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Tubular Framework
Ordered Mesoporous Carbons with Graphitic Tubular Frameworks by
Dual Templating for Efficient Electrocatalysis and Energy Storage
Du San Baek, Kyung Ah Lee, Jaehyun Park, Jae Hyung Kim, Jungsoo Lee, June Sung Lim,
So Young Lee, Tae Joo Shin, Hu Young Jeong, Jae Sung Son, Seok Ju Kang,* Jin Young Kim,*
and Sang Hoon Joo*
Dedicated to Professor Ryong Ryoo on the occasion of his 65th birthday
Abstract: Ordered mesoporous carbons (OMCs) have attract-
ed considerable interest owing to their broad utility. OMCs
reported to date comprise amorphous rod-like or tubular or
graphitic rod-like frameworks, which exhibit tradeoffs between
conductivity and surface area. Here we report ordered
mesoporous carbons constructed with graphitic tubular frame-
works (OMGCs) with tunable pore sizes and mesostructures
via dual templating, using mesoporous silica and molybdenum
carbide as exo- and endo-templates, respectively. OMGCs
simultaneously realize high electrical conductivity and large
surface area and pore volume. Benefitting from these features,
Ru nanoparticles (NPs) supported on OMGC exhibit superior
catalytic activity for alkaline hydrogen evolution reaction and
single-cell performance for anion exchange membrane water
electrolysis compared to Ru NPs on other OMCs and
commercial catalysts. Further, the OMGC-based full-carbon
symmetric cell demonstrates excellent performances for Li-ion
capacitors.
Introduction
The emergence of new forms of carbons, including
fullerene,[1] carbon nanotube (CNT),[2] graphene,[3] and or-
[*] D. S. Baek, J. Park, Dr. J. H. Kim, J. S. Lim, Prof. S. J. Kang,
Prof. S. H. Joo
School of Energy and Chemical Engineering, Ulsan National Institute
of Science and Technology (UNIST)
50 UNIST-gil, Ulsan 44919 (Republic of Korea)
E-mail: sjkang@unist.ac.kr
shjoo@unist.ac.kr
K. A. Lee, Dr. S. Y. Lee, Dr. J. Y. Kim
Center for Hydrogen Fuel Cell Research, Korea Institute of Science
and Technology (KIST)
5 Hwarang-ro 14-gil, Seoul 02792 (Republic of Korea)
E-mail: jinykim@kist.re.kr
J. Lee, Prof. J. S. Son
Department of Materials Science and Engineering, UNIST
50 UNIST-gil, Ulsan 44919 (Republic of Korea)
Prof. T. J. Shin, Prof. H. Y. Jeong
UNIST Central Research Facilities, UNIST
50 UNIST-gil, Ulsan 44919 (Republic of Korea)
Prof. S. H. Joo
Department of Chemistry, UNIST
50 UNIST-gil, Ulsan 44919 (Republic of Korea)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202012936.
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How to cite: Angew. Chem. Int. Ed. 2021, 60, 1441 – 1449
International Edition: doi.org/10.1002/anie.202012936
German Edition: doi.org/10.1002/ange.202012936
dered nanoporous carbons,[4] has revolutionized chemistry,
physics, materials science, and engineering. The new carbon
materials have provided a fertile ground for exploring
unprecedented physical and chemical phenomena, and have
demonstrated great promise in numerous fields. Ordered
mesoporous carbons (OMCs)[4b, 5, 6] are a class of nanostruc-
tured carbon materials that are constructed with periodic
arrays of carbon frameworks and uniform mesopores. Since
the synthesis of first OMC,[7] OMCs have garnered significant
interest[5–13] owing to their widespread utility in catalysis,[4b]
adsorption,[8] energy conversion and storage,[9] and environ-
mental remediation.[10] OMCs can be synthesized by hard
nanocasting using ordered mesoporous silicas (OMSs) or
silica sphere arrays as templates as well as by micelle
assembly-based soft-templating. These materials generally
have a large surface area and pore volume and interconnected
mesoporosity, which account for their superior performances
over those of conventional carbons, such as carbon blacks and
activated carbons, in many applications.[6]
Despite the remarkable progress in OMC synthesis, most
of OMCs reported to date comprise amorphous rod-like or
tubular carbon frameworks with low electrical conductivity.
