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A New Approach to Tuning Carbon Ultramicropore Size at
Sub-Angstrom Level for Maximizing Specific Capacitance
and CO2 Uptake
Jin Zhou, Zhaohui Li, Wei Xing,* Honglong Shen, Xu Bi, Tingting Zhu, Zhipeng Qiu,
and Shuping Zhuo*
Ultramicroporous carbon materials with uniform pore size accurately
adjusted to the dimension of electrolyte ions or CO2 molecule are highly
desirable for maximizing specific capacitance and CO2 uptake. However,
efficient ways to fine-tuning ultramicropore size at angstrom level are scarce.
A completely new approach to precisely tuning carbon ultramicropore size at
sub-angstrom level is proposed herein. Due to the varying activating strength
and size of the alkali ions, the ultramicropore size can be finely tuned in the
range of 0.60–0.76 nm as the activation ion varies from Li+ to Cs+. The car-
bons prepared by direct pyrolysis of alkali salts of carboxylic phenolic resins
yield ultrahigh capacitances of up to 223 F g-1 (205 F cm-3) in ionic liquid
electrolyte, and superior CO2 uptake of 5.20 mmol g-1 at 1.0 bar and 25 °C.
Such outstanding performance of the finely tuned carbons lies in its adjust-
able pore size perfectly adapted to the electrolyte ions and CO2 molecule. This
work paves the way for a new route to finely tuning ultramicropore size at the
sub-angstrom level in carbon materials.
1. Introduction
Carbon materials have received considerable attention in super-
capacitors and CO2 capture.[1] Recent studies have shown that
ultramicropores (diameter <0.80 nm) play a key role in deter-
mining specific capacitance and CO2 uptake of carbon mate-
rials.[2–8] Chmiola et al. pointed out that micropores with a
diameter smaller than 1.0 nm to be responsible for an anom-
alous increase in specific capacitance in organic electrolyte
media.[3] It is suggested that desolvated ions rather than larger-
sized solvated ionic species are stored in these ultramicropores.
In the case of ionic liquid (IL) media, maximum capacitance
Dr. J. Zhou, Z. Li, H. Shen, X. Bi, T. Zhu, Z. Qiu,
Prof. S. Zhuo
School of Chemical Engineering
Shandong University of Technology
Zibo 255049, P. R. China
E-mail: zhuosp_academic@yahoo.com
Prof. W. Xing
School of Science
State Key Laboratory of Heavy Oil Processing
China University of Petroleum
Qingdao 266580, P. R. China
E-mail: xingwei@upc.edu.cn
DOI: 10.1002/adfm.201601904
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was obtained when the pore size of carbon
materials matched the dimensions of
the electrolyte ion.[4] With regard to CO2
capture applications, it has been widely
accepted that CO2 uptake at ambient
pressure is determined by the volume
of ultramicropores rather than the total
pore volume.[5,6] Presser et al. reported
that most of the CO2 uptake capacity of
carbide derived carbons at ambient pres-
sure to be originated by pores with a
diameter smaller than 0.8 nm.[7] Further
studies showed that CO2 uptake is lim-
ited by ultramicropores smaller than a
certain diameter at different pressures or
temperatures.[7,8] On the other hand, the
volumetric performance is of great impor-
tance for practical application of carbon
materials in supercapacitors and CO2 cap-
ture. In this sense, high packing density of
the carbon materials is preferred. As large
pore size and broad pore size distribution are usually in contra-
diction with high packing density, uniform ultramicroporosity
are highly desirable for maximizing volumetric capacitance and
CO2 uptake for carbon materials.
As pointed out above, carbons with uniform and fine tai-
lored ultramicropore size matching the dimensions of the
electrolyte ions or the CO2 molecule may result in materials
exhibiting optimal performance. These impressively show the
importance of uniformly adjusting the ultramicropore size at
sub-angstrom levels. Well-established methods such as chem-
ical activation,[9,10] physical activation,[11] template methods,[12]
and polymer carbonization[13] allow production of porous
carbon materials with developed porosity. These methods, how-
ever, typically lead to poor fine tuning of ultramicropore size
at sub-angstrom levels. The most successful synthesis strate-
gies to control micropore size are based on the selective deal-
loying of metal carbides by chlorination, although chlorine gas
is very toxic.[14] Hou et al. reported a hot-pressing method to
adjust the average pore size of zeolite-templated carbons from
0.7 to 1.0 nm at the expense of using ultrahigh pressures of up
to 147 MPa.[15] Cyclic oxidation/thermal desorption treatment
allows gradual adjustment of average pore size, although the
time- and energy-consuming features of this process seriously
hinder large-scale carbon manufacturing.[16] In a word, efficient
ways to precise fine-tuning the ultramicropore size of carbons
are scarce. It is still very challenging to develop facile approach
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to tuning carbon ultramicropore size at sub-angstrom level
when keeping the pore uniformity.
