Direct fabrication of metal-free hollow graphene balls with a self-supporting structure as efficient cathode catalysts of fuel cell

Research Paper

Abstract

Despite the good progress in developing carbon catalysts for oxygen reduction reaction (ORR), the current metal-free carbon catalysts are still far from satisfactory for large-scale applications of fuel cell. Developing hollow graphene balls with a self-supporting structure is considered to be an ideal method to inhibit graphene stacking and improve their catalytic performance. Herein, we fabricated metal-free hollow graphene balls with a self-supporting structure, through using a new strategy that involves direct metal-free catalytic growth from assembly of SiO2 spheres. To our knowledge, although much researches involving the synthesis of graphene balls have been reported, investigations into the direct metal-free catalytic growth of hollow graphene balls are rare. Furthermore, the electrocatalytic performance shows that the resulting hollow graphene balls have significantly high catalytic activity. More importantly, such catalysts also possess much improved stability and better methanol tolerance in alkaline media during the ORR compared with commercial Pt/C catalysts. The outstanding performances coupled with an easy and inexpensive preparing method indicated the great potential of the hollow graphene balls with a self-supporting structure in large-scale applications of fuel cell.

Graphical Abstract

Hollow graphene balls with a self-supporting structure have been successfully fabricated, through using a new strategy that involves direct metal-free catalytic growth from 3D assembly of SiO2 spheres. The hollow graphene balls can exhibit a high catalytic activity, long-term stability, and an excellent methanol tolerance for the oxygen reduction reaction

Keywords

Fuel cell Graphene Oxygen reduction reaction Metal-free catalysts Energy conversion 

Supplementary material

11051_2016_3457_MOESM1_ESM.doc (47.1 mb)
Supplementary material 1 (DOC 48,191 kb)