This has limited their potential use in electrocatalysis and
energy applications where high electrical conductivity is
critical. Toward the pursuit of highly conductive OMCs,
aromatic precursors and high-temperature annealing above
2,000 8C have been exploited.[12] However, for the resulting
OMCs, high electrical conductivity was attained at the
expense of the surface area. Hence, the generation of OMCs
having both high conductivity and a large surface area
remains challenging.
Herein, we report the synthesis of ordered mesoporous
carbons comprising three-dimensionally (3D) interconnected
graphitic tubular frameworks (OMGCs) via dual templating
route. Nanocasting of an OMS exo-template with molybde-
num carbide generated ordered mesoporous molybdenum
carbide coated with in situ generated few-layer graphitic
carbon layer, and subsequent etching of the molybdenum
carbide endo-template produced the OMGC structure (Fig-
ure 1). The pore size and mesostructure of OMGCs could be
readily tuned with the choice of an appropriate OMS
template. OMGCs combine an ordered mesostructure, large
surface area (1,000 m2 g@1) and pore volume (2.2 cm3 g@1), and
high electrical conductivity that is two orders of magnitude
greater than those of OMCs with amorphous frameworks.
Benefitting from these properties, OMGCs demonstrated
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Figure 1. Schematic illustration for the dual templating route to OMGC.
great potential as excellent electrocatalyst supports and
energy storage materials. Ru nanoparticles (NPs) supported
on OMGC (Ru/OMGC) exhibited superior catalytic activity
for the alkaline hydrogen evolution reaction (HER) in terms
of overpotential, Tafel slope, specific activity, and turnover
frequency (TOF), compared to Ru NPs supported on other
OMCs as well as commercial Ru/C and Pt/C catalysts. Ru/
OMGC also demonstrated enhanced single-cell performance
for anion exchange membrane water electrolysis (AEMWE).
Furthermore, the OMGC-based electrodes exhibited excel-
lent energy storage performances as full-carbon symmetric
OMGC//OMGC Li-ion capacitors (LICs) with high energy
and power densities and a reliable cycle stability for up to
10,000 cycles.
Results and Discussion
Synthesis and characterization of OMGCs
Figure 1 displays the dual templating route to the
preparation of OMGCs. The generation of graphitic tubular
carbon structure inside the mesopores of OMS template is
inspired by the formation of molybdenum carbide via vapor
phase carburization.[14] In this method, the carburization of
a molybdenum precursor using a gas-phase carbon source
such as methane initially generates molybdenum oxide
particles, which are subsequently transformed into molybde-
num carbide in a topotactic manner. During the carburiza-
tion, an excess carbon source is segregated out of molybde-
num carbide interstitial sites forming graphitic carbon layer
on the molybdenum carbide particles. Indeed, when we
directly carburized phosphomolybdic acid (PMA, Mo pre-
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cursor), the resulting molybdenum carbide particles were
covered with a few graphitic carbon layers (Figure S1). We
posited that the formation of graphitic carbon coated
molybdenum carbide inside the mesopores of OMS and the
removal of OMS and molybdenum carbide can generate an
ordered mesoporous structure comprising graphitic tubular
carbon framework.
In an optimized synthesis (see the Supporting Informa-
tion), an OMS with cubic Ia3d double gyroid symmetry (KIT-
6; Figure 2 a) was impregnated with an aqueous solution of
PMA and carburized with a methane/hydrogen/argon (CH4/
H2/Ar, 60/30/10 vol. %) gas mixture at 650 8C for 5 h. Sub-
sequent etching of the KIT-6 exo-template afforded an
ordered mesostructure composed of molybdenum carbide
(MoC1@x), as revealed by transmission electron microscopy
(TEM; Figure 2 b) and wide-angle X-ray diffraction (XRD)
data (Figure S2). Interestingly, closer observation of ordered
mesostructured MoC1@x by high-resolution TEM (HR-TEM;
Figure 2 c) revealed the presence of few-layer graphitic
carbon on the surface of molybdenum carbide, which form
the MoC1@x@C structure. Further removal of the MoC1@x
endo-template from MoC1@x@C via acid etching liberated
the OMGC structure, which contained a negligible amount of
Mo (0.1 wt %) as determined by inductively coupled plasma
optical emission spectroscopy (ICP-OES) analysis (Table S1).
