4926

Langmuir 2002, 18, 4926-4932

Intercalation of Organic Ammonium Ions into Layered

Graphite Oxide
Zong-huai Liu, Zheng-Ming Wang, Xiaojing Yang, and Kenta Ooi*
Marine Resources and Environment Research Institute, National Institute of Advanced
Industrial Science and Technology, 2217-14 Hayashi, Takamatsu, 761-0395 Japan
Received November 15, 2001. In Final Form: March 18, 2002
The intercalation of large organic ammonium ions (tetramethylammonium ions (TMA+), tetraethylammonium ions (TEA+), tetrapropylammonium ions (TPA+), and tetrabutylammonium ions (TBA+)) into
layered graphite oxide (GO) was systematically investigated. The intercalation reactions were completed
at 25 C after 3 days, and stable colloidal suspensions were obtained at TAAl/Hs ) 5 (molar ratio of
tetraalkylammonium ions (TAA+) over exchangeable protons in GO). The sediments after centrifuging the
colloidal suspensions showed amorphous phase X-ray diffraction patterns, indicating that exfoliation of
the layered structure into nanosheets took place in the suspension. When the sediments were dried at 70
C for 3 days, layered structures of TAA+-intercalated GO materials with basal spacings of 1.56, 1.67, 1.84,
and 2.37 nm, respectively, appeared. The basal spacing of the layered compounds decreased with a decrease
of relative humidity during drying. When the dried TAA+-intercalated GO compounds were exposed to a
humid saturated atmosphere, the basal spacing increased gradually, finally becoming an amorphous
structure. The maximum saturation of intercalated TAA+ ions into GO decreased with the increase in alkyl
chain length. When the TAA+-intercalated materials were washed with distilled water and acid-treated,
a process of deintercalation of TAA+ ions from the interlayer occurred. A schematic model for the
deintercalation-intercalation involving a exfoliation process is proposed. The layered structure of TAA+intercalated GO materials is discussed in terms of the dimension of the GO layer and the sizes of H2O
molecules and TAA+ ions.

Introduction
Intercalation into layered compounds has drawn much
attention from both the fundamental and practical
viewpoints.1-4 Graphite oxide (GO) is a typical twodimensional solid in bulk form, with strong covalent
bonding within the layers. Weaker interlayer contact is
made by hydrogen bonds between intercalated water
molecules.5-7 Some functional groups, such as hydroxyl,
carbonyl, and other groups, embedded in carbon sheets in
GO lamellae make graphite oxide hydrophilic and exhibit
a rich intercalation chemistry. So far, many intercalated
GO materials have been synthesized and their physicochemical properties investigated.8-17 To control the space
occurring between intercalated surfactant ions, Matsuo
et al. have used various kinds of surfactants with different
* Address correspondence to this author. Telephone: +81-87869-3511. Fax: +81-87-869-3551. E-mail: k-ooi@aist.go.jp.
E-mail: zonghuai-liu@aist.go.jp.
(1) Barrer, R. M. Zeolites and Clay Minerals as Sorbents and
Molecular Sieves; Academic Press: London, 1978; p 407.
(2) Clearfield, A., Ed. Inorganic Ion Exchange Materials; CRC Press:
Boca Raton, FL, 1982.
(3) Ogawa, M.; Kuroda, K. Bull. Chem. Soc. Jpn. 1997, 70, 2593.
(4) Schollhorn, R. Chem. Mater. 1996, 8, 1747.
(5) Nakajima, T.; Mabuchi, A.; Hagiwara, R. Carbon 1988, 26, 357.
(6) Lerf, A.; He, H.; Forster, M.; Klinowski, J. J. Phys. Chem. B 1998,
102, 4477.
(7) Mermoux, M.; Chabre, Y.; Rousseau, A. Carbon 1991, 29, 469.
(8) Matsuo, Y.; Niwa, T.; Sugie, Y. Carbon 1999, 37, 897.
(9) Liu, P.; Gong, K. Carbon 1999, 37, 701.
(10) Inagaki, M.; Suwa, T. Carbon 2001, 39, 915.
(11) Cassagneau, T.; Fendler, J. H. J. Phys. Chem. B 1999, 103, 1789.
(12) Matsuo, Y.; Tahara, K.; Sugie, Y. Carbon 1997, 35, 113.
(13) Cassagneau, T.; Cuerin, F.; Fendler, J. H. Langmuir 2000, 16,
7318.
(14) Matsuo, Y.; Tahara, K.; Sugie, Y. Carbon 1996, 34, 672.
(15) Matsuo, Y.; Hatase, K.; Sugie, Y. Chem. Mater. 1998, 10, 2266.
(16) Kotov, N. V.; Dekany, I.; Fendler, J. H. Adv. Mater. 1996, 8, 637.
(17) Kyotani, T.; Moriyama, H.; Tomita, A. Carbon 1997, 35, 1185.

