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Nano Research 2012, 5(12): 875-887 https://doi.org/10.1007/s12274-012-0271-9
Research Article | Issue | Published: 10 November 2012

Preparation, Characterization, and Application of Electrochemically Functional Graphene Nanocomposites by One-Step Liquid-Phase Exfoliation of Natural Flake Graphite with Methylene Blue

Show Author's Information Dongdong Zhang1,3,4( ),  Lei Fu2,3,  Lei Liao3,  Nan Liu3,  Boya Dai3,  Chengxiao Zhang4( )
School of MedicineXi'an Jiaotong UniversityXi'an710061China
College of Chemistry and Molecular ScienceWuhan UniversityWuhan430072China
Center for Nanochemistry (CNC)Academy for Advanced Interdisciplinary StudiesPeking UniversityBeijing100871China
Key Laboratory of Applied Surface and Colloid ChemistryMinistry of EducationSchool of Chemistry and Chemical EngineeringShanxi Normal UniversityXi'an710062China
Keywords:
Graphene, nanocomposite, liquid-phase exfoliation, electrochemistry, methylene blue
Cite this article:
Zhang D, Fu L, Liao L, et al. Preparation, Characterization, and Application of Electrochemically Functional Graphene Nanocomposites by One-Step Liquid-Phase Exfoliation of Natural Flake Graphite with Methylene Blue. Nano Research, 2012, 5(12): 875-887. https://doi.org/10.1007/s12274-012-0271-9
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Abstract Full text About this article

Electrochemically functional graphene nanocomposites have been directly prepared by one-step liquid-phase exfoliation of natural flake graphite with methylene blue (MB). UV-visible spectra of the obtained aqueous dispersions of graphene-methylene blue (G-MB) nanocomposite at different exfoliation time indicate that the concentration of graphene dispersion increased markedly with increasing exfoliation time. Atomic force microscopy (AFM) and Raman spectroscopy verified that the graphene was exfoliated into single-layer or bilayer states. FT-IR spectroscopy of G-MB suggests that a π-π stacking interaction is involved in the structure-associated interactions between graphene and adsorbed MB molecules. A G-MB nanocomposite modified glassy carbon (GC) electrode exhibits excellent electrochemical properties and good electrochemical stability. Additionally, the G-MB/GC modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with reduced graphene oxide (RGO)-MB/GC, RGO/GC, bare GC and graphite/GC electrodes. Furthermore, the G-MB/GC modified electrode exhibits good electrocatalytic activity toward hydrogen peroxide (H2O2) and β-nicotinamide adenine dinucleotide (NADH). The excellent electroactivity, electrochemical stability and electrocatalytic activity of the G-MB nanocomposites prepared in this work are potentially very useful for basic electrochemical studies and for the practical development of electronic devices such as biosensors and photovoltaic cells.


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Preparation, Characterization, and Application of Electrochemically Functional Graphene Nanocomposites by One-Step Liquid-Phase Exfoliation of Natural Flake Graphite with Methylene Blue

Show Author's information Dongdong Zhang1,3,4( ), Lei Fu2,3, Lei Liao3, Nan Liu3, Boya Dai3, Chengxiao Zhang4( )
School of MedicineXi'an Jiaotong UniversityXi'an710061China
College of Chemistry and Molecular ScienceWuhan UniversityWuhan430072China
Center for Nanochemistry (CNC)Academy for Advanced Interdisciplinary StudiesPeking UniversityBeijing100871China
Key Laboratory of Applied Surface and Colloid ChemistryMinistry of EducationSchool of Chemistry and Chemical EngineeringShanxi Normal UniversityXi'an710062China

Abstract

Electrochemically functional graphene nanocomposites have been directly prepared by one-step liquid-phase exfoliation of natural flake graphite with methylene blue (MB). UV-visible spectra of the obtained aqueous dispersions of graphene-methylene blue (G-MB) nanocomposite at different exfoliation time indicate that the concentration of graphene dispersion increased markedly with increasing exfoliation time. Atomic force microscopy (AFM) and Raman spectroscopy verified that the graphene was exfoliated into single-layer or bilayer states. FT-IR spectroscopy of G-MB suggests that a π-π stacking interaction is involved in the structure-associated interactions between graphene and adsorbed MB molecules. A G-MB nanocomposite modified glassy carbon (GC) electrode exhibits excellent electrochemical properties and good electrochemical stability. Additionally, the G-MB/GC modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with reduced graphene oxide (RGO)-MB/GC, RGO/GC, bare GC and graphite/GC electrodes. Furthermore, the G-MB/GC modified electrode exhibits good electrocatalytic activity toward hydrogen peroxide (H2O2) and β-nicotinamide adenine dinucleotide (NADH). The excellent electroactivity, electrochemical stability and electrocatalytic activity of the G-MB nanocomposites prepared in this work are potentially very useful for basic electrochemical studies and for the practical development of electronic devices such as biosensors and photovoltaic cells.

