Journal of Materials Science

, Volume 54, Issue 7, pp 5412–5423 | Cite as

Facile in situ fabrication of Co nanoparticles embedded in 3D N-enriched mesoporous carbon foam electrocatalyst with enhanced activity and stability toward oxygen reduction reaction

  • Chunyang Xu
  • Zheng Lin
  • Dian Zhao
  • Yulin Sun
  • Yijun ZhongEmail author
  • Jiqiang NingEmail author
  • Changcheng Zheng
  • Ziyang Zhang
  • Yong HuEmail author
Chemical routes to materials


Oxygen reduction reaction (ORR) is a crucial reaction for various energy conversion and storage devices, but the sluggish kinetics and the usage of noble metals greatly restrict its practical device applications. In this work, a well-designed high-performance catalyst for ORR was synthesized via a facile one-step Co-MOF carbonization method, in which Co-MOF was prepared using the cobalt acetate tetrahydrate and 2,2′-bipyridyl-5,5′-dicarboxylic acid (H2bpydc) as the only raw materials and H2bpydc as the favorable carbon and nitrogen source for in situ nitrogen doping and metallic cobalt reduction. The resultant 3D mesoporous carbon foam catalyst with embedded Co nanoparticles (CoN–CF) is enriched with nitrogen, which exhibits high specific surface area and abundant N-doping active sites for catalytic ORR. In particular, the optimized CoN–CF-700 sample displays the best catalytic performances including onset potential of 0.94 V, half-wave potential of 0.85 V, long-term durability and superior resistance to methanol poisoning. The demonstrated synthetic strategy provides a new insight into easy-synthesis and high-economy routes for metal–N–C catalysts and a deeper understanding of the effects of microstructures on catalytic mechanisms.



Y. Hu acknowledges the financial support from Natural Science Foundation of China (21671173). J. Q. Ning acknowledges the financial support from Natural Science Foundation of China (11874390), Cutting-edge Key Research Program of Chinese Academy of Sciences (QYZDB-SSW-JSC014) and Hundred Talents Program of Chinese Academy of Sciences.

Supplementary material

10853_2018_3255_MOESM1_ESM.doc (1.3 mb)
Supplementary material 1 (DOC 1361 kb)


