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Materials Chemistry A
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COMMUNICATION View Journal | View Issue
10626
Junping Zhang* and Bucheng Li
Received 13th June 2013
Accepted 24th July 2013
DOI: 10.1039/c3ta12284k
www.rsc.org/MaterialsA
Universal dispersion of single-walled carbon nanotubes (SWNTs) in inevitably damage the electronic structure, and then their
the liquid phase using Laponite RD (LRD) is achieved via a simple inherent functionalities.11–13 Alternatively, noncovalent func-
grinding–ultrasonication procedure inspired by Maya Blue. The tionalization is proved to be a powerful strategy for stabilizing
marriage between SWNTs and water-soluble LRD via van der Waals CNTs in aqueous solution while maintaining the intact elec-
interactions and electron donating–accepting interactions generates tronic structure.3,14,15 Pyrene-containing compounds,16 surfac-
a water-dispersible hybrid, which we term LRD/SWNTs. The tants17,18 (e.g., sodium dodecyl benzenosulfonate (SDBS),
concentration of LRD and hand-grinding play important roles in sodium dodecyl sulphate (SDS) and Pluronic F-127), bio-
effectively dispersing SWNTs. The LRD/SWNT aqueous dispersion macromolecules19–23 (e.g., chitosan, peptides and DNA) and
features excellent stability (over 6 months without any sediment) synthetic polymers24,25 (e.g., poly(acrylic acid) and poly(N-iso-
and a high SWNT concentration of 1.83 mg mL 1, which is obviously propylacrylamide)) have been successfully used for noncovalent
superior to the frequently used surfactants and other materials dispersion of CNTs. The pioneering work on dispersing CNTs is
for noncovalent dispersion of carbon nanotubes. Moreover, the encouraging but has some limitations.5 For example, each
LRD/SWNT aqueous dispersion is miscible with and stable in the modication is specic of the solvent (polar/apolar, hydro-
other common organic solvents, e.g., methanol, DMF and DMSO. philic/hydrophobic) and the effectiveness of dispersants for
CNTs remains to be improved.
In fact, dispersion and/or solubility issues are among the
most frequently encountered problems for chemical experi-
Introduction mentalists owing to the big difference in polarity between
the solid and liquid phase. Recently, Kynast et al. found that the
Carbon nanotubes (CNTs) have drawn much attention since
apolar dye indigo, which is not normally encountered in
their discovery in 1991 owing to their unique electronic and
aqueous solution owing to the intra- and intermolecular
mechanical properties.1–3 However, CNTs tend to form entan- hydrogen bonds, can be solubilized in the aqueous phase by the
gled bundles and aggregates in solution, especially in aqueous aid of nanoscopic clay shuttles.26 Also, montmorillonite clay has
solution, because of strong van der Waals forces.3,4 Thus, stable an affinity for single-walled carbon nanotubes (SWNTs) and
dispersion of CNTs is a major challenge but a prerequisite for could improve dispersibility of SWNTs.27
many of their potential applications such as high performance
Here, inspired by the ancient Maya Blue, we present the
polymer/CNT nanocomposites, conductive plastics or adhe-
effective dispersion of SWNTs in aqueous solution using a
sives, electronics, sensors and actuators.5–8
commercially available clay mineral, Laponite RD (LRD). Maya
In general, CNTs are dispersed in solution by two ways:
Blue, a pigment used by Mayas in the Yucatan, is an inorganic/
chemical modication and noncovalent functionalization.9,10 organic hybrid composed of rodlike clay mineral palygorskite
Chemical modication by introducing appropriate solubiliza- and indigo.28–30 Typically, Maya Blue pigments are prepared by
tion groups (such as –COOH, –OH and –NH2) or graing poly- dry mixing and grinding palygorskite with indigo, and then
mers on to the surface defects or sp2 sidewalls of CNTs would dispersed with deionized H2O and heated up to 190 C for a
period of time.29 LRD, Na0.7[Mg5.5Li0.3Si8O20(OH)4](H2O)n, is a
Center of Eco-material and Green Chemistry, Lanzhou Institute of Chemical Physics, synthetic hectorite-type clay mineral consisting of relatively
Chinese Academy of Sciences, Lanzhou, 730000, P. R. China. E-mail: jpzhang@licp.