Herein, we proposed a completely new strategy to finely
tune the pore size of ultramicroporous carbons using different
alkali metal ions (Li+, Na+, K+, Rb+, Cs+) as activating agents.
Ultramicroporous carbons with highly uniform pores and high
packing density were prepared by direct carbonization of alkali
salts of carboxylic phenolic resins. Due to the varying activating
strength and size of alkali ions, the ultramicropore size can be
finely tuned in the range of 0.60–0.76 nm as the activation ion
varies from Li+ to Cs+. The resulting carbons present ultrahigh
capacitances of up to 223 F g−1 or 205 F cm−3 in ionic liquid
electrolyte, and superior CO2 uptake of 5.20 mmol g−1 at 1.0 bar
and 25 °C. To the best of knowledge, these values are much
higher than most of the reported carbon materials. The out-
standing performance of the finely tuned carbons was proved
to lie in its pore size perfectly adjusted to dimensions of the
ions composing the ionic liquids and the CO2 molecule.
2. Results and Discussion
2.1. Formation of the Ultramicroporous Carbon Materials
Figure 1 illustrates the preparation of the ultramicroporous
carbon materials. In a typical synthesis, 2,4-dihydroxybenzoic
acid, alkali hydroxide (MOH), and formaldehyde were dis-
solved in deionized water to form a pale yellow homogeneous
solution. Immediately, a complete neutral reaction will occur
between strongly basic MOH and carboxyl groups (COOH)
of 2,4-dihydroxybenzoic acid to form carboxylates (COOM).
This solution was then hydrothermally treated at 120 °C for
24 h to promote polymerization of phenols with formaldehyde
resulting in alkali salts of carboxylic phenolic resins. Initially,
Figure 1.  Schematic diagram of the synthesis of MAC.
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the nucleophilic addition reaction between phenols and for-
maldehyde leads to the formation of hydroxymethyl derivatives
that subsequently undergo intermolecular condensation (i.e.,
dehydration) to yield methylene and methylene ether bridges.
The formation of hydroxymethyl derivatives is very fast at
the basic conditions used herein (pH ≈10), this resulting in a
large number of primary particles and thus small-sized resin
gels (about 200 nm, Figure S1 (Supporting Information)).[17]
The high surface tension generated during the hydrothermal
process causes the packing texture of gel nanoparticles to col-
lapse, thereby resulting in compacting of gel particles.[18] The
resulting red hydrogels were dried to form dark red xerogels
(Figure S2, Supporting Information), followed by carboniza-
tion at 900 °C (3 °C min−1) for 2 h in argon. The alkali metal
ion-activated carbon materials were finally obtained by washing
with diluted HCl and deionized water to neutrality. For conven-
ience, the alkali salts of carboxylic phenolic resin and its corre-
sponding carbon material are denoted as PR-COOM and MAC,
where PR and M stand for phenolic resin and alkali metal ion,
respectively.
As illustrated by X-ray energy dispersive spectroscopy (EDS)
mapping (Figure S3, Supporting Information), the distribu-
tions of alkali ions are homogeneous. These monodispersed
ions as a form of COOM could produce a homogeneous “in
situ activation” effect. To study the carbonization process and
activation mechanism, thermogravimetry-mass spectrometry
(TG-MS) analysis and in situ X-ray diffraction (XRD) were per-
formed. Figure 2a–d shows the TG curves and MS responses
of potassium salt of carboxylic phenolic resin (PR-COOK)
and phenolic resin carboxylic acid (PR-COOH). Three gases,
including H2O (m/z 18), CO (m/z 28), and CO2 (m/z 44), were
detected by mass spectrometry. The little weight loss (<10 wt%)
at T < 200 °C could be attributed to the evaporation of mois-
ture and decarboxylation confirmed by the release of H2O
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Figure 2.  a) TG curves, MS responses of evolved gases in TG-MS analysis b) H2O, c) CO2, and d) CO, e) in situ XRD patterns (Cu Ka) during the
carbonization of PR-COOK, and f) possible activation mechanism.
and CO2 (Figure 2a–c). In the case of PR-COOH, a significant
weight loss of 38.3 wt% in 200–800 °C is due to the continual
thermal decomposition of PR-COOH, and a negligible weight
loss <0.5 wt% at the last step between 800 and 1000 °C were
observed, confirming stable carbon structure was formed
above 800 °C. By contrast, the pyrolysis process of PR-COOK
is much more complicated at the temperatures above 200 °C.