High-angle annular dark-field scanning TEM (HAADF-
STEM; Figure 2 d) and HR-TEM (Figure 2 e) images showed
that OMGC comprises a 3D interconnected tubular structure
of few-layer graphitic carbon with a distance of approximately
0.445 nm between adjacent carbon layers (Figure 2 e). Wide-
angle XRD pattern of OMGC (Figure S2) presented a peak at
1888, suggesting the formation of carbon layers intercalated
with guest species.[15]
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Figure 2. Structural characterization of OMGC. a) HR-TEM image of KIT-6. b) TEM and c) HR-TEM images of MoC1@x@C. d) HAADF-STEM and
e) HR-TEM images of OMGC. Scale bars: (a,b) 30 nm and (c–e) 10 nm, respectively. f) SAXS patterns of KIT-6, MoC1@x@C, and OMGC. g) N2
adsorption isotherms of KIT-6, MoC1@x@C, and OMGC. The isotherms of MoC1@x@C and OMGC are shifted 600 cm3 g@1 and 900 cm3 g@1
upwards, respectively, for clarity. h) BJH pore size distribution curves of KIT-6, MoC1@x@C, and OMGC obtained from the adsorption branches of
the isotherms. Inset: magnified BJH pore size distribution curves of MoC1@x@C and OMGC.

The mesostructural order of OMGC was confirmed by its pattern of KIT-6, which is commensurate with cubic Ia3d
small-angle X-ray scattering (SAXS) pattern with a (110) symmetry, OMGC and MoC1@x@C exhibited different SAXS
reflection (Figure 2 f). Notably, compared to the SAXS patterns with a newly emerged (110) peak. This change could

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originate from the partial formation of the MoC1@x in a single
channel of an enantiomeric pair of mesopores in KIT-6. The
nitrogen (N2) adsorption isotherms (Figure 2 g and Fig-
ure S3a) and Barrett-Joyner-Halenda (BJH) pore size distri-
bution curves (Figure 2 h and Figure S3b) indicated the
formation of multiple mesopores in OMGC. Indeed, 4.3-
and 18.5-nm mesopores were generated after etching of the
KIT-6 exo-template, whereas 3.8-nm mesopores emerged
upon the removal of the MoC1@x endo-template. The highly
porous nature of OMGC gave rise to a large Brunauer–
Emmett–Teller (BET) surface area of 1,000 m2 g@1 and pore
volume of 2.2 cm3 g@1 (Table S2).
The syntheses of these carbon structures were extensively
explored by controlling the carburization gas, time, and
temperature, and the amount of precursor. The use of pure
CH4 as a carburization gas resulted in a sample comprising
both disordered and ordered domains (Figure S4). The high
flux of carbonaceous gas attained by pure CH4 could have led
to an uncontrollable generation of carbogenic species outside
the particles of the KIT-6 template. The carburization time
significantly affected the structure of the resulting carbons
(Figures S5 and S6). The carbon synthesis with a shorter
carburization time (1 h) than the optimum condition gener-
ated a non-periodic structure (Figure S5a), whereas a longer
time (9 h) yielded a periodic structure with, however, a thick
carbon layer (Figure S5c). The carburization temperatures
also influenced the structure of the carbon products (Figur-
es S7 and S8a). The carburization at 750 8C afforded a highly
ordered structure (Figure S7b); however, the resulting carbon
comprised a thick carbon layer and contained a significant
amount of MoC1@x species (Figure S8b). Further increase of
the carburization temperature to 850 8C resulted in a less
ordered structure (Figure S7c) with remnant MoC1@x (Fig-
ure S8b). We also investigated the influence of the amount of
Mo precursor (Figure S9). The sample with a lower Mo/Si
molar ratio (0.32) than that for the optimized condition (0.63)
afforded an ordered structure, however, the yield of the
resulting carbon was very low. As the Mo/Si molar ratio was
increased to 0.95 and 1.26, the structural deformation became
severe for the resulting carbon products.
