Journal of Materials Science

, Volume 54, Issue 9, pp 7087–7095 | Cite as

Prussian blue analogues-derived bimetallic phosphide hollow nanocubes grown on Ni foam as water splitting electrocatalyst

  • Gang YanEmail author
  • Xiaotong Zhang
  • Liguang XiaoEmail author
Energy materials


The development of highly active and stable electrocatalysts for the water splitting using the earth-abundant transition metal as precursor is important for the renewable energy application. Prussian blue analogues (PBAs) are regarded as an ideal precursor for the preparation of electrocatalysts because of its abundant metal elements and various derived porous nanostructures. In this work, the (NiCo)2P hollow nanocubes, which are firmly grown on Ni foam, are prepared by PBAs and used as an water splitting electrocatalyst with high activity and stability in 1 M KOH solution. Benefiting from the synergistic effect of nickel and cobalt, hollow structure and high double-layer capacitance, the as-synthesized (NiCo)2P/NF catalyst shows an excellent electrocatalytic performance for the water splitting. To achieve current density of 10 mA cm−2, for HER and OER, this material requires overpotentials of 162 mV and 220 mV, respectively. As an integrated electrocatalyst for water splitting, the (NiCo)2P/NF needs a cell voltage of 1.62 V to achieve current density of 10 mA cm−2. Furthermore, this material has long-term electrocatalytic stability (over 30 h). The high catalytic activity of this material is attributed to the synergistic effect of component and the hollow structure of catalyst. This facile and novel method of preparing bimetallic phosphide electrocatalysts with hollow structure provides a broadened space for the design and synthesis of non-noble metal catalysts in the future.



We acknowledge financial support from 13th 5-Year Science and Technology Research Program of the Department of Education of Jilin Province (No. JJKH20190858KJ) and Opening Project of Key Laboratory of Polyoxometalate Science of the Ministry of Education (Grant No. 130028808).

Supplementary material

10853_2019_3362_MOESM1_ESM.docx (3 mb)
Supplementary material 1 (DOCX 3095 kb)


