3D Network nanostructured NiCoP nanosheets supported on N-doped carbon coated Ni foam as a highly active bifunctional electrocatalyst for hydrogen and oxygen evolution reactions

Abstract

A highly active bi-functional electrocatalyst towards both hydrogen and oxygen evolution reactions is critical for the water splitting. Herein, a self-supported electrode composed of 3D network nanostructured NiCoP nanosheets grown on N-doped carbon coated Ni foam (NiCoP/NF@NC) has been synthesized by a hydrothermal route and a subsequent phosphorization process. As a bifunctional electrocatalyst, the NiCoP/NF@NC electrode needs overpotentials of 31.8 mV for hydrogen evolution reaction and 308.2 mV for oxygen evolution reaction to achieve the current density of 10 mA·cm⁻² in 1 mol·L⁻¹ KOH electrolyte. This is much better than the corresponding monometal catalysts of CoP/NF@NC and NiP/NF@NC owing to the synergistic effect. NiCoP/NF@NC also exhibits low Tafel slope, and excellent long-term stability, which are comparable to the commercial noble catalysts of Pt/C and RuO₂.

Graphical abstract

Keywords

bimetallic phosphides / N-doped carbon / self-support / hydrogen evolution / oxygen evolution

References

[1] Dresselhaus M S, Thomas I L. Alternative energy technologies. Nature, 2001, 414(6861): 332–337

[2] Liu W, Hu E, Jiang H, Xiang Y, Weng Z, Li M, Fan Q, Yu X, Altman E I, Wang H. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide. Nature Communications, 2016, 7: 10771

[3] Jiao Y, Zheng Y, Davey K, Qiao S Z. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nature Energy, 2016, 1(10): 16130

[4] Nφrskov J K, Bligaard T, Rossmeisl J, Christensen C H. Towards the computational design of solid catalysts. Nature Chemistry, 2009, 1(1): 37–46

[5] Alapati S V, Johnson J K, Sholl D S. Using first principles calculations to identify new destabilized metal hydride reactions for reversible hydrogen storage. Physical Chemistry Chemical Physics, 2007, 9(12): 1438–1452

[6] Zou X X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chemical Society Reviews, 2015, 44(15): 5148–5180

[7] Zhang B, Zheng X L, Voznyy O, Comin R, Bajdich M, García-Melchor M, Han L L, Xu J X, Liu M, Zheng L R, et al. Homogeneously dispersed, multimetal oxygen-evolving catalysts. Science, 2016, 352(6283): 333–337

[8] Wang J H, Cui W, Liu Q, Xing Z C, Asiri A M, Sun X P. Recent progress in cobalt-based heterogeneous catalysts for electrochemical water splitting. Advanced Materials, 2016, 28(2): 215–230

[9] Jin Y, Wang H, Li J, Yue X, Han Y, Shen P K, Cui Y, Jin Y S, Wang H T, Li J J, et al. Porous MoO₂ nanosheets as non-noble bifunctional electrocatalysts for overall water splitting. Advanced Materials, 2016, 28(19): 3785–3790

[10] Feng L L, Yu G T, Wu Y Y, Li G D, Li H, Sun Y H, Asefa T, Chen W, Zou X 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): 14023–14026

[11] Chen Y Y, Zhang Y, Zhang X, Tang T, Luo H, Shuai N, Dai Z H, Wan L J, Hu J S. Self-templated fabrication of MoNi₄/MoO_3−x nanorod arrays with dual active components for highly efficient hydrogen evolution. Advanced Materials, 2017, 29(39): 1703311

[12] Guo X X, Kong R M, Zhang X P, Du H T, Qu F L. Ni(OH)₂ nanoparticles embedded in conductive microrod array: An efficient and durable electrocatalyst for alkaline oxygen evolution reaction. ACS Catalysis, 2017, 7(7): 4381–4385

[13] Xu X J, Du P Y, Chen Z K, Huang M H. An electrodeposited cobalt-selenide-based film as an efficient bifunctional electrocatalyst for full water splitting. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2016, 4(28): 10933–10939

[14] Lee J E, Jang Y J, Xu W Q, Feng Z X, Park H Y, Kim J Y, Kim D H. PtFe nanoparticles supported on electroactive Au–PANI core@shell nanoparticles for high performance bifunctional electrocatalysis. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(26): 13692–13699

[15] Feng J X, Wu J Q, Tong Y X, Li G R. Efficient hydrogen evolution on Cu nanodots-decorated Ni₃S₂ nanotubes by optimizing atomic hydrogen adsorption and desorption. Journal of the American Chemical Society, 2018, 140(2): 610–617

[16] Feng J X, Xu H, Ye S H, Ouyang G F, Tong Y X, Li G R. Silica-polypyrrole hybrids as high-performance metal-free electrocatalysts for the hydrogen evolution reaction in neutral media. Angewandte Chemie-Internatioanal Edition, 2017, 56(28): 8120–8124