The weight loss of about 9.6 wt% in 200–400 °C may be due
to further cross-linking and initial thermal degradation of the
phenolic resin with the formation of K2CO3 and evolution of
CO2 and H2O at about 350 °C. The weight loss in 400–600 °C
could be partially attributed to the transformation of K2CO3
into K2O. The sharp weight loss (>20 wt%) above 800 °C indi-
cates that the carbon framework is severely etched to form the
microporosity.
Figure 2e presents the in situ XRD patterns at 200, 400,
600, and 800 °C during the pyrolysis of PR-COOK. It can be
observed that the PR-COOK began to decompose into K2CO3
(PDF card 71-1466) at around 200 °C. At 600 °C, the diffrac-
tion peaks of K2CO3 are no longer visible and K2O (PDF card
26-1327) can be detected, indicating that most of K2CO3 has
been transformed into K2O. We further designed a simple
experiment to prove the decomposition of K2CO3. As shown
in Figure S5 (Supporting Information), no precipitates
were observed when the extract of carbonization residual of
PR-COOK at 600 °C was dropped into BaCl2 solution, indi-
cating the absence of CO32− in the residual. This further proves
that most K2CO3 have been transformed into K2O at 600 °C.
Considering the evolution of CO2 and CO at about 520 °C, the
generation of K2O could be explained by the possible reactions
of K2CO3 → K2O + CO2 or K2CO3 + C → K2O + 2CO. When the
carbonization temperature was increased up to 800 °C, besides
the peaks of K2O, new peaks at 10.4° and 16.5° appeared,
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which are attributed to K (100) (PDF card 01-0500) and KC8
(100) (PDF card 04-0221), and large amount of CO were
detected (Figure 2d). These facts indicate that K2O is reduced
by carbon to metallic potassium via the reaction of K2O + C →
2K + CO, and partial carbon atoms were etched into CO to give
rise to the porosity.[19] Meanwhile, potassium vapors may inter-
calate between the carbon layers to form graphite intercalation-
like compounds (e.g., KC8 here) and cause swelling and the
disruption of the carbon microstructure, which thereby gener-
ates even more ultramicroporosity. Similar results of TG-MS
analyses were obtained for the other alkali salts of carboxylic
phenolic resins (Figure S4, Supporting Information), indi-
cating the carbonization process is essentially same for all the
samples.
Overall, based on the above observations, a homogeneous
“in situ activation” process was presented in Figure 2f. That is:
First, alkali salts of phenolic resins decompose into alkali car-
bonate (M2CO3), H2O, and CO2 below 400 °C. Second, alkali
oxides (M2O) are generated via the thermal decomposition of
M2CO3 or the redox reaction between M2CO3 and C. Third,
framework carbon atoms are etched by M2O via the vigorous
redox reaction of M2O + C → 2M + CO, leading to a significant
weight loss, then the produced metallic alkali intercalates into
the lattices of the carbon matrix, which is responsible for both
stabilization and widening of the interlayer spacing.[20] The
interlayer spacing will be primarily determined by the size of
metal intercalate, and this spacing (i.e., pore size) will be sys-
tematically widened with increasing metal ion size from Li+ to
Cs+ (Figure S6, Supporting Information).[21] After the removal
of the intercalated metallic alkali and other alkali compounds
by washing, the expanded carbon lattices cannot return to their
previous nonporous structure and thus achieved to finely tun-
able ultramicropore size.
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Figure 3.  SEM images of: a,b) KAC and e,f) CsAC. TEM images of: c,d) KAC and g,h) CsAC.
2.2. Structural Characteristics and Chemical Properties of MAC
Materials
Microscopic morphology and pore texture of MAC materials
were imaged by scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) techniques (Figure 3).
As revealed by SEM images, the MAC materials were shown
as compact blocks with a smooth surface and no clear pores.
However, when observed by TEM, the as-prepared carbons
were found to possess abundant micropores without apparent
mesopore or macropore signs. High resolution TEM images
(Figure 3c,d,g,h and Figure S7 (Supporting Information))
clearly evidenced highly connected and worm-like micropores
within the MAC structures. These pore morphology resulted
from the homogeneous “in situ activation” produced by highly
dispersed (at atomic level) alkali ions.
