. Jian Wang, Yang Gao, Hui Kong, Juwon Kim, Subin Choi, Francesco Ciucci, Yong Hao, Shihe Yang, Zongping Shao, Jongwoo Lim. Non-precious-metal catalysts for alkaline water electrolysis: operando characterizations, theoretical calculations, and recent advances. Chemical Society Reviews 2020, 49 (24) , 9154-9196.
  24. Hao Wan, Fashen Chen, Wei Ma, Xiaohe Liu, Renzhi Ma. Advanced electrocatalysts based on two-dimensional transition metal hydroxides and their composites for alkaline oxygen reduction reaction. Nanoscale 2020, 12 (42) , 21479-21496.
  25. Mengya Yang, Weiwei Zhu, Rong Zhao, Huan Wang, Tian-Nan Ye, Yi Liu, Dongming Yan. MOF-derived hollow spherical [email protected] composite with micro-nanostructure for highly efficient oxygen evolution reaction in alkaline solution. Journal of Solid State Chemistry 2020, 288 , 121456.
  26. Guanhua Zhang, Xueqiang Zhang, Yue Meng, Guoxiang Pan, Zheming Ni, Shengjie Xia. Layered double hydroxides-based photocatalysts and visible-light driven photodegradation of organic pollutants: A review. Chemical Engineering Journal 2020, 392 , 123684.
  27. Josué M. Gonçalves, Paulo R. Martins, Lucio Angnes, Koiti Araki. Recent advances in ternary layered double hydroxide electrocatalysts for the oxygen evolution reaction. New Journal of Chemistry 2020, 44 (24) , 9981-9997.
  28. Wen-Da Zhang, Hao Yu, Tao Li, Qing-Tao Hu, Yu Gong, Du-Ying Zhang, Yong Liu, Qiu-Ting Fu, Hai-Yan Zhu, Xiaodong Yan, Zhi-Guo Gu. Hierarchical trimetallic layered double hydroxide nanosheets derived from 2D metal-organic frameworks for enhanced oxygen evolution reaction. Applied Catalysis B: Environmental 2020, 264 , 118532.
  29. Hsiao‐Chien Chen, Tai‐Lung Chen, Sheng‐Chih Lin, Chia‐Shuo Hsu, Ting‐Shan Chan, Mei‐Yi Liao, Hao Ming Chen. Comprehensively Probing the Contribution of Site Activity and Population of Active Sites toward Heterogeneous Electrocatalysis. ChemCatChem 2020, 12 (7) , 1926-1933.
  30. Hongying Li, Xueliang Wang, Tao Wang, Mingcheng Zhao. A facile method for preparing amorphous Co-Ni-Cu ternary hydroxides as an efficient oxygen evolution reaction electrocatalyst. Materials Letters 2020, 264 , 127307.
  31. Debabrata Chakraborty, Sanjib Shyamal, Asim Bhaumik. A New Porous Ni‐W Mixed Metal Phosphonate Open Framework Material for Efficient Photoelectrochemical OER. ChemCatChem 2020, 12 (5) , 1504-1511.
  32. Dongjun Wang, Yongliang An, Shiyong Gao. Synthesis and characterization of urchin-like CuO nanorod/TiCu-based metallic glass core-shell powders with surface photovoltage performance. Applied Surface Science 2020, 506 , 144871.
  33. J. Liu, L. Xie, X. Yue, C. Xu, X. Lu. Removal of fluoride and hardness by layered double hydroxides: property and mechanism. International Journal of Environmental Science and Technology 2020, 17 (2) , 673-682.
  34. Kaihang Wang, Yingying Si, Zunhang Lv, Tianpeng Yu, Xin Liu, Guixue Wang, Guangwen Xie, Luhua Jiang. Efficient and stable Ni–Co–Fe–P nanosheet arrays on Ni foam for alkaline and neutral hydrogen evolution. International Journal of Hydrogen Energy 2020, 45 (4) , 2504-2512.
  35. Yan-Yan Dong, Dong-Dong Ma, Xin-Tao Wu, Qi-Long Zhu. Electron-withdrawing anion intercalation and surface sulfurization of NiFe-layered double hydroxide nanoflowers enabling superior oxygen evolution performance. Inorganic Chemistry Frontiers 2020, 7 (1) , 270-276.
  36. Yoshiyuki Kuroda, Takeshi Nishimoto, Shigenori Mitsushima. Self-repairing hybrid nanosheet anode catalysts for alkaline water electrolysis connected with fluctuating renewable energy. Electrochimica Acta 2019, 323 , 134812.
  37. Weiyang Jin, Fang Liu, Xiaoliang Guo, Jun Zhang, Lekai Zheng, Yongchuan Hu, Jing Mao, Hui Liu, Yanming Xue, Chengchun Tang. Self-supported CoFe LDH/Co 0.85 Se nanosheet arrays as efficient electrocatalysts for the oxygen evolution reaction. Catalysis Science & Technology 2019, 9 (20) , 5736-5744.
  38. Michaela Burke Stevens, Lisa J. Enman, Ester Hamal Korkus, Jeremie Zaffran, Christina D. M. Trang, James Asbury, Matthew G. Kast, Maytal Caspary Toroker, Shannon W. Boettcher. Ternary Ni-Co-Fe oxyhydroxide oxygen evolution catalysts: Intrinsic activity trends, electrical conductivity, and electronic band structure. Nano Research 2019, 12 (9) , 2288-2295.