Activation Routes For High Surface Area Graphene Monoliths From Graphene Oxide Colloids

CARBON x x x ( 2 0 1 4 ) x x x –x x x
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Activation routes for high surface area graphene

monoliths from graphene oxide colloids
Shuwen Wang a,1, Ferdinando Tristan a,2, Daiki Minami a,1, Toshihiko Fujimori a,1,
Rodolfo Cruz-Silva a,3, Mauricio Terrones a,4, Kenji Takeuchi b, Katsuya Teshima b,
Francisco Rodrı́guez-Reinoso c, Morinobu Endo a,3, Katsumi Kaneko a,1,*
a
Research Center for Exotic Nanocarbons (JST), Shinshu University, Wakasato, Nagano 380-8553, Japan
b
Faculty of Engineering, Shinshu University, Wakasato, Nagano 380-8553, Japan
c
Department of Inorganic Chemistry, University of Alicante, Apartado 99, E-03080 Alicante, Spain
A R T I C L E I N F O A B S T R A C T
Article history: Graphene monoliths made from graphene oxide colloids by unidirectional freeze-drying
Received 20 December 2013 method were activated by typical activation processes of CO2 activation, chemical activa-
Accepted 17 April 2014 tion using ZnCl2 or H3PO4, and KOH activation. The porosity development of graphene
Available online xxxx monolith markedly depends on the activation method. The monoliths with highest surface
area are obtained by the KOH activation method; only the KOH activation is effective for
production of the graphene monolith of which surface area is in the range of
1760–2150 m2 g 1. The mechanism of the porosity development by KOH activation method
is proposed. This work provides a promising route for the bottom-up design of pore
width-tunable nanoporous carbons.
2014 Elsevier Ltd. All rights reserved.
1. Introduction weight [9]. Furthermore, it has another merit of slit-shaped

pores which enable to guarantee excellent accessibility for
Nanoporous carbon of high surface area has contributed to molecules and ions, being indispensable to industrial applica-
environmental, energy, and chemical technologies [1–5]. This tions [10]. The high accessibility of the slit-shaped pores is
is because nanoporous carbons have distinguished merits essentially important, because the pre-adsorbed molecules
such as high electrical and thermal conductivities [6,7], excel- near the pore entrance of the cylindrical pores often intervene
lent water resistivity [8], and considerably high chemical the intrapore diffusion [11].
stability except for that in an oxidative atmosphere, although The most serious issue of nanoporous carbons is ill-
the tunability of pore width is not sufficiently established yet. tunability of the pore width. Recently developed carbide-
The high electrical and thermal conductivities are superior to derived carbon has a considerably high tunability of the pore
other nanoporous materials such as zeolites and metal width [12–14]. The tunability, however, is inferior to that of
organic frameworks (MOFs). Also nanoporous carbon has zeolites with ion-exchange and of MOFs with changing
the strongest interaction potential for molecules per unit ligands and metal ions. One promising route for a better pore
* Corresponding author: Fax: +81 (0)26 269 5737.

