Ultramicroporous Carbon Synthesis Using Lithium-Ion Effect in ZSM-5 Zeolite Template

Article abstract of DOI:10.1021/acs.chemmater.8b03132

Zeolite templating is a versatile synthesis route to produce various types of ordered microporous carbon. However, the synthesis thus so far has been limited to the use of wide-pore zeolites with 12-membered ring (12MR) pore mouths or more because of the diffusion limitation of organic carbon precursors. Here, we report an extension of the carbon synthesis to a 10MR zeolite, through acetylene carbonization in Li⁺-ion-exchanged ZSM-5 zeolite. The promoting effect of the Li⁺ ions on the carbon synthesis could be relevant to the carbide-forming property of the element, similar to the recently reported cases of La³⁺, Y³⁺, and Ca²⁺ cations in 12MR zeolites. The resultant carbon exhibited an ordered array of ultramicropores of 0.5 nm diameter, which corresponded to the thickness of the zeolite framework. Because of the ultramicroporosity, the ZSM-5-templated carbon exhibited an anomalously high value of surface-area-normalized electrical double-layer capacitance.

Full text of DOI:10.1021/acs.chemmater.8b03132

Subscriber access provided by EKU Libraries
Article
Ultramicroporous carbon synthesis using
lithium ion effect in ZSM-5 zeolite template
Taekyoung Lee, Seung Hyeon Ko, Sung June Cho, and Ryong Ryoo
Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.8b03132 • Publication Date (Web): 24 Aug 2018
Downloaded from http://pubs.acs.org on August 27, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 10
Chemistry of Materials
1
2
3
4
5
6
Ultramicroporous carbon synthesis using lithium ion effect in
ZSM-5 zeolite template
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
†
,‡
*,‡
§
*,†,‡
Taekyoung Lee, Seung Hyeon Ko, Sung June Cho and Ryong Ryoo
†
Department of Chemistry, KAIST, Daejeon 34141, Korea
‡
Center for Nanomaterials and Chemical Reactions, Institute for Basic Science, Daejeon 34141, Korea
§
Clean Energy Technology Laboratory and Department of Chemical Engineering, Chonnam National University, Gwangju
6
1186, Korea.
ABSTRACT: Zeolite templating is a versatile synthesis route to produce various types of ordered microporous carbon. However,
the synthesis thus so far has been limited to the use of wideꢀpore zeolites with 12ꢀmembered ring (12MR) pore mouths or more, due
to the diffusion limitation of organic carbon precursors. Here we report an extension of the carbon synthesis to a 10MR zeolite,
+
+
through acetylene carbonization in Li ionꢀexchanged ZSMꢀ5 zeolite. The promoting effect of the Li ions on the carbon synthesis
3+
3+
2+
could be relevant to the carbideꢀforming property of the element, similar to the recently reported cases of La , Y and Ca cations
in 12MR zeolites. The resultant carbon exhibited an ordered array of ultramicropores of 0.5 nm diameter, which corresponded to
the thickness of the zeolite framework. Due to the ultramicroporosity, the ZSMꢀ5ꢀtemplated carbon exhibited an anomalously high
value of surface areaꢀnormalized electrical doubleꢀlayer capacitance.
3
+
1
. Introduction
strategy to solve this problem, Kim et al. incorporated La ,
3+ 2+
Y
or Ca ions into the zeolite template pores through a
Ordered nanoporous carbons with controlled pore diameters
have attracted increasing attention in recent years, due to their
pore sizeꢀspecific effects in catalysis, adsorption, water
and air purification, and electrical energy storage. One of
the most interesting methods for the synthesis of nanoporous
carbons is to use mesoporous silica, such as MCMꢀ48, SBAꢀ
22
simple ion exchange process. These cations promoted the
carbonization of ethylene or acetylene selectively inside the
zeolite pores. Using the catalytic effect of the cations, they
synthesized highly ordered microporous carbons without
carbon deposition at the external surfaces, even when the
amount of zeolite was increased to 200 g with a bed height of
1
ꢀ3
4,5
6,7
8ꢀ10
11ꢀ13
1
5, or KITꢀ6, as a template.
The silica mesopores are wide
23
10 cm. A single crystal Xꢀray diffraction analysis indicated
that the carbon formed threeꢀdimensional grapheneꢀlike
frameworks along the surface of the zeolite pore walls. The
resultant zeoliteꢀtemplated carbons (ZTCs) were composed of
uniform micropores, and had a high specific surface area (~
enough (2 ~ 50 nm) for the infiltration of organic compounds
without diffusion limitations. Pyrolytic carbonization of the
organic compounds can be performed inside the template
pores to produce rigidly interconnected carbon frameworks
through the pores. After the dissolution of the silica template
with HF or NaOH, the resultant carbon exhibits an ordered
mesoporous structure, which corresponds to an inverse replica
of the silica template.
2
ꢀ1
3
000 m g ).
Most zeolites have very narrow pore apertures, composed of
a ring of 8, 10 or 12 –OSi– units. Each aperture is called an 8,
0 or 12 membered ring (MR) pore. Zeolites of 12MR, e.g.,
1
Similar to mesoporous silica, microporous zeolites have
also been used as carbon templates. However, carbon
synthesis using zeolite suffers from diffusion limitations for
organic carbon precursors. Most zeolites have pore apertures
of less than 0.9 nm in diameter, and this often leads to carbon
FAU, beta and EMT, have pore apertures that are 0.7 ~ 0.9 nm
in diameter, and these zeolites are called ‘wideꢀpore’ zeolites.
Thus far, all successful syntheses of ordered microporous
1
7ꢀ21,24
ZTCs have been achieved with the 12MR zeolites.
When
14ꢀ21
1
0MR zeolites were used as templates, the pore apertures were
deposition on the external surfaces of the zeolite particles.
too narrow to form rigid carbon frameworks. Recently, ZSMꢀ5
zeolite with 10MR apertures was tested for ZTC synthesis
The external carbon prevents the diffusion of the carbon
source into the internal pores of the zeolite, resulting in a
failure to replicate the entire pore system faithfully. To prevent
external carbon deposition, the carbon precursor was fed as
highly diluted in an inert gas flow, and the height of the zeolite
bed in the carbon deposition reactor was minimized,
preferably to a few millimetres. Nevertheless, when the carbon
synthesis was scaled up to produce a zeolite bed greater than 1
cm in height, inhomogeneous carbon formation occurred
between the upper and lower parts of the zeolite bed. As a
2+
22
using acetylene as a precursor after Ca ion exchange. The
ZSMꢀ5 zeolite has an MFIꢀtype framework, wherein
sinusoidal channels of 0.55 x 0.51 nm intersect with straight
25,26
channels of 0.56 x 0.53 nm.
