Professional Documents
Culture Documents
The chemistry of graphene oxide is discussed in this critical review. Particular emphasis is directed
toward the synthesis of graphene oxide, as well as its structure. Graphene oxide as a substrate for
a variety of chemical transformations, including its reduction to graphene-like materials, is also
Published on 03 November 2009. Downloaded on 5/20/2019 11:00:24 AM.
discussed. This review will be of value to synthetic chemists interested in this emerging field of
materials science, as well as those investigating applications of graphene who would find a more
thorough treatment of the chemistry of graphene oxide useful in understanding the scope and
limitations of current approaches which utilize this material (91 references).
a
2. Synthesis and structural characterization of GO
Department of Chemistry and Biochemistry, The University of Texas
at Austin, 1 University Station, A5300, Austin, TX, 78712, USA. 2.1 Synthetic approaches
E-mail: bielawski@cm.utexas.edu; Fax: +1 512-471-5884;
Tel: +1 512-232-3839 Despite the relative novelty of graphene as a material of broad
b
Department of Mechanical Engineering, Texas Materials Institute, interest and potential,1,3 GO has a history that extends back
The University of Texas at Austin, 204 E. Dean Keeton St., Austin,
TX, 78712, USA. E-mail: r.ruoff@mail.utexas.edu; many decades to some of the earliest studies involving the
Fax: +1 512-471-7681; Tel: +1 512-471-4691 chemistry of graphite.4–6 The first, well-known example came
in 1859 when British chemist B. C. Brodie was exploring the procedure resulted in an overall extent of oxidation similar to
structure of graphite by investigating the reactivity of flake Brodie’s multiple oxidation approach (C : O B 2 : 1), but
graphite. One of the reactions he performed involved adding performed more practically in a single reaction vessel.8
‘‘potash of chlorate’’ (potassium chlorate; KClO3) to a slurry Nearly 60 years after Staudenmaier, Hummers and Offeman
of graphite in fuming nitric acid (HNO3).7 Brodie determined developed an alternate oxidation method by reacting graphite
that the resulting material was composed of carbon, hydrogen, with a mixture of potassium permanganate (KMnO4) and
and oxygen, resulting in an increase in the overall mass of the concentrated sulfuric acid (H2SO4), again, achieving similar
flake graphite. He isolated crystals of the material, but the levels of oxidation.9 Though others have developed slightly
interfacial angles of the crystal lattice were unable to be modified versions, these three methods comprise the primary
measured via reflective goniometry. Successive oxidative routes for forming GO, and little about them has changed.
treatments resulted in a further increase in the oxygen content, Importantly, it has since been demonstrated that the products
reaching a limit after four reactions. The C : H : O composition of these reactions show strong variance, depending not only
was determined to be 61.04 : 1.85 : 37.11; a net molecular on the particular oxidants used, but also on the graphite
formula of C2.19H0.80O1.00. Brodie found the material to be source and reaction conditions. This point will be borne out
Published on 03 November 2009. Downloaded on 5/20/2019 11:00:24 AM.
dispersible in pure or basic water, but not in acidic media, in the discussions that follow. Because of the lack of under-
which prompted him to term the material ‘‘graphic acid.’’ standing of the direct mechanisms involved in these processes,
After heating to a temperature of 220 1C, the C : H : O it is instructive to consider examples of the reactivities of these
composition of this material changed to 80.13 : 0.58 : 19.29 chemicals in other, more easily studied, systems. The Brodie
(C5.51H0.48O1.00), coupled with a loss of carbonic acid and and Staudenmaier approaches both use KClO3 and nitric acid
‘‘carbonic oxide.’’ (most commonly fuming [>90% purity]) and will be treated
Throughout his studies, Brodie was interested in the together.