E-mail address: [email protected] (K. Kaneko).
1
Present address: Center for Energy and Environmental Science, Shinshu University, Wakasato, Nagano 380-8553, Japan.
2
Present address: Faculty of Natural Science, Universidad Nacional Autonoma de Mexico, Deleg Alvaro Obregon 01120, Mexico.
3
Present address: Center for Acqua Innovation, Shinshu University, Wakasato, Nagano 380-8553, Japan.
4
Present address: Department of Physics, Pennsylvania State University, University Park, PA 16802, USA.
http://dx.doi.org/10.1016/j.carbon.2014.04.071
0008-6223/ 2014 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Wang S et al. Activation routes for high surface area graphene monoliths from graphene oxide colloids. Carbon
(2014), http://dx.doi.org/10.1016/j.carbon.2014.04.071
2 CARBON x x x ( 2 0 1 4 ) x x x –x x x
width-tunability of nanoporous carbons is on the bottom-up after an intensive centrifugation; the produced monoliths
designing using graphene chemistry. In particular, the bot- have a relatively lower carbon density, being unsuitable for
tom-up synthesis of graphene-based nanoporous carbons an efficient activation process. On the other hand, GO suspen-
using graphene oxide colloids (GOCs) is the most promising. sion produced from Bay carbon graphite is less viscous and
However, no systematic study on the bottom-up designing forms the highly concentrated precipitates after the intensive
using GOCs has been reported, although the effectiveness of centrifugation. However, thus produced monoliths are too
KOH-activation was shown for production of the high surface weak to maintain a constant shape. To compromise this prob-
area graphene with relevance to supercapacitors [3]. This arti- lem, we produced the RGO monoliths from the mixture of
cle describes effectiveness of different activation processes these two kinds of GO suspensions at the carbon mole ratio
for GOCs derived carbon, which have been applied to produc- of Bay carbon graphite to Madagascar graphite of 2 to 1.
tion of traditional activated carbons. In this study, we investi- The RGO monoliths were activated as follows. The mono-
gated three typical activation processes of CO2 activation, lith was heated under a flow of pure Ar (200 mL min 1) from
chemical activation using ZnCl2 or H3PO4, and KOH activation. room temperature to target temperature at a heating rate of
10 K min 1. The activation was carried out by feeding 30%
2. Experimental CO2 diluted with Ar at a total flow rate of 200 mL min 1, with
varying activation time and temperature. Subsequently, the
2.1. Graphene oxide colloid (GOC) preparation sample was purged by pure Ar during cooling down to room
temperature. Activation using chemical reagents like ZnCl2,
GOCs were prepared from natural graphite (Bay carbon H3PO4, and KOH was carried out by a one-step activation
graphite from Michigan, USA and Madagascar graphite from method. Before the preparation of GO monoliths, the chemi-
Madagascar) by an improved method using KMnO4, H2SO4 cal reagents were mixed with GO-P suspensions in advance,
and H3PO4 [15]. In the preparation process, concentrated then the reduced GO monoliths were produced from the mix-
H2SO4 (96%, 200 mL, Wako), H3PO4 (85%, 25 mL, Wako) and tures using the unidirectional freeze drying method followed
graphite (5 g) were added into a beaker, followed by a slow by reduction method as mentioned above. The GO monoliths
addition of KMnO4 (25 g, Wako). The mixture was then kept prepared with chemical reagents shrank after the freeze dry-
at 308–313 K and stirred at 250 rpm for 2 h. After the reaction, ing process, due to the aggregation of GO colloids on addition
500 mL distilled water was added slowly into the mixture fol- of the chemical reagents. This is because addition of the
lowed by a 10% H2O2 solution (100 mL). The oxidation product chemical reagent into the colloids removes the effective
was then washed by 1 M HCl and distilled water respectively, charges of the GO colloids by adsorption of ions having oppo-
followed by a centrifugation step to remove the supernatant. site charges, resulting in the aggregation. The obtained mono-
It is noticed that in the acid washing process, the oxidation liths were heated from room temperature to 573 K at a
product was highly condensed and occupied a small volume heating rate of 1.5 K min 1, then from 573 K to target temper-
in the centrifuge tubes after centrifugation, thus the liquid atures at a heating rate of 30 K min 1. Then the samples were
residue was small and the metal ion removal was efficient. kept at the target temperature for 1 h before cooling down to
During the water washing process the oxidation product room temperature. The system was purged with an Ar flow of