Structural control and stability of OMGCs
The general utility of dual templating route could be
verified with the syntheses of pore size- and pore structure-
controlled OMGCs. The pore size-controlled OMGCs could
be synthesized by nanocasting KIT-6 silicas with tailored pore
sizes, which were prepared by increasing hydrothermal treat-
ment temperatures from 100 8C to 130 8C (OMGC_130) and
150 8C (OMGC_150). The TEM and HR-TEM images of
OMGC_130 and OMGC_150 (Figure S10) respectively vi-
sualized periodic pore structures and graphitic tubular frame-
works. The SAXS patterns (Figure S11) and N2 adsorption
analyses (Figure S12) of OMGC_130 and OMGC_150 also
revealed the formation of a mesostructure with unit cells and
pore sizes in the order of OMGC_150 > OMGC_130 >
OMGC (Table S3). The pore structure of OMGCs could also
be tuned using OMSs of different pore connectivities. For
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instance, the use of hexagonal OMS (SBA-15) yielded
hexagonally ordered OMGCs [OMGC(S); Figure S13]. The
TEM (Figure S13a) and HR-TEM (Figure S13b) images of
OMGC(S) clearly demonstrated a hexagonal array of nano-
tubes with graphitic tubular frameworks. The small-angle
XRD pattern (Figure S13c) and N2 adsorption analysis (Fig-
ure S13d) of OMGC(S) confirmed the formation of hexago-
nal mesostructure and a large BET surface area and pore
volume, respectively.
We investigated the structural stability of OMGC by
annealing at 800 and 1,000 8C under Ar (Ar800 and Ar1000,
respectively) and at 600 8C under H2 (H2600). The HR-TEM
images (Figure S14) and small-angle XRD patterns (Fig-
ure S15a) revealed that the annealed OMGCs retained their
mesostructure. Interestingly, the XRD peak at 1888 observed
for OMGC disappeared in the patterns of the annealed
samples (Figure S15b), suggesting that the intercalated spe-
cies between the carbon layers were removed. Thermogravi-
metric analysis results (Figure S16) revealed that combustion
temperatures increased in the order of Ar1000 > Ar800 >
H2600 > OMGC, indicating the enhanced thermal stability of
the annealed OMGCs.
Comparison of OMGC with other OMCs
We next compared the physicochemical properties of
OMGC with those of OMCs templated from KIT-6 but with
different carbon frameworks (Figure 3). Nanocasting of KIT-
6 silica with furfuryl alcohol via surface templating and with
sucrose via volume templating afforded amorphous tubular
(OMC_AT) and amorphous rod-like (OMC_AR) carbon
frameworks, respectively (Figure 3 a). SAXS patterns (Fig-
ure 3 b) suggested the formation of highly ordered meso-
structures in OMC_AT and OMC_AR, similar to those of
CMK-9 and CMK-8,[16] respectively. Comparison of the
porosity of the three OMCs (Figure 3 c, Figure S17, and
Table S4) indicated that OMGC had the largest pore volume
of 2.2 cm3 g@1, followed by OMC_AT (1.9 cm3 g@1) and OM-
C_AR (1.2 cm3 g@1). The BET surface area of OMGC
(1,000 m2 g@1) compared favorably with those of OMC_AT
(1,440 m2 g@1) and OMC_AR (1,120 m2 g@1). Notably, the BET
surface area of OMGC far exceeds those of the highly
graphitic OMC, CMK-3G (300 m2 g@1).[12a] Such a large differ-
ence in the surface areas of OMGC and CMK-3G is
reasonable since the former has a tubular structure whereas
the latter consists of rod-like framework. The surface area of
OMGC is also greater than those of commercial graphitic
carbons such as CNT and Ketjen Black (KB; Figure S18 and
Table S4).
The graphitic nature of OMGC was confirmed by X-ray
photoelectron spectroscopy (XPS; Figure 3 d) and Raman
spectroscopy (Figure 3 e). In contrast to the other two OMCs,
OMGC presented a noticeable p-p* satellite peak at 291 eV
in the XPS spectrum, which is attributed to its high graph-
iticity and extended delocalized electrons.[17] In the Raman
spectra, OMGC exhibited a sharper G band peak at
approximately 1,580 cm@1 than those in OMC_AT and
OMC_AR. Moreover, the ID/IG ratio in OMGC was 2.14,
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Figure 3. Comparison of the structural and electrical properties of OMGC and other OMCs. a) Pore structure models for OMGC, OMC_AT, and
OMC_AR illustrating their graphitic tubular, amorphous tubular, and amorphous rod-like structures, respectively. b) SAXS patterns of OMGC,
OMC_AT, and OMC_AR. c) N2 adsorption isotherms of OMGC, OMC_AT, and OMC_AR. The isotherms of OMC_AT and OMC_AR are upward-
shifted to 600 and 1,200 cm3 g@1, respectively, for clarity. BET surface areas and total pore volumes for the samples are given. d) C 1s XPS spectra
of OMGC, OMC_AT, and OMC_AR. e) Raman spectra of OMGC, OMC_AT, and OMC_AR. ID/IG ratios of the samples are given. f) Bar graphs for
electrical conductivity of OMGC, OMC_AT, and OMC_AR obtained from current–voltage curves (inset).