The resulting carbon had
ultramicropores of 0.5 nm, corresponding to the thickness of
the pentasil framework. However, the carbon product failed to
exhibit the zeoliteꢀinherited pore order.
ACS Paragon Plus Environment

Chemistry of Materials
In the present work, we revisited the ZSMꢀ5ꢀtemplated
Page 2 of 10
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
carbon synthesis using various carbon sources such as
acetylene, ethylene, propylene, and bulky organic compounds.
In the case of bulky organics, the carbon sources could not
enter the 10 MR pore apertures due to their large molecular
size. On the other hand, ethylene, propylene, and acetylene
had sufficiently small molecular diameters to enter the zeolite
2
.2. TGA analysis of carbon deposition on zeolite
The amount of carbon deposition in ZSMꢀ5 zeolite was
monitored in situ using a thermogravimetric analyzer (TGAꢀ
0, SHIMADZU). The gas flow system of the TGA apparatus
was modified to flow a mixture of N , acetylene, and H O
5
2
2
21,27
vapor at controlled rates. Typically, 8 mg of zeolite was
loaded on a fusedꢀquartz pan. The sample on the pan was
slowly heated to 500 °C under a dry N flow of 30 mL min .
When the temperature reached 500 °C, the N2 flow was
merged with an acetylene gas flow. The combined gas flow
was passed through a water bubbler, and the N /acetylene/H O
ratios = 94/2/4 in vol%. The sample weight was monitored
over time under this condition.
pores.
However, only acetylene gave a significant amount
of carbon deposition in the zeolite micropores. Ethylene and
propylene gave very little amounts of carbon deposition at all
tested temperatures up to 650 °C. This indicated that the ZSMꢀ
ꢀ1
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
zeolite pores were highly resistant to coke (or carbonaceous)
28,29
2 2
depositions,
and that only the acetylene gas with a low H/C
ratio was suitable for the ZTC synthesis.
2
+
We conjectured that ZTC synthesis using acetylene in Ca
ionꢀexchanged ZSMꢀ5 zeolite might be improved if the Ca
2
+
2
.3. Carbon synthesis
ion (0.23 nm in diameter) is replaced by a smaller catalytic
+
cation. We thereupon tested H ionꢀexchanged ZSMꢀ5, but the
Carbon was synthesized using acetylene as a carbon source
and LiZSMꢀ5 (or CaZSMꢀ5) as a template. In a typical
synthesis, 0.2 g of LiZSMꢀ5 was loaded in a vertical plugꢀflow
fusedꢀquartz reactor, which was equipped with a fritted quartz
disk. The reactor temperature was increased to 500 °C and
maintained there for a given time under a N ꢀacetyleneꢀH O
mixed gas flow of 94/2/4 vol% composition, as in the TGA
experiment, except that the total flow rate was 50 mL min .
The gas flow was then switched to dry N . Subsequently, the
reactor temperature was increased to 900 °C and maintained
there for 2 h before cooling to room temperature. The resultant
carbon/zeolite composite was slurried in a 0.3ꢁM HF/0.15ꢁM
HCl solution to release the carbon product from the template.
The carbon was filtered, washed with distilled water, and dried
in an oven at 100 °C.
+
result was poor. As a second attempt, we chose Li ion (0.18
+
nm in diameter), considering the high chemical affinity of Li
ions with carbon to form graphite intercalation compounds,
3
0,31
acetylides, and carbides.
With this assumption, we
+
investigated the Li effect on ZSMꢀ5ꢀbased ZTC synthesis via
a thermogravimetric analysis (TGA). The synthesized carbon
product was characterized using transmission electron
microscopy (TEM), scanning electron microscopy (SEM), Ar
gas adsorption, powder Xꢀray diffraction (XRD) analysis, and
electrical doubleꢀlayer capacitance (EDLC) measurements. In
particular, the EDLC characteristics were investigated to
assess the recently reported effect of ultramicroporosity on
2
2
ꢀ1
2
3
2
anomalously increasing the capacitance.
2. Experimental section
2.4. Characterization
2
.1. Preparation of zeolite template.
+
Elemental analysis for Si, Al, and Li in zeolite was performed
by ICPꢀAES, using a Perkin Elmer OPTIMA 4300 DV
instrument. Powder XRD data except for Rietveld analysis
were collected on a Rigaku Multiplex instrument, using Cu Kα
radiation (30 kV, 40 mA). SEM images were taken with a FEI
Verios 460 instrument at a landing voltage of 1 kV in a
deceleration mode (stage bias voltage = 4 kV). TEM images
were collected with an aberrationꢀcorrected FEI Titan EꢀTEM
G2 instrument, operating at a 300 kV acceleration voltage.
Two ZSMꢀ5 zeolite samples were used after Li ion exchange.
The first zeolite was purchased from Zeolyst (CBV 2314,
+
NH4 ionic form). The zeolite exhibited irregular particle
morphologies over 100ꢀ300 nm in diameter. The Si/Al molar
ratio of the zeolite was 11, which was determined by
inductively coupled plasma atomic emission spectroscopy
(
ICPꢀAES). This zeolite sample was used in all synthesis and
characterization studies, except for the synchrotron powder
XRD analysis and carbonꢀparticle contraction analysis. The
second zeolite sample was synthesized with wellꢀdefine
crystal morphologies with Si/Al = 11, following the procedure
Ar adsorptionꢀdesorption isotherms were measured at liquid
argon temperature (87 K) with a Quantachrome AutosorbꢀiQ
instrument. Prior to the adsorption measurement, all samples
were outgassed for 6 h at 250 °C. The specific surface area
33
in the literature. This sample with high crystallinity was used
for the synchrotron XRD measurement, and for investigation
of carbon particle contraction upon template dissolution.
was calculated from the adsorption branch in a range of P/P =
0
+
0
.05 ꢀ 0.20, using the BrunauerꢀEmmettꢀTeller (BET) equation.
