Frontiers of Chemical Science and Engineering

, Volume 12, Issue 4, pp 838–854 | Cite as

Structural engineering of transition metal-based nanostructured electrocatalysts for efficient water splitting

  • Yueqing Wang
  • Jintao ZhangEmail author
Review Article


Water splitting is a highly promising approach for the generation of sustainable, clean hydrogen energy. Tremendous efforts have been devoted to exploring highly efficient and abundant metal oxide electrocatalysts for oxygen evolution and hydrogen evolution reactions to lower the energy consumption in water splitting. In this review, we summarize the recent advances on the development of metal oxide electrocatalysts with special emphasis on the structural engineering of nanostructures from particle size, composition, crystalline facet, hybrid structure as well as the conductive supports. The special strategies relay on the transformation from the metal organic framework and ion exchange reactions for the preparation of novel metal oxide nanostructures with boosting the catalytic activities are also discussed. The fascinating methods would pave the way for rational design of advanced electrocatalysts for efficient water splitting.


water splitting structure engineering metal organic framework ion exchange synergistic effect hybrid structure conductive supports 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



This work was financially supported by the National Natural Science Foundation of China (No. 21503116). Taishan Scholars Program of Shandong Province (No. tsqn20161004) and the Youth 1000 Talent Program of China are also acknowledged.