which is lower than those of OMC_AT (2.42) and OMC_AR
(3.11). OMGC also displayed a sharp D band peak at
approximately 1,350 cm@1, which is attributed to its high
oxygen content (Table S1) and defects in OMGC, which could
be generated during the strong acid etching of MoC1@x. Next,
the electrical conductivity of the pelletized OMCs was
measured by the four-point van der Pauw method (Figure 3 f).
OMGC exhibited a very high electrical conductivity of 590 S
m@1, a value that is two orders of magnitude greater than
those of OMC_AT (12.6 S m@1) and OMC_AR (7.5 S m@1;
Table S5).
Collectively, the above results suggest that OMGCs
represent a new class of porous carbon materials that can
simultaneously realize high electrical conductivity and a large
surface area and pore volume. The OMGC structure com-
bines the characteristics of OMCs, graphene, and CNT.
Notably, despite the continuous advances in the field of
OMCs, such a combination of desirable properties has not
been attained to date; OMC framework structures have been
limited to amorphous rod-like or tubular or graphitic rod-like
structures (Figure S19).
We suppose that MoC1@x could play a pivotal role in the
formation of highly graphitic carbon layer on its surfaces
during the carburization process. We monitored the carburi-
zation temperature-dependent phase transformation of the
PMA precursor inside the mesopores of OMS template. The
wide-angle XRD patterns of MoC1@x@C intermediates (Fig-
ure S20) suggested that the silica-confined PMA precursor
was transformed to MoO2 phase at a carburization temper-
ature of 550 8C. The increase in carburization temperature to
650 8C invoked a transformation into MoC1@x phase with
small crystallite size, which was preserved at higher carburi-
zation temperatures (750 and 850 8C).[18] The TEM images of
carbon products obtained after the etching of MoC1@x from
MoC1@x@C intermediates (Figure S7) indicated that the
graphitic layer number increased from three layers for the
carbon product carburized at 650 8C to five layers for the
carbon treated at 850 8C. As the carburization temperature
was increased, a larger amount of carbon species could be
dissolved into MoC1@x interstitial sites and segregated onto
the MoC1@x surfaces, supporting the dissolution-segregation
mechanism for the formation of graphitic carbon.[19] Overall,
the formation of graphitic carbon layer coated MoC1@x inside
the mesopores of OMS template makes the generation of
graphitic carbon in the interfacial region between MoC1@x and
OMS. Hence, sequential removal of OMS and MoC1@x can

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afford OMGC. In contrast, when we attempted the carbon
syntheses in the presence of other transition metal (Fe, Co,
and Ni) species, 1D carbon nanotubes or large metallic
nanoparticles encaged in graphitic carbon shells were uncon-
trollably generated (Figure S21).
Alkaline HER activity and AEMWE performance of the Ru/
OMGC catalysts
We next explored the applicability of OMGC in electro-
catalysis and energy storage. To exploit OMGC as an
electrocatalyst support, Ru NPs were supported on OMGC
via impregnation and H2 reduction to afford Ru/OMGC
catalysts with a nominal Ru loading of 20 wt % (20Ru/
OMGC). The Ru loadings of the samples were determined by
ICP-OES analysis (Table S6). The STEM images of 20Ru/
OMGC (Figure 4 a,b) clearly revealed that the Ru NPs were
uniformly distributed on the graphitic frameworks of OMGC.
The average particle size of 20Ru/OMGC was 1.66 nm
: 0.21 nm (Figure S22). The HAADF-STEM (Figure S23a)
and corresponding elemental mapping images (Figure S23b,c)
of 20Ru/OMGC confirmed the presence of C and Ru species.