started to exfoliate and occupied a much larger volume, 400 mL min 1 during the whole process. The products were
which retained a larger amount of liquid residue thus the dipped in distilled water for 4 h and then such washing was
metal ion removal became less effective. In this article, graph- repeated 4 times. After the fourth washing the electric resis-
ene oxide (GO) after single acid washing is named as GO-I tance of the supernatant was (1.3 ± 0.1) · 106 X cm, being
(impure GO), while that after 5 times acid washing is named close to (1.5 ± 0.1) · 106 X cm of the used distilled water.
as GO-P (highly pure GO), when the classification is necessary; Finally the products were dried at 393 K for 24 h. The activated
only GO-P was used in the absence of the classification. After RGO is named as A-RGO.
the acid washing, both of GO-I and GO-P were further washed
five times with distilled water. 2.3. Characterization methods
2.2. Preparation of highly porous reduced GO monoliths Electronic states of C1s of as-prepared GO monolith, GO
monoliths reduced at 573 and 873 K, and RGO monolith
The GO monoliths were produced with unidirectional freeze activated by KOH were examined by X-ray photoelectron
drying method used for production of other materials spectroscopy (XPS: JEOL JPS-9010MX, Japan) with Mg Ka radia-
[16–20]. The obtained monoliths were heated up to 573 K at tion; the applied voltage and current were 10 kV and 10 mA,
a rate of 1.5 K min 1 and then the reduced GO (RGO) mono- respectively. The reduction state of the GO monolith was also
liths were obtained. The RGO from impure graphene oxide examined by qualitative electrical resistance measurement of
is nominated as RGO-I, and that from highly pure graphene the monolith using two point-electrodes method at the inter-
oxide is nominated as RGO-P. It is noticed that the property electrode distance of 5 cm. Porosity analysis was performed
of GO suspensions produced from different graphites are very by N2 adsorption at 77 K with a Micromeritics ASAP 2020 sur-
different from each other. After the oxidation process, the GO face analyzer. The samples were pre-evacuated at 473 K for
derived from Madagascar graphite is easy to exfoliate in water 3 h before N2 adsorption. The total surface area and external
to form a larger volume of GO suspension. Besides, the GO surface area were determined by the subtracting pore effect
suspension produced by this way is highly viscous, so that (SPE) method using high resolution as-plot of the N2 adsorp-
it’s very difficult to get highly condensed GO suspension even tion isotherm [21,22]. The surface area was also determined
CARBON xxx (2014) xxx–xxx 3
according to the Brunauer–Emmett–Teller (BET) method in a are CAO at 286.1 eV, C@O at 287.0 eV, and COO at 289.0 eV
relative pressure range of 0.05–0.30 for comparison, although [15,28,29]. After the thermal reduction process, a distinct
the BET analysis gives an overestimated surface area. The lin- decrease of peaks at the high binding energy region is
ear region sometimes shifts to the lower relative pressure in observed, indicating that oxygen functional groups are
case of microporous materials [23]. The micropore volume decomposed on the heating treatment.
of the samples was evaluated by the Dubinin–Radushkevich Table 1 lists the percents of each carbon state in GO and
(DR) equation [24] and the mesopore volume was determined RGOs treated at different temperatures. The amount of the
by Dollimore–Heal (DH) method [25,26] at the relative pres- surface functional groups of RGO treated at 573 K is similar
sure of 0.95. to that of the RGO treated at 873 K. Even heating treatment
Some samples were observed by a field emission scanning at 573 K can reduce GO sufficiently and thereby heating at
electron microscope (FE-SEM: JEOL, JSM-6330F, Japan) and a 573 K is used for reduction of all GO samples. Fig. 1(d) shows
high-resolution transmission electron microscope (HR-TEM: the XPS spectrum of high surface area A-RGO prepared from
JEOL, JEM2100, Japan). KOH activation (KOH/C = 5, 1073 K, 1 h), which will be dis-
cussed in Section 3.4.2.
3. Results and discussion The electrical resistance of GO monoliths without
reduction could not be measured due to the high resistance.
3.1. Surface chemistry analysis of graphene oxide (GO) While the electrical resistances of RGO monoliths treated at
monolith, reduced graphene oxide (RGO) monolith and 573 and 873 K were (1.5 ± 0.3) kX and (1.4 ± 0.3) kX, respec-
activated RGO (A-RGO) monolith tively. The electrical resistance measurement supports that
the heating treatment at 573 K can reduce GO sufficiently.