  1. 1.
    Morales-Guio C G, Stern L A, Hu X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chemical Society Reviews, 2014, 43(18): 6555–6569Google Scholar
  2. 2.
    Chen W F, Muckerman J T, Fujita E. Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chemical Communications, 2013, 49(79): 8896–8909Google Scholar
  3. 3.
    Gong M, Wang D Y, Chen C C, Hwang B J, Dai H. A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Research, 2015, 9(1): 28–46Google Scholar
  4. 4.
    Chen H M, Chen C K, Liu R S, Zhang L, Zhang J, Wilkinson D P. Nano-architecture and material designs for water splitting photoelectrodes. Chemical Society Reviews, 2012, 41(17): 5654–5671Google Scholar
  5. 5.
    Zeng M, Li Y. Recent advances in heterogeneous electrocatalysts for the hydrogen evolution reaction. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2015, 3(29): 14942–14962Google Scholar
  6. 6.
    Chen M, Wang L, Yang H, Zhao S, Xu H, Wu G. Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review. Journal of Power Sources, 2018, 375: 277–290Google Scholar
  7. 7.
    Suen N T, Hung S F, Quan Q, Zhang N, Xu Y J, Chen H M. Electrocatalysis for the oxygen evolution reaction: Recent development and future perspectives. Chemical Society Reviews, 2017, 46(2): 337–365Google Scholar
  8. 8.
    Tahir M, Pan L, Idrees F, Zhang X, Wang L, Zou J J, Wang Z L. Electrocatalytic oxygen evolution reaction for energy conversion and storage: A comprehensive review. Nano Energy, 2017, 37: 136–157Google Scholar
  9. 9.
    Zhao Q, Yan Z, Chen C, Chen J. Spinels: Controlled preparation, oxygen reduction/evolution reaction application, and beyond. Chemical Reviews, 2017, 117(15): 10121–10211Google Scholar
  10. 10.
    Tian J, Liu Q, Asiri A M, Sun X. Self-supported nanoporous cobalt phosphide nanowire arrays: An efficient 3D hydrogen-evolving cathode over the wide range of pH 0–14. Journal of the American Chemical Society, 2014, 136(21): 7587–7590Google Scholar
  11. 11.
    Feng L, Vrubel H, Bensimon M, Hu X. Easily-prepared dinickel phosphide (Ni2P) nanoparticles as an efficient and robust electrocatalyst for hydrogen evolution. Physical Chemistry Chemical Physics, 2014, 16(13): 5917–5921Google Scholar
  12. 12.
    Chen P, Xu K, Fang Z, Tong Y, Wu J, Lu X, Peng X, Ding H, Wu C, Xie Y. Metallic Co4N porous nanowire arrays activated by surface oxidation as electrocatalysts for the oxygen evolution reaction. Angewandte Chemie International Edition, 2015, 54(49): 14710–14714Google Scholar
  13. 13.
    Zhang Y, Ouyang B, Xu J, Jia G, Chen S, Rawat R S, Fan H J. Rapid synthesis of cobalt nitride nanowires: Highly efficient and low-cost catalysts for oxygen evolution. Angewandte Chemie International Edition, 2016, 55(30): 8670–8674Google Scholar
  14. 14.
    Kong D, Wang H, Lu Z, Cui Y. CoSe2 nanoparticles grown on carbon fiber paper: An efficient and stable electrocatalyst for hydrogen evolution reaction. Journal of the American Chemical Society, 2014, 136(13): 4897–4900Google Scholar
  15. 15.
    Gao M R, Liang J X, Zheng Y R, Xu Y F, Jiang J, Gao Q, Li J, Yu S H. An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation. Nature Communications, 2015, 6(1): 5982Google Scholar
  16. 16.
    Vrubel H, Hu X. Molybdenum boride and carbide catalyze hydrogen evolution in both acidic and basic solutions. Angewandte Chemie International Edition, 2012, 51(51): 12703–12706Google Scholar
  17. 17.
    McCrory C C, Jung S, Peters J C, Jaramillo T F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. Journal of the American Chemical Society, 2013, 135(45): 16977–16987Google Scholar
  18. 18.
    Jirkovský J, Makarova M, Krtil P. Particle size dependence of oxygen evolution reaction on nanocrystalline RuO2 and Ru0.8Co0.2O2-x. Electrochemistry Communications, 2006, 8(9): 1417–1422Google Scholar
  19. 19.
    Reier T, Oezaslan M, Strasser P. Electrocatalytic oxygen evolution reaction (OER) on Ru, Ir, and Pt catalysts: A comparative study of nanoparticles and bulk materials. ACS Catalysis, 2012, 2(8): 1765–1772Google Scholar
  20. 20.