  1. 1.
    Cao X, Tan C, Sindoro M, Zhang H (2017) Hybrid micro-/nanostructures derived from metal–organic frameworks: preparation and applications in energy storage and conversion. Chem Soc Rev 46:2660–2677CrossRefGoogle Scholar
  2. 2.
    Chu S, Majumdar A (2012) Opportunities and challenges for a sustainable energy future. Nature 488:294CrossRefGoogle Scholar
  3. 3.
    Debe MK (2012) Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486:43CrossRefGoogle Scholar
  4. 4.
    Fan Z, Zhang H (2016) Crystal phase-controlled synthesis, properties and applications of noble metal nanomaterials. Chem Soc Rev 45:63–82CrossRefGoogle Scholar
  5. 5.
    Nie Y, Li L, Wei Z (2015) Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction. Chem Soc Rev 44:2168–2201CrossRefGoogle Scholar
  6. 6.
    Wu G, More KL, Johnston CM, Zelenay P (2011) High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332:443CrossRefGoogle Scholar
  7. 7.
    Song P, Luo M, Liu XZ, Xing W, Xu WL, Jiang Z, Gu L (2017) Zn single atom catalyst for highly efficient oxygen reduction reaction. Adv Funct Mater 27:1700802CrossRefGoogle Scholar
  8. 8.
    Feng Y, Xu C, Hu E, Xia B, Ning J, Zheng C, Zhong Y, Zhang Z, Hu Y (2018) Construction of hierarchical FeP/Ni2P hollow nanospindles for efficient oxygen evolution. J Mater Chem A 6:14103–14111CrossRefGoogle Scholar
  9. 9.
    Sun D, Ye L, Sun F, García H, Li Z (2018) From mixed-metal MOFs to carbon-coated core–shell metal alloy@metal oxide solid solutions: transformation of Co/Ni-MOF-74 to CoxNi1−x@CoyNi1−yO@C for the oxygen evolution reaction. Inorg Chem 56:5203–5209CrossRefGoogle Scholar
  10. 10.
    Wang X, Yu L, Bu Y, Song S, Lou XW (2018) Metal–organic framework hybrid-assisted formation of Co3O4/Co–Fe oxide double-shelled nanoboxes for enhanced oxygen evolution. Adv Mater 30:1801211CrossRefGoogle Scholar
  11. 11.
    Hu E, Feng Y, Nai J, Zhao D, Hu Y, Lou XW (2018) Construction of hierarchical Ni–Co–P hollow nanobricks with oriented nanosheets for efficient overall water splitting. Energy Environ Sci 11:872–880CrossRefGoogle Scholar
  12. 12.
    Hu E, Ning J, Zhao D, Xu C, Lin Y, Zhong Y, Zhang Z, Wang Y, Hu Y (2018) A room-temperature postsynthetic ligand exchange strategy to construct mesoporous Fe-doped CoP hollow triangle plate arrays for efficient electrocatalytic water splitting. Small 14:1704233CrossRefGoogle Scholar
  13. 13.
    Jiao Y, Zheng Y, Jaroniec M, Qiao SZ (2015) Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem Soc Rev 44:2060–2086CrossRefGoogle Scholar
  14. 14.
    Zhang W, Wu ZY, Jiang HL, Yu SH (2014) Nanowire-directed templating synthesis of metal–organic framework nanofibers and their derived porous doped carbon nanofibers for enhanced electrocatalysis. J Am Chem Soc 136:14385–14388CrossRefGoogle Scholar
  15. 15.
    Yang HB, Miao J, Hung SF, Chen J, Tao HB, Wang X, Zhang L, Chen R, Gao J, Chen HM, Dai L, Liu B (2016) Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: development of highly efficient metal-free bifunctional electrocatalyst. Sci Adv 2:e1501122CrossRefGoogle Scholar
  16. 16.
    Ren Q, Wang H, Lu X, Tong Y, Li G (2018) Recent progress on MOF-derived heteroatom-doped carbon-based electrocatalysts for oxygen reduction reaction. Adv Sci 5:1700515CrossRefGoogle Scholar
  17. 17.
    Wang Y, Chen W, Chen Y, Wei B, Chen L, Peng L, Xiang R, Li J, Wang Z, Wei Z (2018) Carbon-based catalysts by structural manipulation with iron for oxygen reduction reaction. J Mater Chem A 6:8405–8412CrossRefGoogle Scholar
  18. 18.