molecular formula of ‘‘graphite’’ and its discrete molecular Nitric acid is a common oxidizing agent (e.g. aqua regia)
weight. Ultimately, he determined the molecular weight of and is known to react strongly with aromatic carbon surfaces,
graphite to be 33, saying: including carbon nanotubes.10,11 The reaction results in the
‘‘This form of carbon should be characterized by a name formation of various oxide-containg species including carboxyls,
marking it as a distinct element. I propose to term it Graphon.’’ lactones, and ketones. Oxidations by HNO3 result in the
Nearly 150 years later, ‘‘graphene’’ would take the physics liberation of gaseous NO2 and/or N2O4 (as demonstrated in
and chemistry communities by storm. Brodie’s observation of yellow vapors).12 Likewise, potassium
We now know that Brodie was mistaken in his search for a chlorate is a strong oxidizing agent commonly used in blasting
discrete molecular formula for graphite, and the indeterminate caps or other explosive materials. KClO3 typically is an in situ
nature of this material shall be discussed more fully in the source of dioxygen, which acts as the reactive species.12 These
following sections. Nearly 40 years after Brodie’s seminal were among the strongest oxidation conditions known at the
discovery of the ability to oxidize graphite, L. Staudenmaier time, and continue to be some of the strongest used on a
improved Brodie’s KClO3-fuming HNO3 preparation by preparative scale.
adding the chlorate in multiple aliquots over the course of The Hummers method uses a combination of potassium
the reaction (also, with the addition of concentrated sulfuric permanganate and sulfuric acid. Though permanganate is a
acid, to increase the acidity of the mixture), rather than in a commonly used oxidant (e.g. dihydroxylations), the active
single addition as Brodie had done. This slight change in the species is, in fact, diamanganese heptoxide (Scheme 1). This
This journal is
c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 228–240 | 229
View Article Online
This journal is
c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 228–240 | 231
Published on 03 November 2009. Downloaded on 5/20/2019 11:00:24 AM. View Article Online
This journal is
c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 228–240 | 233
Published on 03 November 2009. Downloaded on 5/20/2019 11:00:24 AM. View Article Online
Fig. 6 Digital pictures of as-prepared GO dispersed in water and 13 organic solvents through ultrasonication (1 h). Top: dispersions immediately
after sonication. Bottom: dispersions 3 weeks after sonication. The yellow color of the o-xylene sample is due to the solvent itself (from ref. 41).
This journal is
c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 228–240 | 235
View Article Online
Table 1 Sheet resistance and elemental composition of reduced graphene oxide films using NaBH4 or N2H4 as the reducing agents (adapted from
ref. 55)
NaBH4 N2H2
XPS XPS
Total elemental Heterocarbon component Sheet resistance Total elemental Heterocarbon component N-1s peak Sheet resistance
C : O ratio of C-1s peak (%) (kO sq1) C : O ratio of C-1s peak (%) intensity (%) (kO sq1)
2.8 74.1 — 2.8 74.1 — —
4.3 27.9 — 3.9 26.4 1.3 69 0000
4.9 16.2 79 4.5 19.0 2.1 12 000
5.3 13.4 59 5 18.6 2.6 3460
— — — 6.2 14.5 2.4 780
enormous pressure within the stacked layers. Based on state the reaction pathway shown in Scheme 3, highlighting the
Published on 03 November 2009. Downloaded on 5/20/2019 11:00:24 AM.
equations, a pressure of 40 MPa is generated at 300 1C, while crucial role of hydrogen ions in the buffer solution. Though
as much as 130 MPa is generated at 1000 1C.61 Evaluation of this route appears to be extremely effective (and yet mild) at
the Hamaker constant predicts that a pressure of only 2.5 MPa reducing the extant oxide functionality, and it precludes the
is necessary to separate two stacked graphene oxide platelets.61 need for hazardous chemical reactants and their byproducts,
BET surface areas of 600–900 m2 g1 have been reported for electrochemical reduction has not been demonstrated on a
this material (a methylene blue absorption method is also large sample. The deposition of reduced graphene oxide onto
applied, giving a surface area of 1850 m2 g1); roughly 80% of the electrodes is likely to render bulk electrochemical reduction
the platelets investigated by AFM are single platelets.61 difficult on a preparative scale. Scalability is a fundamental
A notable effect of thermal exfoliation is the structural requirement of a useful synthetic protocol if graphene is to be
damage caused to the platelets by the release of carbon broadly utilized.