chain lengths to synthesize surfactant-intercalated GO

materials. These materials can be used as hosts for
molecular recognition.8 The exfoliation of GO particles
occurs easily in dilute (alkaline) aqueous solution; polyaniline-intercalated GO material and nanometer compounds with particle properties have been synthesized by
an exfoliation/adsorption process.9-11 Using the hydrophilicity of GO, some polar organic molecules and polymers, such as alcohol,12 poly(ethylene oxide) (PEO),13,14
poly(vinyl alcohol) (PVA),15 poly(diallyldimethylammonium chloride) (PDDA),16 poly(furfuryl alcohol) (PFA),17
and even others,18 can be easily inserted into its lamellae
to form intercalated GO nanocomposites by different
methods with different c-axis repeat distances. The
existence of these polymers enables the physicochemical
properties of GO to be greatly changed. Liu et al.19 have
synthesized a poly(vinyl acetate) intercalated GO nanocomposite using poly(vinyl acetate) (PVAc), with an oilsoluble polymer as guest molecules. The compound has a
high stability against extraction by organic solvent due
to a strong interaction between the GO layers and PVAc
chains.
In the present work, systematic studies on the
intercalation reaction of large organic ions into layered GO were conducted using tetraalkylammonium ions
with different methylene chain lengths. The TAA+intercalated GO materials were obtained by an exfoliation/
reassembling process, and a structural model for the
exfoliation/reassembling process involving the intercalation reaction is proposed.
(18) Kovtyukhova, N. I.; Ollivier, P. J.; Martin, B. R.; Mallouk, T. E.;
Chizhik, S. A.; Buzaneva, E. V.; Gorchinskiy, A. D. Chem. Mater. 1999,
11, 771.
(19) Liu, P.; Gong, K.; Xiao, P.; Xiao, M. J. Mater. Chem. 2000, 10,
933.