    Bu Y, Lu Y, Wang Y, Wu M, Lou XW (2018) Porous iron–cobalt alloy/nitrogen-doped carbon cages synthesized via pyrolysis of complex metal–organic framework hybrids for oxygen reduction. Adv Funct Mater 28:1706738CrossRefGoogle Scholar
  19. 19.
    Hu E, Yu X, Chen F, Wu Y, Hu Y, Lou XW (2018) Graphene layers-wrapped Fe/Fe5C2 nanoparticles supported on N-doped graphene nanosheets for highly efficient oxygen reduction. Adv Energy Mater 8:1702476CrossRefGoogle Scholar
  20. 20.
    Li M, Bai L, Wu S, Wen X, Guan J (2018) Co/CoOx nanoparticles embedded on carbon for efficient catalysis of oxygen evolution and oxygen reduction reactions. Chem Sus Chem 11:1722–1727CrossRefGoogle Scholar
  21. 21.
    Li S, Cheng C, Liang H, Feng X, Thomas A (2017) 2D porous carbons prepared from layered organic–inorganic hybrids and their use as oxygen-reduction electrocatalysts. Adv Mater 29:1700707CrossRefGoogle Scholar
  22. 22.
    Fu X, Zamani P, Chio J, Hassan F, Jiang F, Higgins D, Zhang Y, Hoque M, Chen Z (2017) In situ polymer graphenization ingrained with nanoporosity in a nitrogenous electrocatalyst boosting the performance of polymer-electrolyte-membrane fuel cells. Adv Mater 29:1604456CrossRefGoogle Scholar
  23. 23.
    Zhan T, Lu S, Rong H, Hou W, Teng H, Wen Y (2018) Metal–organic-framework-derived Co/nitrogen-doped porous carbon composite as an effective oxygen reduction electrocatalyst. J Mater Sci 53:6774–6784. CrossRefGoogle Scholar
  24. 24.
    Kim H, Kim Y, Noh Y, Lee S, Sung J, Kim WB (2017) Thermally-converted CoO nanoparticles embedded into N-doped carbons as highly efficient bi-functional electrocatalysts for oxygen reduction and evolution reactions. Chem Cat Chem 9:1503–1510Google Scholar
  25. 25.
    Hou Y, Wen Z, Cui S, Ci S, Shun Mao, Chen J (2015) An advanced nitrogen-doped graphene/cobalt-embedded porous carbon polyhedron hybrid for efficient catalysis of oxygen reduction and water splitting. Adv Funct Mater 25:872–882CrossRefGoogle Scholar
  26. 26.
    Tang H, Zeng Y, Zeng Y, Wang R, Cai S, Liao C, Cai H, Lu X, Tsiakaras P (2017) Iron-embedded nitrogen doped carbon frameworks as robust catalyst for oxygen reduction reaction in microbial fuel cells. Appl Catal B Environ 202:550–556CrossRefGoogle Scholar
  27. 27.
    Zhang Y, Ge J, Wang L, Wang D, Ding F, Tao X, Chen W (2013) Manageable N-doped graphene for high performance oxygen reduction reaction. Sci Rep 3:2771CrossRefGoogle Scholar
  28. 28.
    Chen Y, Wang C, Wu Z, Xiong Q, Xu Q, Yu SH, Jiang HL (2015) From bimetallic metal–organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater 27:5010–5016CrossRefGoogle Scholar
  29. 29.
    Xia B, Yan Y, Li N, Wu HB, Lou XW, Wang X (2016) A metal–organic framework-derived bifunctional oxygen electrocatalyst. Nat Energy 1:15006CrossRefGoogle Scholar
  30. 30.
    Huang Y, Liang J, Wang X, Cao R (2017) Multifunctional metal–organic framework catalysts: synergistic catalysis and tandem reactions. Chem Soc Rev 46:126–157CrossRefGoogle Scholar
  31. 31.
    Kaneti Y, Tang J, Salunkhe R, Jiang X, Yu A, Wu K, Yamauchi Y (2017) Nanoarchitectured design of porous materials and nanocomposites from metal–organic frameworks. Adv Mater 29:1604898CrossRefGoogle Scholar
  32. 32.
    Zhu L, Liu XQ, Jiang HL, Sun LB (2017) Metal–organic frameworks for heterogeneous basic catalysis. Chem Rev 117:8129–8176CrossRefGoogle Scholar
  33. 33.
    Xu J, Lawson T, Fan H, Su D, Wang G (2018) Updated metal compounds (MOFs, S, OH, N, C) used as cathode materials for lithium–sulfur batteries. Adv Energy Mater 8:1702607CrossRefGoogle Scholar
  34. 34.
    Kitao T, Zhang Y, Kitagawa S, Wang B, Uemura T (2017) Hybridization of MOFs and polymers. Chem Soc Rev 46:3108–3133CrossRefGoogle Scholar