Keywords: Graphene, nanocomposite, liquid-phase exfoliation, electrochemistry, methylene blue

References(52)

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.
DOI Google Scholar
2

Allen, M. J.; Tung, V. C.; Kaner, R. B. Honeycomb carbon: A review of graphene. Chem. Rev. 2010, 110, 132–145.
DOI Google Scholar
3

Novoselov, K. S.; Jiang, D.; Schedin, F.; Booth, T. J.; Khotkevich, V. V.; Morozov, S. V.; Geim, A. K. Twodimensional atomic crystals. Proc. Natl. Acad. Sci. USA 2005, 102, 10451–10453.
DOI Google Scholar
4

Vallés, C.; Drummond, C.; Saadaoui, H.; Furtado, C. A.; He, M.; Roubeau, O.; Ortolani, L.; Monthioux, M.; Pénicaud, A. Solutions of negatively charged graphene sheets and ribbons. J. Am. Chem. Soc. 2008, 130, 15802–15804.
DOI Google Scholar
5

Bourlinos, A. B.; Georgakilas, V.; Zboril, R.; Steriotis, T. A.; Stubos, A. K. Liquid-phase exfoliation of graphite towards solubilized graphenes. Small 2009, 5, 1841–1845.
DOI 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.; Heer, W. A. Electronic confinement and coherence in patterned epitaxial graphene. Science 2006, 312, 1191–1196.
DOI Google Scholar
7

Sutter, P. W.; Flege, J. I.; Sutter, E. A. Epitaxial graphene on ruthenium. Nat. Mater. 2008, 7, 406–411.
DOI Google Scholar
8

Li, X.; Cai, W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.; Velamakanni, A.; Jung, I.; Tutuc, E.; Banerjee, S. K.; Colombo, L.; Ruoff, R. S. Large-area synthesis of highquality and uniform graphene films on copper foils. Science 2009, 324, 1312–1314.
DOI Google Scholar
9

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. 2009, 9, 30–35.
DOI Google Scholar
10

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.
DOI Google Scholar
11

Lu, C. H.; Yang, H. H.; Zhu, C. L.; Chen, X.; Chen, G. N. A graphene platform for sensing biomolecules. Angew. Chem. Int. Ed. 2009, 48, 4785–4787.
DOI Google Scholar
12

Zhou, M.; Zhai, Y.; Dong, S. Electrochemical sensing and biosensing platform based on chemically reduced graphene oxide. Anal. Chem. 2009, 81, 5603–5613.
DOI Google Scholar
13

Jasuja, K.; Berry, V. Implantation and growth of dendritic gold nanostructures on graphene derivatives: Electrical property tailoring and Raman enhancement. ACS Nano 2009, 3, 2358–2366.
DOI Google Scholar
14

Goncalves, G.; Marques, P. A. A. P.; Granadeiro, C. M.; Nogueira, H. I. S.; Singh, M. K.; Grácio, J. Surface modification of graphene nanosheets with gold nanoparticles: The role of oxygen moieties at graphene surface on gold nucleation and growth. Chem. Mater. 2009, 21, 4796–4802.
DOI Google Scholar
15

Salavagione, H. J.; Gómez, M. A.; Martínez, G. Polymeric modification of graphene through esterification of graphite oxide and poly(vinyl alcohol). Macromolecules 2009, 42, 6331–6334.
DOI Google Scholar
16

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.
DOI Google Scholar
17

Shen, J.; Hu, Y.; Li, C.; Qin, C.; Ye, M. Synthesis of amphiphilic graphene nanoplatelets. Small 2009, 5, 82–85.
DOI Google Scholar
18

Cui, X.; Zhang, C.; Hao, R.; Hou, Y. Liquid-phase exfoliation, functionalization and applications of graphene. Nanoscale 2011, 3, 2118–2126.
DOI Google Scholar
19

Tung, V. C.; Allen, M. J.; Yang, Y.; Kaner, R. B. Highthroughput solution processing of large-scale graphene. Nat. Nanotechnol. 2009, 4, 25–29.
DOI Google Scholar
20

