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One-step electrochemical approach to the synthesis of Graphene/MnO2 nanowall hybrids

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Abstract

We have demonstrated a one-step and effective electrochemical method to synthesize graphene/MnO2 nanowall hybrids (GMHs). Graphene oxide (GO) was electrochemically reduced to graphene (GN), accompanied by the simultaneous formation of MnO2 with a nanowall morphology via cathodic electrochemical deposition. The morphology and structure of the GMHs were systematically characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Raman spectroscopy. The resulting GMHs combine the advantages of GN and the nanowall array morphology of MnO2 in providing a conductive network of amorphous nanocomposite, which shows good electrochemical capacitive behavior. This simple approach should find practical applications in the large-scale production of GMHs.

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References

  1. Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306, 666–669.

    Article  CAS  Google Scholar 

  2. Geim, A. K.; Novoselov, K. S. The rise of graphene. Nat. Mater. 2007, 6, 183–191.

    Article  CAS  Google Scholar 

  3. Park, S.; Ruoff, R. S. Chemical methods for the production of graphenes. Nat. Nanotechol. 2009, 4, 217–224.

    Article  CAS  Google Scholar 

  4. Wang, X.; Zhi, L. J.; Mullen, K. Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett. 2008, 8, 323–327.

    Article  CAS  Google Scholar 

  5. Reina, A.; Jia, X.; Ho, J.; Nezich, D.; Son, H.; Bulovic, V.; Dresselhaus, M. S.; Kong, J. Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 2008, 9, 30–35.

    Article  Google Scholar 

  6. Berger, C.; Song, Z.; Li, X.; Wu, X.; Brown, N.; Naud, C.; Mayou, D.; Li, T.; Hass, J.; Marchenkov, A. N.; Conrad, E. H.; First, P. N.; de Heer, W. A. Electronic confinement and coherence in patterned epitaxial graphene. Science 2006, 312, 1191–1196.

    Article  CAS  Google Scholar 

  7. Li, D.; Muller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G. Processable aqueous dispersions of graphene nanosheets. Nat. Nanotechol. 2008, 3, 101–105.

    Article  CAS  Google Scholar 

  8. Zhu, C.; Guo, S.; Fang, Y.; Dong, S. Reducing sugar: New functional molecules for the green synthesis of graphene nanosheets. ACS Nano 2010, 4, 2429–2437.

    Article  CAS  Google Scholar 

  9. Zhou, M.; Wang, Y.; Zhai, Y.; Zhai, J.; Ren, W.; Wang, F.; Dong, S. Controlled synthesis of large-area and patterned electrochemically reduced graphene oxide films. Chem.-Eur. J. 2009, 15, 6116–6120.

    Article  CAS  Google Scholar 

  10. Guo, H. L.; Wang, X. F.; Qian, Q. Y.; Wang, F. B.; Xia, X. H. A green approach to the synthesis of graphene nanosheets. ACS Nano 2009, 3, 2653–2659.

    Article  CAS  Google Scholar 

  11. Shao, Y.; Wang, J.; Engelhard, M.; Wang, C.; Lin, Y. Facile and controllable electrochemical reduction of graphene oxide and its applications. J. Mater. Chem. 2010, 20, 743–748.

    Article  CAS  Google Scholar 

  12. Wang, Z.; Zhou, X.; Zhang, J.; Boey, F.; Zhang, H. Direct electrochemical reduction of single-layer graphene oxide and subsequent functionalization with glucose oxidase. J. Phys. Chem. C 2009, 113, 14071–14075.

    Article  CAS  Google Scholar 

  13. Geng, X.; Niu, L.; Xing, Z.; Song, R.; Liu, G.; Sun, M.; Cheng, G.; Zhong, H.; Liu, Z.; Zhang, Z.; Sun, L.; Xu, H.; Lu, L.; Liu, L. Aqueous-processable noncovalent chemically converted graphene-quantum dot composites for flexible and transparent optoelectronic films. Adv. Mater. 2010, 22, 638–642.

    Article  CAS  Google Scholar 

  14. Guo, C.; Yang, H.; Sheng, Z.; Lu, Z.; Song, Q.; Li, C. Layered graphene/quantum dots for photovoltaic devices. Angew. Chem. Int. Ed. 2010, 49, 3014–3017.