Fig. 1(a–c) shows the C1s XPS spectra of as-prepared GO mono- Thus we can obtain low-density graphene monolith samples;
lith, GO monoliths reduced at 573 and 873 K. The main peaks the apparent densities of RGO monoliths treated at 573 and
were deconvoluted using the Voigt function after the back- 873 K were (1.1 ± 0.1) · 10 2 g cm 3 and (1.0 ± 0.1) · 10 2
ground subtraction with Shirley method [27]. The peak at g cm 3, respectively.
284.4 eV is assigned to double bonding carbons for GO and
RGOs, which is designated as ‘‘C@C’’. The peak at 285.5 eV is 3.2. CO2 activation method
assigned to a single bonding carbon, which is designated as
‘‘CAC’’. Some other peaks assigned to oxygen functional Fig. 2(a) and (b) show N2 adsorption isotherms at 77 K on
groups are observed at the higher binding energy region. They non-activated RGO-I and those activated by CO2 at different
(a) (b)
Intensity / a. u.
Intensity / a. u.
294 292 290 288 286 284 282 280 294 292 290 288 286 284 282 280
Binding energy / eV Binding energy / eV
(c) (d)
Intensity / a. u.
Intensity / a. u.
294 292 290 288 286 284 282 280 294 292 290 288 286 284 282 280
Binding energy / eV Binding energy / eV
Fig. 1 – The C1s XPS spectra and the deconvoluted spectra of (a) GO, (b) GO reduced at 573 K, (c) GO reduced at 873 K and (d) RGO
activated by KOH (KOH/C = 5, 1073 K, 1 h). Carbon states: C@C (green), CAC (blue), CAO (pink), C@O (orange), COO (purple).
Table 1 – Percents of different carbon states in GO, RGO and A-RGO. Here RGO at 573 K and RGO at 873 K are RGO samples
obtained by heating at 573 and 873 K, respectively.
Sample C@C (%) CAC (%) CAO (%) C@O (%) COO (%)
GO 35 6 37 17 5
RGO at 573 K 71 12 7 6 4
RGO at 873 K 75 13 6 4 2
A-RGO 74 13 5 5 3
conditions. The shapes of these isotherms are combination of of the ice front. This structure is similar to the previously
type I and type II according to the IUPAC classification [30,31]. reported materials which prepared by ice freezing method
The porosity parameters and burn off of RGO-I and RGO-I [16–18]. However, no ordered structure can be observed in
activated by CO2 at different conditions are shown in Table 2. the region within the colonies. Large numbers of nano-parti-
Here Sas and SBET are the SPE and BET surface areas, respec- cles are observed in the magnified image of Fig. 3(b), which
tively; VDR and VDH are the micropore volume from DR plot are derived from the metal residual in the GO preparation
and the mesopore volume from DH method, respectively. process. We activated RGO of high purity (RGO-P) by CO2 to
The Sas and VDR increase with the elevation of the activation obtain the products with less impurity, as mentioned in
temperature, and RGO-I obtained from CO2 activation at Section 2.1.
1123 K for varying times also show higher Sas and VDR with Fig. 4 shows the adsorption isotherms of non-activated
increasing activation time. However, the activation effect is RGO-P and RGO-P monoliths activated by CO2 at 1223 K for
not so obvious comparing with activation of ligneous precur- 1 h and 4 h. The adsorption isotherm of RGO-P activated for
sors [32–34]. Thus the CO2 activation is not efficient for the 1 h has a hysteresis of type H4, being similar to that of
production of micropores in RGO-I. RGO-P [30]. However the adsorption hysteresis of RGO-P
The SEM images of the product activated by CO2 with the activated for 4 h has a type H3, suggesting the broadening
highest surface area are shown in Fig. 3. The RGO-I monolith of slit-shaped mesopores after the longer activation. The
has a local unidirectional structure and the colonies of locally maximum surface area (Sas) of RGO-P activated for 4 h was
aligned region are observed, which is in the parallel directions 64 m2 g 1, being smaller than those obtained from RGO-I.
200 200
non-activated non-activated
1073 K (a) 20 min (b)
150 1123 K 150 40 min
1148 K
-1
60 min
-1
Vads(STP)/cm g
Vads(STP)/cm g
3
100 100
50 50
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0
Fig. 2 – N2 adsorption isotherms of (a) RGO-I activated by CO2 at different temperatures for 20 min, (b) RGO-I activated by CO2 at
1123 K for different times. (A colour version of this figure can be viewed online.)
Table 2 – Porosity parameters of RGO-I and RGO-I activated by CO2 at various conditions.
Sample Sas (m2 g 1) SBET (m2 g 1) Sas-external (m2 g 1) VDR (cm3 g 1) VDH (cm3 g 1) Burn off (wt%, ±5%)
RGO-I 26 28 – – – –
1073 K, 20 min 110 113 32 0.04 0.07 22
1123 K, 20 min 133 153 35 0.05 0.07 31
1148 K, 20 min 240 257 63 0.09 0.11 53
1123 K, 40 min 195 210 78 0.07 0.10 49
1123 K, 60 min 320 320 79 0.12 0.15 72
Fig. 3 – SEM images of RGO-I activated by CO2 at 1123 K for 60 min.
and ZnCl2 and H3PO4 at the weight ratio of carbon to chemical