mono-dispersed and well-dened platelets with a diameter of
cas.cn; Tel: +86 931 4968251
† Electronic supplementary information (ESI) available: SWNT concentration,
25–30 nm and a thickness of approximately 1 nm.31 LRD is
viscosity, TEM images, IR spectra and digital images. See DOI: 10.1039/c3ta12284k soluble in aqueous solution at concentrations below 5 wt% with
10626 | J. Mater. Chem. A, 2013, 1, 10626–10630 This journal is ª The Royal Society of Chemistry 2013
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negative face charges and positive edge charges on the platelets. The micrographs of the samples were taken using a eld
The marriage between SWNTs and LRD generates a water- emission transmission electron microscope (TEM, JEM-1200EX,
dispersible hybrid, which we term LRD/SWNTs. The LRD/SWNT FEI). A drop of the LRD-SWNT aqueous dispersion was put on a
hybrids feature high dispersion stability in water (over 6 months copper microgrid and dried in the open atmosphere. FTIR
without any sediment) with a high SWNT concentration of 1.83 spectra of samples were recorded on a Thermo Nicolet NEXUS
mg mL 1. Moreover, the LRD/SWNT aqueous dispersion is TM spectrophotometer using KBr pellets.
stable in the other organic liquids, e.g., methanol, DMF and
DMSO. The concentration of LRD and hand-grinding play Results and discussion
crucial roles in dispersing SWNTs.
The LRD/SWNT hybrids were prepared simply by hand-grinding
the physical mixture of LRD and SWNT powders with an
Experimental section
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Characterization
To evaluate the concentration of SWNTs in the liquid phase, the
nal solutions were analyzed by measuring the absorbance
at 600 nm using a UV-vis spectrophotometer (Specord 200,
Analytik Jena AG). At this wavelength, LRD does not interfere
with the absorbance of SWNTs (Fig. S1†). The corresponding
LRD solution was used as the blank. The relationship between
the concentration of SWNTs in the liquid phase and the
absorbance at 600 nm can be seen from the standard curve
(Fig. S2†). The standard curve was obtained according to the Fig. 1 (a) Schematic illustration of solid LRD, SWNT bundles and homogeneous
following procedure. First, the stock LRD/SWNT dispersion was dispersion of LRD/SWNTs in aqueous solution. Photographic images of (b) pristine
obtained by centrifugation at 5000 rpm for 30 min to remove SWNTs in water, (c) LRD/SWNT hybrid of various concentrations in water (from
left to right: 0.007, 0.018, 0.037, 0.092, 0.366 and 1.83 mg mL 1 SWNTs), SWNTs
any aggregates. Then, working dispersions for preparing the
modified with (d) SDBS (0.04 mg mL 1 SWNTs in 4 mg mL 1 SDBS) and (e) SDS
standard curve were prepared by diluting the stock dispersion (0.02 mg mL 1 SWNTs in 4 mg mL 1 SDS) in water. (f) Optical micrograph of
with water. The viscosity of the samples was measured using a (b). (g) Optical micrograph of (c, 1.83 mg mL 1 SWNTs). (h) TEM image of (c,
rheometer (Anton Paar Physica, MCR301) at 25 C and 30 rpm. 0.366 mg mL 1 SWNTs).