10.1021/la011677i CCC: $22.00 2002 American Chemical Society

Published on Web 05/15/2002

Intercalation of Organic Ammonium Ions into GO

Langmuir, Vol. 18, No. 12, 2002 4927

Experimental Section
Materials. The starting material, GO, was synthesized from
natural graphite by the Staudenmaier method.20 The pH titration
toward Na+ ions was obtained in (0.1 M NaCl + NaOH) solutions
with different NaOH concentrations at 25 C. The ion-exchange
capacity was evaluated from the titration curve.
Tetraalkylammonium hydroxides were purchased from Wako
Pure Chemical Co. They included tetramethylammonium hydroxide (15 wt % solution), tetraethylammonium hydroxide (10
wt %), tetrapropylammonium hydroxide (10 wt %), and tetrabutylammonium hydroxide (10 wt %).
Intercalation Reaction. Intercalation reactions of tetramethylammonium ions (TMA+) were studied batchwise. Weighed
samples (0.1 g) of GO were soaked in TMA+ hydroxide solutions
(20 cm3) with different concentrations at 25 C for 3 days. The
amount of tetramethylammonium hydroxide added ranged from
1 to 25-fold that of the exchangeable capacity of GO (1 e TMAl/
Hs e 25). After soaking, the solutions were separated by
centrifugation, and the resultant colloids were subjected to X-ray
diffraction (XRD) analyses in their wet state, followed by airdrying at a relative humidity of 40% at 25 C or heating at 70
C for 3 days. The influence of relative humidity on the basal
spacing was studied by equilibrating the sample with an
atmosphere at a different humidity. The hydroxide ion concentrations in the supernatant solutions were determined by acid
titration.
Intercalation reactions of TEA+, TPA+, and TBA+ ions were
carried out at TAAl/Hs ) 5, and the colloids obtained were treated
by the same procedure as that for TMA+-intercalated colloids.
The colloids in the wet state were washed with 30 cm3 of water
three times, and the gels obtained were air-dried at a relative
humidity of 40% at 25 C for 2 days.
Deintercalation of TAA+ ions from the interlayer of GO was
carried out by mixing the TAA+-intercalated GO materials with
0.1 M HCl solution at 25 C for 2 days. The extractability of
TAA+ ions was calculated from the difference between TN
concentrations in the samples before and after the acid treatment.
Chemical Analyses. The TN (total nitrogen) and TC (total
carbon) contents of the TAA+-intercalated GO compounds, the
acid-treated compounds, and the water-washed compounds were
determined by a Sumigraph type NCH-21 NCH analyzer.
Physical Properties. The sediment from each different
humidity state was subjected to XRD analysis using a Rigaku
type RINT 1200 X-ray diffractometer with a graphite monochromator at 25 C. TG-DTA curves were obtained on a MAC
Science thermal analyzer (System 001, TG-DTA 2000) at a
heating rate of 10 C/min. SEM observation was carried out with
a Hitachi S-246N scanning electron microscope.

Results and Discussion

Characterization of GO. An SEM image of synthesized GO is given in Figure 1. The sample shows platelike
forms without any amorphous or other kinds of crystallized
phase particles. XRD analysis shows diffraction patterns
corresponding to a layered structure with a basal spacing
of 0.88 nm.
The pH titration curve of GO toward Na+ ions is given
in Figure 2. The total exchange capacity of GO is evaluated
as 4.4 mmol/g from the ion-exchange reaction in a 0.1 M
NaOH solution. The titration curve shows a multi-base
acid character, suggesting that the synthesized GO
contains more than one kind of exchangeable protons.
The dispersibility of GO in solution depends on the degree
of neutralization (R). Colloidal suspensions were not
observed, and the supernatant solutions were transparent
at R < 0.4. The peptization of GO takes place at R > 0.4,
and completely dispersed colloidal suspensions are obtained at R > 0.9. This shows that the neutralization of
most of the acid sites is necessary in order to have a
(20) Standenmaier, L. Ber. Dtsch. Chem. Ges. 1989, 31, 1481.

Figure 1. SEM image of starting GO.

Figure 2. The pH titration curve of GO toward Na+.

sufficient electrostatic repulsion between each sheet to

form stable colloidal suspensions.
Exfoliation by the Intercalation of TAA+ Ions. All
of the intercalation reactions were carried out at 25 C for
3 days to make sure the intercalation was complete. Stable
colloidal suspensions were obtained by treating GO with
TAA hydroxide solutions at TAAl/Hs ) 5. The suspensions
were centrifuged, and the colloidal sediments were
subjected to XRD measurement in the wet state. The water
contents, roughly evaluated from the weight loss by
maintaining at 150 C, were around 80% for all the TAA+intercalated GO samples. The XRD patterns of all sediments obtained are shown in Figure 3. The patterns gave
no clear peaks but only a broad diffraction halo in a 2
range of 20-40, in striking contrast to that of starting
GO (Figure 3a). The broad halo is most likely related to
scattering from dispersed single sheets of GO and water
as a solvent, similar to the case of layered titanic acid.21,22
This indicates that the stacked sheets of GO are exfoliated
when GO is soaked in TAA hydroxide solution. Because
GO contains acidic groups, negatively charged sites are
(21) Sasaki, T.; Watanabe, M.; Hashizume, H.; Yamada, H.; Nakazawa, H. J. Am. Chem. Soc. 1996, 118, 8329.
(22) Sasaki, T.; Watanabe, M. J. Am. Chem. Soc. 1998, 120, 4682.