  35. 35.
    Furukawa H, Cordova KE, O’Keeffe M, Yaghi OM (2013) The chemistry and applications of metal–organic frameworks. Science 341:1230444CrossRefGoogle Scholar
  36. 36.
    Fang X, Jiao L, Yu SH, Jiang HL (2017) Metal–organic framework-derived FeCo–N-doped hollow porous carbon nanocubes for electrocatalysis in acidic and alkaline media. Chem Sus Chem 10:3019–3024CrossRefGoogle Scholar
  37. 37.
    Li X, Jiang Q, Dou S, Deng L, Huo J, Wang S (2016) ZIF-67-derived Co–NC@CoP–NC nanopolyhedra as an efficient bifunctional oxygen electrocatalyst. J Mater Chem A 4:15836–15840CrossRefGoogle Scholar
  38. 38.
    Hu H, Han L, Yu M, Wang Z, Lou XW (2016) Metal–organic-framework-engaged formation of Co nanoparticle-embedded carbon@Co9S8 double-shelled nanocages for efficient oxygen reduction. Energy Environ Sci 9:107–111CrossRefGoogle Scholar
  39. 39.
    Wang J, Jing X, Cao Y, Li G, Huo Q, Liu Y (2015) Structural diversity and magnetic properties of three metal–organic frameworks assembled from a T-shaped linker. Cryst Eng Commun 17:604–611CrossRefGoogle Scholar
  40. 40.
    Liu Y, Hu Y, Zhou M, Qian H, Hu X (2012) Microwave-assisted non-aqueous route to deposit well-dispersed ZnO nanocrystals on reduced graphene oxide sheets with improved photoactivity for the decolorization of dyes under visible light. Appl Catal B Environ 125:425–431CrossRefGoogle Scholar
  41. 41.
    Hu W, Wang Q, Wu S, Huang Y (2016) Facile one-pot synthesis of a nitrogen-doped mesoporous carbon architecture with cobalt oxides encapsulated in graphitic layers as a robust bicatalyst for oxygen reduction and evolution reactions. J Mater Chem A 4:16920–16927CrossRefGoogle Scholar
  42. 42.
    Jiang H, Liu Y, Li W, Li J (2018) Co nanoparticles confined in 3D nitrogen-doped porous carbon foams as bifunctional electrocatalysts for long-life rechargeable Zn–air batteries. Small 14:1703739CrossRefGoogle Scholar
  43. 43.
    Guo C, Liao W, Li Z, Chen C (2015) Exploration of the catalytically active site structures of animal biomass-modified on cheap carbon nanospheres for oxygen reduction reaction with high activity, stability and methanol-tolerant performance in alkaline medium. Carbon 85:279–288CrossRefGoogle Scholar
  44. 44.
    Wu Z, Xu X, Hu B, Liang H, Lin Y, Chen L, Yu SH (2015) Iron carbide nanoparticles encapsulated in mesoporous Fe–N-doped carbon nanofibers for efficient electrocatalysis. Angew Chem Int Ed 127:8297–8301CrossRefGoogle Scholar
  45. 45.
    Guo C, Hu R, Liao W, Li Z, Sun L, Shi D, Li Y, Chen C (2017) Protein-enriched fish “biowaste” converted to three-dimensional porous carbon nano-network for advanced oxygen reduction electrocatalysis. Electrochim Acta 236:228–238CrossRefGoogle Scholar
  46. 46.
    Yoon KR, Choi J, Cho SH, Jung JW, Kim C, Cheong JY, Kim ID (2018) Facile preparation of efficient electrocatalysts for oxygen reduction reaction: one-dimensional meso/macroporous cobalt and nitrogen Co-doped carbon nanofibers. J Power Sources 380:174–184CrossRefGoogle Scholar
  47. 47.
    Tan AD, Wan K, Wang YF, Fu ZY, Liang ZX (2018) N, S-containing MOF-derived dual-doped mesoporous carbon as a highly effective oxygen reduction reaction electrocatalyst. Catal Sci Technol 8:335–343CrossRefGoogle Scholar
  48. 48.
    Liu Y, Jiang H, Zhu Y, Yang X, Li C (2016) Transition metals (Fe Co, and Ni) encapsulated in nitrogen-doped carbon nanotubes as bi-functional catalysts for oxygen electrode reactions. J Mater Chem A 4:1694–1701CrossRefGoogle Scholar
  49. 49.
    Zhang E, Xie Y, Ci S, Jia J, Cai P, Yi L, Wen Z (2016) Multifunctional high-activity and robust electrocatalyst derived from metal–organic frameworks. J Mater Chem A 4:17288–17298CrossRefGoogle Scholar