This journal is ª The Royal Society of Chemistry 2013 J. Mater. Chem. A, 2013, 1, 10626–10630 | 10627
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via electrostatic interaction,36 which contributes to the excellent More than 90% of SWNTs are successfully transported into the
stability of the LRD/SWNT aqueous dispersion. The subsequent aqueous phase. LRD is capable of adsorbing neutral organic
ultrasonication helps to disintegrate and disperse the agglom- molecules and eventually brings them into aqueous solution.26
erated LRD/SWNT hybrid formed during hand-grinding, and For example, pyrene could be adsorbed onto LRD by van der
then further enhances the concentration of SWNTs in the Waals interactions with the siloxane planes of LRD and by the
aqueous solution. The performance of LRD in dispersing electron accepting ability of the lateral surface of LRD.37,38 As is
SWNTs is obviously superior to the frequently used surfactants, well known, pyrene-containing compounds are frequently used
e.g., SDBS and SDS (Fig. 1d and e, S3 and S4†), and other for noncovalent functionalization of the graphitic surface of
materials for noncovalent dispersion of CNTs. The aggregates of CNTs via p–p stacking interactions, and then bring them into
pristine SWNTs can be seen clearly via an optical microscope the aqueous phase.16,39 Thus, SWNTs may interact with LRD
and a TEM (Fig. 1f and S5b†). Whereas a well-dispersed LRD/ according to the same mechanism like the adsorption of pyrene
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SWNT hybrid can be seen via the TEM (Fig. 1h and S5c†) and no onto LRD since pyrene and SWNTs have a similar well-ordered
aggregate of SWNTs was detected by the optical microscope benzene ring array. The shi of the FTIR absorption band of
(Fig. 1g). LRD from 3684.1 cm 1 (stretching vibration of MgO–H) to
The concentration of LRD in the aqueous solution has a 3675.8 cm 1 and the broadening of the absorption band of LRD
predominant inuence on the dispersibility of SWNTs (Fig. 2a). at 3421.0 cm 1 (stretching vibration of SiO–H) support the
The concentration of SWNTs in the aqueous phase was deter- proposed mechanism (Fig. S6†).37,40 Sufficient LRD is needed to
mined according to their absorbance at 600 nm using a UV-vis fully modify the surface of SWNTs, and then disperses them
spectrophotometer (Fig. S1 and S2†). There is a critical well in water. The increase in the viscosity of the LRD/SWNT
concentration of 20 mg mL 1 LRD for effectively dispersing aqueous dispersion with increasing LRD concentration may
SWNTs. Below the critical concentration, the concentration of also contribute to the high concentration of SWNTs (Fig. S7†).
SWNTs in the aqueous solution increases slowly with increasing The dispersed SWNTs could slightly increase the viscosity of the
the LRD concentration and remains less than 0.2 mg mL 1. The aqueous dispersion.
concentration of SWNTs suddenly increases to 1.83 mg mL 1 With a LRD concentration of 20 mg mL 1, SWNTs of various
with further increasing the LRD concentration to 20 mg mL 1. dosages can be dispersed very well in aqueous solution (Fig. 2b).
The concentration of SWNTs increases linearly and more than
90% of SWNTs are transported into aqueous solution with
increasing dosage of SWNTs when the dosage is not more than
2 mg mL 1. The SWNT concentration reaches 2.18 mg mL 1
with further increasing the SWNT dosage to 4 mg mL 1, but the
percentage of dispersed SWNTs drops to 54.5%.