4928

Langmuir, Vol. 18, No. 12, 2002

Liu et al.
Table 2. Structural Models of Samples of
Ammonium-Intercalated GOa Dried at 70 C for 3 days

cation

cation size,b
nm

TMA

0.50-0.60

TEA

0.65-0.75

TPA

0.80-0.90

TBA

0.95-1.05

model of sample
one layer of TMA
one layer of water
one layer of TEA
one layer of water
one layer of TPA
one layer of water
one layer of TBA
two layers of water

observed interlayer
spacing of sample,
nm
1.56
1.67
1.84
2.37

a Based on GO slab thickness of 0.60 nm and a van der Waals

radius of water of 0.28 nm. b Szostak, R. Molecular Sieves: Principal
of Synthesis and Identification; Van Nostrand Reinhold: New York,
1989; p 95.

Figure 3. Wet-state XRD patterns of GO treated with TAAOH

solutions at TAAl/Hs ) 5. (a) Starting GO; (b) GO treated with
TMAOH; (c) GO treated with TEAOH; (d) GO treated with
TPAOH; (e) GO treated with TBAOH.
Table 1. Amounts of TAA+ Intercalated at Different
Molar Ratios of TAAOH in Solution over Exchangeable
Protons in GO
intercalated
TAA+
TMA+

TEA+
TPA+
TBA+

TAA+/H+

OH- consumed
(mmol/g)

degree of
neutralization (R)

1
5
10
25
5
5
5

3.12
4.11
4.35
4.12
2.72
2.24

0.71
0.94
0.99
0.94
0.62
0.51

formed in every GO layer when GO is neutralized by dilute

TAA hydroxide solution. The electrostatic repulsive force
operating between negatively charged sites between GO
layers causes the formation of exfoliated GO.12 The hump
of the broad diffraction halo differs in shape depending
on the size of TAA+ ions; it decreases with an increase in
the length of the methylene chain. From detailed analysis
of the diffraction envelope, Sasaki et al. have concluded
that their exfoliated nanosheets of titanic acid were
arranged in a nearly amorphous manner except for a
nearest-neighbor correlation.22 In the TPA-GO and TBAGO systems, which have smaller humps in their diffraction
halos, the nearest-neighbor correlation of the exfoliated
GO nanosheet may be smaller and the nanosheets may
behave more freely in the aggregates.
The OH- concentrations of the supernatant solutions
were determined by acid titration and the amounts of
OH- consumed, and the R values were evaluated from the
decrease of OH- concentrations relative to the initial
solutions. The R values evaluated are 0.94, 0.94, 0.62, and
0.51 for GO-TMA, GO-TEA, GO-TPA, and GO-TBA
systems, respectively (Table 1). The latter two systems
show very low R values although the supernatant solution
contains an excess of OH- ions. The TPA+ and TBA+ ions
may be too large to neutralize all the acidic sites in GO
sheets freely without any steric influence. Since exfoliation
takes place in all the systems, the volume fraction of guest