For Li ion exchange, 1 g of zeolite was added to a 32 mL
The pore volume and pore size distribution were calculated
based on the nonlocal density functional theory (NLDFT) with
the assumption of a slitꢀshaped pore geometry. The microporeꢀ
and ultramicropore volumes were determined from the DFT
cumulative volume in a pore diameter range of d < 2 nm and d
aqueous solution of 0.5 M LiCl. The solution with the zeolite
was stirred for 3 h at 60 °C and then filtered. This treatment
was repeated three times in total, in order to increase the ionꢀ
exchange level. Subsequently, the zeolite was washed with
distilled water, dried at 100°C, and calcined at 550 °C in air.
The Li/Al molar ratio of the resultant zeolite was 0.8. The Li
ionꢀexchanged zeolite was designated as LiZSMꢀ5. Calcium
ion exchange was conducted with a 0.5 M CaCl aqueous
solution instead of LiCl. The Ca/Al molar ratio of the resultant
CaZSMꢀ5 zeolite was 0.4. Both the Zeolyst zeolite and the
laboratoryꢀsynthesized sample gave the same ion exchange
levels.
+
<
0.7 nm, respectively. The total pore volume was determined
at P/P = 0.95.
0
13
2
The C solidꢀstate NMR spectrum was acquired with a
magic angle spinning (MAS) rate of 12 kHz using a Bruker
Digital Avance HD 400WB spectrometer (9.4 T) at room
13
temperature. The observed frequency for C was 100.613
ACS Paragon Plus Environment

Page 3 of 10
Chemistry of Materials
13
MHz. The C MAS NMR spectrum was recorded with a π/2
pulse width of 3.8 ꢀs and a relaxation delay of 2 s.
time while the zeolite was heated under a mixed gas flow of
, acetylene, and H O (94/2/4 in volume ratio) at 500 °C. As
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
N
2
2
+
the TGA profiles show, the H ionꢀexchanged form of ZSMꢀ5
zeolite (HZSMꢀ5) exhibited a sharp increase in carbonaceous
content until the deposition time reached 20 min. Afterwards,
the rate of carbonaceous deposition suddenly slowed down.
The initial sharp increase could be assigned to carbonaceous
deposition in the internal zeolite micropores, while the later
slow increase could be interpreted as external deposition
outside the zeolite particles. In fact, both the external and
internal deposition should simultaneously occur from the
beginning of the deposition process. For this reason, it was
difficult to distinguish them accurately in a quantitative
manner based on the TGA profile. As roughly judged by the
TGA curvature changes, the internal deposition appeared to
2
.5. Synchrotron powder XRD and data analysis
Synchrotron powder XRD data of the zeolite/carbon
composite were collected at a wavelength of 1.5178 Å over a
range of 2
Accelerator Laboratory. Powder XRD patterns of the
composite were indexed using the DICVOL program
θ = 5° ꢀ 125°, on Beamline 9B of the Pohang
34,35
implemented in the FULLPROF program suite.
The initial
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
zeolite framework of the zeolite/carbon composite was
obtained from the database of the International Zeolite
Association. The profile function and background parameters
were obtained from the Le Bail refinement. Rietveld
refinement was performed using the JANA2006 program
ꢀ
1
rapidly saturate at around 0.10 g g zeolite. The rapid
deposition in the HZSMꢀ5 micropores seemed to be due to the
36
suite. The detailed refinement process is the same as in a
22
+
37
previous work. In the refinement, the Li ion distribution was
ignored because its Xꢀray scattering crossꢀsection is very small.
The final Rietveld refinement was obtained with a high fitting
quality (R = 3.71%, R = 4.72%; Figure S1 and Table S1).
The details of the refinement data are summarized in Table S1.
A final electronꢀdensity map corresponding to the carbon
structure was obtained using the difference Fourier method
again, after removing all carbon atoms obtained from structure
refinement with constraints. The resultant map was equivalent
to the difference between the total electronꢀdensity map and an
electronꢀdensity map that corresponds to the zeolite
framework.
acidꢀcatalyzed polymerization of acetylene.
p
wp
2.5. EDLC measurements
Specific capacitance was measured with a twoꢀelectrode
cell configuration in an aqueous solution of 6 M KOH. For
preparation of the electrodes, a mixture of carbon sample (80
wt%), polyvinylidene fluoride binder (10 wt%), and carbon
black (10 wt%) was dispersed in an Nꢀmethylꢀ2ꢀpyrrolidone
Figure 1. Quantities of carbonaceous deposition onto ZSMꢀ5
zeolite with exchanged cations are plotted as a function of
time under a N ꢀacetyleneꢀH O mixed gas flow at 500 °C.
2
2
Elemental symbols indicate cations that were exchanged into
the zeolite.
(NMP) solution. After stirring for an hour, the resulting slurry
was cast onto a nickel foam, and dried at 343 K for 12 h to
remove NMP. Subsequently, the Ni foam containing the
carbon sample was pressed under 20 MPa to form a sheet. The
sample sheet was cut into a circular electrode with a diameter
of 12 mm, using a punching machine. The electrode was
thoroughly dried in a vacuum oven at 383 K.
Compared to the HZSMꢀ5 zeolite, the other cationꢀ
exchanged zeolites exhibited slow rates of carbon deposition
in the internal micropores. Nevertheless, the total amounts of
internal deposition upon saturation were noticeably higher
than that of HZSMꢀ5. In particular, the carbonaceous
deposition in NaZSMꢀ5 occurred very slowly. This result
Two electrodes were packed with a separator, as an
assembly. The assembled cell was soaked in an aqueous
solution of 6 M KOH for 12 h to allow the electrolyte to fully
penetrate the pores of the carbon materials.
+
indicates that there were weak interactions between Na and
22
acetylene. When the carbonaceous deposition was slow in
the internal pores, it was difficult to deꢀconvolute the TGA
profile to extract the saturation value of the internal pore
deposition. On the other hand, the TGA profiles of LiZSMꢀ5
and CaZSMꢀ5 exhibited moderately fast deposition. Based on
the TGA profile curvatures, the quantity of carbonaceous
deposits upon saturation for CaZSMꢀ5 was estimated to be
Galvanostatic charge/discharge measurements were carried
out in a voltage range of 0 ~ 0.9 V using a WBCS3000 battery
cycler (WonaTech). The specific capacitance was calculated
according to the equation C = 2 х I х ꢂt / ꢂV х m, where I is
the constant discharging current, ꢂt is the discharging time,
ꢂV is the voltage charge, and m is the mass of active material
on one electrode.