100 reagents of 1 to 1, and then those were reduced as described
non-activated in Section 2.2. The RGO monoliths containing ZnCl2 were acti-
1h
80 vated at 773 and 873 K for 1 h, whereas the RGO monoliths
4h
containing H3PO4 were activated at 623 and 673 K for 1 h.
-1
Vads(STP)/cm g
3
60 Fig. 5(a) shows the N2 adsorption isotherms of RGO mono-

liths activated by ZnCl2 at 773 and 873 K. The isotherms are of
40
typical type IV of the IUPAC classification. A distinct hystere-
sis with a steep uptake at high relative pressure is observed,
indicating the presence of wide mesopores. The surface areas
20
evaluated by SPE method for both samples are 210 and
120 m2 g 1, and the corresponding external surface area are
0
0.0 0.2 0.4 0.6 0.8 1.0 105 and 170 m2 g 1, respectively, as shown in Table 3. The
P/P0 similarity between SPE surface area and external surface area
indicates that the ZnCl2-activation is not efficient for selective
Fig. 4 – N2 adsorption isotherms of non-activated RGO-P and production of micropores. The mesopore volumes deter-
RGO-P activated by CO2 at 1223 K for 1 h and 4 h. (A colour mined by DH method are rather large, being 0.41 and
version of this figure can be viewed online.) 0.63 cm3 g 1, respectively.
Fig. 5(b) shows the N2 adsorption isotherms of RGO mono-
liths activated by H3PO4 at 623 and 673 K. The shape of
A small amount of metal in carbon can play a significant adsorption isotherms of the H3PO4-activation sample is simi-
role in its gasification reaction according to Marsh et al. [35]. lar to that of the ZnCl2-activation sample, but the adsorption
The catalytic effects depend on the metal used, the metal par- amount is much less. Hence the activation with H3PO4
ticle size, the dispersion state in the carbon, the amount of increases large mesoporosity and external surfaces, although
metal present and the reaction temperature, etc. Accordingly, it is less efficient than the activation with ZnCl2. The porosity
RGO-P of less impurities is not efficiently activated compared parameters are shown in Table 3. The surface area and micro-
with RGO-I of more impurities; the surface area of activated pore volume of these activated RGOs are too small compared
RGO-I is smaller than that of activated RGO-I. Nevertheless, with those of activated carbon produced by ZnCl2 or H3PO4
even the activation of RGO-I gives the surface area of activation [38–43]. The ZnCl2 or H3PO4 activation induces
320 m2 g 1 at best, as shown in Table 2. Then the CO2 activa- marked dehydration effect on the cellulose, hemicellulose
tion is not effective for RGO samples. This is because the CO2 and lignin compounds in the carbon precursor during heat
molecules undergo reaction at the edges of the graphene treatment [37]. However, the graphene based materials like
planes (prismatic edges) rather than the basal planes [36]; RGO has less aquo-complexes and thereby the activation with
the oxidation reaction at the prismatic edges are 102–103 ZnCl2 or H3PO4 does not develop the porosity effectively, as
times faster than that on the basal planes [37]. RGO has rela- mentioned above.
tively large amount of basal planes than its prismatic edges
comparing with other carbon materials, so that CO2 activa- 3.4. KOH activation
tion is not an effective method for RGO. Consequently, the
RGO activation by CO2 with metal catalysts must be no appro- The mechanism of the chemical activation of carbons by KOH
priate route for development of the porosity. is very different from that by ZnCl2 or H3PO4. Instead of devel-
oping the porosity by the dehydrating effect, KOH activation
3.3. ZnCl2 and H3PO4 activation consists of a series of redox reactions where carbon is oxi-
dized to CO, CO2 and carbonate, while KOH is converted into
The optimized activation conditions for RGO samples with K2CO3 or metallic potassium [44–46]. The porosity can be
ZnCl2 and H3PO4 are adopted from literature [38–40] and developed from the gasification and separation of graphene
[41–43], respectively. The GO monoliths having ZnCl2 and layers in the graphitic structure. Therefore, the KOH activa-
H3PO4 were prepared from the mixture of GO suspension tion appears to be a more promising route for activation of
500 100
773 K (a) 80
623 K (b)
400 873 K 673 K
-1
-1
Vads(STP)/cm g
Vads(STP)/cm g
3
3
300 60
200 40
100 20
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0
Fig. 5 – N2 adsorption isotherms of RGO activated by (a) ZnCl2 and (b) H3PO4 at different temperatures for 1 h. (A colour version
of this figure can be viewed online.)
Table 3 – Porosity parameters of RGO activated by ZnCl2 and H3PO4 at various conditions.
Activation conditions Sas (m2 g 1) SBET (m2 g 1) Sas-external (m2 g 1) VDR (cm3 g 1) VDH (cm3 g 1)
None 24 26 – – –
ZnCl2, 773 K, 1 h 120 125 105 0.04 0.41
ZnCl2, 873 K, 1 h 210 210 170 0.08 0.63
H3PO4, 623 K, 1 h 36 40 33 0.01 0.09
H3PO4, 673 K, 1 h 49 53 43 0.02 0.12
RGO. In this work, we examined the effect of the activation for the KOH-activated samples, although the non-activated
temperature and the KOH to carbon weight ratio, as the RGO contains a small amount of mesoporosity and almost
amount of KOH and the reaction temperature have a strong no microporosity. The KOH-activation shows an evident
effect on the porosity development [35,47,48]. enhancement of N2 uptake at whole relative pressure range.
Also, the RGO activated at 1073 K shows slightly higher N2
3.4.1. Structure evolution during activation of RGO monolith uptake than those activated at 973 and 1023 K, which are very
Fig. 6 shows the SEM images of the RGO samples before acti- close to each other. In case of KOH/C = 1, the frameworks of
vation and RGO activated at 1073 K with different KOH to car- macropores should be broken into smaller and randomly
bon ratio (KOH/C). The RGO consists of many crumpled arranged pieces, leading to the increase of mesoporosity.
sheets, which are detached from each other and construct a Also, the metallic potassium produced from the redox reac-
lot of macroporous space. The sheets start to aggregate into tion between KOH and carbon species can be intercalated
agglomerates and the surface of these sheet become more between the graphene walls, being responsible for the devel-
crumpled by the KOH activation at KOH/C = 1. A thick wall opment of microporosity by the separation, gasification, and
structure can be observed at KOH/C = 3, indicating the forma- degradation of the graphene layers [49,50], even if micropo-
tion of highly aggregated structure. The thickness of the wall rosity development is still not so remarkable. Fig. 7(b) shows
structure further increases in the case of KOH/C = 5. The mor- the type I N2 adsorption isotherms of the RGOs activated at
phology change from the detached graphene sheets to the KOH/C = 2, being different from those at KOH/C = 1. This