ions in the interlayer may play an important role for

exfoliation, in addition to that of the surface charge density,
similar to the case of layered manganese oxide.23
The surface density of the exchange site can be
calculated from the total ion exchange capacity (4.4 mmol/
g) by assuming that the density of the carbon skeleton of
GO is equal to that (2.3 g/cm3) of graphite and the thickness
of GO is 0.6 nm. The specific surface area of nanosheets
can be evaluated as 103 m2/g from these values. The
number of exchange sites per unit area can be derived as
2.6/nm2, which corresponds to an area per exchange site
of 0.38 nm2. The area per TAA+ ion can be calculated as
0.15, 0.33, 0.57, and 0.92 nm2 for TMA+, TEA+, TPA+, and
TBA+ ions, respectively, assuming spherical ions. The
TMA+ and TEA+ ions are small enough to exchange fully
with the protons of the exchange sites, while the TPA+
and TBA+ ions are too large to exchange freely without
steric influence. The maximum exchange capacities are
calculated as 3 and 1.8 mmol/g for TPA-GO and TBAGO systems, respectively, which agreed comparatively
well with the experimentally determined exchange capacities (Table 1). These calculations suggest that the
exchange sites are distributed homogeneously throughout
the surface of GO layers.
Reassembling by Drying. When the colloidal sediments were dried at 70 C for 3 days, the layered structure
with different basal spacings reappeared as shown in
Figure 4. The XRD patterns of TMA+-intercalated GO
material showed peaks at 1.56, 0.79, and 0.52 nm
corresponding to the (001), (002), and (003) reflections,
respectively. Since the d-values of the (001) crystal spacing
reflections correspond to the interlayer distances, the
interlayer distance is 1.56 nm for the TMA+-intercalated
GO material. The XRD pattern analyses for the other
TEA+-, TPA+-, and TBA+-intercalated GO materials show
interlayer distances of 1.67, 1.84, and 2.37 nm, respectively. Sharp diffraction lines up to the fourth order for
these samples indicate a highly ordered hydrate structure,
similar to the cases of TBA+-intercalated protonic titanate
and TMA+-intercalated birnessite.22,23 The individual
sheets of exfoliated GO are reassembled together by drying
at 70 C; the interlayer distance depends on the size of the
intercalated TAA+ ions.
The rate of intercalation reaction was studied by
changing the soaking time for the TMA-GO system at
TMAl/Hs ) 5. The colloidal suspension could be obtained
after only 2 h of soaking. The sediment obtained by
centrifugation had an interlayer distance similar to that
of the TMA+- intercalated GO materials obtained by drying
(23) Liu, Z.-h.; Ooi, K.; Kanoh, H.; Tang, W.; Tomida, T. Langmiur
2000, 16, 4154.

Intercalation of Organic Ammonium Ions into GO

Figure 4. Changes of XRD patterns of TAA+-intercalated

samples at TAAl /Hs ) 5 after drying at 70 C for 3 days. (a)
TMA+-intercalated GO; (b) TEA+-intercalated GO; (c) TPA+intercalated GO; (d) TBA+-intercalated GO.

at 70 C. The intensity of the XRD peaks was hardly

changed by soaking for 1 day. This indicates that the
intercalation reaction of TAA+ into GO is fast. GO may
be easily dispersed in TAA hydroxide solutions, and is
subject to rapid exfoliation.
Effects of TMA+ Concentration and Drying Conditions. The influence of TMA+ concentration on the
intercalation reaction was investigated by changing TMAl/
Hs to 1, 5, 10, and 25. Seventy percent of the acidic sites
were occupied by TMA+ ions at TMAl/Hs ) 1. The XRD
analysis of the sediment in wet state shows a new layered
structure with a basal spacing of 0.98 nm (Figure 5a).
This shows that short-range swelling takes place to form
stable layers having a basal spacing a little larger than
starting GO. At TMAl/Hs g 5, the R values are above 0.9
and the XRD patterns show only amorphous halos in wet
state, corresponding to an exfoliated state.
The sediments at different TMA+ concentrations were
dried at 70 C for 3 days and subjected to XRD analysis
(Figure 5b-e). The layered structure with a basal spacing
of 0.98 nm was retained for the sample at TMAl/Hs ) 1.
The other dried samples show a layered structure with
basal spacing of 1.56 nm, independent of the TMA+
concentration. The exfoliation by TMA+ intercalation and
the reassembling of GO sheets by drying take place
independent of TMA+ concentration in the region TMAl/
Hs g 5.
The TMA+-intercalated GO material obtained at TMAl/
Hs ) 5 was dried under different conditions. The XRD
patterns of the dried samples show that the layered
structure is retained after drying, but the basal spacing
decreases slightly with a decrease of the relative humidity
of the atmosphere (Figure 6). The basal spacing around
1.54 nm hardly changes even after vacuum-drying at 70
C for 1 day. This indicates that the free water molecules
existing in the interlayer of GO dehydrate easily, but there
are some hydrated water molecules that are strongly
attached between TMA+ ions and GO layers. The drying
behavior is different from that in TMA+-intercalated
layered manganese oxide, in which most of the water
molecules are easily dissipated from the interlayer by
vacuum-drying for 1 day.23