ꢀ
1
approximately 0.13 g g zeolite. This value was based on the
mass of aluminosilicate framework only, excluding the mass
of the metal cations. The saturation quantity for LiZSMꢀ5
ꢀ
1
obtained in this manner was 0.15 g g zeolite, which was 20%
+
more than that of CaZSMꢀ5, indicating that the Li ions
3. Results and discussion
promoted acetylene carbonization in the zeolite micropores
+
3
.1. Effect of Li ion on carbonaceous deposition
2+
more effectively than Ca . Both the LiZSMꢀ5 and CaZSMꢀ5
+
+
2+
+
Figure 1 shows the TGA profiles for H , Li , Ca , and Na
zeolites have very weak acidity. The deposition process by
these metal ions appeared to be slower than the acidꢀcatalyzed
polymerization in HZSMꢀ5. In this regard, their promotion
effects for carbonaceous deposition could be mainly attributed
cationꢀexchanged ZSMꢀ5 zeolites during the carbon deposition
process using acetylene. The TGA profiles were obtained by
monitoring the weight changes in the zeolite as a function of
ACS Paragon Plus Environment

Chemistry of Materials
Page 4 of 10
to interactions between the metal ions and acetylene, such as were further heated for 2 h at 900 °C to complete the
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
the formation of acetylides.
carbonization. Subsequently, the zeolite framework was
removed by dissolution in a solution of HF/HCl, and thus the
residual silica and alumina content could be neglected. Figure
In fact, the carbonaceous deposition in HZSMꢀ5 could
occur at remarkably low temperatures compared with other
cationꢀexchanged ZSMꢀ5. When the TGA profile was
measured with increasing temperature under constant flow rate
and gas composition, the HZSMꢀ5 exhibited a sharp increase
for carbonaceous deposition even at 300 °C (Figure S2). In
the case of CaZSMꢀ5 and LiZSMꢀ5 zeolites, the carbonaceous
deposition from acetylene began to occur at 400 °C. The
deposition at low temperature by HZSMꢀ5 was in good
agreement with the acidꢀcatalyzed polymerization of acetylene
to linear polymers, which is well known with ZSMꢀ5 zeolite
containing strong Brønsted acid sites. The linear polymers
would not easily fill the zigꢀzag channels in the zeolite. This
could be the reason why the deposition quantity was smaller in
the HZSMꢀ5 zeolite. In comparison, the carbonaceous
deposition in CaZSMꢀ5 and LiZSMꢀ5 appeared to require
higher temperatures, similar to the formation of polycyclic
2
shows representative SEM images of the Zeolyst ZSMꢀ5
zeolite, and the carbon products synthesized with various
cationꢀexchanged ZSMꢀ5. As shown in Figure 2a, the starting
zeolite exhibited polycrystalline morphologies, which were
somewhat difficult to define precisely. Roughly, the individual
particles had 300ꢀnm long cylindrical shapes with irregularly
polygonal crossꢀsections. Compared to the zeolite template,
the carbon product from NaZSMꢀ5 exhibited shrivelled
balloonꢀlike morphologies (Figure 2b). This result indicates
that the carbonaceous deposition occurred mainly at the
external surfaces, leaving the internal pores almost empty in
this zeolite. The external carbon layers must have collapsed to
the shrivelled structure when the zeolite template was
dissolved out. In the case of the carbon from HZSMꢀ5, the
shrivelling occurred to a lesser extent. However, the carbon
product completely lost the edged cylinderꢀlike morphology of
the mother zeolite. On the other hand, in the cases of CaZSMꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
7
2
+
27
aromatic hydrocarbons in Ca ionꢀexchanged LTA zeolites.
We suggest that the 20% higher carbonaceous deposition in
LiZSMꢀ5 compared to the deposition in CaZSMꢀ5 could be
due to the smaller ionic diameter of Li (Li 0.18 nm vs. Ca
5
and LiZSMꢀ5, the carbon products could inherit the original
+
+
2+
zeolite morphologies to a much better extent. Still, the carbon
product underwent conspicuous shrinkage in the directions
perpendicular to the long axis of individual particles.
0
0
.23 nm) in the 10MR channels. The10MR channels (0.55 x
.51 nm, and 0.56 x 0.53 nm) are extremely narrow for
carbonaceous deposition, and only a slight further decrease of
the channel diameter by a cation could result in serious
blocking of the access of acetylene (kinetic diameter = 0.33
3.2. Ultramicropores in zeolite-templated carbon
+
nm). Under this circumstance, the small Li ion could have a
significant advantage for carbonaceous deposition. However,
this explanation should be limited to the case of 10MR zeolite.
If the zeolite pores were sufficiently wide, as in 12MR zeolites,
the presence of cations in the zeolite channels would not
seriously cause any additional diffusion barriers.
Figure 3. NLDFT pore size distribution of (a) LiZSMꢀ5ꢀ
templated carbon and (b) CaZSMꢀ5ꢀtemplated carbon. The insets
show the corresponding Ar adsorptionꢀdesorption isotherm for
each carbon.
Pore diameters of the LiZSMꢀ5 and CaZSMꢀ5 zeoliteꢀ
templated carbons were analyzed by Ar adsorptionꢀdesorption
measurements (Figure 3). Both carbon products gave Type II
adsorption isotherms exhibiting a sharp increase of the
Figure 2. SEM images of (a) ZSMꢀ5 zeolite and (b)ꢀ(e) carbon
products from different cationꢀexchanged ZSMꢀ5 zeolites.
adsorption quantity in the lowꢀpressure range of P/P < 0.02.