    Wang H, Lee H W, Deng Y, Lu Z, Hsu P C, Liu Y, Lin D, Cui Y. Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting. Nature Communications, 2015, 6(1): 7261Google Scholar
  21. 21.
    Zou X, Su J, Silva R, Goswami A, Sathe B R, Asefa T. Efficient oxygen evolution reaction catalyzed by low-density Ni-doped Co3O4 nanomaterials derived from metal-embedded graphitic C3N4. Chemical Communications, 2013, 49(68): 7522–7524Google Scholar
  22. 22.
    Friebel D, Louie M W, Bajdich M, Sanwald K E, Cai Y, Wise A M, Cheng M J, Sokaras D, Weng T C, Alonso-Mori R, Davis R C, Bargar J R, Nørskov J K, Nilsson A, Bell A T. Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. Journal of the American Chemical Society, 2015, 137(3): 1305–1313Google Scholar
  23. 23.
    Trotochaud L, Young S L, Ranney J K, Boettcher S W. Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: The role of intentional and incidental iron incorporation. Journal of the American Chemical Society, 2014, 136(18): 6744–6753Google Scholar
  24. 24.
    Tang T, Jiang W J, Niu S, Liu N, Luo H, Chen Y Y, Jin S F, Gao F, Wan L J, Hu J S. Electronic and morphological dual modulation of cobalt carbonate hydroxides by Mn doping toward highly efficient and stable bifunctional electrocatalysts for overall water splitting. Journal of the American Chemical Society, 2017, 139(24): 8320–8328Google Scholar
  25. 25.
    Yu J, Wang Q, O’ Hare D, Sun L. Preparation of two dimensional layered double hydroxide nanosheets and their applications. Chemical Society Reviews, 2017, 46(19): 5950–5974Google Scholar
  26. 26.
    Quan Z, Wang Y, Fang J. High-index faceted noble metal nanocrystals. Accounts of Chemical Research, 2013, 46(2): 191–202Google Scholar
  27. 27.
    Liu G, Yang H G, Pan J, Yang Y Q, Lu G Q, Cheng H M. Titanium dioxide crystals with tailored facets. Chemical Reviews, 2014, 114(19): 9559–9612Google Scholar
  28. 28.
    Falkowski J M, Concannon N M, Yan B, Surendranath Y. Heazlewoodite, Ni3S2: A potent catalyst for oxygen reduction to water under benign conditions. Journal of the American Chemical Society, 2015, 137(25): 7978–7981Google Scholar
  29. 29.
    Feng L L, Yu G, Wu Y, Li G D, Li H, Sun Y, Asefa T, Chen W, Zou X. High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting. Journal of the American Chemical Society, 2015, 137(44): 14023–14026Google Scholar
  30. 30.
    Nai J, Kang J, Guo L. Tailoring the shape of amorphous nanomaterials: Recent developments and applications. Science China Materials, 2015, 58(1): 44–59Google Scholar
  31. 31.
    Mas-Ballesté R, Gómez-Navarro C, Gómez-Herrero J, Zamora F. 2D materials: To graphene and beyond. Nanoscale, 2011, 3(1): 20–30Google Scholar
  32. 32.
    Huang J, Chen J, Yao T, He J, Jiang S, Sun Z, Liu Q, Cheng W, Hu F, Jiang Y, Pan Z, Wei S. CoOOH nanosheets with high mass activity for water oxidation. Angewandte Chemie International Edition, 2015, 54(30): 8722–8727Google Scholar
  33. 33.
    Sun Y, Gao S, Xie Y. Atomically-thick two-dimensional crystals: Electronic structure regulation and energy device construction. Chemical Society Reviews, 2014, 43(2): 530–546Google Scholar
  34. 34.
    Gao X, Zhang H, Li Q, Yu X, Hong Z, Zhang X, Liang C, Lin Z. Hierarchical NiCo2O4 hollow microcuboids as bifunctional electrocatalysts for overall water-splitting. Angewandte Chemie International Edition, 2016, 55(21): 6290–6294Google Scholar
  35. 35.
    Sun MH, Huang S Z, Chen L H, Li Y, Yang X Y, Yuan Z Y, Su B L. Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine. Chemical Society Reviews, 2016, 45(12): 3479–3563Google Scholar
  36. 36.
    Feng J X, Xu H, Dong Y T, Ye S H, Tong Y X, Li G R. FeOOH/Co/FeOOH hybrid nanotube arrays as high-performance electrocatalysts for the oxygen evolution reaction. Angewandte Chemie International Edition, 2016, 55(11): 3694–3698Google Scholar
  37. 37.
    Feng J X, Ye S H, Xu H, Tong Y X, Li G R. Design and synthesis of FeOOH/CeO2 heterolayered nanotube electrocatalysts for the oxygen evolution reaction. Advanced Materials, 2016, 28(23): 4698–4703Google Scholar
  38. 38.
