One-Step Electrochemical Approach to the Synthesis of Graphene/MnO2 Nanowall Hybrids
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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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One-Step Electrochemical Approach to the Synthesis of Graphene/MnO2 Nanowall Hybrids
)
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.
References(55)
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.
Geim, A. K.; Novoselov, K. S. The rise of graphene. Nat. Mater. 2007, 6, 183–191.
Park, S.; Ruoff, R. S. Chemical methods for the production of graphenes. Nat. Nanotechol. 2009, 4, 217–224.
Wang, X.; Zhi, L. J.; Mullen, K. Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett. 2008, 8, 323–327.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Pasricha, R.; Gupta, S.; Srivastava, A. K. A facile and novel synthesis of Ag–graphene-based nanocomposites. Small 2009, 5, 2253–2259.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Chen, S.; Zhu, J.; Wu, X.; Han, Q.; Wang, X. Graphene oxide–MnO2 nanocomposites for supercapacitors. ACS Nano 2010, 4, 2822–2830.
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.
Jiao, F.; Bruce, P. G. Mesoporous crystalline β-MnO2—a reversible positive electrode for rechargeable lithium batteries. Adv. Mater. 2007, 19, 657–660.
Chen, J.; Zhang, W. D.; Ye, J. S. Nonenzymatic electro-chemical glucose sensor based on MnO2/MWNTs nano-composite. Electrochem. Commun. 2008, 10, 1268–1271.
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.
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.
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.
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.
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.
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.
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.
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.
Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. The chemistry of graphene oxide. Chem. Soc. Rev. 2010, 39, 228–240.
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.
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.
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.
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.
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.
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.
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.
Ferrari, A. C.; Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 2000, 61, 14095–14107.
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.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos. 20935003 and 20820102037) and the 973 Project (No. 2010CB933603).
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