References

  1. Cao RG, Thapa RJ, Kim HJ, Xu XD, Kim MG, Li Q, Park NJ, Liu ML, Cho J (2013) Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst. Nat Commun 4:2076. doi:10.1038/ncomms3076 Google Scholar
  2. Chen SS, Cai WW, Piner RD, Su JW, Wu YP, Ren YJ, Kang JY, Ruoff RS (2011a) Synthesis and characterization of large-area graphene and graphite films on commercial Cu-Ni alloy foils. Nano Lett 11:3519–3525. doi:10.1021/nl201699j CrossRefGoogle Scholar
  3. Chen ZP, Ren WC, Gao LB, Liu BL, Pei SF, Cheng HM (2011b) Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition. Nat Mater 10:424–428. doi:10.1038/nmat3001 CrossRefGoogle Scholar
  4. Chen S, Bi JY, Zhao Y, Yang LJ, Zhang C, Ma YW, Wu Q, Wang XZ, Hu Z (2012) Nitrogen-doped carbon nanocages as efficient metal-free electrocatalysts for oxygen reduction reaction. Adv Mater 24:5593–5597. doi:10.1002/adma.201202424 CrossRefGoogle Scholar
  5. Choi BG, Yang MH, Hong WH, Choi JW, Huh YS (2012) 3D macroporous graphene frameworks for supercapacitors with high energy and power densities. ACS Nano 5:4020–4028. doi:10.1021/nn3003345 CrossRefGoogle Scholar
  6. Gong KP, Du F, Xia ZH, Durstock M, Dai LM (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–764. doi:10.1126/science.1168049 CrossRefGoogle Scholar
  7. Hernandez Y, Nicolosi V, Lotya M, Blighe FM, Sun ZY, De S, McGovern IT, Holland B, Byrne M, Gun’ko YK, Boland JJ, Niraj P, Duesberg G, Krishnamurthy S, Goodhue R, Hutchison J, Scardaci V, Ferrari AC, Colemon HN (2008) High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotech 3:563–568. doi:10.1038/nnano.2008.215 CrossRefGoogle Scholar
  8. Jeong HM, Lee JW, Shin WH, Choi YJ, Shin HJ, Kang JK, Choi JW (2011) Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett 6:2472–2477. doi:10.1021/nl2009058 CrossRefGoogle Scholar
  9. Jiang P, Bertone JF, Hwang KS, Colvin VL (1999) Single-crystal colloidal multilayers of controlled thickness. Chem Mater 8:2132–2140. doi:10.1021/cm990080+ CrossRefGoogle Scholar
  10. Jin ZP, Nie HG, Yang Z, Zhang J, Liu Z, Xu XJ, Huang SM (2012) Metal-free selenium doped carbon nanotube/graphene networks as a synergistically improved cathode catalyst for oxygen reduction reaction. Nanoscale 4:6455–6460. doi:10.1039/C2NR31858J CrossRefGoogle Scholar
  11. Kim KS, Zhao Y, Jang H, Lee SY, Kim JM, Kim KS, Ahn JH, Kim P, Choi JY, Hong BH (2009) Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 7230:706–710. doi:10.1038/nature07719 CrossRefGoogle Scholar
  12. Lee JS, Kim SI, Yoon JC, Jang JH (2013) Chemical vapor deposition of mesoporous graphene nanoballs for supercapacitor. ACS Nano 7:6047–6055. doi:10.1021/nn401850z CrossRefGoogle Scholar
  13. Qu LT, Liu Y, Beak JB, Dai LM (2010) Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4:321–1326. doi:10.1021/nn901850u Google Scholar
  14. Reina A, Jia XT, Ho J, Nezich D, Son HB, Bulovic V, Dresselhaus MS, Kong J (2009) Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett 9:30–35. doi:10.1021/nl801827v CrossRefGoogle Scholar
  15. Sheng ZH, Shao L, Chen JJ, Bao WJ, Wang FB, Xia XH (2011) Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano 6:4350–4358. doi:10.1021/nn103584t CrossRefGoogle Scholar
  16. Stober W, Fink A, Bohn E (1968) Controlled growth of monodisperse silica spheres in the micron size range. J Colloid Interface Sci 1:62–69. doi:10.1016/0021-9797(68)90272-5 CrossRefGoogle Scholar
  17. Wang SY, Yu DS, Dai LM, Chang DW, Beak JB (2011) Polyelectrolyte-functionalized graphene as metal-free electrocatalysts for oxygen reduction. ACS Nano 5:6202–6209. doi:10.1021/nn200879h CrossRefGoogle Scholar
  18. Wang XB, Zhang YJ, Zhi CY, Wang X, Tang DM, Xu YB, Weng QH, Jiang XF, Metome M, Golberg D, Bando Y (2013) Three-dimensional strutted graphene grown by substrate-free sugar blowing for high-power-density supercapacitors. Nat Commun 4:2905. doi:10.1038/ncomms3905 Google Scholar
  19. Wu W, Jauregui LA, Su ZH, Liu ZH, Bao JM, Chen YP, Yu QK (2011) Growth of single crystal graphene arrays by locally controlling nucleation on polycrystalline Cu using chemical vapor deposition. Adv Mater 23:4898–4903. doi:10.1002/adma.201102456 CrossRefGoogle Scholar
  20. Xing T, Zheng Y, Li LH, Cowie BCC, Gunzelmann D, Qiao SZ, Huang SM, Chen Y (2014) Observation of active sites for oxygen reduction reaction on nitrogen-doped multilayer graphene. ACS Nano 8:6856–6862. doi:10.1021/nn501506p CrossRefGoogle Scholar
  21. Yang Z, Yao Z, Li GF, Fang GY, Nie HG, Liu Z, Zhou XM, Chen XA, Huang SM (2012) Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano 6:205–211. doi:10.1021/nn203393d CrossRefGoogle Scholar
  22. Yang Z, Zhou XM, Jin ZP, Liu Z, Nie HG, Chen XA, Huang SM (2014) A facile and general approach for the direct fabrication of 3D vertically aligned carbon nanotube array/transition metal oxide composites as non-Pt catalysts for oxygen reduction reactions. Adv Mater 26:3156–3161. doi:10.1002/adma.201305513 CrossRefGoogle Scholar
  23. Yao Z, Nie HG, Yang Z, Zhou XM, Liu Z, Huang SM (2012) Catalyst-free synthesis of iodine-doped graphene via a facile thermal annealing process and its use for electrocatalytic oxygen reduction in an alkaline medium. Chem Commun 48:1027–1029. doi:10.1039/C2CC16192C CrossRefGoogle Scholar
  24. Ye TN, Lv LB, Li XH, Xu M, Chen JS (2014) Strongly veined carbon nanoleaves as a highly efficient metal-free electrocatalyst. Angew Chem Int Ed 53:6905–6909. doi:10.1002/anie.201403363 CrossRefGoogle Scholar
  25. Yoon SM, Choi WM, Baik H, Shin HJ, Song I, Kwon MS, Bae JJ, Kim H, Lee YH, Choi JY (2012) Synthesis of multilayer graphene balls by carbon segregation from nickel nanoparticles. ACS Nano 8:6803–6811. doi:10.1021/nn301546z CrossRefGoogle Scholar
  26. Yoon JC, Lee JS, Kim SI, Kim KH, Jang JH (2013) Three-dimensional graphene nano-networks with high quality and mass production capability via precursor-assisted chemical vapor deposition. Sci Rep 3:1788. doi:10.1038/srep01788 Google Scholar
  27. Yu QK, Lian J, Siriponglert S, Li H, Chen YP, Pei SS (2008) Graphene segregated on Ni surfaces and transferred to insulators. Appl Phys Lett 11:113103. doi:10.1063/1.2982585 CrossRefGoogle Scholar
  28. Zhao MQ, Zhang Q, Huang JQ, Tian GL, Nie JQ, Peng HJ, Wei F (2014) Unstacked double-layer templated graphene for high-rate lithium-sulphur batteries. Nat Commun 5:3410. doi:10.1038/ncomms4410 Google Scholar
  29. Zhong MJ, Jiang SY, Tang YF, Gottlieb E, Kim EK, Star A, Matyjaszewski K, Kowalewski T (2014) Block copolymer-templated nitrogen-enriched nanocarbons with morphology-dependent electrocatalytic activity for oxygen reduction. Chem Sci 5:3315–3319. doi:10.1039/C4SC01477D CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  1. 1.Nanomaterials and Chemistry Key LaboratoryWenzhou UniversityWenzhouChina

Personalised recommendations