Park, S.; An, J.; Piner, R. D.; Jung, I.; Yang, D.; Velamakanni, A.; Nguyen, S. T.; Ruoff, R. S. Aqueous suspension and characterization of chemically modified graphene sheets. Chem. Mater. 2008, 20, 6592–6594.
DOI Google Scholar
21

Li, D.; Müller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G. Processable aqueous dispersions of graphene nanosheets. Nat. Nanotechnol. 2008, 3, 101–105.
DOI Google Scholar
22

Fan, X.; Peng, W.; Li, Y.; Li, X.; Wang, S.; Zhang, G.; Zhang, F. Deoxygenation of exfoliated graphite oxide under alkaline conditions: A green route to graphene preparation. Adv. Mater. 2008, 20, 4490–4493.
DOI Google Scholar
23

Dua, V.; Surwade, S. P.; Ammu, S.; Agnihotra, S. R.; Jain, S.; Roberts, K. E.; Park, S.; Ruoff, R. S.; Manohar, S. K. All-organic vapor sensor using inkjet-printed reduced graphene oxide. Angew. Chem. Int. Ed. 2010, 49, 2154–2157.
DOI Google Scholar
24

Liu, J.; Fu, S.; Yuan, B.; Li, Y.; Deng, Z. Toward a universal "adhesive nanosheet" for the assembly of multiple nanoparticles based on a protein-induced reduction/decoration of graphene oxide. J. Am. Chem. Soc. 2010, 132, 7279–7281.
DOI Google Scholar
25

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.
DOI Google Scholar
26

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.
DOI Google Scholar
27

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.
DOI Google Scholar
28

Dai, B.; Fu, L.; Liao, L.; Liu, N.; Yan, K.; Chen, Y.; Liu, Z. High-quality single-layer graphene via reparative reduction of graphene oxide. Nano Res. 2011, 4, 434–439.
DOI Google Scholar
29

Huang, X.; Yin, Z.; Wu, S.; Qi, X.; He, Q.; Zhang, Q.; Yan, Q.; Boey, F.; Zhang, H. Graphene-based materials: Synthesis, characterization, properties, and applications. Small 2011, 7, 1876–1902.
DOI Google Scholar
30

Hernandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F. M.; Sun, Z.; De, S.; McGovern, I. T.; Holland, B.; Byrne, M.; Gun'Ko, Y. K.; Boland, J. J.; Niraj, P.; Duesberg, G.; Krishnamurthy, S.; Goodhue, R.; Hutchison, J.; Scardaci, V.; Ferrari, A. C.; Coleman, J. N. High-yield production of graphene by liquidphase exfoliation of graphite. Nat. Nanotechnol. 2008, 3, 563–568.
DOI Google Scholar
31

Lotya, M.; Hernandez, Y.; King, P. J.; Smith, R. J.; Nicolosi, V.; Karlsson, L. S.; Blighe, F. M.; De, S.; Wang, Z.; McGovern, I. T.; Duesberg, G. S.; Coleman, J. N. Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions. J. Am. Chem. Soc. 2009, 131, 3611–3620.
DOI Google Scholar
32

Wang, D.; Li, Y.; Hasin, P.; Wu, Y. Preparation, characterization, and electrocatalytic performance of graphene-methylene blue thin films. Nano Res. 2011, 4, 124–130.
DOI Google Scholar
33

Mao, K.; Wu, D.; Li, Y.; Ma, H.; Ni, Z.; Yu, H.; Luo, C.; Wei, Q.; Du, B. Label-free electrochemical immunosensor based on graphene/methylene blue nanocomposite. Anal. Biochem. 2012, 422, 22–27.
DOI Google Scholar
34

Qin, H.; Liu, J.; Chen, C.; Wang, J.; Wang, E. An electrochemical aptasensor for chiral peptide detection using layer-by-layer assembly of polyelectrolyte-methylene blue/polyelectrolyte-graphene multilayer. Anal. Chim. Acta 2012, 712, 127–131.
DOI Google Scholar
35

Zhang, D.; Fu, L.; Liao, L.; Dai, B.; Zou, R.; Zhang, C. Electrochemically functional graphene nanostructure and layer-by-layer nanocomposite incorporating adsorption of electroactive methylene blue. Electrochim. Acta 2012, 75, 71–79.
DOI Google Scholar
36

Sagara, T.; Niki, K. Surface Processes and adsorption states of methylene blue at graphite electrode surfaces in an acidic medium: An electroreflectance study. Langmuir 1993, 9, 831–838.
DOI Google Scholar
37