The porosity properties of the MAC materials were further
analyzed by N2 and CO2 adsorption at −196 and 0 °C, respec-
tively. As shown in Figure 4a, all the MAC samples except
RbAC presented a standard type I N2 adsorption isotherm with
a narrow knee at very low relative pressures (P/P0 < 0.02) and
nearly unchanged adsorption amount at higher relative pres-
sures. This shape is characteristic of porous materials showing
a narrow micropore size distribution and a minimal presence
of mesopores. As shown in Table 1, the SBET versus Smicro and
VT versus Vmicro values were very similar in all cases, further
demonstrating the microporous nature of MAC materials.
Remarkably, the porosity of LiAC is much undeveloped, and the
pore volume and the apparent surface areas sharply increased
(from 0.07 to 0.70 cm3 g−1 and from 111 to 1312 m2 g−1, respec-
tively) (Table 1) while varying the activating ion from Li+ to Cs+,
thereby revealing activation strength significantly increasing
from Li+ to Cs+. The observed trend in activating strengths of
alkali ions can be explained by the reactivity difference of M2O
and carbon. Gibbs free energies change (ΔG) calculated by Van’t
Hoff equation (Table S1, Supporting Information), revealed
the reduction process to be more thermodynamically feasible
at 900 °C with increasingly larger negative values (i.e., higher
reactivity of M2O and carbon) from Li to Cs. Furthermore, the
difference of boiling points for alkali metals (1347 °C for Li,
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<900 °C for other alkali metals) may be a reason. At 900 °C,
the alkali metals except Li become metallic vapor with high
diffusivity, and could easily intercalate into the deep of carbon
lattices, thus resulting in much more developed porosity. Even
though the dosage of activation agents used herein was much
lower compared to traditional chemical activation processes
(30 wt% of resins as counted in KOH vs 100–400 wt%), the sur-
face area of KAC material (897 m2 g−1) was comparable to that
of KOH-activated carbons.[10,22]
Dubinin−Radushkevich (D–R) plots from CO2 adsorption
data provide instructive information about the size of ultrami-
cropores (diameter <0.8 nm). The slope from the linear D–R
plots can be used to estimate micropore size and uniformity
(see the Supporting Information for further details). All the
MAC materials except LiAC exhibited well-defined linear D–R
plots (correlation coefficient R2 > 0.995, Figure 4c–f). In the
case of excellent linear fittings, Dubinin postulated the exist-
ence of highly uniform ultramicropores.[6,23] LiAC showed a
D–R plot with two well-defined linear ranges, thereby indi-
cating the narrow microporosity to be composed of two
micropore systems (Figure S8, Supporting Information). Due
to the weak basicity of LiOH, the neutral reaction between
2,4-dihydroxybenzoic acid and LiOH is incomplete. The exist-
ence of unreacted LiOH leads to an uneven dispersion of Li+
in the phenolic resins, thus resulting in a wide pore size dis-
tribution of LiAC. Apparently, as the activation ions vary from
Li+ to Cs+, a systematic widening of micropores takes place,
whose size gradually increases from 0.60 up to 0.76 nm. Thus,
N2 and CO2 adsorption data, along with SEM and TEM obser-
vations revealed a purely uniform ultramicropore texture for
MAC samples. Remarkably, the ultramicropore size can be
finely and simply adjusted at sub-angstrom level by varying
the alkali metal ion exchanged in the parent carboxylic phe-
nolic resins. The pore size tuning resulted from the varying
activating strength and ion sizes of the alkali metals from Li+
to Cs+.
The crystalline structure of MAC samples was characterized
by XRD (Figure S9a, Supporting Information). XRD profiles
typical of activated carbon materials were obtained with two
broad bands centered at 23.4° and 43° corresponding to the
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Figure 4.  a) Nitrogen adsorption isotherms. b) CO2 adsorption isotherms. Analysis of the narrow microporosity by Dubinin−Radushkevich equation
of: c) NaAC, d) KAC, e) RbAC, and f) CsAC.

Table 1.  Textural properties of MAC samples. reflections of the (002) and (101) graphitic planes, respectively.