0
The lowꢀpressure jump could be assigned to sudden filling of
argon in the carbon micropores. As the pressure was increased
As mentioned above, the total flow rate of N ꢀacetyleneꢀ
2
to P/P = 0.9, the adsorption quantity increased gradually. This
0
ꢀ
1
H O for TGA was 30 mL min with 8 mg of zeolite. Because
2
result indicated low mesoporosity with a wide poreꢀsize
distribution. The NLDFT analysis of the pore diameters gave
the distribution curves shown in Figure 3. These curves
showed a very sharp ultramicropore peak centered at 0.5 nm, a
mediumꢀintensity micropore peak at 1.2 nm, and a lowꢀ
intensity mesopore peak at 2.6 nm. There was also a broad
the gas flow rate was excessively high, it was adjusted to 50
ꢀ
1
mL min to synthesize carbon using 0.2 g of commercially
available ZSMꢀ5 zeolite obtained from Zeolyst. For sufficient
carbon deposition, the deposition time was also adjusted to 3 h
for HZSMꢀ5, 12 h for NaZSMꢀ5, 7 h for CaZSMꢀ5, and 8 h
for LiZSMꢀ5. The resultant carbon/zeolite composite samples
ACS Paragon Plus Environment

Page 5 of 10
Chemistry of Materials
shoulder in the mesopore range of 3 ~ 6 nm, but the intensity
was not comparable to the three main peaks.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Among the three kinds of pores, the ultramicroporous 0.5ꢀ
nm diameter was very close to the thickness of a pentasil layer
2
2
in the ZSMꢀ5 zeolite framework (Figure S3). Accordingly,
the ultramicropores could be interpreted to be a result of
faithful templation of the carbon pores by the pentasil
frameworks. On the other hand, the larger pores could be
attributed to incomplete carbon filling inside the 10MR
micropores. That is, in the narrow 10MR zeolite, a significant
fraction of the pores could remain empty. The empty pores
could be merged from one or more adjacent carbon pores
when the zeolite framework was dissolved. In particular, the
pores of 1.2ꢀnm diameter could originate from the merging
effect of one empty pore. Similarly, larger pores in the range
of 2 ~ 5 nm could be formed by coalescence of multiple pores.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
+
The analysis of the adsorption isotherms revealed that Li ion
exchange could improve the ultramicroporous textural
Figure 5. HRSEM images of (a) LiZSMꢀ5 zeolite and (b) LiZSMꢀ
5ꢀtemplated carbon. Schematic illustrations of (c) ZSMꢀ5 zeolite
and (d) anisotropic contraction of carbon particle after removal of
the zeolite template, depending on the axis.
2+
properties of the resultant carbon, as compared to the Ca
exchange (Figure 3, Table 1, and Table S2). The BET
2
ꢀ1
surface area of the LiZSMꢀ5ꢀtemplated carbon (710 m g )
2
ꢀ1
was remarkably larger than that from CaZSMꢀ5 (600 m g ).
3
ꢀ1
Moreover, the micropore volume (0.28 cm g ) of the LiZSMꢀ
ꢀtemplated carbon was higher than the carbon from CaZSMꢀ5
In the previous sections, the Zeolyst ZSMꢀ5 zeolite was used
as a template for carbon, due to the advantage of facile
diffusion of acetylene in the small zeolite particles. However,
the irregular agglomeration of tiny particles obscured the
detailed morphological changes occurring in the carbonization
process (SEM images in Figure 2). In this section, we
investigate the SEM images more precisely using a laboratoryꢀ
synthesized ZSMꢀ5 zeolite with a wellꢀdefined hexagonal
plateꢀlike morphology.
5
3
ꢀ1
(0.22 cm g ).
As shown in Figure 5, the ZSMꢀ5 hexagonal plates were
approximately 400 ꢀ 700 nm in diameter and about 150 nm in+
thickness. When this zeolite was used as a template after Li
ion exchange, the resultant carbon exhibited similar porous
properties to the result from the commercial ZSMꢀ5 zeolite
Figure 4. TEM images of (a) LiZSMꢀ5ꢀtemplated carbon, and (b)
CaZSMꢀ5ꢀtemplated carbon.
(Figure S6). The crossꢀsectional SEM image of the carbon
showed that the carbon was not a hollow particle, indicating
that the carbon was deposited inside the zeolite pores, not near
the external surface (Figure S7). More importantly, the SEM
images of the carbon showed that the carbon particles
underwent anisotropic contraction, compared to the wellꢀ
defined hexagonal ZSMꢀ5 crystals. The contraction was more
severe along the cꢀaxis than the aꢀ and bꢀaxes, which were
parallel to the ZSMꢀ5 sinusoidal and straight channels,
respectively (Figures 5c and 5d). This indicated that the
connectivity of the carbon framework along the cꢀaxis was not
rigid enough to retain the pore structures.
The TEM image of the LiZSMꢀ5ꢀtemplated carbon in
Figure 4 shows lattice fringes with a d value of ~1.0 nm. The
lattice spacing is consistent with an ordered array of carbon
frameworks possessing the aforementioned 0.5ꢀnm
ultramicropores. The structural order was limited to a short
range, but the order was corroborated by a lowꢀintensity peak
at 2θ = 8.2° (d = 1.0 nm) in the powder XRD pattern (Figure
S4). Hence, we believe that the carbon pore order could be
inherited from the ordering of the (101) plane of the zeolite
template. However, in the shortꢀrange order, each domain of
the regular 0.5ꢀnm micropores would be connected to the
neighboring disordered regions of larger pores that were
formed by the collapse of two or more layers of the carbon
framework. A broad XRD peak over 20 ~ 30° (Figure S4)
supported the presence of the disordered regions. This broad
XRD peak is often observed with amorphous carbons
To further investigate the framework connectivity, a powder
XRD analysis by Rietveld refinement was performed after
acetylene carbonization in LiZSMꢀ5 zeolite at 500°C. In
particular, we obtained an electron density map for the carbon
atoms using the difference Fourier method (see Experimental
Section for details). The electron density in Figure 6 shows
that the carbon atoms formed a rodꢀlike shape inside the
narrow 10MR channels in the ZSMꢀ5 zeolite. This was
markedly different from the hollow nanotubeꢀlike shape of
2
3
containing sp and sp bonds together. In the present LiZSMꢀ
2
5
ꢀtemplated carbon, however, only sp bonding was detected
13
in the C solidꢀstate MAS NMR spectrum (Figure S5).
carbon that was formed in the case of carbon synthesis using
22
1
2MR FAU zeolites. It is reasonable that the ZSMꢀ5 zeolite
channels would be too narrow to build a nanotubeꢀlike hollow
carbon structure. The electron density map shows that the rodꢀ
like carbon frameworks were rigidly built inside the straight
3
.3. Carbon framework analysis by powder XRD
ACS Paragon Plus Environment

Chemistry of Materials
Page 6 of 10
channels along the bꢀaxis of the ZSMꢀ5 zeolite. However, in Microporous carbons with a high specific surface area are
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
the sinusoidal channels running perpendicular to the bꢀaxis
(i.e., in the ac plane), the carbon frameworks had many empty
defects. The channel tortuosity in the sinusoidal channels
appeared to hinder continuous growth of the carbon
currently used as an electrode material in the fabrication of
supercapacitors, which store and discharge electric energies at
high speeds. The supercapacitors are based on the EDLC
phenomena involving ionic attractions to the carbon electrode
surfaces when immersed in an electrolyte solution under an
applied voltage. The carbon electrodes often incorporate a
transition metal oxide that possesses multiple oxidation states.