  1. 1.
    Wang H, Xu S, Tsai C, Li Y, Liu C, Zhao J, Liu Y, Yuan H, Abild-Pedersen F, Prinz FB, Nørskov JK, Cui Y (2016) Direct and continuous strain control of catalysts with tunable battery electrode materials. Science 354(6315):1031–1036CrossRefGoogle Scholar
  2. 2.
    Huang X, Zhao Z, Cao L, Chen Y, Zhu E, Lin Z, Li M, Yan A, Zettl A, Wang YM, Duan X, Mueller T, Huang Y (2015) High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 348(6240):1230–1234CrossRefGoogle Scholar
  3. 3.
    Walter MG, Warren EL, McKone JR, Boettcher SW, Mi Q, Santori NS, Lewis EA (2010) Solar water splitting cells. Chem Rev 110(11):6446–6473CrossRefGoogle Scholar
  4. 4.
    Yu XY, Feng Y, Guan BY, Lou XWD, Paik U (2016) Carbon coated porous nickel phosphides nanoplates for highly efficient oxygen evolution reaction. Energy Environ Sci 9(4):1246–1250CrossRefGoogle Scholar
  5. 5.
    Zhang W, Wu YZ, Qi J, Chen MX, Cao R (2017) A thin NiFe hydroxide film formed by stepwise electrodeposition strategy with significantly improved catalytic water oxidation efficiency. Adv Energy Mater 7(9):1602547CrossRefGoogle Scholar
  6. 6.
    Hu F, Zhu SL, Chen SM, Li Y, Ma L, Wu TP, Zhang Y, Wang CM, Liu CC, Yang XJ, Song L, Yang XW, Xiong YJ (2017) Amorphous metallic NiFeP: a conductive bulk material achieving high activity for oxygen evolution reaction in both alkaline and acidic media. Adv Mater 29(32):1606570CrossRefGoogle Scholar
  7. 7.
    Xie LS, Zhang R, Cui LA, Liu DN, Hao S, Ma YJ, Du G, Asiri AM, Sun XP (2017) High-performance electrolytic oxygen evolution in neutral media catalyzed by a cobalt phosphate nanoarray. Angew Chem Int Ed 56(4):1064–1068CrossRefGoogle Scholar
  8. 8.
    Guo CX, Zheng Y, Ran JR, Xie FX, Jaroniec M, Qiao SZ (2017) Engineering high-energy interfacial structures for high-performance oxygen-involving electrocatalysis. Angew Chem Int Ed 56(29):8539–8543CrossRefGoogle Scholar
  9. 9.
    Du YM, Li ZJ, Liu YR, Yang Y, Wang L (2018) Nickel–iron phosphides nanorods derived from bimetallic-organic frameworks for hydrogen evolution reaction. Appl Surf Sci 457:1081–1086CrossRefGoogle Scholar
  10. 10.
    Cao LM, Hu YW, Tang SF, IIjin A, Wang JW, Zhang ZM, Lu TB (2018) Fe-CoP electrocatalyst derived from a bimetallic Prussian blue analogue for large-current-density oxygen evolution and overall water splitting. Adv Sci 5(10):1800949CrossRefGoogle Scholar
  11. 11.
    Zhang FS, Wang JW, Luo J, Liu RR, Zhang ZM, He CT, Lu TB (2017) Extraction of nickel from NiFe–LDH into Ni2P@NiFe hydroxide as a bifunctional electrocatalyst for efficient overall water splitting. Chem Sci 9(5):1375–1384CrossRefGoogle Scholar
  12. 12.
    Tan JB, Sahoo P, Wang JW, Hu YW, Zhang ZM, Lu TB (2017) Highly efficient oxygen evolution electrocatalysts prepared by using reduction-engraved ferrites on graphene oxide. Inorg Chem Front 5(2):310–318CrossRefGoogle Scholar
  13. 13.
    Nai JW, Lu Y, Yu L, Wang X, Lou XWD (2017) Formation of Ni–Fe mixed diselenide nanocages as a superior oxygen evolution electrocatalyst. Adv Mater 29(41):1703870CrossRefGoogle Scholar
  14. 14.
    Yu XY, Yu L, Wu HB, Lou XWD (2015) Formation of nickel sulfide nanoframes from metal–organic frameworks with enhanced pseudocapacitive and electrocatalytic properties. Angew Chem Int Ed 54(18):5331–5335CrossRefGoogle Scholar
  15. 15.
    Fang YJ, Yu XY, Lou XWD (2018) formation of hierarchical Cu-doped CoSe2 microboxes via sequential ion exchange for high-performance sodium-ion batteries. Adv Mater 30(21):1706668CrossRefGoogle Scholar
  16. 16.
    Kang BK, Woo MH, Lee J, Song YH, Wang ZL, Guo YN, Yamauchi Y, Kim JH, Lim B, Yoon DH (2017) Mesoporous Ni–Fe oxide multi-composite hollow nanocages for efficient electrocatalytic water oxidation reactions. J Mater Chem A 5(9):4320–4324CrossRefGoogle Scholar
  17. 17.
    Guo YN, Tang J, Wang ZL, Kang YM, Bando Y, Yamauchi Y (2018) Elaborately assembled core-shell structured metal sulfides as a bifunctional catalyst for highly efficient electrochemical overall water splitting. Nano Energy 47:494–502CrossRefGoogle Scholar
  18. 18.
    Zhu XH, Liu MJ, Liu Y, Chen RW, Nie Z, Li JH, Yao SZ (2016) Carbon-coated hollow mesoporous FeP microcubes: an efficient and stable electrocatalyst for hydrogen evolution. J Mater Chem A 4(23):8974–8977CrossRefGoogle Scholar
  19. 19.
    Sivanantham A, Ganesan P, Estevez L, Mcgrail BP, Motkuri RK, Shanmugam S (2018) A stable graphitic, nanocarbon-encapsulated, cobalt-rich core-shell electrocatalyst as an oxygen electrode in a water electrolyzer. Adv Energy Mater 8(14):1702838CrossRefGoogle Scholar
  20. 20.
    Cai XJ, Gao W, Ma M, Wu MY, Zhang LL, Zheng YY, Chen HR, Shi JL (2015) A Prussian blue-based core-shell hollow-structured mesoporous nanoparticle as a smart theranostic agent with ultrahigh pH-responsive longitudinal relaxivity. Adv Mater 27(41):6382–6389CrossRefGoogle Scholar
  21. 21.
    Ma TY, Dai S, Qiao SZ (2016) Self-supported electrocatalysts for advanced energy conversion processes. Mater Today 19(5):265–273CrossRefGoogle Scholar
  22. 22.
    Indra A, Paik U, Song T (2018) Boosting electrochemical water oxidation with metal hydroxide carbonate templated Prussian blue analogues. Angew Chem Int Ed 57(5):1241–1245CrossRefGoogle Scholar
  23. 23.
    Guo TR, Wang T, Chen J, Zheng J, Li XG, Ostrikov K (2018) Air plasma activation of catalytic sites in a metal–cyanide framework for efficient oxygen evolution reaction. Adv Energy Mater 8(18):1800085CrossRefGoogle Scholar
  24. 24.
    Ge YC, Dong P, Craig SR, Ajayan PM, Ye MX, Shen JF (2018) Transforming nickel hydroxide into 3D Prussian blue analogue array to obtain Ni2P/Fe2P for efficient hydrogen evolution reaction. Adv Energy Mater 8(21):1800484CrossRefGoogle Scholar
  25. 25.
    Stern LA, Feng LG, Song F, Hu XL (2015) Ni2P as a Janus catalyst for water splitting: the oxygen evolution activity of Ni2P nanoparticles. Energy Environ Sci 8(8):2347–2351CrossRefGoogle Scholar
  26. 26.
    Liang H, Gandi AN, Anjum DH, Wang X, Schwingenschlögl HN, Alshareef U (2016) Plasma-assisted synthesis of NiCoP for efficient overall water splitting. Nano Lett 16(12):7718–7725CrossRefGoogle Scholar
  27. 27.
    You B, Jiang N, Sheng ML, Bhushan MW, Sun YJ (2016) Hierarchically porous urchin-like Ni2P superstructures supported on nickel foam as efficient bifunctional electrocatalysts for overall water splitting. ACS Catal 6(2):714–721CrossRefGoogle Scholar
  28. 28.
    Yu XY, Feng Y, Guan BY, Lou XW, Paik U (2016) Carbon coated porous nickel phosphides nanoplates for highly efficient oxygen evolution reaction. Energy Environ Sci 9(4):1246–1250CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Material Science and EngineeringJilin Jianzhu UniversityChangchunPeople’s Republic of China

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