The intensities of these bands decreased from Li+ to Cs+, in
N2 sorption CO2 sorption agreement with the higher activating strength of Cs+ that leads
SBETa) Smicrob) VTc) Vmicrod) V0e) Lf) to a carbonaceous structure with more defects. Raman spectra
Sample [m2 g−1] [m2 g−1] [cm3 g−1] [cm3 g−1] [cm3 g−1] [nm] (Figure S9b, Supporting Information) showed well-resolved G
LiAC 111 93 0.07 0.05 0.05 0.60/1.17 and D bands centered at 1589 and 1340 cm−1, corresponding
NaAC 668 621 0.35 0.32 0.36 0.63 to the reflections of the ideal and the disordered graphitic lat-
tice, respectively. The low value of IG/ID (about 0.8) further
KAC 897 816 0.49 0.42 0.42 0.66
revealed the amorphous nature of MAC materials. X-ray pho-
RbAC 1243 1073 0.70 0.55 0.51 0.75 toelectron spectroscopy (XPS) measurements were conducted
CsAC 1312 1239 0.67 0.63 0.53 0.76 to determine the surface chemical properties of MAC mate-
a)Brunauer–Emmett–Teller surface area; b)Micropore surface area calculated by
rials (Figure S10, Supporting Information). Only C and O
the t-plot method; c)Total pore volume; d)Micropore volume calculated by the
species were detected, thereby revealing complete removal of
t-plot method; e)Micropore volume given by CO2 adsorption; f)Average micropore surface metal species by thorough washing with diluted HCl
size. and deionized water. The oxygen contents of MAC materials

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(M = Li, Na, K, Rb, Cs) were determined to be 12.3, 5.5, 5.2,

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2.3. Capacitive Performance of MAC Materials

6.1, and 8.2 at%, respectively. It could be seen that LiAC pos-
sesses much higher oxygen content than the others. The cause
is not clear exactly. One possible reason is the difference of
alkali metals in boiling point (1347 °C for Li, <900 °C for other
alkali metals). At high temperatures (e.g., 900 °C), the alkali
metals except Li become metallic vapor with high diffusivity,
and could easily contact with carbon surface and efficiently
remove surface oxygen. This explains why surface oxygen con-
tent of LiAC is apparently higher than the others. High reso-
lution XPS was used to investigate the atom binding states of
the prepared carbons (Figure S11, Supporting Information). In
the case of C-species, the peaks at 284.7, 285.4, and 286.4 eV
are assigned to sp2 hybridized carbon, carbon atoms single or
double bonded to oxygen, respectively. In the case of O-spe-
cies, three types of O-containing groups could be verified on
the surface of the prepared carbons, including CO, OCO,
and OCO, corresponding to the peaks at 531.2, 532.3, and
533.5 eV, respectively.[24]
Capacitive performance of MAC materials was studied both
in 6 m KOH and pure IL of 1-ethyl-3-methylimidazolium
tetrafluoroborate (EMImBF4) electrolytes (Figure 5). Nearly
rectangular-like cyclic voltammetry (CV) curves, characteristic
of double-layer capacitance, were obtained in all cases. To fur-
ther investigate the electrochemical performance of the MAC
materials, galvanostatic charge/discharge measurements were
carried out (Figure S12, Supporting Information). At 0.2 A g−1
and in KOH, the specific capacitances were measured to be 43,
140, 205, 200, and 221 F g−1 for LiAC, NaAC, KAC, RbAC, and
CsAC, respectively. At 0.2 A g−1 and in EMImBF4, those were
48, 97, 128, 189, and 223 F g−1 for LiAC, NaAC, KAC, RbAC,
and CsAC, respectively. The specific capacitance was plotted
versus discharge current density (Figures 5c,d). Clearly, CsAC
showed the highest specific capacitance among the MAC sam-
ples in the entire range of current densities. CsAC showed
ultrahigh specific capacitance (223 F g−1) at 0.2 A g−1 in ionic

Figure 5.  Capacitive performance: a) CV curves at 10 mV s−1 in KOH electrolyte; b) CV curves at 5 mV s−1 in EMImBF4; c) specific capacitances in KOH
electrolyte; and d) specific capacitance in EMImBF4; e) areal capacitance at 0.2 A g−1; f) capacitance ratio.

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liquid electrolyte, and this value is one of the highest among
carbon electrode materials (Table S2, Supporting Information).
When evaluating the potential of a porous carbon for superca-
pacitor applications (especially in portable electronic devices),
the specific volumetric capacitance is a more reliable parameter
as compared to the gravimetric one. CsAC (packing density of
ca 0.92 cm3 g−1) showed very high volumetric capacitances of
203 and 205 F cm−3 in KOH and EMImBF4, respectively.
The ultrahigh capacitance properties can be better under-
stood by studying the relationship between pore and ion size.