Langmuir, Vol. 18, No. 12, 2002 4929

Figure 5. Changes of XRD patterns of TMA+-intercalated

samples at different concentrations dried at 70 C for 3 days.
(a) TMAl/Hs ) 1 in wet state; (b) TMAl/Hs ) 1; (c) TMAl/Hs )
5; (d) TMAl/Hs ) 10; (e) TMAl/Hs ) 25.

Figure 6. XRD patterns of TMA+-intercalated samples under

different drying conditions. (a) TMA+-intercalated sample at
TMAl/Hs ) 5 in wet state; (b) sample a dried at 25 C for 1 day;
(c) sample b dried on silica gel for 1 day; (d) sample c dried at
70 C for 1 day; (e) sample d vacuum-dried at 70 C for 1 day;
(f) sample e exposed to saturated humidity at 25 C for 1 day;
(g) sample e exposed to saturated humidity at 25 C for 5 days.

When the vacuum-dried sample was exposed to an

atmosphere with saturated humidity, the basal spacing
of the layered compound increased again from 1.54 to 1.82
nm after 1 day of exposure (Figure 6f), and finally returned
to an amorphous phase after 5 days (Figure 6g). This
indicates that the dehydration-rehydration of TMA+intercalated GO material involving an exfoliation process

4930

Langmuir, Vol. 18, No. 12, 2002

Liu et al.

Figure 7. Changes of XRD patterns of TAA+-intercalated

samples at TAAl/Hs ) 5 by washing and after drying at 25 C
for 1 day. (a) TMA+-intercalated GO; (b) TEA+-intercalated
GO; (c) TPA+-intercalated GO; (d) TBA+-intercalated GO; (e)
TMA+-intercalated GO acid-treated for 2 days.

is a reversible reaction. This is similar to those of clay

minerals such as montmorillonite and smectite which
swell and exfoliate in wet state by some soft-chemical
procedures, returning to a layered structure in a dried
state.24,25
Effect of Water Washing and Acid Treatment. The
colloidal suspension prepared at TAAl/Hs ) 5 was centrifuged and then washed 3 times with 30 mL of distilled
water, and the sediments were dried at 25 C for 2 days.
The XRD patterns of the dried samples show that the
basal spacings of all compounds decrease to around 1 nm
by water washing, due to the partial deintercalation of
the TAA+ ions from the interlayers. The basal spacing of
the TMA+-intercalated layer is equal to that obtained
directly from the solution with TMAl/Hs ) 1. The total
nitrogen analysis showed that 1.2 mmol/g TMA+ ions
remained in the compound, which means that 70% of
TMA+ ions were deintercalated by water washing.
SEM images of water-washed samples are shown in
Figure 8. The particle morphology of the GO nanocomposite is dependent on preparation procedure. The
air-dried sample has a distinct lamellar morphology with
thin ribbons of about 2 m in width lined up in a regular
parallel arrangement (Figure 8a). On the other hand, the
freeze-dried sample has a thin flaky appearance with
thickness less than 0.5 m (Figure 8b). These results
indicate that the significant reassembling of GO nanosheets progresses during air-drying with each nanosheet
stacked regularly to maintain minimum energy conditions.
The TMA+-intercalated compound obtained at TMAl/
Hs ) 5 was treated with a 0.1 M HCl solution at 25 C for
2 days to extract TMA+ ions from the interlayer. The XRD
pattern (Figure 7e) shows that the layered structure
(24) Norrish, K. Faraday Discuss. R. Soc. Chem. 1954, 18, 120.
(25) (a) Smalley, M. V. Langmuir 1994, 10, 2884. (b) Smalley, M. V.;
Thomas, R. K.; Braganza, L. F.; Matsuo, T. Clay Clays Miner. 1989, 37,
474.