dioxide.63 Approximately 30% of the mass of the GO is lost
during the exfoliation process, leaving behind vacancies 3.2 Chemical functionalization
and topological defects throughout the plane of the reduced
graphene oxide platelet.62 Defects inevitably affect the electronic We have discussed removing oxygen functional groups
properties of the product by decreasing the ballistic transport (reduction) from graphene oxide platelets in the previous
path length and introducing scattering sites. Despite sections. In this section, we will discuss the addition of other
these structural defects, however, bulk conductivities of groups to graphene oxide platelets using various chemical
1000–2300 S m1 were measured, indicating effective overall reactions that provide for either covalent or non-covalent
reduction and restoration of the planes’ electronic structure. attachment to the resulting chemically modified graphenes
Although it has not been studied to date, these defects may (CMGs). Such approaches, which add functionality to groups
also have an effect on the mechanical properties of the already present on the graphene oxide, render graphene/graphite
product, compared to a chemically-reduced sample.64–66 oxide a more versatile precursor for a wide range of applications.
Graphene oxide platelets have chemically reactive oxygen
functionality, such as carboxylic acid, groups at their edges
3.1.3 Electrochemical reduction. Another final method that
(according to the widely accepted Lerf–Klinowski model), and
shows promise for the reduction of graphene oxide relies on
epoxy and hydroxyl groups on the basal planes. An ideal
the electrochemical removal of the oxygen functionalities.
approach to the chemical modification of graphene oxide
Though chemically-reduced graphene oxide had previously
would utilize orthogonal reactions of these groups to selectively
been coated with metallic nanoparticles via electrodeposition,
functionalize one site over another. Demonstration of the
representing one of the few uses of CMGs in electrochemistry,67
selectivity of these chemical transformations remains challenging,
only recently has electrochemical reduction been used to alter
however. In some instances, reaction with multiple functionalities
the structure of graphene oxide or graphene itself.68 In
is possible, and the wide range of chemical compositions
principle, this could avoid the use of dangerous reductants
present in the reactant known as ‘‘graphene oxide’’ makes
(e.g. hydrazine) and the need to dispose of the byproducts.
isolation and rigorous characterization of the products
After depositing thin films of graphene oxide on a variety of
practically impossible. Nevertheless, reactions involving
substrates (glass, plastic, ITO, etc.), electrodes were placed at
individual functional groups found on graphene oxide will
opposite ends of the film and linear sweep voltammetry
be discussed separately.
was run in a sodium phosphate buffer. Reduction began
at 0.60 V and reached a maximum at 0.87 V. Rapid
3.2.1 At the carboxylic acid group of graphene oxide. A
reduction was observed during the first 300 s, followed by a
wide range of reactions utilizing carboxylic acids has been
reduced rate of reduction up to 2000 s, and finally a decrease
to background current levels up to 5000 s. Elemental analysis
of the resultant material revealed a C : O ratio of 23.9 : 1; the
conductivity of the film was measured to be approximately
8500 S m1. As with many of the aforementioned methods, the Scheme 3 Proposed reaction for the electrochemical reduction of
reduction mechanism remains unclear. The authors proposed graphene oxide in a sodium phosphate buffer (adapted from ref. 68).
This journal is
c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 228–240 | 237
View Article Online
Acknowledgements
We gratefully acknowledge the Defense Advanced Research
Projects Agency Carbon Electronics for RF Applications
Center, the National Science Foundation (DMR-0907324),
Fig. 16 Covalent functionalization of reduced graphene oxide platelets
with diazonium salts (SDBS, sodium dodecylbenzenesulfonate)
the Welch Foundation (F-1621) and the University of Texas
(adapted from ref. 90). at Austin for support.