This increased the total energy storage capacity by the faradaic
28,29
framework,
causing the formation of defects. Due to the
defects, the carbon framework could undergo conspicuous
contraction when the zeolite template was dissolved. More
contraction could occur in the cꢀdirection among aꢀ and cꢀaxes
as the zeolite channels were connected more tortuously in this
direction. This may explain why the carbon morphologies in
Figure 5 show noticeable anisotropic shrinkage in the cꢀ
direction.
38
pseudoꢀcapacitance of the metal oxide. However, the main
function of supercapacitors is based on the EDLC
phenomenon taking place on the surface of the microporous
carbon. The EDLC capacitance of the carbon is affected by
various experimental parameters, such as the specific surface
area, electrolyte species and concentration, solvent, and
discharge current density. As shown in Figure 7, the
capacitance value decreases as the current density is increased.
This is due to an increase in the electric resistance under high
current densities. Carbons with similar surface properties are
expected to exhibit capacitance values that are approximately
proportional to their specific surface areas, if all measurements
are performed under the same conditions except for the current
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
39,40
density.
However, according to a recent work by Gogotsi
3
2
et al. ultramicroporous carbons exhibited an anomalously
high EDLC capacitance value when compared to microporous
carbons with the same specific surface area. The high EDLC
capacitance of the ultramicroporous carbon was attributed to
increasing concentration of the electrolyte ions when the pores
were too small to form electrical double layers and solvation
shells. Since the work of Gogotsi et al., the EDLC of
ultramicroporous carbons has been a hot topic that is also still
somewhat under debate. In this light, we analyzed the EDLC
capacitance of the LiZSMꢀ5ꢀtemplated ultramicroporous
carbon (LiZSMꢀ5ꢀC), in comparison with those of a beta
zeoliteꢀtemplated microporous carbon (βꢀZTC) and an
activated carbon (AC) sample. The results are presented in
Figure 7.
Figure 6. Electron density map of ZSMꢀ5 zeolite after
carbonization of acetylene. Electron density map of the carbon
framework (cyan) is visualized from different viewpoints: along
the (a) [010] and (b) [100] axis. Yellow lines represent the ZSMꢀ5
zeolite framework. The isoꢀsurface level of the electron density is
set to 0.37 electrons Å . Blue areas represent crossꢀsectional cuts.
Red arrows represent disconnected parts of the carbon framework.
Compared to the left panel, the right panel shows the
corresponding electron density maps without the zeolite
framework.
ꢀ
3
The βꢀZTC sample in Figure 7 was synthesized as reported
22
in the literature. This carbon exhibited a narrow distribution
of pore diameters with a peak at 0.95 nm. The specific BET
2
ꢀ1
surface area was 2950 m g (Figure S8). On the other hand,
the AC sample was purchased from SigmaꢀAldrich, and it
exhibited a broad distribution of micropore diameters over 1 ~
3
.4. Anomalously high EDLC capacitance
2
3
nm. The specific surface area of the AC sample was 1520 m
−1
g . As shown in Figure 7a, the βꢀZTC and AC samples
provided EDLC values that were roughly proportional (or
corresponding) to their specific surface areas. Hence, the
EDLC values of the microporous carbons became very similar
when divided by the BET areas (Figure 7b). However, in the
case of the ZSMꢀ5 zeoliteꢀtemplated carbon, the surfaceꢀ
normalized EDLC value was 2.5 ~ 3 times higher than those
of βꢀZTC and AC. This result is in good agreement with a
32
previous report by Gogotsi et al. The abnormal increase in
capacitance in the case of the LiZSMꢀ5ꢀC sample can be
attributed to the ultramicropores, which are too narrow to
allow full solvation of ions. It appears that in the narrow pores
each ion can only exist with a partially solvated and distorted
shell. Under this situation, it is likely that an electrical double
layer would be difficult to form, and that the capacitance
would increase dramatically. We measured the adsorption
Figure 7. (a) Specific capacitance and (b) specific capacitance
normalized by BET surface area of various carbons, as a function
of discharge current density in an aqueous solution of 6M KOH.
capacities of the LiZSMꢀ5ꢀC, βꢀZTC, and AC samples for CO
and methane. The measured values of the adsorption
capacities were proportional to the BET surface areas of the
2
ACS Paragon Plus Environment

Page 7 of 10
Chemistry of Materials
carbon samples, regardless of the presence of ultramicropores
or micropores (Figure S9). This result confirmed that only the
EDLC capacitance anomalously increases in the case of the
(4) Morris, R. E.; Wheatley, P. S. Gas Storage in Nanoporous
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Materials. Angew. Chem., Int. Ed. 2008, 47, 4966ꢀ4981.
(
5) Xia, Y.; Mokaya, R.; Walker, G. S.; Zhu, Y. Superior CO
2
Adsorption Capacity on Nꢀdoped, HighꢀSurfaceꢀArea,
Microporous Carbons Templated from Zeolite. Adv. Energy
Mater. 2011, 1, 678ꢀ683
ultramicroporous carbon, unlike the gas adsorption of CO and
2
methane.
(6) Mayes, R. T.; Tsouris, C.; Kiggans, J. O.; Mahurin, S. M.;
DePaoli, D. W.; Dai, S. Hierarchical Ordered Mesoporous
Carbon from PhloroglucinolꢀGlyoxal and Its Application in
Capacitive Deionization of Brackish Water. J. Mater. Chem.
2010, 20, 8674ꢀ8678.
(7) Zou, L.; Li, L.; Song, H.; Morris, G. Using Mesoporous
Carbon Electrodes for Brackish Water Desalination. Water
Res. 2008, 42, 2340ꢀ2348.