Figure 8. SEM images of TMA+-intercalated GO nanocomposites: (a) washed with water followed by air-dried; (b)
washed with water followed by freeze-dried.

remains after TMA+ extraction, but the intensity of the

peak becomes weaker and broader. In addition, the basal
spacing decreases to 0.72 nm, which does not coincide
with that of the starting GO. This suggests that some
destruction or rearrangement of layers takes place during
the acid treatment.
DTA-TG Analysis. TG-DTA curves of the starting GO,
TMA+-intercalated GO, TMA+-intercalated GO after
water washing, and TMA+-intercalated GO after acid
treatment are shown in Figure 9. Two exothermic peaks
at 213 and 521 C are observed for the starting GO, similar
to the results by several authors.12,15,19,26 The former is
attributed to the destruction of the carbonyl group, and
the latter to the combustion of the carbon skeleton of GO.19
For TMA+-intercalated GO, small exothermic peaks are
observed at 163 and 313 C below 400 C. The weight loss
between 120 and 400 C is 53%, which is 1.5 times larger
than that (34%) for the starting GO. The large weight loss
may be due to the destruction of TMA+ ions in the
interlayer in addition to the destruction of carbonyl groups
of GO. Water washing causes the deintercalation of 70%
of TMA+ ions, so the weight loss between 120 and 400 C
is due to the decrease of TMA+ content. The acid-treated
sample shows the smallest weight loss in this temperature
range; this suggests that some of the carbonyl groups of
GO are destroyed by the acid treatment.
(26) Dekany, I.; Kruger-Grasser, R.; Weiss, A. Colloid Polym. Sci.
1998, 276, 570.

Intercalation of Organic Ammonium Ions into GO

Figure 9. TG-DTA curves of (a) starting GO, (b) TMA+intercalated GO, (c) TMA+-intercalated GO washed with
distilled water, and (d) TMA+-intercalated GO acid-treated.

Structural Model for the Intercalation-Deintercalation. Schematic representation of structural change

during the intercalation-deintercalation reaction is given
in Figure 10. Pristine GO has a layered structure with a

Langmuir, Vol. 18, No. 12, 2002 4931

basal spacing of 0.88 nm. It is well-known that the basal

spacing of GO varies widely between 1.1 and 0.6 nm
depending on ambient humidity, which has made it
difficult to determine the ideal structure of GO. Two types
of model have been proposed for the structure of GO: one
is the stage-1 type with Ic ) 0.6 nm7 and the other is the
stage-2 type with Ic ) 0.55-0.82 nm.5 The present result
is close to the stage-2 type structural model of well
hydrated GO (basal spacing ) 0.82 nm). Therefore, we
made our structural model based on the stage-2 type. Since
the thickness of GO is known to be 0.61 nm,26 the galley
height can be calculated as 0.27 nm, being close to the van
der Waals diameter (0.28 nm) of water molecules. This
suggests the formation of one molecular layer of water in
the interlayer of GO. The intercalation of TMA+ results
in a short-range swelling in the region 0.3 < R < 0.8; the
basal spacing widens a little to 0.98 nm by the intercalation. The galley height can be calculated as 0.37 nm, which
is close to the ionic size (0.44 nm) of TMA+ ions. Since
there are no water layers between TMA+ ions and GO
sheets, it is stable against drying. The stacked GO layers
are exfoliated into nanosheets in the region R > 0.9. The
layered structure disappears in the XRD patterns, and
only halos are observed.
The swelling and exfoliation behavior of layered materials can be classified into three categories: short-range
swelling, long-range swelling, and exfoliation. The shortrange swelling is characterized by the formation of hydrate
layers in the interlayer. The long-range swelling is
associated with the formation of diffuse double layers and
the consequent change of the electrostatic attractive force
to an osmotic repulsive one. Exfoliation is regarded as the
limiting case of long-range swelling, where the electrostatic
repulsive force between neighboring electrical double
layers occurs even at a very great distance. Long-range