thick lamellar structure should come from the aggregation indicates that the mesopores are deteriorated while microp-
of GO suspensions caused by the neutralization of its surface ores are further developed. A slight adsorption increase is
charge with KOH. On the other hand, the effect of KOH observed near P/P0 = 1 for all adsorption isotherms and
activation at high temperature can also modify the surface thereby some wide mesopores and/or macropores still remain
nano-structure, which can be analyzed by the N2 adsorption after this activation. The adsorption isotherms of the RGO
experiment. activated at KOH/C = 3 have a significant enhancement of N2
uptake in the low relative pressure range, as shown in
3.4.2. Porosity evolution on activation of RGO monoliths Fig. 7(c), indicating the striking development of the microp-
Fig. 7(a) shows the N2 adsorption isotherms of RGO prepared ores. A gradual adsorption increase is observed in the P/P0
by KOH activation with KOH/C = 1 at different temperatures range up to 0.4, which stems from the presence of larger
for 1 h. The adsorption isotherms are of type IV with a slight micropores [21]. The adsorption is almost saturated above
combination of type I, indicating the presence of predomi- P/P0 = 0.5, being indicative of disappearance of wide mesopores
nant mesopores with a little contribution of microporosity and macropores. On the other hand, a hysteresis loop can
Fig. 6 – SEM images of (a) RGO before activation and RGO activated at 1073 K for 1 h with KOH/C of (b) 1; (c) 3; (d) 5.
200 200
non-activated (a) 973 K (b)
973 K 1023 K
150 1023 K 150 1073 K
-1
-1
Vads(STP)/cm g
Vads(STP)/cm g
1073 K
3
100 100
50 50
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0
1000 1600
973 K (c) 973 K (d)
1023 K 1023 K
800
1073 K 1200 1073 K
-1
-1
Vads(STP)/cm g
Vads(STP)/cm g
3
3
600
800
400
400
200
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0
Fig. 7 – N2 adsorption isotherms of RGO activated at different temperatures with KOH/C = 1 (a), 2 (b), 3 (c) and 5 (d) for 1 h. (A
colour version of this figure can be viewed online.)
be observed between 0.4 and 0.6 of P/P0 for RGO activated at when KOH/C = 5, the initial N2 uptake in the low relative pres-
1023 and 1073 K, which stems from the presence of small sure range is larger than those at KOH/C = 3, being indicative
mesopores. The newly developed small mesoporosity is of the further development of microporosity. No distinct uptake
attributed to the continuous enlargement of micropores by is observed above P/P0 = 0.4 for RGO activated at 973 K, and
degradation and gasification of graphene units. Furthermore, then the structure mainly consists of microporosity. On the
contrary the activation at 1023 and 1073 K induces the contin- compared with the microporosity except for RGO activated at
uous increase of N2 adsorption even above P/P0 = 0.4 with a KOH/C = 5. The mesopore volume increases markedly with
distinct hysteresis loop, indicating the notable development the activation temperature at KOH/C = 5. The RGO activated
of mesoporosity from the continuous enlargement of microp- at 1073 K and KOH/C = 5 has the largest mesoporosity and
ores. The adsorption hysteresis loops belong to Type H2 microporosity, having a great application potential.
according to IUPAC classification [30]. The H2 loop was attrib- Fig. 9 shows high resolution TEM images and a photo of
uted to different mechanism in the condensation and evapo- the graphene monoliths from RGO activated at 1073 K with
ration processes occurring in pores having narrow necks and KOH/C = 5, having the largest surface area in Fig. 8. Three
wide bodies (‘ink bottle’ pores) in the past. However, this dimensional networks of carbon sheets with entangled and
model neglects network effects of mesopores [30] and then crumpled structures are observed, being responsible for the
we cannot clearly conclude that these RGO samples have presence of the meso- and microporosity. The carbon sheets
‘‘ink bottle’’ type mesopores. mainly consist of monolayer or few-layer graphene sheets
The porosity parameters of RGOs activated at different of considerably large size, which is very different from con-
conditions with KOH are shown in Table 4. Fig. 8 illustrates ventional activated carbons (or activated carbon fibers) of
the porosity parameters as a function of the activation tem- high surface area which mainly consist of tiny carbon units
perature and KOH/C. of several nanometers at maximum in the scale [51–53]. The
The surface area from the as-plot increases with the KOH/C graphene-based frameworks developed in this work are
ratio at the same activation temperature, while surface area expected to be more mechanically and chemically stable.
increases with the activation temperature at the same KOH/C The graphene monoliths activated at 1073 K with KOH/C = 5,
ratio. The steep jump between the samples prepared with having a surface area of 1760 m2 g 1, still maintain their free
KOH/C ratio of 2 and 3 indicates the remarkable development standing nature, as shown in Fig. 9(c). The free standing
of microporosity within this KOH/C ratio range. The external monolith is really promising in the application fields such
surface areas from as-plot method are shown in Fig. 8(b). The as catalysis [54,55], electrochemistry [56,57], sensors [58],
external surface area drops and then increases with the energy storage [59] and environment technologies [60]. In this
increase of KOH/C ratio at the same activation temperature. aspect, we need to design the robust graphene monolith of
As we prefer graphene having higher surface area and less high surface area in future. The ash content of this sample
external surface for future application, we can choose the is only 1.4 wt%, which is very close to that of RGO-P, being
promising activation conditions from Fig. 8(a) and (b); activa- 1.3 wt%, indicating that KOH intercalated in graphene layers
tion at 1073 K and KOH/C = 3 should be appropriate for produc- during activation process can be mostly removed by the sim-
tion of the high performance adsorbent, for example. Fig. 8(c) ple water washing. The surface chemistry analysis of the high
shows the changes of the micropore volume. The micropore surface area A-RGO is shown in Fig. 1(d) and Table 1. The
volume increases with the activation temperature and KOH/C A-RGO has a small amount of oxygen functional groups
ratio; there is a steep jump between the KOH/C ratio of 2 similar to those of GO reduced at 873 K. The apparent density
and 3. Fig. 8(d) shows the variations of the mesopore volume. of high surface area A-RGO monoliths ranges from 30 to
Generally speaking, the mesoporosity is not predominant 65 mg cm 3 depending on the preparation and activation
Table 4 – Porosity parameters for RGO activated by KOH at various conditions.