[17] Feng J X, Xu H, Dong Y T, Lu X F, Tong Y X, Li G R. Efficient hydrogen evolution electrocatalysis using cobalt nanotubes decorated with titanium dioxide nanodots. Angewandte Chemie-Internatioanal Edition, 2017, 56(11): 2960–2964

[18] Li J S, Wang Y, Liu C H, Li S L, Wang Y G, Dong L Z, Dai Z H, LiY F, Lan Y Q. Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution. Nature Communications, 2016, 7: 11204

[19] Qin J S, Du D Y, Guan W, Bo X J, Li Y F, Guo L P, Su Z M, Wang Y Y, Lan Y Q, Zhou H C. Ultrastable polymolybdate-based metal organic frameworks as highly active electrocatalysts for hydrogen generation from water. Journal of the American Chemical Society, 2015, 137(22): 7169–7177

[20] Tang Y J, Gao M R, Liu C H, Li S L, Jiang H L, Lan Y Q, Han M, Yu S H. Porous molybdenum-based hybrid catalysts for highly efficient hydrogen evolution. Angewandte Chemie-Internatioanal Edition, 2015, 54(44): 12928–12932

[21] Li Z M, Han M, Xu D D, Yang J, Lin Y, Shi N E, Lu Y A, Yang R, Liu B T, Dai Z H, et al. Defect-rich Ni₃FeN nanocrystals anchored on N-doped graphene for enhanced electrocatalytic oxygen evolutionshulin. Advanced Functional Materials, 2018, doi: 10.1002/adfm.201706018

[22] Deng D R, Xue F, Jia Y J, Ye J C, Bai C D, Zheng M S, Dong Q F. Co₄N nanosheet assembled mesoporous sphere as a matrix for ultrahigh sulfur content lithium-sulfur batteries. ACS Nano, 2017, 11(6): 6031–6039

[23] Chen P Z, Xu K, Fang Z W, Tong Y, Wu J C, Lu X L, Peng X, Ding H, Wu C Z, 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): 14710–14714

[24] Wan J, Wu J B, Gao X, Li T Q, Hu Z M, Yu H M, Huang L. Structure confined porous Mo₂C for efficient hydrogen evolution. Advanced Functional Materials, 2017, 27(45): 1703933

[25] Zhou X F, Yang X L, Li H, Hedhili M N, Huang K W, Li L J, Zhang W J. Symmetric synergy of hybrid CoS₂-WS₂ electrocatalysts for the hydrogen evolution reaction. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(30): 15552–15558

[26] Yu L, Yang J F, Lou X W. Formation of CoS₂ nanobubble hollow prisms for highly reversible lithium storage. Angewandte Chemie International Edition, 2016, 55: 13422–13426

[27] Splendiani A, Sun L, Zhang Y, Li T, Kim J, Chim C Y, Galli G, Wang F. Emerging photoluminescence in monolayer MoS₂. Nano Letters, 2010, 10(4): 1271–1275

[28] 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): 7296–7299

[29] Fang H, Chuang S, Chang T C, Takei K, Takahashi T, Javey A. High-performance single layered WSe₂ p-FETs with chemically doped contacts. Nano Letters, 2012, 12(7): 3788–3792

[30] Ross J S, Klement P, Jones A M, Ghimire N J, Yan J, Mandrus D G, Taniguchi T, Watanabe K, Kitamura K, Yao W, Electrically tunable excitonic light-emitting diodes based on monolayer WSe₂ p-n junctions. Nature Nanotechnology, 2014, 9(4): 268–272

[31] Kong D, Wang H, Cha J J, Pasta M, Koski K J, Yao J, Cui Y. Synthesis of MoS₂ and MoSe₂ films with vertically aligned layers. Nano Letters, 2013, 13(3): 1341–1347

[32] Zhang Y, Chang T R, Zhou B, Cui Y T, Yan H, Liu Z K, Schmitt F, Lee J, Moore R, Chen Y L. Direct observation of the transition from indirect to direct bandgap in atomically thin epitaxial MoSe₂. Nature Nanotechnology, 2014, 9(2): 111–115

[33] Park H, Zhang Y, Scheifers J P, Jothi P R, Encinas A, Fokwa B P T. Graphene- and phosphorene-like boron layers with contrasting activities in highly active Mo₂B₄ for hydrogen evolution. Journal of the American Chemical Society, 2017, 139(37): 12915–12918

[34] Liang H, Gandi A N, Anjum D H, Wang X, Schwingenschllögl U, Alshareef H N. Plasma-assisted synthesis of NiCoP for efficient overall water splitting. Nano Letters, 2016, 16(12): 7718–7725

[35] Li Y, Zhang H, Jiang M, Kuang Y, Sun X, Duan X. Ternary NiCoP nanosheet arrays: An excellent bifunctional catalyst for alkaline overall water splitting. Nano Research, 2016, 9(8): 2251–2259