CMG platelets were readily dispersed in several polar organic Notes and references
solvents. Most covalent chemical modifications of graphene
1 A. K. Geim and K. S. Novoselov, Nat. Mater., 2007, 6, 183–191.
Published on 03 November 2009. Downloaded on 5/20/2019 11:00:24 AM.
oxide previously discussed occurred at one or more of the 2 S. Park and R. S. Ruoff, Nat. Nanotechnol., 2009, 4, 217–224.
various oxygen-containing functional groups present in 3 V. C. Tung, M. J. Allen, Y. Yang and R. B. Kaner,
graphene oxide. Hence, the reactivity observed in materials Nat. Nanotechnol., 2009, 4, 25–29.
4 H.-P. Boehm and E. Stumpp, Carbon, 2007, 45, 1381–1383.
derived from the reduction of graphene oxide could be caused 5 C. Schafheutl, J. Prakt. Chem., 1840, 21, 129–157.
by residual functional groups left intact after incomplete 6 C. Schafheutl, Phil. Mag., 1840, 16, 570–590.
reduction. 7 B. C. Brodie, Philos. Trans. R. Soc. London, 1859, 149, 249–259.
8 L. Staudenmaier, Ber. Dtsch. Chem. Ges., 1898, 31, 1481–1487.
9 W. S. Hummers and R. E. Offeman, J. Am. Chem. Soc., 1958, 80,
1339.
Conclusions and perspectives 10 P. V. Lakshminarayanan, H. Toghiani and C. U. P. Jr, Carbon,
2004, 42, 2433–2442.
In summary, graphene oxide has an extensive history that can 11 N. Zhang, L.-y. Wang, H. Liu and Q.-K. Cai, Surf. Interface Anal.,
2008, 40, 1190–1194.
be understood independent of its relationship to graphene. In 12 F. A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochmann,
addition to providing this historical perspective, we have Advanced Inorganic Chemistry, Wiley India, Singapore, 2004.
presented an overview of GO and graphene oxide in their 13 K. R. Koch and P. F. Krause, J. Chem. Ed., 1982, 59, 973–974.
contemporary settings. Using flake graphite as a starting 14 A. Simon, R. Dronskowski, B. Krebs and B. Hettich, Angew.
Chem., Int. Ed. Engl., 1987, 26, 139–140.
material, a variety of strong chemical oxidants have been used 15 M. Trömel and M. Russ, Angew. Chem., 1987, 99, 1037–1038.
for the synthesis of graphene oxide, although its amorphous, 16 M. Wissler, J. Power Sources, 2006, 156, 142–150.
berthollide composition has made understanding its true 17 USPTO, ed. T. Ishikawa, T. Kanmaru, H. Teranishi and
K. Onishi, Nippon Carbon Co., Ltd., USA, 1978.
chemical structure an ongoing challenge. The most commonly
18 U. Hofmann and R. Holst, Ber. Dtsch. Chem. Ges. B, 1939, 72,
accepted model remains the Lerf-Klinowski model, though 754–771.
others, such as the Dékány model, have been proposed as 19 G. Ruess, Monatsh. Chem., 1946, 76, 381–417.
alternatives. 20 M. Mermoux, Y. Chabre and A. Rousseau, Carbon, 1991, 29,
469–474.
Among the most important chemical transformation of 21 M. Dubois, J. Giraudet, K. Guerin, A. Hamwi, Z. Fawal,
graphene oxide is its reduction to graphene-like materials. P. Pirotte and F. Masin, J. Phys. Chem. B, 2006, 110, 11800–11808.
This can be achieved chemically through the use of strong 22 W. Scholz and H. P. Boehm, Z. Anorg. Allg. Chem., 1969, 369,
327–340.
reductants (such as hydrazine or sodium borohydride)
23 T. Nakajima, A. Mabuchi and R. Hagiwara, Carbon, 1988, 26,
thermally, or electrochemically. The resulting product is very 357–361.
similar to pristine graphene and has been used in a wide range 24 T. Nakajima and Y. Matsuo, Carbon, 1994, 32, 469–475.
of materials with potential physical and engineering applications. 25 H. He, T. Riedl, A. Lerf and J. Klinowski, J. Phys. Chem., 1996,
100, 19954–19958.