Results of the areal capacitance and retention ratio as a func-
tion of MAC material clearly pointed out a pore size effect
(Figure 5e, please note that LiAC was not included because of
its broad pore size distribution[25]). A maximum in specific areal
capacitance is reached by KAC in KOH electrolyte, with signifi-
cantly lower values obtained for the rest of carbon materials. In
contrast, the specific areal capacitance in EMImBF4 was found
to monotonously increase with pore size, with CsAC showing
the maximum normalized capacitance. Even though KAC and
NaAC have very fine difference in pore sizes (≈0.66 vs 0.63 nm),
the specific areal capacitance of the latter in KOH electro-
lyte is much larger than that of NaAC. These results can be
explained in terms of pore size and electrolyte ion size (EMIm+:
0.76 nm, BF4−: 0.45 nm, solvated K+: 0.31 nm, and solvated
OH−: 0.35 nm). According to the equation of C = εA/d, the
capacitance (C) of a supercapacitor electrode mainly depends on
the electrode specific surface area (A), which must be as high as
possible, and the distance (d) between the adsorbed ions and
the electrode surface which should be minimized. In this sense,
most efficient ion adsorption is achieved in the pores perfectly
adapted to the ion size. Theoretical studies have revealed that
the capacitance shows an oscillatory behavior as a function
of nanopore size in a theoretical slit pore.[26] The capacitance
versus pore size was found to exhibit two peaks located at the
diameters equal to ion size or twice of that, respectively. CsAC
possesses a uniform pore size (0.76 nm) that perfectly matches
with that of EMIm+, thus leading to efficient ion adsorption
and maximum specific areal capacitance.[4] The pore size of
KAC is approximately twice that of the KOH ions (especially
solvated OH− in distortion). Since ions can be adsorbed on both
pore walls in KOH electrolyte, there may be a contribution to
the capacitance of KAC from both compact layers of ions. This
result is also in good agreement with the experimental results
by Béguin and co-workers.[27]
CsAC showed standard rectangular-like CV curves in KOH
electrolyte at a very high scan rate of 500 mV s−1 (Figure S13a,
Supporting Information), and preserved 73% of its specific
capacitance (162 F g−1) after increasing current density to
20 A g−1. These results reveal excellent power performance,
being indicative of the good characteristics of the carbon pore
system (i.e., high uniformity and short pore length) designed
herein. The as-prepared carbons showed much higher capaci-
tance retention ratio in KOH than in IL (Figure 5f), and this
may be ascribed to the high conductivity, low viscosity, and
small ion size of the KOH electrolyte. The retention ratio also
showed a pore size effect. The capacitance retention of MAC
increases with pore size being attributed to the fast diffusion of
ions in larger pores. Ragone plots (Figure S13b,c, Supporting
Information) revealed remarkable energy densities values of
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32.5 and 6.2 Wh kg−1 for CsAC in IL and KOH electrolytes,
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respectively. The cycling stability of CsAC against charge–dis-
charge cycles was investigated at 1 A g−1 in KOH (Figure S13d,
Supporting Information). Remarkably, the specific capacitance
of the electrode was maintained at ≈191 F g−1 (nearly 100%
capacitance retention), even after 10 000 cycles.
2.4. CO2 Sorption Performance of MAC Materials
CO2 capture has attracted considerable attention in recent
years as CO2 is the main anthropogenic contributor to climate
change. In consideration of the microporous characteristics of
MAC, we carried out CO2 adsorption measurements at 1.0 and
20 bar (Figure 6). As reported in Table S3 (Supporting Infor-
mation), CsAC showed very high CO2 uptake values at 1.0 bar
(6.77 and 5.20 mmol g−1 at 0 and 25 °C, respectively) well above
than those reported for carbon materials under identical condi-
tions (Table S4, Supporting Information) and higher than those
of metal-organic frameworks (MOFs)[28] and covalent organic
frameworks (COFs)[29] that are also considered as good CO2
adsorbents. Figure 6c shows the CO2 adsorption isotherms of
the MAC materials at 25 °C and 0–20 bar. RbAC exhibits the
highest CO2 capacity, i.e., 9.63 mmol g−1 (42.4 wt%) at 25 °C
and 20 bar. The trend of CO2 uptakes at 20 bar is in good agree-
ment with that of total pore volume. As shown in Table S5 (Sup-
porting Information), the CO2 uptakes of CsAC are much less
at high pressure, but much higher at low pressure than those of
the carbon materials previously reported. This can be explained
by the highly exclusive ultramicroporosity but low total pore
volumes (<1.0 cm3 g−1) of MAC materials because the CO2
uptake at low pressure is determined by the volume of ultra-
micropores,[7] and the high-pressure CO2 capacity largely cor-
relates to the volumes of micropores and narrow mesopores.[30]
Therefore, the prepared MAC materials are more suitable to
CO2 sorption at low pressure.
For large-scale CO2 capture applications, an adsorbent should
ideally have high CO2/N2 selectivity, good stability during repet-
itive adsorption–desorption cycles, and low regeneration energy.