4
. Summary
ZSMꢀ5 zeoliteꢀtemplated carbon synthesis has remained a
challenge, due to the diffusion limitations in the extremely
narrow 10MR pores. Regarding this issue, we discovered that
Li ion exchange into ZSMꢀ5 is an effective means to promote
acetylene carbonization in the zeolite pores. The use of Li
ions improved the connectivity and microporosity of the
resultant carbon product by enabling a 20% greater amount of
carbon deposition, compared to the previously reported Ca
ionꢀexchanged ZSMꢀ5. The synthesis using LiZSMꢀ5 zeolite
successfully produced an ordered array of 0.5ꢀnm
ultramicroporous carbon. We expect that the Li ion effect
would be useful for the synthesis of ultramicroporous carbons
using narrowꢀpore zeolites. Furthermore, we confirmed that
the ZSMꢀ5 zeoliteꢀtemplated carbon exhibited an anomalously
high EDLC capacitance due to the presence of the
ultramicropores.
+
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
+
(
(
8) VixꢀGuterl, C.; Frackowiak, E.; Jurewicz, K.; Friebe, M.;
Parmentier, J.; Béguin, F. Electrochemical Energy Storage in
Ordered Porous Carbon Materials. Carbon 2005, 43, 1293ꢀ
1302.
9) Zhang, L. L.; Zhao, X. S. Carbonꢀbased Materials as
Supercapacitor Electrodes. Chem. Soc. Rev. 2009, 38, 2520ꢀ
2531.
2
+
+
(10) Itoi, H.; Nishihara, H. Kogure, T.; Kyotani, T. Threeꢀ
Dimensionally Arrayed and Mutually Connected 1.2ꢀnm
Nanopores for HighꢀPerformance Electric Double Layer
Capacitor. J. Am. Chem. Soc. 2011, 133, 1165ꢀ1167.
(
11) Ryoo, R.; Joo, S. H.; Jun, S. Synthesis of Highly Ordered
Carbon Molecular Sieves via TemplateꢀMediated Structural
Transformation. J. Phys. Chem. B. 1999, 103, 7743ꢀ7746.
(12) Jun, S.; Joo, S. H.; Ryoo, R.; Kruk, M.; Jaroniec, M.; Liu, Z.;
Ohsuna, T.; Terasaki, O. Synthesis of New, Nanoporous
Carbon with Hexagonally Ordered Mesostructure. J. Am.
Chem. Soc. 2000, 122, 10712ꢀ10713.
ASSOCIATED CONTENT
Supporting Information.
The Supporting Information is available free of charge on the
ACS Publications websites at DOI : xx.
(
13) Kim, T.; Kleitz, F.; Paul, B.; Ryoo, R. MCMꢀ48ꢀlike Large
Mesoporous Silicas with Tailored Pore Structure: Facile
Synthesis Domain in a Ternary Triblock CopolymerꢀButanolꢀ
Water System. J. Am. Chem. Soc. 2005, 127, 7601ꢀ7610.
Crystallographic data (CIF)
Analysis results of the prepared samples (Rietveld
refinement fits, refinement parameters, TGA, pore size
analysis, XRD, C solidꢀstate MAS NMR, Ar sorption,
SEM); Ar sorption and CO and CH gas adsorption
isotherms of beta zeoliteꢀtemplated microporous carbon
and activated carbon (PDF)
(14) Kyotani, T.; Nagai, T.; Inoue, S.; Tomita, A. Formation of
New Type of Porous Carbon by Carbonization in Zeolite
Nanochannels. Chem. Mater. 1997, 9, 609ꢀ615.
(15) RodriguezꢀMirasol, J.; Cordero, T.; Radovic, L. R.;
Rodriguez J. J. Structural and Textural Properties of Pyrolytic
Carbon Formed within a Microporous Zeolite Template.
Chem. Mater. 1998, 10, 550ꢀ558.
(16) Johnson, S. A.; Brigham, E. S.; Ollivier, P. J.; Mallouk, T. E.
Effect of Micropore Topology on the Structure and Properties
of Zeolite Polymer Replicas. Chem. Mater. 1997, 9, 2448ꢀ
1
3
2
4
AUTHOR INFORMATION
Corresponding Authors
*sarahko@ibs.re.kr and shsarahko@gmail.com
*rryoo@kaist.ac.kr
2
458.
(
(
17) Ma, Z.; Kyotani, T.; Tomita, A. Preparation of a High Surface
Area Microporous Carbon having the Structural Regularity of
Y Zeolite. Chem. Comm. 2000, 2365ꢀ2366.
18) Ma, Z.; Kyotani, T.; Tomita, A. Synthesis Methods for
Preparing Microporous Carbons with a Structural Regularity
of Zeolite Y. Carbon 2002, 40, 2367ꢀ2374.
ORCID
Seung Hyeon Ko: 0000ꢀ0003ꢀ2875ꢀ1095
Ryong Ryoo: 0000ꢀ0003ꢀ0047ꢀ3329
Notes
(19) Yang, Z.; Xia, Y.; Mokaya, R. Hollow Shells of High Surface
Area Graphitic Nꢀdoped Carbon Composites Nanocast using
Zeolite Templates. Micropor. Mesopor. Mat. 2005, 86, 69ꢀ80.
(20) Gaslain, F. O. M.; Parmentier, J.; Valtchev, V. P.; Patarin, J.
First Zeolite Carbon Replica with a Well Resolved Xꢀray
Diffraction Pattern. Chem. Comm. 2006, 991ꢀ993.
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by IBSꢀR004.
(
21) Hou, P.; Yamazaki, T.; Orikasa, H.; Kyotani, T. An Easy
Method for the Synthesis of Ordered Microporous Carbons by
the Template Technique. Carbon 2005, 43, 2618ꢀ2641.
REFERENCES
(
1) Antolini, E. Carbon Supports for LowꢀTemperature Fuel Cell
Catalysts. Appl. Catal. B: Environ. 2009, 88, 1ꢀ24.
(22) Kim, K.; Lee, T.; Kwon, Y.; Seo, Y.; Song, J.; Park, J. K.;
Lee, H.; Park. J. Y.; Ihee, H.; Cho, S. J.; Ryoo, R.
LanthanumꢀCatalyzed Synthesis of Microporous 3D
Grapheneꢀlike Carbons in a Zeolite Template. Nature 2016,
535, 131ꢀ135.
(23) Kim, K.; Kwon, Y.; Lee, T.; Cho, S. J.; Ryoo, R. Facile
LargeꢀScale Synthesis of ThreeꢀDimensional Grapheneꢀlike
Ordered Microporous Carbon via Ethylene Carbonization in
CaX Zeolite Template. Carbon 2017, 118, 517ꢀ523.