  50. 50.
    Yang W, Liu X, Chen L, Liang L, Jia J (2017) A metal–organic framework devised Co–N doped carbon microsphere/nanofiber hybrid as a free-standing 3D oxygen catalyst. Chem Commun 53:4034–4037CrossRefGoogle Scholar
  51. 51.
    Chen Y, Guo Y, Cui H, Xie Z, Zhang X, Wei J, Zhou Z (2018) Bifunctional electrocatalysts of MOF-derived Co–N/C on bamboo-like MnO nanowires for high-performance liquid- and solid-state Zn–air batteries. J Mater Chem A 6:9716–9722CrossRefGoogle Scholar
  52. 52.
    Guan B, Yu L, Lou XW (2017) Formation of single-holed cobalt/N-doped carbon hollow particles with enhanced electrocatalytic activity toward oxygen reduction reaction in alkaline media. Adv Sci 4:1700247CrossRefGoogle Scholar
  53. 53.
    You B, Jiang N, Sheng M, Drisdell WS, Yano J, Sun Y (2015) Bimetal–organic framework self-adjusted synthesis of support-free nonprecious electrocatalysts for efficient oxygen reduction. ACS Catal 5:7068–7076CrossRefGoogle Scholar
  54. 54.
    Li Z, Zhao D, Xu C, Ning J, Zhong Y, Zhang Z, Wang Y, Hu Y (2018) Reduced CoNi2S4 nanosheets with enhanced conductivity for high-performance supercapacitors. Electrochim Acta 278:33–41CrossRefGoogle Scholar
  55. 55.
    Hu E, Ning J, He B, Li Z, Zheng C, Zhong Y, Zhang Z, Hu Y (2017) Unusual formation of tetragonal microstructures from nitrogen-doped carbon nanocapsules with cobalt nanocores as a bi-functional oxygen electrocatalyst. J Mater Chem A 5:2271–2279CrossRefGoogle Scholar
  56. 56.
    Huang L, Zhang X, Han Y, Wang Q, Fang Y, Dong S (2017) In situ synthesis of ultrathin metal–organic framework nanosheets: a new method for 2D metal-based nanoporous carbon electrocatalysts. J Mater Chem A 5:18610–18617CrossRefGoogle Scholar
  57. 57.
    Liang HW, Zhuang X, Brüller S, Feng X, Müllen K (2014) Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction. Nat Commun 5:4973CrossRefGoogle Scholar
  58. 58.
    Deng D, Pan X, Yu L, Cui Y, Jiang Y, Qi J, Li WX, Fu Q, Ma X, Xue Q, Sun G, Bao X (2011) Toward N-doped graphene via solvothermal synthesis. Chem Mater 23:1188–1193CrossRefGoogle Scholar
  59. 59.
    Guo C, Li Y, Liao W, Liu Y, Li Z, Sun L, Chen C, Zhang J, Si Y, Li L (2018) Boosting the oxygen reduction activity of a three-dimensional network Co–N–C electrocatalyst via space-confined control of nitrogen-doping efficiency and the molecular-level coordination effect. J Mater Chem A 6:13050–13061CrossRefGoogle Scholar
  60. 60.
    Nandan R, Nanda KK (2017) Designing N-doped carbon nanotubes and Fe–Fe3C nanostructures Co-embedded in B-doped mesoporous carbon as an enduring cathode electrocatalyst for metal–air batteries. J Mater Chem A 5:16843–16853CrossRefGoogle Scholar
  61. 61.
    Lai L, Potts JR, Zhan D, Wang L, Poh C, Tang C, Gong H, Shen Z, Lin J, Ruoff R (2012) Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ Sci 5:7936–7942CrossRefGoogle Scholar
  62. 62.
    Hu F, Yang H, Wang C, Zhang Y, Lu H, Wang Q (2017) Co–N-doped mesoporous carbon hollow spheres as highly efficient electrocatalysts for oxygen reduction reaction. Small 13:1602507CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of ChemistryZhejiang Normal UniversityJinhuaChina
  2. 2.School of Materials Science and EngineeringBeihang UniversityBeijingChina
  3. 3.Vacuum Interconnected Nanotech Workstation, Suzhou Institute of Nano-Tech and Nano-BionicsChinese Academy of SciencesSuzhouChina
  4. 4.Mathematics and Physics Centre, Department of Mathematical SciencesXi’an Jiaotong-Liverpool UniversitySuzhouChina

Personalised recommendations