CsAC showed promising CO2 uptakes (1.52 mmol g−1) at typical
flue gas conditions (25 °C and P(CO2): 0.15 bar) while main-
taining low N2 uptakes (0.61 mmol g−1, <1/8 of the CO2 uptake)
at 25 °C and 1.0 bar (Figure 6c). Additionally, CsAC showed a
CO2/N2 selectivity (calculated from the ratio of the initial slopes
of N2 and CO2 adsorption isotherms) of 18 (Figure S14a, Sup-
porting Information),[31,32] this value being comparable (or even
superior) than that of some nitrogen-doped carbons.[32,33] With
the aim to test the recyclability of CsAC, four consecutive CO2
adsorption cycles were carried out at 25 °C, and nearly identical
isotherms were obtained (Figure S14b, Supporting Informa-
tion). With the aim to investigate the energy needed for regen-
eration, we calculated the isosteric heat of adsorption (Qst) by
applying the Clausius–Clapeyron equation to the CO2 adsorp-
tion isotherm data at 0 and 25 °C. As shown in Figure 6e, CsAC
showed a relative low Qst (17–21 kJ mol−1) that envisages low
energy consumption during regeneration. We believe that the
presence of a well-developed ultramicropore network with
narrow pore size distribution (diameter ≈0.76 nm) in CsAC
results in a high utilization degree of the overall porosity and
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full paper

Figure 6.  a) CO2 adsorption isotherms at 0 °C and 1.0 bar. b) CO2 adsorption isotherms at 25 °C and 1.0 bar. c) CO2 adsorption isotherms at 25 °C
and 20 bar. d) CO2 and N2 adsorption isotherms on CsAC at 25 °C. e) CO2 heats of adsorption on MACs. f) Water vapor adsorption isotherms at 25 °C.

surface area of the carbon material. These characteristics are
responsible for excellent CO2 adsorption performance at room
temperature and ambient pressure.
In practice, flue gas is a mixture of mostly N2, CO2, and
H2O, while its exact composition depends on the design of
the power plant and the source of natural gas or coal. H2O is
strongly adsorbed on many adsorbents (e.g., zeolites), and thus,
its presence can cause a reduction in the adsorption capacity
of CO2. Figure 6f represents the water vapor adsorption iso-
therms over MAC materials at 25 °C. Although the capacity of
water vapor (20.54 mmol g−1 for CsAC) is very high compared
to that of CO2 (5.20 mmol g−1), it has to be pointed that there is
negligible H2O adsorption on hydrophobic carbon pore surface
until pressures above 10 mbar (corresponding to a relative pres-
sure of about 0.33). In contrast, zeolite 13X, intensively studied
for CO2 capture, presents much higher adsorption capacity
of water vapor at very low relative pressures (7.7 mmol g−1
at 10 mbar).[34] As long as the partial pressure of H2O is kept
below 10 mbar, H2O adsorption may not be expected to inter-
fere with CO2 adsorption. Over 10 mbar, a sharp increase in the
amount of H2O adsorbed was observed, and then the presence
of water in the pores will lead to a decrease of the accessible
volume causing a decrease of CO2 adsorption capacity. It is also
important to note that the partial pressure of H2O in flue gases
is always over 10 mbar, especially in those after wet desulphuri-
zation. So the flue gases would likely need to be dried to below
10 mbar for H2O adsorption to remain negligible. Another con-
siderable method is appropriately controlling the adsorption
time for CO2 sorption to maximize the concentration of CO2
in the adsorbents due to the difference of diffusivity between
CO2 and H2O.[35] The higher diffusivity of CO2 will facilitate the
kinetic separation of CO2 from H2O.

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3. Conclusion
A simple ultramicropore size tuning method for carbon mate-
rials was proposed herein. The pore size can be finely tuned in
the range of 0.60–0.76 nm. The pore size tuning resulted from
the varying activating strength and ion sizes of the alkali metals
from Li+ to Cs+. The carbon materials prepared by direct pyrol-
ysis of alkali salts of carboxylic phenolic resins showed highly
developed and uniform short length ultramicroporosity. The
prepared carbon materials showed ultrahigh specific capaci-
tances of 205 F cm−3 in ionic liquid electrolyte as a result of a
perfect match in pore and ion sizes. The CsAC material showed
superior CO2 adsorption capacity of 5.20 mmol g−1 at 25 °C
and 1.0 bar, high CO2-to-N2 selectivities and full regenerability
for four consecutive cycles. This work paves the way for a new
route to finely tuning ultramicropores size at the sub-angstrom
level in carbon materials. It is anticipated that these intriguing
carbon materials might also find applications as molecular
sieves, catalysts, battery electrodes, and water/air filters.