In addition to its reduction, however, graphene oxide is a 26 A. Lerf, H. He, M. Forster and J. Klinowski, J. Phys. Chem. B,
useful platform for the fabrication of functionalized graphene 1998, 102, 4477–4482.
platelets that can potentially confer improved mechanical, 27 T. Szabo, O. Berkesi, P. Forgo, K. Josepovits, Y. Sanakis,
thermal and/or electronic properties. Both small molecules D. Petridis and I. Dekany, Chem. Mater., 2006, 18, 2740–2749.
28 A. Lerf, H. He, T. Riedl, M. Forster and J. Klinowski, Solid State
and polymers have been covalently attached to graphene Ionics, 1997, 101–103, 857–862.
oxide’s highly reactive oxygen functionalities, or non-covalently 29 A. Buchsteiner, A. Lerf and J. Pieper, J. Phys. Chem. B, 2006, 110,
attached on the graphitic surfaces of CMGs, for potential use 22328–22338.
30 A. Lerf, A. Buchsteiner, J. Pieper, S. Schöttl, I. Dekany, T. Szabo
in polymer composites, paper-like materials, sensors, photo-
and H. P. Boehm, J. Phys. Chem. Solids, 2006, 67, 1106–1110.
voltaic applications, and drug-delivery systems. 31 H. P. Boehm and W. Scholz, Z. Anorg. Allg. Chem., 1965, 335,
A knowledge of graphene oxide’s chemistry provides 74–79.
valuable insight into its reactivity and ultimately its properties, 32 D. Hadzi and A. Novak, Faraday Trans., 1955, 51, 1514.
33 A. M. Rodriguez and P. S. V. Jimenez, Carbon, 1986, 24, 163.
as well as those of graphenes that are derived therefrom. Much 34 H. He, J. Klinowski, M. Forster and A. Lerf, Chem. Phys. Lett.,
work remains to be done, however, in developing reliable 1998, 287, 53–56.
characterization methods that will aid in unambiguous 35 U. Hofmann, A. Frenzel and E. Csalan, Justus Liebigs Ann. Chem.,
structural identification as well as synthetic procedures that 1934, 510, 1.
36 W. Cai, R. D. Piner, F. J. Stadermann, S. Park, M. A. Shaibat,
lead to relatively uniform products. Finally, the development Y. Ishii, D. Yang, A. Velamakanni, S. J. An, M. Stoller, J. An,
of reduction methods that minimize residual oxygen functionality D. Chen and R. S. Ruoff, Science, 2008, 321, 1815–1817.
This journal is
c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 228–240 | 239
View Article Online
37 W. Gao, L. B. Alemany, L. Ci and P. M. Ajayan, Nat. Chem., 63 K. N. Kudin, B. Ozbas, H. C. Schniepp, R. K. Prud’homme,
2009, 1, 403–408. I. A. Aksay and R. Car, Nano Lett., 2008, 8, 36–41.
38 T. Szabo, O. Berkesi and I. Dekany, Carbon, 2005, 43, 3186–3189. 64 S. Park, D. A. Dikin, S. T. Nguyen and R. S. Ruoff, J. Phys. Chem. C,
39 T. Szabo, E. Tombacz, E. Illes and I. Dekany, Carbon, 2006, 44, 2009, 113, 15801–15804.
537–545. 65 S. Park, K.-S. Lee, G. Bozoklu, W. Cai, S. T. Nguyen and
40 D. W. Boukhvalov and M. I. Katsnelson, J. Am. Chem. Soc., 2008, R. S. Ruoff, ACS Nano, 2008, 2, 572–578.
130, 10697–10701. 66 J. T. Robinson, M. Zalalutdinov, J. W. Baldwin, E. S. Snow,
41 J. I. Paredes, S. Villar-Rodil, A. Martinez-Alonso and J. M. D. Z. Wei, P. Sheehan and B. H. Houston, Nano Lett., 2008, 8,
Tascon, Langmuir, 2008, 24, 10560–10564. 3441–3445.