Yan, Y.; Zhang, M.; Gong, K.; Su, L.; Guo, Z.; Mao, L. Adsorption of methylene blue dye onto carbon nanotubes: A route to an electrochemically functional nanostructure and its layer-by-layer assembled nanocomposite. Chem. Mater. 2005, 17, 3457–3463.
DOI Google Scholar
38

Liu, H.; Gao, J.; Xue, M.; Zhu, N.; Zhang, M.; Cao, T. Processing of graphene for electrochemical application: noncovalently functionalize graphene sheets with watersoluble electroactive methylene green. Langmuir 2009, 25, 12006–12010.
DOI Google Scholar
39

Liu, N.; Fu, L.; Dai, B.; Yan, K.; Liu, X.; Zhao, R.; Zhang, Y.; Liu, Z. Universal segregation growth approach to wafer-Size graphene from non-noble metals. Nano Lett. 2011, 11, 297–303.
DOI Google Scholar
40

Naujok, R. R.; Duevel, R. V.; Corn, R. M. Fluorescence and fourier transform surface-enhanced Raman scattering measurements of methylene blue adsorbed onto a sulfurmodified gold electrode. Langmuir 1993, 9, 1771–1774.
DOI Google Scholar
41

Xiao, G. N.; Man, S. Q. Surface-enhanced Raman scattering of methylene blue adsorbed on cap-shaped silver nanoparticles. Chem. Phys. Lett. 2007, 447, 305–309.
DOI Google Scholar
42

Paek, S. M.; Yoo, E. J.; Honma, I. Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. Nano Lett. 2009, 9, 72–75.
DOI Google Scholar
43

Szabó, T.; Berkesi, O.; Dékány, I. DRIFT study of deuteriumexchanged graphite oxide. Carbon 2005, 43, 3186–3189.
DOI Google Scholar
44

Li, X.; Wang, X.; Zhang, L.; Lee, S.; Dai, H. Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Science 2008, 319, 1229–1232.
DOI Google Scholar
45

Manna, A. K.; Pati, S. K. Tuning the electronic structure of graphene by molecular charge transfer: A computational study. Chem. Asian J. 2009, 4, 855–860.
DOI Google Scholar
46
Bard, A. J.; Faulkner, L. R. Electrochemical methods: Fundamentals and Applications. 2nd ed.; John Wiley & Sons, Inc. : New York, 2001.
47

Shang, N. G.; Papakonstantinou, P.; McMullan, M.; Chu, M.; Stamboulis, A.; Potenza, A.; Dhesi, S. S.; Marchetto, H. Catalyst-free Efficient growth, orientation and biosensing properties of multilayer graphene nanoflake films with sharp edge planes. Adv. Funct. Mater. 2008, 18, 3506–3514.
DOI Google Scholar
48

Zhang, M.; Gorski, W. Electrochemical sensing platform based on the carbon nanotubes/redox mediators-biopolymer system. J. Am. Chem. Soc. 2005, 127, 2058–2059.
DOI Google Scholar
49

Zhang, D.; Peng, Y.; Qi, H.; Gao, Q.; Zhang, C. Application of multielectrode array modified with carbon nanotubes to simultaneous amperometric determination of dihydroxybenzene isomers. Sens. Actuator, B-Chem 2009, 136, 113–121.
DOI Google Scholar
50

Li, W.; Tan, C.; Lowe, M. A.; Abruña, H. D.; Ralph, D. C. Electrochemistry of individual monolayer graphene Sheets. ACS Nano 2011, 5, 2264–2270.
DOI Google Scholar
51

Brownson, D. A. C.; Kampouris, D. K.; Banks, C. E. Graphene electrochemistry: Fundamental concepts through to prominent applications. Chem. Soc. Rev. 2012, 41, 6944–6976.
DOI Google Scholar
52

Zhou, M.; Shang, L.; Li, B.; Huang, L.; Dong, S. Highly ordered mesoporous carbons as electrode material for the construction of electrochemical dehydrogenase- and oxidase-based biosensors. Biosens. Bioelectron. 2008, 24, 442–447.
DOI Google Scholar
Publication history
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Acknowledgements

Publication history

Received: 13 July 2012
Revised: 12 September 2012
Accepted: 11 October 2012
Published: 10 November 2012
Issue date: December 2012

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2012

Acknowledgements

Acknowledgements

Financial support from the National Science Foundations of China (Nos. 20973006, 21245002 and 21027007) and the National Science Foundation for Post-doctoral Scientists of China (No. 2012M511990) is gratefully acknowledged.

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