    Xiao C, Li Y, Lu X, Zhao C. Bifunctional porous NiFe/NiCo2O4/Ni foam electrodes with triple hierarchy and double synergies for efficient whole cell water splitting. Advanced Functional Materials, 2016, 26(20): 3515–3523Google Scholar
  39. 39.
    Xu L, Jiang Q, Xiao Z, Li X, Huo J, Wang S, Dai L. Plasmaengraved Co3O4 nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction. Angewandte Chemie International Edition, 2016, 55(17): 5277–5281Google Scholar
  40. 40.
    Zhao Y, Chang C, Teng F, Zhao Y, Chen G, Shi R, Waterhouse G I N, Huang W, Zhang T. Defect-engineered ultrathin d-MnO2 nanosheet arrays as bifunctional electrodes for efficient overall water splitting. Advanced Energy Materials, 2017, 7(18): 1700005Google Scholar
  41. 41.
    Han L, Yu X Y, Lou X W. Formation of prussian-blue-analog nanocages via a direct etching method and their conversion into Ni-Co-mixed oxide for enhanced oxygen evolution. Advanced Materials, 2016, 28(23): 4601–4605Google Scholar
  42. 42.
    Lee J, Farha O K, Roberts J, Scheidt K A, Nguyen S T, Hupp J T. Metal-organic framework materials as catalysts. Chemical Society Reviews, 2009, 38(5): 1450–1459Google Scholar
  43. 43.
    Nai J, Lu Y, Yu L, Wang X, Lou X W D. Formation of Ni-Fe mixed diselenide nanocages as a superior oxygen evolution electrocatalyst. Advanced Materials, 2017, 29(41): 1703870Google Scholar
  44. 44.
    Yu X Y, Yu L, Wu H B, Lou X W. Formation of nickel sulfide nanoframes from metal-organic frameworks with enhanced pseudocapacitive and electrocatalytic properties. Angewandte Chemie International Edition, 2015, 54(18): 5331–5335Google Scholar
  45. 45.
    Zhang L, Wu H B, Lou X W. Metal-organic-frameworks-derived general formation of hollow structures with high complexity. Journal of the American Chemical Society, 2013, 135(29): 10664–10672Google Scholar
  46. 46.
    Tan C F, Azmansah S A, Zhu H, Xu Q H, Ho G W. Spontaneous electroless galvanic cell deposition of 3D hierarchical and interlaced S-M-S heterostructures. Advanced Materials, 2017, 29(1): 1604417Google Scholar
  47. 47.
    Wang Y, Zhang B, Pan W, Ma H, Zhang J. 3D porous Nickel-Cobalt nitrides supported on nickel foam as efficient electrocatalysts for overall water splitting. ChemSusChem, 2017, 10(21): 4170–4177Google Scholar
  48. 48.
    Wang J, Tan C F, Zhu T, Ho G W, WeiHo G. Topotactic consolidation of monocrystalline CoZn hydroxides for advanced oxygen evolution electrodes. Angewandte Chemie, 2016, 128(35): 10482–10486Google Scholar
  49. 49.
    Hou Y, Lohe M R, Zhang J, Liu S, Zhuang X, Feng X. Vertically oriented cobalt selenide/NiFe layered-double-hydroxide nanosheets supported on exfoliated graphene foil: An efficient 3D electrode for overall water splitting. Energy & Environmental Science, 2016, 9(2): 478–483Google Scholar
  50. 50.
    Maiyalagan T, Jarvis K A, Therese S, Ferreira P J, Manthiram A. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions. Nature Communications, 2014, 5(1): 3949Google Scholar
  51. 51.
    Li H, Shao Y, Su Y, Gao Y, Wang X. Vapor-phase atomic layer deposition of nickel sulfide and its application for efficient oxygenevolution electrocatalysis. Chemistry of Materials, 2016, 28(4): 1155–1164Google Scholar
  52. 52.
    Yu X Y, Feng Y, Guan B, Lou X W, Paik U. Carbon coated porous nickel phosphides nanoplates for highly efficient oxygen evolution reaction. Energy & Environmental Science, 2016, 9(4): 1246–1250Google Scholar
  53. 53.
    Dong Q, Wang Q, Dai Z, Qiu H, Dong X. MOF-derived Zn-doped CoSe2 as an efficient and stable free-standing catalyst for oxygen evolution reaction. ACS Applied Materials & Interfaces, 2016, 8(40): 26902–26907Google Scholar
  54. 54.
    Barman B K, Nanda K K. Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts. Green Chemistry, 2016, 18(2): 427–432Google Scholar
  55. 55.
    Ganesan P, Prabu M, Sanetuntikul J, Shanmugam S. Cobalt sulfide nanoparticles grown on nitrogen and sulfur codoped graphene oxide: An efficient electrocatalyst for oxygen reduction and evolution reactions. ACS Catalysis, 2015, 5(6): 3625–3637Google Scholar