42 H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao and 67 R. S. Sundaram, C. Gomez-Navarro, K. Balasubramanian,
Y. Chen, ACS Nano, 2008, 2, 463–470. M. Burghard and K. Kern, Adv. Mater., 2008, 20, 3050–3053.
43 C. Gomez-Navarro, R. T. Weitz, A. M. Bittner, M. Scolari, 68 M. Zhou, Y. Wang, Y. Zhai, J. Zhai, W. Ren, F. Wang and
A. Mews, M. Burghard and K. Kern, Nano Lett., 2007, 7, S. Dong, Chem.–Eur. J., 2009, 15, 6116–6120.
3499–3503. 69 S. Niyogi, E. Bekyarova, M. E. Itkis, J. L. McWilliams,
44 S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas, M. A. Hamon and R. C. Haddon, J. Am. Chem. Soc., 2006, 128,
E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen and 7720–7721.
R. S. Ruoff, Nature, 2006, 442, 282–286. 70 Y. Xu, Z. Liu, X. Zhang, Y. Wang, J. Tian, Y. Huang, Y. Ma,
Published on 03 November 2009. Downloaded on 5/20/2019 11:00:24 AM.
45 Z. Li, W. Zhang, Y. Luo, J. Yang and J. G. Hou, J. Am. Chem. X. Zhang and Y. Chen, Adv. Mater., 2009, 21, 1–5.
Soc., 2009, 131, 6320–6321. 71 Z.-B. Liu, Y.-F. Xu, X.-Y. Zhang, X.-L. Zhang, Y.-S. Chen and
46 L. Zhang, J. Liang, Y. Huang, Y. Ma, Y. Wang and Y. Chen, J.-G. Tian, J. Phys. Chem. B, 2009, 113, 9681–9686.
Carbon, 2009, 47, 3365–3380. 72 X. Zhang, Y. Huang, Y. Wang, Y. Ma, Z. Liu and Y. Chen,
47 Y. Si and E. T. Samulski, Nano Lett., 2008, 8, 1679–1682. Carbon, 2009, 47, 334–337.
48 S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas, 73 Z. Liu, J. T. Robinson, X. Sun and H. Dai, J. Am. Chem. Soc.,
A. Kleinhammes, Y. Jia, Y. Wu, S. T. Nguyen and R. S. Ruoff, 2008, 130, 10876–10877.
Carbon, 2007, 45, 1558–1565. 74 L. M. Veca, F. Lu, M. J. Meziani, L. Cao, P. Zhang, G. Qi, L. Qu,
49 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, M. Shrestha and Y.-P. Sun, Chem. Commun., 2009, 2565–2567.
S. V. Dubonos, I. V. Grigorieva and A. A. Firsov, Science, 2004, 75 N. Mohanty and V. Berry, Nano Lett., 2008, 8, 4469–4476.
306, 666–669. 76 Y. Yang, J. Wang, J. Zhang, J. Liu, X. Yang and H. Zhao,
50 F. A. Carey and R. J. Sundberg, in Advanced Organic Chemistry Part Langmuir, 2009, 25, 11808–11814.
B: Reactions and Synthesis, Springer, New York, 2007, pp. 367–471. 77 M. Fang, K. Wang, H. Lu, Y. Yang and S. Nutt, J. Mater. Chem.,
51 S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 2009, 19, 7098–7105.
60, 309–319. 78 S. H. Lee, D. R. Dreyer, J. An, A. Velamakanni, R. D. Piner,
52 A. Das, B. Chakraborty and A. K. Sood, Bull. Mater. Sci., 2008, S. Park, Y. Zhu, S. O. Kim, C. W. Bielawski and R. S. Ruoff,
31, 579–584. Macromol. Rapid Commun., 2009, DOI: 10.1002/marc.200900641.
53 J. H. Warner, M. H. Rümmeli, L. Ge, T. Gremming, 79 S. Stankovich, R. Piner, S. T. Nguyen and R. S. Ruoff, Carbon,
B. Montanari, N. M. Harrison, B. Büchner and G. A. D. Briggs, 2006, 44, 3342–3347.
Nat. Nanotechnol., 2009, 4, 500–504. 80 S. Wang, P.-J. Chia, L.-L. Chua, L.-H. Zhao, R.-Q. Png,
54 H. K. Chae, D. Y. Siberio-Perez, J. Kim, Y. Go, M. Eddaoudi, S. Sivaramakrishnan, M. Zhou, R. G.-S. Goh, R. H. Friend,
A. J. Matzger, M. O’Keeffe and O. M. Yaghi, Nature, 2004, 427, A. T. S. Wee and P. K.-H. Ho, Adv. Mater., 2008, 20, 3440–3446.