(
2) Chai, G. S.; Yoon, S. B.; Yu, J.; Choi, J.; Sung, Y. Ordered
Porous Carbons with Tunable Pore Sizes as Catalyst Supports
in Direct Methanol Fuel Cell. J. Phys. Chem. B. 2004, 108,
7
074ꢀ7079.
(
3) Yu, J.; Kang, S.; Yoon, S. B.; Chai, G. Fabrication of Ordered
Uniform Porous Carbon Networks and Their Application to a
Catalyst Supporter. J. Am. Chem. Soc. 2002, 124, 9382ꢀ9383.
ACS Paragon Plus Environment

Chemistry of Materials
Page 8 of 10
(
(
24) Moon, G.; Bähr, A.; Tüysüz, H. Structural Engineering of 3D
Pore Sizes Less Than 1 Nanometer. Science 2006, 313, 1760ꢀ
1763.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Carbon Materials from Transition Metal IonꢀExchanged Y
Zeolite Templates. Chem. Mater. 2018, 30, 3779ꢀ3788.
25) Olson, D. H.; Kokotailo, G. T.; Lawton, S. L.; Meier, W. M.
Crystal Structure and StructureꢀRelated Properties of ZSMꢀ5.
J. Phys. Chem. 1981, 85, 2238ꢀ2243.
(33) Ren, N.; Yang, Z.; Lv, X.; Shi, J.; Zhang, Y.; Tang, Y. A
Seed Surface Crystallization Approach for Rapid Synthesis of
Submicron ZSMꢀ5 Zeolite with Controllable Crystal Size and
Morphology. Micropor. Mesopor. Mat. 2010, 131, 103ꢀ114.
(34) Louër, D.; Boultif, A. Indexing with the Successive
Dichotomy Method, DICVOL04. Z. Kristallogr. Suppl. 2006,
23, 225ꢀ230.
(35) Frontera, C.; RodríguezꢀCarvajal, J. FULLPROF as a New
Tool for Flipping Ratio Analysis. Physica B. 2003, 335, 219ꢀ
222.
(36) Petříček, V.; Dušek, M.; Palatinus, L. Crystallographic
Computing System JANA2006: General Features. Z.
Kristallogr. 2014, 229, 345–352.
(37) Pereira, C.; Kokotailo, G. T.; Gorte, R. J. Acetylene
Polymerization in a HꢀZSMꢀ5 Zeolite. J. Phys. Chem. 1991,
95, 705ꢀ709.
(26) Kokotailo, G. T.; Lawton, S. L.; Olson, D. H.; Meier, W. M.
Structure of Synthetic Zeolite ZSMꢀ5. Nature 1978, 272, 437ꢀ
4
38.
(
(
27) Ko, S. H.; Lee, T.; Park, H.; Ahn, D.; Kim, K.; Kwon, Y.;
Cho, S. J.; Ryoo, R. NanocageꢀConfined Synthesis of
Fluorescent Polycyclic Aromatic Hydrocarbons in Zeolite. J.
Am. Chem. Soc. 2018, 140, 7101ꢀ7107.
28) Dejaifve, P.; Auroux, A.; Gravelle, P. C.; Védrine, J. C.;
Gabelica, Z.; Derouane, E. G. Methanol Conversion on
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Acidic ZSMꢀ5, Offretite, and Mordenite Zeolites:
A
Comparative Study of the Formation and Stability of Coke
Deposits. J. Catal. 1981, 70, 123ꢀ136.
(
(
29) Walsh, D. E.; Rollmann, L. D. Radiotracer Experiments on
Carbon Formation in Zeolites. J. Catal. 1979, 56, 195ꢀ197.
30) Schleyer, P. R.; Würthwein, E.; Kaufmann, E.; Clark, T.;
(38) Zhi, M.; Xiang, C.; Li, J.; Li, M.; Wu, N. Nanostructured
CarbonꢀMetal
Oxide
Composite
Electrodes
for
Supercapacitors: A Review. Nanoscale 2013, 5, 72ꢀ88.
Pople, J. A. CLi
5
,
CLi
6
,
and the Related Effectively
(39) LozanoꢀCastelló, D.; CazorlaꢀAmorós, D.; LinaresꢀSolano, A.;
Shiraishi, S.; Kurihara, H.; Oya, A. Influence of Pore
Structure and Surface Chemistry on Electric Double Layer
Capacitance in NonꢀAqueous Electrolyte. Carbon 2003, 41,
1765ꢀ1775.
(40) Barbieri, O.; Hahn, M.; Herzog, A.; Kötz, R. Capacitance
Limits of High Surface Area Activated Carbons for Double
Layer Capacitors. Carbon 2005, 43, 1303ꢀ1310.
n n
Hypervalent FirstꢀRow Molecules, CLi5ꢀnH and CLi6ꢀnH . J.
Am. Chem. Soc. 1983, 105, 5930ꢀ5932.
(
31) Shu, Z. X.; McMillan, R. S.; Murray, J. J. Electrochemical
Intercalation of Lithium into Graphite. J. Electrochem. Soc.
1
993, 140, 922ꢀ927.
(32) Chmiola, J.; Yushin, G.; Gogotsi, Y.; Portet, C.; Simon, P.;
Taberna, P. L. Anomalous Increase in Carbon Capacitance at
ACS Paragon Plus Environment

Page 9 of 10
Chemistry of Materials
Table 1. Textural properties of carbon products obtained by various ion-exchanged ZSM-5 zeolite templates.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
a
2
ꢀ1
b
3
ꢀ1
c
3
ꢀ1
d
3
ꢀ1
Cation
SBET (m g )
710
Vtotal (cm g )
0.46
Vmicro (cm g )
0.28
Vultramicro (cm g )
Vmicro/Vtotal
0.61
+
Li
0.09
0.06
2+
Ca
600
0.44
0.22
0.50
a
b
c,d
BET surface areas were calculated in a range of P/P = 0.05ꢀ0.20. Total pore volume was determined at P/P = 0.95. Ultramicropore
0
0
and micropore volumes were determined in a pore diameter range of d < 0.7 nm and d < 2 nm, respectively, from the DFT cumulative
volume.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
9
ACS Paragon Plus Environment

Chemistry of Materials
Page 10 of 10
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Table of Contents Graphic
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
10
ACS Paragon Plus Environment