Figure 10. Schematic representation of changes of crystal phase and basal spacing of wet and dried TMA+-intercalated GO
compounds.

4932

Langmuir, Vol. 18, No. 12, 2002

Liu et al.

Figure 11. Structural model of TAA+-intercalated GO materials.

swelling was not observed in the present system. The sharp

basal diffraction series with intersheet spacing of above
2 nm was not observed in a low angular range. The
flexibility of the present sheets may leave the long-range
swelling incomplete, resulting in a simultaneous exfoliation with irregularly arranged GO sheets. Similar
results have been observed for TMA+ intercalation into
layered manganese oxide.23 When the exfoliated slurry is
dried at room temperature for 1 day, reassembling takes
place and the layered structure with a basal spacing of
1.64 nm reappears. The basal spacing corresponds to the
distance that two molecular layers of water occupy in the
interlayer. Drying at 70 C results in a slight decrease of
basal spacing to 1.56 nm, which corresponds roughly to
the presence of one molecular layer of water. The
dehydration-rehydration reaction on TMA+-intercalated
GO progresses reversibly depending on the relative
humidity of the atmosphere, accompanied by the exfoliation reaction. These results show that the TMA+intercalated GO exhibits reversibly short-range swelling
and exfoliation, similar to clay minerals.
The water washing caused a deintercalation of TMA+
from the interlayer to give a layered compound with a
basal spacing of 0.97 nm. This phase can be described as
a stable phase since it forms in both the intercalation and
deintercalation reactions. Acid treatment results in the
deintercalation of most of TMA+ ions in the interlayer.
The acid-treated sample retains the layered structure,
but the intensities of the diffraction peaks become weaker
and broader. The resultant basal spacing does not coincide
with that of the starting GO. This suggests that some
destruction or rearrangement of nanosheets takes place
during the acid treatment.
The schematic models of TAA+-intercalated GO compounds are depicted in Figure 11. The intercalation of

TAA+ ions results in the exfoliation of GO nanosheets

independent of the species of TAA+ ions. The drying of the
exfoliated slurry at 70 C results in the reassembling of
nanosheets in stacked layers, with the interlayer distance
depending on the species of TAA+ ions. The structural
model was calculated on the basis of the dimension of the
GO layer, the van der Waals size of water molecules and
the size of the TAA+ ions. The ionic size of TAA+ ions,
evaluated by semiempirical MO calculations with a
MOPAC program, are 0.44, 0.65, 0.85, and 1.08 nm for
TMA+, TEA+, TPA+, and TBA+ ions, respectively. The
galley heights are therefore calculated to be 0.95, 1.06,
1.23, and 1.76 nm for the TMA-GO, TEA-GO, TPAGO, and TBA-GO composites, respectively. The numbers
of molecular layers of water are calculated as one for the
first three composites and two for the last. This indicates
that the basal spacing of the layered compound exhibiting
short-range swelling depends mainly on the ionic size of
the guest ions.
Conclusion
The GO compound shows swelling and exfoliation
behavior during the intercalation of tetraalkylammonium
ions, depending on the neutralization degree of the GO
sheet and the species of the guest ammonium ions. The
exfoliated nanosheets in wet state reassemble into stacked
layers following air-drying with the interlayer distance
depending on the size of guest ions. The exfoliationreassembling process is attractive since it is applicable to
the development of novel nanocomposite materials or
nanoporous materials.
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