523–527. 81 H. Yang, C. Shan, F. Li, D. Han, Q. Zhang and L. Niu, Chem.
55 H.-J. Shin, K. K. Sim, A. Benayad, S.-M. Yoon, H. K. Park, Commun., 2009, 3880–3882.
I.-S. Jung, M. H. Jin, H.-K. Jeong, J. M. Kim, J.-Y. Choi and 82 H. Yang, F. Li, C. Shan, D. Han, Q. Zhang, L. Niu and A. Ivaska,
Y. H. Lee, Adv. Funct. Mater., 2009, 19, 1987–1992. J. Mater. Chem., 2009, 19, 4632–4638.
56 S. J. Kanh, C. Kocabas, T. Ozel, M. Shim, N. Pimparkar, 83 C.-H. Lu, H.-H. Yang, C.-L. Zhu, X. Chen and G.-N. Chen,
M. A. Alam, S. V. Rotkin and J. A. Rogers, Nat. Nanotechnol., Angew. Chem., Int. Ed., 2009, 48, 4785–4787.
2007, 2, 230–236. 84 X. Yang, X. Zhang, Z. Liu, Y. Ma, Y. Huang and Y. Chen,
57 G. Wang, J. Yang, J. Park, X. Gou, B. Wang, H. Liu and J. Yao, J. Phys. Chem. C, 2008, 112, 17554–17558.
J. Phys. Chem. C, 2008, 112, 8192–8195. 85 S. Stankovich, R. Piner, X. Chen, N. Wu, S. T. Nguyen and
58 Z.-S. Wu, W. Ren, L. Gao, B. Liu, C. Jiang and H.-M. Cheng, R. S. Ruoff, J. Mater. Chem., 2006, 16, 155–158.
Carbon, 2009, 47, 493–499. 86 H. Bai, Y. Xu, L. Zhao, C. Li and G. Shi, Chem. Commun., 2009,
59 X. Fan, W. Peng, Y. Li, X. Li, S. Wang, G. Zhang and F. Zhang, 1667–1669.
Adv. Mater., 2008, 20, 4490–4493. 87 S.-Z. Zu and B.-H. Han, J. Phys. Chem. C, 2009, 113,
60 H. P. Boehm, A. Clauss, G. O. Fischer and U. Hofmann, Z. Anorg. 13651–13657.
Allg. Chem., 1962, 316, 119–127. 88 R. Hao, W. Qian, L. Zhang and Y. Hou, Chem. Commun., 2008,
61 M. J. McAllister, J.-L. Li, D. H. Adamson, H. C. Schniepp, 6576–6578.
A. A. Abdala, J. Liu, M. Herrera-Alonso, D. L. Milius, R. Car, 89 Y. Xu, H. Bai, G. Lu, C. Li and G. Shi, J. Am. Chem. Soc., 2008,
R. K. Prud’homme and I. A. Aksay, Chem. Mater., 2007, 19, 130, 5856–5857.
4396–4404. 90 Q. Su, S. Pang, V. Alijani, C. Li, X. Feng and K. Müllen, Adv.
62 H. C. Schniepp, J.-L. Li, M. J. McAllister, H. Sai, M. Herrera- Mater., 2009, 21, 3191–3195.
Alonso, D. H. Adamson, R. K. Prud’homme, R. Car, D. A. Saville 91 J. R. Lomeda, C. D. Doyle, D. V. Kosynkin, W.-F. Hwang and
and I. A. Aksay, J. Phys. Chem. B, 2006, 110, 8535–8539. J. M. Tour, J. Am. Chem. Soc., 2008, 130, 16201–16206.