Activation conditions Sas (m2 g 1) SBET (m2 g 1) Sas-external (m2 g 1) VDR (cm3 g 1) VDH (cm3 g 1)
None 24 26 – – –
KOH/C = 1
973 K 78 87 54 0.02 0.19
1023 K 90 100 68 0.03 0.2
1073 K 123 123 86 0.05 0.19
KOH/C = 2
973 K 270 270 28 0.10 0.04
1023 K 320 335 20 0.11 0.04
1073 K 405 415 65 0.14 0.07
KOH/C = 3
973 K 1060 1100 80 0.39 0.12
1023 K 1400 1450 58 0.53 0.14
1073 K 1645 1765 50 0.61 0.24
KOH/C = 5
973 K 1080 1160 185 0.42 0.31
1023 K 1450 1510 100 0.59 0.52
1073 K 1760 1840 325 0.67 1.33
KOH/C = 10
1073 K 2150 2200 360 0.81 1.36
2000 400
(a) (b)
1600
300
2 -1 3 -1
Salpha-S / cm g 1200 Sexternal / cm g
200
800
100
400
0 0
1073 1073
5 5
4 1023 4 1023
3 3
2 Temperature / K 2 Temperature / K
1 973 1 973
KOH/C weight ratio 0 KOH/C weight ratio 0
0.8 1.5
(c) (d)
0.6
1.0
3 -1 3 -1
Vmicro / cm g Vmeso / cm g
0.4
0.5
0.2
0 0
1073 1073
5 5
4 1023 4 1023
3 3
2 2 Temperature / K
973 Temperature / K 1 973
1
0 KOH/C weight ratio 0
KOH/C weight ratio
Fig. 8 – Three dimensional histograms of surface area by as-plot and pore volume of RGOs activated at different temperature
and KOH/C ratio.
Fig. 9 – High-resolution TEM images and a photo of RGO activated by KOH at 1073 K with KOH/C = 5. (A colour version of this
figure can be viewed online.)
conditions. These densities are higher than that of the non- 3.4.3. Activation model of reduced graphene oxide monoliths
activated RGO monoliths due to the compaction of the mono- with KOH
liths in the preparation stage, as described in Section 2.2. It is The changes in microporosity and mesoporosity of the RGO
noteworthy that A-RGO has a considerably high electrical samples with the KOH activation enable us to propose the
conductivity. (electrical resistance: (1.5 ± 0.3) kX, being close activation model of the RGO. We assume the unit plate as
to that of non-activated RGO monolith, whereas the apparent monolayer graphene with thickness of 0.355 nm. The non-
density of this A-RGO monolith is about 3 times larger than activated RGO consists of randomly bridged carbon sheets
that of non-activated one.). with many stacked graphene layers, as shown in Fig. 10(a).
Fig. 10 – Model of the porosity development on (a) non-activated RGO and RGO activated at 1073 K with KOH/C = 1 (b), 2 (c), 3 (d)
and 5(e) for 1 h.
The interspaces constructed by such randomly bridged car- 4. Conclusions