The wide-angle XRD patterns of 20Ru/OMGC (Figure S24)
exhibited very broad featureless peaks due to the very small
size of Ru, in line with the TEM data. We also prepared 20Ru/
OMC_AT and 20Ru/OMC_AR catalysts for comparison
(Figures S24 and S25). The chemical states of Ru species in
the Ru-based catalysts were analyzed by XPS spectra. The
deconvoluted Ru 3p XPS spectra (Figure S26) for 20Ru/
OMGC, 20Ru/OMC_AT, and 20Ru/OMC_AR catalysts ex-
hibited three peaks, corresponding to Ru0 (461.2 eV; metal-
lic), Ru4+ (463.2 eV; RuO2), and Ru6+ (465.9 eV; RuOx)
states.[20] Notably, the 20Ru/OMGC showed a greater relative
peak area ratio of Ru0/Ru4+ (0.57) than those of 20Ru/
OMC_AT (0.52) and 20Ru/OMC_AR (0.47), suggesting the
presence of highest portion of electrochemically active
metallic Ru0 species rather than inactive Ru4+ species.[21]
We investigated the electrocatalytic properties of 20Ru/
OMGC, along with those of 20Ru/OMC_AT, 20Ru/OM-
C_AR, and commercial 20Ru/C (Premetek) and 20Pt/C
(Johnson-Matthey), for alkaline HER in 1 M KOH with
a 14-mg precious metal loading on the electrode. The linear
sweep voltammetry (LSV) curves of the catalysts (Figure 4 c)
indicated that among the compared catalysts, 20Ru/OMGC
exhibited the highest alkaline HER activity. 20Ru/OMGC
required an overpotential of 30 mV to reach a current density
of @10 mA cm@2, which is lower than those of 20Ru/OMC_AT
(47 mV), 20Ru/OMC_AR (52 mV), 20Ru/C (41 mV), and
20Pt/C (84 mV). Notably, OMGC itself exhibited negligible
alkaline HER activity, suggesting that the catalytic activity of
supported Ru catalysts originated from Ru NPs. The catalytic
activity trend was corroborated by electrochemical impe-
dance spectroscopy (EIS) analysis (Figure S27). The Nyquist
plots displayed the smallest semi-circle for 20Ru/OMGC,
indicating the lowest charge transfer resistance for OMGC.
The high activity of 20Ru/OMGC was further verified by its
excellent kinetics. 20Ru/OMGC presented a Tafel slope of
30 mV dec@1, which is lower than or similar to those of 20Ru/
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OMC_AT (42 mV dec@1), 20Ru/OMC_AR (45 mV dec@1),
20Ru/C (31 mV dec@1), and 20Pt/C (90 mV dec@1), indicating
that the alkaline HER of 20Ru/OMGC may proceed via the
Volmer-Tafel mechanism (Figure 4 d and Table S7). The
catalytic activity was also evaluated by specific activity, which
was calculated by normalizing the current density with the
electrochemically active surface areas (ECSAs; Figure S28).
20Ru/OMGC displayed the highest specific activity at an
overpotential of 50 mV, followed by those of 20Ru/C, 20Ru/
OMC_AT, 20Ru/OMC_AR, and 20Pt/C (Figure 4 e). The
alkaline HER activity of the catalysts was also assessed by
TOFs. For the calculation of TOFs, the amount of under-
potentially deposited hydrogen desorption charge was used to
calculate the electrochemically active surface sites. As a result,
20Ru/OMGC showed 1.5 times higher TOF than 20Ru/C at
an overpotential of 50 mV, followed by 20Ru/OMC_AT,
20Ru/OMC_AR, 20Pt/C (Figure 4 e). Importantly, 20Ru/
OMGC sustained its high catalytic activity for up to 12 h
during long-term stability assessment by chronopotentiome-
try (CP) at @10 mA cm@2 (Figure 4 f), which was superior to
the result of 20Ru/C. After the stability test, 20Ru/OMGC
well preserved mesostructured carbon frameworks without
severe agglomeration of Ru NPs (Figure S29). We also
analyzed the amounts of dissolved Ru metals in the electro-
lyte after the stability test. A lower amount of dissolved Ru
(1.9 ng mL@1) was found for 20Ru/OMGC after the test than
that of 20Ru/C (2.5 ng mL@1), indicating strong anchoring
between Ru NPs and OMGC that could mitigate the Ru
dissolution. Ru 3p XPS spectra after the stability test
exhibited (Figure S30) an increase in peak area for metallic
Ru0 for both 20Ru/OMGC and 20Ru/C due to the reductive
potential of HER condition. Overall, the combined effects of
a large surface area and highly conductive frameworks in
OMGC allowed efficient mass transport and low charge
transfer resistance as well as relatively reduced state of Ru
NPs for boosting the alkaline HER activity of Ru/OMGC
catalyst.