    Article  CAS  Google Scholar 

  15. Guo, S.; Dong, S.; Wang, E. Three-dimensional Pt-on-Pd bimetallic nanodendrites supported on graphene nanosheet: Facile synthesis and used as an advanced nanoelectrocatalyst for methanol oxidation. ACS Nano 2010, 4, 547–555.

    Article  CAS  Google Scholar 

  16. Pasricha, R.; Gupta, S.; Srivastava, A. K. A facile and novel synthesis of Ag-graphene-based nanocomposites. Small 2009, 5, 2253–2259.

    Article  CAS  Google Scholar 

  17. Zhou, X.; Huang, X.; Qi, X.; Wu, S.; Xue, C.; Boey, F. Y. C.; Yan, Q.; Chen, P.; Zhang, H. In situ synthesis of metal nanoparticles on single-layer graphene oxide and reduced graphene oxide surfaces. J. Phys. Chem. C 2009, 113, 10842–10846.

    Article  CAS  Google Scholar 

  18. Huang, X.; Zhou, X.; Wu, S.; Wei, Y.; Qi, X.; Zhang, J.; Boey, F.; Zhang, H. Reduced graphene oxide-templated photochemical synthesis and in situ assembly of Au nanodots to orderly patterned Au nanodot chains. Small 2010, 6, 513–516.

    Article  CAS  Google Scholar 

  19. Zhu, C.; Guo, S.; Wang, P.; Xing, L.; Fang, Y.; Zhai, Y.; Dong, S. One-pot, water-phase approach to high-quality graphene/TiO2 composite nanosheets. Chem. Commun. 2010, 46, 7148–7150.

    Article  CAS  Google Scholar 

  20. Yang, X.; Zhang, X.; Ma, Y.; Huang, Y.; Wang, Y.; Chen, Y. Superparamagnetic graphene oxide-Fe3O4 nanoparticles hybrid for controlled targeted drug carriers. J. Mater. Chem. 2009, 19, 2710–2714.

    Article  CAS  Google Scholar 

  21. Yin, Z.; Wu, S.; Zhou, X.; Huang, X.; Zhang, Q.; Boey, F.; Zhang, H. Electrochemical deposition of ZnO nanorods on transparent reduced graphene oxide electrodes for hybrid solar cells. Small 2010, 6, 307–312.

    Article  CAS  Google Scholar 

  22. Wu, S.; Yin, Z.; He, Q.; Huang, X.; Zhou, X.; Zhang, H. Electrochemical deposition of semiconductor oxides on reduced graphene oxide-based flexible, transparent, and conductive electrodes. J. Phys. Chem. C 2010, 114, 11816–11821.

    Article  CAS  Google Scholar 

  23. Qiu, L.; Yang, X.; Gou, X.; Yang, W.; Ma, Z. F.; Wallace, G. G.; Li, D. Dispersing carbon nanotubes with graphene oxide in water and synergistic effects between graphene derivatives. Chem.-Eur. J. 2010, 16, 10653–10658.

    Article  CAS  Google Scholar 

  24. Fan, Z.; Yan, J.; Zhi, L.; Zhang, Q.; Wei, T.; Feng, J.; Zhang, M.; Qian, W.; Wei, F. A three-dimensional carbon nanotube/graphene sandwich and its application as electrode in supercapacitors. Adv. Mater. 2010, 22, 3723–3728.

    Article  CAS  Google Scholar 

  25. Xu, J.; Wang, K.; Zu, S. Z.; Han, B. H.; Wei, Z. Hierarchical nanocomposites of polyaniline nanowire arrays on graphene oxide sheets with synergistic effect for energy storage. ACS Nano 2010, 4, 5019–5026.

    Article  CAS  Google Scholar 

  26. Zhou, X.; Wu, T.; Hu, B.; Yang, G.; Han, B. Synthesis of graphene/polyaniline composite nanosheets mediated by polymerized ionic liquid. Chem. Commun. 2010, 46, 3663–3665.

    Article  CAS  Google Scholar 

  27. Qi, X.; Pu, K. Y.; Zhou, X.; Li, H.; Liu, B.; Boey, F.; Huang, W.; Zhang, H. Conjugated-polyelectrolyte-functionalized reduced graphene oxide with excellent solubility and stability in polar solvents. Small 2010, 6, 663–669.