bon sheets are too large to be analyzed with N2 adsorption,
giving a small surface area. Activation with KOH/C = 1 sepa- This work shows that the KOH activation method is highly
rates the thick carbon sheets into thinner and finer graphene efficient for production of the high surface area graphene
layers, as shown in Fig. 10(b), correspondingly the macropo- monolith. The porosity development of the reduced graphene
rous frameworks collapse into smaller interspaces, leading oxide monoliths with the KOH activation can be interpreted
to the formation of mesoporosity. The carbon sheets start to by the following activation scheme:
separate to much smaller pieces with fewer graphene layers
at KOH/C = 2, as shown in Fig. 10(c), even if some mesoporous (1) Development of mesoporosity by partial exfoliation of
spaces still remain under this activation condition. The sepa- thick graphene sheets accompanying with reconstruc-
rated thin graphene layers can form a highly porous assembly tion of the thinner sheets.
due to their partial interstacking. As the predominant surface (2) Marked microporosity development by full occupancy
area should come from the basal plane of the graphene of the void spaces with monolayer and/or few layers
sheets, the average graphene layer number is estimated to graphene sheets.
be 6.5 at this stage from the surface area [61,62]. The (3) Formation of bimodal pore structured graphene-based
remained mesoporous space is filled with newly produced carbon with mesoporosity and microporosity due to
single and/or few layers of graphene, when KOH/C = 3, as the further exfoliation and partial gasification of the
shown in Fig. 10(d). In this case, surface area gives 1.6 layer edges of the graphene sheets.
number of graphene, supporting this model structure. The
KOH activation with the condition of KOH/C = 5 exfoliates The above activation gives the porous graphene monolith
more the few graphene layers into the single layer. At the with high surface area of 2150 m2 g 1 at most. The walls of the
same time, gasification proceeds from the edges of the extre- porous graphene monolith of the highest surface area should
mely thin graphene layers to form mesopores, as shown in be close to single graphene layers taking account of the loss in
Fig. 10(e). A more intensive activation using the KOH/C = 10 the surface area due to the inter-insertion structure. The newly
condition increases both of meso- and microporosity, as developed graphene monolith has a great application potential.
shown in Table 4. Thus, this activation model can describe Besides, this work provides a promising route for the bottom-up
the whole experimental results on the porosity and TEM design of pore width-tunable nanoporous carbons.
observation. Therefore, this model is helpful to design an
optimum activation process for the target porosity, although
we need to take into account the contribution of the edge car- Acknowledgements
bons in future. The model cannot be applied to the conven-
tional activated carbon which is not produced from the K.K., F.T., T.F., R.C.-S., M.T. and M.E. were supported by Exotic
well-defined unit carbon structures. Nanocarbons, Japan Regional Innovation Strategy Program by
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Activation Routes For High Surface Area Graphene Monoliths From Graphene Oxide Colloids

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CARBON x x x ( 2 0 1 4 ) x x x –x x x

journal homepage: www.elsevier.com/locate/carbon

Activation routes for high surface area graphene

1. Introduction weight [9]. Furthermore, it has another merit of slit-shaped

* Corresponding author: Fax: +81 (0)26 269 5737.

Fig. 3 – SEM images of RGO-I activated by CO2 at 1123 K for 60 min.

and ZnCl2 and H3PO4 at the weight ratio of carbon to chemical

60 Fig. 5(a) shows the N2 adsorption isotherms of RGO mono-

Table 4 – Porosity parameters for RGO activated by KOH at various conditions.

The interspaces constructed by such randomly bridged car- 4. Conclusions

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