4. Experimental Section
Preparation of MAC Materials: In a typical synthesis,
2,4-dihydroxybenzoic acid (0.5 g, 3.2 mmol), alkali hydroxide (3.5 mmol),
and formaldehyde (0.53 g, 37 wt%, 0.64 mmol) were dissolved into
6 mL H2O, and stirred for 1 h to form a pale yellow clear solution. The
solution was then solidified at 120 °C for 24 h. The resulting solid was
dried at 100 °C overnight and carbonized at 900 °C for 2 h with a heating
ramp of 3 °C min−1 in argon. Finally, the alkali metal ion-activated carbon
materials were liberated by washing with diluted HCl and deionized
water to neutrality.
Characterization of MAC Materials: Microscopic morphology of the
prepared carbon materials were observed with a scanning electron
microscope (Sirion 200 FEI Netherlands) and a transmission electron
microscope (JEM2100, JEOL, Japan). Surface chemical properties were
determined by X-ray energy dispersive spectroscopy (EDS, BRUKER
AXS) and X-ray photoelectron spectroscopy (XPS, Escalab 250, USA).
XRD patterns of the carbon materials were conducted on a Bruker D8
Advance diffractometer with Cu Kα radiation. In situ XRD patterns
during the pyrolysis of PR-COOK were collected on a PANalytical X’Pert
Pro system operated at 40 kV and 40 mA current with Cu Kα source
under N2. TG-MS studies were performed on a thermogravimetric
analyzer (NETZSCH STA 409 thermobalance) coupled to Balzers MID
mass spectrometer (heating rate 20 °C min−1, helium flow). Raman
spectra were collected by a LabRAM HR800 from JY Horiba. N2
adsorption–desorption isotherms were measured at liquid nitrogen
temperature (−196 °C) and CO2 adsorption was performed at 0 °C
using a surface area and porosity analyzer (ASAP2020M, Micromeritics,
USA). N2 and CO2 gases with super high purity (99.999%) were used for
the physisorption measurements. The carbon samples were degassed
at 350 °C for 6 h under turbomolecular vacuum before sorption
measurements. Brunauer–Emmett–Teller (BET) surface area was
calculated using the N2 adsorption isotherm data within the relative
pressure ranging from 0.05 to 0.25. Total pore volume was obtained at a
relative pressure of 0.995. Micropore surface area and micropore volume
were calculated by the t-plot method. CO2 sorption of MAC materials at
low pressure (0–1.0 bar) were determined by a static adsorption method
carried on the ASAP2020M analyzer. The measurements of high-
pressure CO2 adsorption and water vapor adsorption were performed on
an intelligent gravimetric analyzer.
Fabrication of Electrodes and Electrochemical Measurements: Working
electrodes were prepared by mixing 95 wt% carbon materials and
5 wt% polytetrafluoroethylene (PTFE) binders, pressing the mixture
onto nickel foam at 15 MPa, and then drying at 120 °C for 10 h. The
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www.afm-journal.de
mass of the active materials was 2.0 mg for each electrode. The model
full paper
capacitors were assembled in a glove box filled with argon (Mikrouna
Universal 2440, H2O and O2 <1 ppm) by facing two electrodes
sandwiched with a fiber separator for the ionic liquid electrolyte of
EMImBF4. The electrochemical measurements were carried on a
CHI660D electrochemical testing station (Chenhua Instruments Co.
Ltd., Shanghai). The specific capacitance was calculated by the following
equation
4I × t
Cm = (1)
∆V × m
where Cm (F g−1) was the gravimetric specific capacitance of the carbon
samples, I (A) was the discharge current, t (s) was the time spent in
discharge, ΔV (V) was the potential window of the cell, and m (g) was
the total mass of active materials in the cell.
Energy density (E) and powder density (P) could be calculated from
the galvanostatic charge/discharge test using the equations of
1
E= × Cm × V 2 (2)
8
E
P= (3)
t
where the Cm, V, and t were the gravimetric specific capacitance of the
carbon materials, the voltage of a supercapacitor cell before discharge,
and the time spent in discharge, respectively.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors are grateful for the financial supports by National Natural
Science Foundation of China (NSFC51302156, 21476264, 21576158 and
21576159) and Distinguished Young Scientist Foundation of Shandong
Province (JQ201215).
Received: April 16, 2016
Revised: July 11, 2016
Published online: August 29, 2016
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