[36] He P, Yu X Y, Lou X W D. Carbon-incorporated nickel-cobalt mixed metal phosphide nanoboxes with enhanced electrocatalytic activity for oxygen evolution. Angewandte Chemie International Edition, 2017, 56(14): 3897–3900

[37] Li J, Yan M, Zhou X, Huang Z Q, Xia Z, Chang C R, Ma Y, Qu Y. Mechanistic insights on ternary Ni_2−xCo_xP for hydrogen evolution and their hybrids with graphene as highly efficient and robust catalysts for overall water splitting. Advanced Functional Materials, 2016, 26(37): 6785–679

[38] Wang Z, Cao X, Liu D, Hao S, Du G, Asiri A M, Sun X. Ternary NiCoP nanosheet array on a Ti mesh: A high-performance electrochemical sensor for glucose detection. Chemical Communications, 2016, 52(100): 14438–14441

[39] Wang C, Jiang J, Ding T, Chen G, Xu W, Yang Q. Monodisperse ternary NiCoP nanostructures as a bifunctional electrocatalyst for both hydrogen and oxygen evolution reactions with excellent performance. Advanced Materials Interfaces, 2016, 3(4): 1500454–1500458

[40] Li J, Yan M, Zhou X, Huang Z Q, Xia Z, Chang C R, Ma Y, Qu Y. Mechanistic insights on ternary Ni_2−xCo_xP for hydrogen evolution and their hybrids with graphene as highly efficient and robust catalysts for overall water splitting. Advanced Functional Materials, 2016, 26(37): 6785–6796

[41] Liu Q, Tian J, Cui W, Jiang P, Cheng N, Asiri A M, Sun X. Carbon nanotubes decorated with CoP nanocrystals: A highly active non-noble-metal nanohybrid electrocatalyst for hydrogen evolution. Angewandte Chemie International Edition, 2014, 53(26): 6710–6714

[42] Yuan C, Li J, Hou L, Zhang X, Shen L, Lou X W D. Ultrathin mesoporous NiCo₂O₄ nanosheets supported on Ni foam as advanced electrodes for supercapacitors. Advanced Functional Materials, 2012, 22(21): 4592–4597

[43] Yuan C Z, Yang L, Hou L R, Shen L F, Zhang X G, Lou X W. Growth of ultrathin mesoporous Co₃O₄ nanosheet arrays on Ni foam for high-performance electrochemical capacitors. Energy & Environmental Science, 2012, 5(7): 7883–7887

[44] Yu L, Zhang G, Yuan C, Lou X W D. Hierarchical NiCo₂O₄@MnO₂ core-shell heterostructured nanowire arrays on Ni foam as high-performance supercapacitor electrodes. Chemical Communications, 2013, 49(2): 137–139

[45] Du C, Yang L, Yang F L, Cheng G Z, Luo W. Nest-like NiCoP for highly efficient overall water splitting. ACS Catalysis, 2017, 7(6): 4131–4137

[46] Du D H, Li P C, Ouyang J Y. Nitrogen-doped reduced graphene oxide prepared by simultaneous thermal reduction and nitrogen doping of graphene oxide in air and its application as an electrocatalyst. ACS Applied Materials & Interfaces, 2015, 7(48): 26952–26958

[47] Zheng J, Chen X L, Zhong X, Li S Q, Liu T Z, Zhuang G L, Li X N, Deng S W, Mei D H, Wang J G. Hierarchical porous NC@CuCo nitride nanosheet networks: Highly efficient bifunctional electrocatalyst for overall water splitting and selective electrooxidation of benzyl alcohol. Advanced Functional Materials, 2017, 27(46): 1704169

[48] Liang X, Zheng B, Chen L, Zhang J, Zhuang Z, Chen B. MOF-derived formation of Ni₂P-CoP bimetallic phosphides with strong interfacial effect toward electrocatalytic water splitting. ACS Applied Materials & Interfaces, 2017, 9(27): 23222–23229

[49] Liang H, Gandi A N, Anjum D H, Wang X, Schwingenschlögl U, Alshareef H N, Ngenschlögl U S, Alshareef H N. Plasma-assisted synthesis of NiCoP for efficient overall water splitting. Nano Letters, 2016, 16(12): 7718–7725

[50] Wang X, Li W, Xiong D, Petrovykh D Y, Liu L. Bifunctional nickel phosphide nanocatalysts supported on carbon fiber paper for highly efficient and stable overall water splitting. Advanced Functional Materials, 2016, 26(23): 4067–4077

Acknowledgements

We gratefully acknowledge the support of this research by the National Natural Science Foundation of China (Grant Nos. 21631004 and 21771059), the Natural Science Foundation of Heilongjiang Province (No. B2017008), the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (No. UNPYSCT-2016016), the Harbin science and technology innovation talents research Foundation (No. 2015RAQXJ057).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-018-1711-1 and is accessible for authorized users.

RIGHTS & PERMISSIONS

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