    Article  CAS  Google Scholar 

  28. Qi, X.; Pu, K. Y.; Li, H.; Zhou, X.; Wu, S.; Fan, Q. L.; Liu, B.; Boey, F.; Huang, W.; Zhang, H. Amphiphilic graphene composites. Angew. Chem. Int. Ed. 2010, 49, 9426–9429.

    Article  CAS  Google Scholar 

  29. Guo, Y.; Guo, S.; Ren, J.; Zhai, Y.; Dong, S.; Wang, E. Cyclodextrin functionalized graphene nanosheets with high supramolecular recognition capability: Synthesis and host-guest inclusion for enhanced electrochemical performance. ACS Nano 2010, 4, 4001–4010.

    Article  CAS  Google Scholar 

  30. Han, T. H.; Lee, W. J.; Lee, D. H.; Kim, J. E.; Choi, E. Y.; Kim, S. O. Peptide/graphene hybrid assembly into core/shell nanowires. Adv. Mater. 2010, 22, 2060–2064.

    Article  CAS  Google Scholar 

  31. Liu, J.; Fu, S.; Yuan, B.; Li, Y.; Deng, Z. Toward a universal “adhesive nanosheet” for the assembly of multiple nano-particles based on a protein-induced reduction/decoration of graphene oxide. J. Am. Chem. Soc. 2010, 132, 7279–7281.

    Article  CAS  Google Scholar 

  32. Lv, W.; Guo, M.; Liang, M. H.; Jin, F. M.; Cui, L.; Zhi, L.; Yang, Q. H. Graphene-DNA hybrids: Self-assembly and electrochemical detection performance. J. Mater. Chem. 2010, 20, 6668–6673.

    Article  CAS  Google Scholar 

  33. Zhang, H.; Cao, G.; Wang, Z.; Yang, Y.; Shi, Z.; Gu, Z. Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage. Nano Lett. 2008, 8, 2664–2668.

    Article  CAS  Google Scholar 

  34. Chen, S.; Zhu, J.; Wu, X.; Han, Q.; Wang, X. Graphene oxide-MnO2 nanocomposites for supercapacitors. ACS Nano 2010, 4, 2822–2830.

    Article  CAS  Google Scholar 

  35. Luo, J. Y.; Zhang, J. J.; Xia, Y. Y. Highly electrochemical reaction of lithium in the ordered mesoporous β-MnO2. Chem. Mater. 2006, 18, 5618–5623.

    Article  CAS  Google Scholar 

  36. Jiao, F.; Bruce, P. G. Mesoporous crystalline β-MnO2-a reversible positive electrode for rechargeable lithium batteries. Adv. Mater. 2007, 19, 657–660.

    Article  CAS  Google Scholar 

  37. Chen, J.; Zhang, W. D.; Ye, J. S. Nonenzymatic electro-chemical glucose sensor based on MnO2/MWNTs nanocomposite. Electrochem. Commun. 2008, 10, 1268–1271.

    Article  CAS  Google Scholar 

  38. Li, L.; Du, Z.; Liu, S.; Hao, Q.; Wang, Y.; Li, Q.; Wang, T. A novel nonenzymatic hydrogen peroxide sensor based on MnO2/graphene oxide nanocomposite. Talanta 2010, 82, 1637–1641.

    Article  CAS  Google Scholar 

  39. Zhai, Y.; Zhai, J.; Zhou, M.; Dong, S. Ordered magnetic core-manganese oxide shell nanostructures and their application in water treatment. J. Mater. Chem. 2009, 19, 7030–7035.

    Article  CAS  Google Scholar 

  40. Fei, J.; Cui, Y.; Yan, X.; Qi, W.; Yang, Y.; Wang, K.; He, Q.; Li, J. Controlled preparation of MnO2 hierarchical hollow nanostructures and their application in water treatment. Adv. Mater. 2008, 20, 452–456.

    Article  Google Scholar 

  41. Zhang, L.; Liu, C.; Zhuang, L.; Li, W.; Zhou, S.; Zhang, J. Manganese dioxide as an alternative cathodic catalyst to platinum in microbial fuel cells. Biosens. Bioelectron. 2009, 24, 2825–2829.

    Article  CAS  Google Scholar 

  42. Espinal, L.; Suib, S. L.; Rusling, J. F. Electrochemical catalysis of styrene epoxidation with films of MnO2 nanoparticles and H2O2. J. Am. Chem. Soc. 2004, 126, 7676–7682.