Hand-grinding is another important factor besides the
concentration of LRD in dispersing SWNTs (Fig. 3). Solid-state
grinding could enhance the interaction between LRD and
SWNTs. In addition, grinding could generate more electron
acceptor sites on LRD,37 which also facilitates the modication
of SWNTs with LRD. Grinding is necessary to fabricate a LRD/
SWNT hybrid dispersible in water. Without grinding, the
concentration of SWNTs is only 0.06 mg mL 1. Two minutes of
10628 | J. Mater. Chem. A, 2013, 1, 10626–10630 This journal is ª The Royal Society of Chemistry 2013
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hand-grinding surprisingly increases the concentration of noncovalent functionalization of CNTs are specic of the
SWNTs to 1.65 mg mL 1. The concentration further increases to solvent, thus limiting their wide applications.5 For example,
1.83 mg mL 1 with increasing the grinding time to 5 min. CNTs modied with chitosan are dispersible in acidic aqueous
However, beyond our expectation, the concentration of SWNTs solution10 but will quickly precipitate once they come into
sharply decreases to 0.09 mg mL 1 with prolonging the contact with organic solvents. The concentration of SWNTs
grinding time to 20 min. Intensive grinding for a long period of aer dilution with methanol is very close to the theoretical
time damages the platelets of LRD, which is proven by the concentration, indicating the very high stability of the LRD/
evident decrease in the viscosity of the LRD/SWNT aqueous SWNT aqueous dispersion in methanol. The concentration of
dispersion from 1260 mPa s to 120 mPa s aer 20 min of SWNTs only slightly decreases from 0.368 mg mL 1 (the theo-
grinding (Fig. S8†). This phenomenon indicates that the retical concentration) to 0.333 mg mL 1 when the liquid phase
viscosity of the LRD/SWNT dispersion has a great inuence on is composed of 80% of methanol. The LRD/SWNT aqueous
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the dispersibility of SWNTs. dispersion could withstand further dilution with methanol even
The LRD/SWNT hybrid is very hydrophilic and disperses very when the liquid phase is composed of 98% (0.033 mg mL 1
well in water. Different from the intensive ultrasonication SWNTs) or 99.6% (0.007 mg mL 1 SWNTs) methanol. DMF and
frequently used in noncovalent functionalization of CNTs, the DMSO have more inuence on the stability of the LRD/SWNT
LRD/SWNT hybrid disperses very well (1.65 mg mL 1) in water hybrid compared with methanol, but the concentration of
without ultrasonication (Fig. S9†), indicating the very high SWNTs is still in a reasonable range.
hydrophilicity of the hybrid. Whereas, ultrasonication also We also found that bringing hydrophobic materials into
contributes to improve the dispersibility of the LRD/SWNT aqueous solution is a universal feature of LRD. Besides SWNTs,
hybrid in aqueous solution by disintegrating and dispersing the LRD can also disperse multi-walled carbon nanotubes and oil-
agglomerated LRD/SWNT hybrid formed during grinding. soluble dyes e.g., Sudan I and Oil Red O, very well in aqueous
The LRD/SWNT aqueous dispersion is very stable. Centrifu- solution according to the same grinding–ultrasonication
gation at 10 000 rpm for 30 min has no inuence on its stability procedure (Fig. S12†).
(Fig. S10a†). The concentration of SWNTs is still as high as 1.25
mg mL 1 aer increasing the centrifugation speed to 15 000
rpm. The inuence of 2 h of centrifugation at 5000 rpm on the Conclusions
concentration of SWNTs is negligible (Fig. S10b†). In addition, In summary, we fabricated a water-dispersible LRD/SWNT
no sediment can be seen aer being le to stand under hybrid using a simple grinding–ultrasonication procedure
ambient conditions for over 6 months. The LRD/SWNT inspired by Maya Blue. The concentration of LRD and hand-
aqueous dispersion is also resistant to electrolyte of moderate grinding play important roles in effectively dispersing SWNTs.
concentration (Fig. S11†). The concentration of SWNTs is The LRD/SWNT aqueous dispersion features high stability and
1.68 mg mL 1 in 10 mM NaCl solution. a high SWNT concentration. Moreover, the LRD/SWNT aqueous
The LRD/SWNT aqueous dispersion is miscible with and dispersion is miscible with and stable in the other common
stable in the other common organic solvents, e.g., methanol, organic solvents. We believe that the LRD/SWNT hybrid will
DMF and DMSO (Fig. 4). Most of the reported methods for nd applications in various elds, such as the reinforcement of
polymers and hydrogels. In addition, LRD may nd applications
in transporting other hydrophobic materials, e.g., graphene and
quantum dots, into aqueous solution via a similar procedure.
Acknowledgements
We are grateful for nancial support from the “Hundred Talents
Program” of the Chinese Academy of Sciences.
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10630 | J. Mater. Chem. A, 2013, 1, 10626–10630 This journal is ª The Royal Society of Chemistry 2013