To demonstrate the practical viability of the Ru/OMGC
catalyst, AEMWE tests were performed using a polymer
membrane (X37-50 grade T, Dioxide material) as the anion
exchange membrane and a Ru-based catalyst as the cathode
catalyst, respectively. AEMWE has the potential of combin-
ing the benefits of both proton-exchange-membrane- and
alkaline liquid electrolyte-based water electrolysis technolo-
gies, and is thus considered the best system to meet the low-
cost option for hydrogen production.[22] An AEMWE system
generally consists of an anion exchange membrane and non-
precious or low-precious metal electrocatalysts for both the
anode and cathode. Moreover, dilute 1 M KOH is used as an
electrolyte to provide ionic conductivity. The concept of
AEMWE with the membrane electrode assembly (MEA)
used in this study is illustrated in Figure S31. The MEAs were
fabricated using the catalyst-coated substrate method and the
cross section of the fabricated MEA is presented in Fig-
ure S32 (see the Supporting Information for detail). Figure 4 g
illustrates the polarization curves of the AEMWE cells based
on MEAs with 20Ru/OMGC, 20Ru/OMC_AT, 20Ru/OM-
C_AR, or 20Ru/C as the cathode and iridium oxide as the
anode catalysts. The 20Ru/OMGC-based AEMWE cell
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Figure 4. Alkaline HER and AEMWE performances of the Ru/OMGC catalyst. a) Bright-field STEM and b) HAADF-STEM images of 20Ru/OMGC
(scale bar: 10 nm and 2 nm, respectively). c) LSV curves of the 20Ru/OMGC, 20Ru/OMC_AT, 20Ru/OMC_AR, 20Ru/C, 20Pt/C, and OMGC for the
alkaline HER. The loading of platinum group metal (PGM; Ru or Pt) on the electrode was 14 mg cm@2 and the loading of OMGC was 70 mg cm@2.
d) Tafel slopes of 20Ru/OMGC, 20Ru/OMC_AT, 20 Ru/OMC_AR, 20Ru/C, and 20Pt/C catalysts. The values shown in the diagram denote Tafel
slopes in mVdec@1 unit. e) Specific activities and TOFs of the 20Ru/OMGC, 20Ru/OMC_AT, 20Ru/OMC_AR, 20Ru/C, and 20Pt/C catalysts. f) CP
curves of the 20Ru/OMGC and 20Ru/C catalysts at a constant current density of @10 mA cm@2. AEMWE single-cell performances of MEAs
employing 20Ru/OMGC, 20Ru/OMC_AT, 20Ru/OMC_AR, and 20Ru/C as cathode catalysts: g) AEMWE polarization curves, h) bar graph
comparing the MEA current densities at 2.0 V, and i) EIS Nyquist plots obtained at 1.8 V.

presented an excellent cell performance of 0.75 A cm@2 at
2.0 V, outperforming all the other catalyst-based cells with the
same trend of electrical conductivity of carbon supports
(Figure 4 h and Figure S33). The EIS analysis performed at
1.8 V (Figure 4 i) indicated that the enhanced AEMWE
performance of Ru/OMGC is most likely due to the
diminished charge transfer resistance with the smallest
semi-circle in the Nyquist plot. Furthermore, the lowest
ohmic resistance was observed with the 20Ru/OMGC-based
cell, which might be attributed to the better infiltration of
KOH electrolytes into the electrode structure with the help of
high surface area from ordered mesoporous structure of
OMGC.
Full-carbon LIC performance of OMGCs
We next extended the use of OMGC to energy storage, for
which we used the OMGC sample annealed at 600 8C in H2
that is free from intercalated species (Figure S14c and Fig-

Angew. Chem. Int. Ed. 2021, 60, 1441 – 1449 T 2020 Wiley-VCH GmbH www.angewandte.org 1447

Research Articles
Figure 5. Electrochemical energy storage performances of the OMGC-based LIC. Performances of the anode/Li metal half-cells using OMGC,
OMC_AT, and OMC_AR as the anode: a) EIS Nyquist plots and b) rate capabilities. c) Ragone plot of the OMGC//OMGC full-carbon LIC
compared to those of previously reported LICs.