  56. 56.
    Trotochaud L, Ranney J K, Williams K N, Boettcher S W. Solutioncast metal oxide thin film electrocatalysts for oxygen evolution. Journal of the American Chemical Society, 2012, 134(41): 17253–17261Google Scholar
  57. 57.
    Wang Y J, Zhao N, Fang B, Li H, Bi X T, Wang H. Carbonsupported Pt-based alloy electrocatalysts for the oxygen reduction reaction in polymer electrolyte membrane fuel cells: particle size, shape, and composition manipulation and their impact to activity. Chemical Reviews, 2015, 115(9): 3433–3467Google Scholar
  58. 58.
    Chabot V, Higgins D, Yu A, Xiao X, Chen Z, Zhang J. A review of graphene and graphene oxide sponge: Material synthesis and applications to energy and the environment. Energy & Environmental Science, 2014, 7(5): 1564–1596Google Scholar
  59. 59.
    Thostensona E T, Renb Z, Choua T W. Advances in the science and technology of carbon nanotubes and their composites: A review. Composites Science and Technology, 2001, 61(13): 1899–1912Google Scholar
  60. 60.
    Allen M J, Tung V C, Kaner R B. Honeycomb carbon: A review of graphene. Chemical Reviews, 2010, 110(1): 132–145Google Scholar
  61. 61.
    Lu X, Zhao C. Electrodeposition of hierarchically structured three-dimensional nickel-iron electrodes for efficient oxygen evolution at high current densities. Nature Communications, 2015, 6(1): 6616Google Scholar
  62. 62.
    Wei L, Goh K, Birer Ö, Karahan H E, Chang J, Zhai S, Chen X, Chen Y. A hierarchically porous nickel-copper phosphide nanofoam for efficient electrochemical splitting of water. Nanoscale, 2017, 9(13): 4401–4408Google Scholar
  63. 63.
    Gong M, Li Y, Wang H, Liang Y, Wu J Z, Zhou J, Wang J, Regier T, Wei F, Dai H. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation. Journal of the American Chemical Society, 2013, 135(23): 8452–8455Google Scholar
  64. 64.
    Gong M, Zhou W, Tsai M C, Zhou J, Guan M, Lin M C, Zhang B, Hu Y, Wang D Y, Yang J, et al. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis. Nature Communications, 2014, 5(1): 4695Google Scholar
  65. 65.
    Zhou W, Jia J, Lu J, Yang L, Houb D, Li G, Chen S. Recent developments of carbon-based electrocatalysts for hydrogen evolution reaction. Nano Energy, 2016, 28: 29–43Google Scholar
  66. 66.
    Li Y, Wang H, Xie L, Liang Y, Hong G, Dai H. MoS2 nanoparticles grown on graphene: An advanced catalyst for the hydrogen evolution reaction. Journal of the American Chemical Society, 2011, 133(19): 7296–7299Google Scholar
  67. 67.
    Chang Y H, Lin C T, Chen T Y, Hsu C L, Lee Y H, Zhang W, Wei K H, Li L J. Highly efficient electrocatalytic hydrogen production by MoSx grown on graphene-protected 3D Ni foams. Advanced Materials, 2013, 25(5): 756–760Google Scholar
  68. 68.
    Guan C, Liu X, Ren W, Li X, Cheng C, Wang J. Rational design of metal-organic framework derived hollow NiCo2O4 arrays for flexible supercapacitor and electrocatalysis. Advanced Energy Materials, 2017, 7(12): 1602391Google Scholar
  69. 69.
    Pu Z, Liu Q, Jiang P, Asiri A M, Obaid A Y, Sun X. CoP nanosheet arrays supported on a ti plate: An efficient cathode for electrochemical hydrogen evolution. Chemistry of Materials, 2014, 26(15): 4326–4329Google Scholar
  70. 70.
    Jiang P, Liu Q, Liang Y, Tian J, Asiri A M, Sun X. A cost-effective 3D hydrogen evolution cathode with high catalytic activity: FeP nanowire array as the active phase. Angewandte Chemie Interna-tional Edition, 2014, 53(47): 12855–12859Google Scholar
  71. 71.
    Ma T Y, Dai S, Jaroniec M, Qiao S Z. Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrodes. Journal of the American Chemical Society, 2014, 136(39): 13925–13931Google Scholar
  72. 72.
    Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chemical Society Reviews, 2015, 44(15): 5148–5180Google Scholar

Copyright information

© Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Key Laboratory for Colloid and Interface Chemistry (Ministry of Education), School of Chemistry and Chemical EngineeringShandong UniversityJinanChina

Personalised recommendations