    Article  CAS  Google Scholar 

  43. Kovtyukhova, N. I.; Ollivier, P. J.; Martin, B. R.; Mallouk, T. E.; Chizhik, S. A.; Buzaneva, E. V.; Gorchinskiy, A. D. Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations. Chem. Mater. 1999, 11, 771–778.

    Article  CAS  Google Scholar 

  44. Li, Y. G.; Wu, Y. Y. Coassembly of graphene oxide and nanowires for large-area nanowire alignment. J. Am. Chem. Soc. 2009, 131, 5851–5857.

    Article  CAS  Google Scholar 

  45. Kong, B. S.; Geng, J.; Jung, H. T. Layer-by-layer assembly of graphene and gold nanoparticles by vacuum filtration and spontaneous reduction of gold ions. Chem. Commun. 2009, 2174–2176.

  46. Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. The chemistry of graphene oxide. Chem. Soc. Rev. 2010, 39, 228–240.

    Article  CAS  Google Scholar 

  47. Liu, D.; Zhang, Q.; Xiao, P.; Garcia, B. B.; Guo, Q.; Champion, R.; Cao, G. Hydrous manganese dioxide nanowall arrays growth and their Li+ ions intercalation electrochemical properties. Chem. Mater. 2008, 20, 1376–1380.

    Article  CAS  Google Scholar 

  48. Nethravathi, C.; Nisha, T.; Ravishankar, N.; Shivakumara, C.; Rajamathi, M. Graphene-nanocrystalline metal sulphide composites produced by a one-pot reaction starting from graphite oxide. Carbon 2009, 47, 2054–2059.

    Article  CAS  Google Scholar 

  49. Zhou, Y. G.; Chen, J. J.; Wang, F. B.; Sheng, Z. H.; Xia, X. H. A facile approach to the synthesis of highly electroactive Pt nanoparticles on graphene as an anode catalyst for direct methanol fuel cells. Chem. Commun. 2010, 46, 5951–5953.

    Article  CAS  Google Scholar 

  50. Yan, J.; Fan, Z.; Wei, T.; Qian, W.; Zhang, M.; Wei, F. Fast and reversible surface redox reaction of graphene-MnO2 composites as supercapacitor electrodes. Carbon 2010, 48, 3825–3833.

    Article  CAS  Google Scholar 

  51. Chou, S. L.; Wang, J. Z.; Chew, S. Y.; Liu, H. K.; Dou, S. X, Electrodeposition of MnO2 nanowires on carbon nanotube paper as free-standing, flexible electrode for supercapacitors. Electrochem. Commun. 2008, 10, 1724–1727.

    Article  CAS  Google Scholar 

  52. Liu, D.; Garcia, B. B.; Zhang, Q.; Guo, Q.; Zhang, Y.; Sepehri, S.; Cao, G. Mesoporous hydrous manganese dioxide nanowall arrays with large lithium ion energy storage capacities. Adv. Funct. Mater. 2009, 19, 1015–1023.

    Article  CAS  Google Scholar 

  53. McAllister, M. J.; Li, J. L.; Adamson, D. H.; Schniepp, H. C.; Abdala, A. A.; Liu, J.; Herrera-Alonso, M.; Milius, D. L.; Car, R.; Prud’homme, R. K.; Aksay, I. A. Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chem. Mater. 2007, 19, 4396–4404.

    Article  CAS  Google Scholar 

  54. Ferrari, A. C.; Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 2000, 61, 14095–14107.

    Article  CAS  Google Scholar 

  55. Wu, Z. S.; Wang, D. W.; Ren, W.; Zhao, J.; Zhou, G.; Li, F.; Cheng, H. M. Anchoring hydrous RuO2 on graphene sheets for high-performance electrochemical capacitors. Adv. Funct. Mater. 2010, 20, 3595–3602.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    Chengzhou Zhu, Shaojun Guo, Youxing Fang, Lei Han, Erkang Wang & Shaojun Dong

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  1. Chengzhou Zhu
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  2. Shaojun Guo
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  3. Youxing Fang
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  4. Lei Han
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Correspondence to Shaojun Dong.

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Zhu, C., Guo, S., Fang, Y. et al. One-step electrochemical approach to the synthesis of Graphene/MnO2 nanowall hybrids. Nano Res. 4, 648–657 (2011). https://doi.org/10.1007/s12274-011-0120-2

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