ure S15). We first evaluated the LIC performance using
OMGC as the anode or cathode material. The EIS Nyquist
plots for the half-cell structure using OMCs as the anode with
Li metal as the counter electrode (Figure 5 a) displayed the
smallest semi-circle for the OMGC anode. This indicated the
highest charge transfer kinetics, which facilitated efficient
faradaic redox reaction near the OMGC surface. The charge
storage behavior of the OMGC anode was verified from the
cyclic voltammograms (CVs; Figure S34). The OMGC//Li
half-cell maintained a high specific capacity of 128 mA h g@1 at
a high current rate of 10.0 A g@1, attributed to the diffusion-
controlled Li ion intercalation and capacitive surface charge
storage mechanisms (Figure 5 b). Furthermore, the OMGC
anode delivered a reliable cycling stability for up to 1,000
cycles (Figure S35). OMGC also demonstrated an excellent
performance as the cathode, as revealed by the monotonically
increasing and decreasing charge-discharge voltage trajecto-
ries (Figure S36a) and quasi-rectangular shape of the CV
characteristics (Figure S36b). In addition, the OMGC catho-
dic cell displayed a reliable rate capability (Figure S37a), even
at high capacity retentions of up to 10.0 A g@1, and excellent
cycling stability of up to 8,500 cycles with 99.0 % capacity
retention (Figure S37b).
The excellent performances of OMGC as both the anode
and cathode allowed the fabrication of a full-carbon OMGC//
OMGC symmetric cell structure (Figure S38). The OMGC
anode was pre-lithiated using a half-cell (i.e. vs. Li/Li+) before
assembling the LIC. With an increase in the CV scan rate
from 1.0 to 100 mV s@1 within the voltage window of 0.005–
4.5 V, stable quasi-rectangular plots were observed (Fig-
ure S39a). In addition, the galvanostatic charge-discharge
profiles at various current densities in the range of 0.5–
10.0 A g@1 displayed near-linear voltage trajectories repre-
senting the charge storage behavior of the OMGC//OMGC
symmetric cell (Figure S39b). The OMGC//OMGC cell
exhibited an excellent energy density of 312 Wh kg@1 at
a power density of 1,139 Wkg@1 and remarkably maintained
its energy density of 58 Wh kg@1 at a high-power density of
12,168 Wkg@1 (Figure 5 c). A performance comparison with
those of previous LIC cells indicates that the OMGC//OMGC
symmetric LIC displays one of the best LIC performances
reported to date (Figure 5 c and Table S8). Importantly,
1448 www.angewandte.org T 2020 Wiley-VCH GmbH
Angewandte
Chemie
OMGC//OMGC LIC presented superior capacity retention
(86.9 %) of the initial capacity after 10,000 cycles at a fixed
current density of 4.0 Ag@1 (Figure S39c).
Conclusion
We have prepared a new class of carbon materials,
OMGCs, via the dual templating route. OMGCs, which
combine the structural characteristics of OMC, graphene, and
CNT, could realize ordered mesoporosity, a large surface area
and pore volume, and high electrical conductivity simulta-
neously. OMGCs demonstrated great potential for applica-
tion as electrocatalyst supports and energy storage media. Ru/
OMGC displayed very high activity for alkaline HER and
excellent AEMWE single-cell performances. Furthermore,
OMGC-based full-carbon symmetric cells demonstrated
remarkable LIC performances. The dual templating route
developed in this work enabled the generation of unprece-
dented OMGCs beyond OMCs that have been prepared by
hard- or soft-templating methods. We envisage that the
excellent structural properties OMGCs would allow their
use in important energy conversion and storage devices,
chemical and petroleum processes, and gas separation.
Acknowledgements
This work was supported by the National Research Founda-
tion (NRF) of Korea funded by the Ministry of Science and
ICT (NRF-2019M3E6A1064521, NRF-2019M3D1A1079306,
NRF-2019M1A2A2065614, and NRF-2019R1A2C2007311),
and by KIST Institutional Program (2E30380). The SAXS
experiment performed at Beamline 6D and 9A of the Pohang
Accelerator Laboratory was supported in part by the MSIT,
Pohang University of Science of Technology (POSTECH),
and UCRF at UNIST.
Angew. Chem. Int. Ed. 2021, 60, 1441 – 1449

Research Articles
Conflict of interest
The authors declare no conflict of interest.
Keywords: alkaline HER · graphene · Li-ion capacitor ·
ordered mesoporous carbon · tubular frameworks
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Manuscript received: September 24, 2020
Accepted manuscript online: October 11, 2020
Version of record online: November 12, 2020
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