Supporting Information

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*

anie_202012936_sm_miscellaneous_information.pdf
SUPPORTING INFORMATION
Table of Contents

1. Materials and Methods S3

2. Supplementary Figures and Tables

Figure S1. TEM images of MoC1−x synthesized in the absence of KIT-6 template. S9
Figure S2. XRD patterns of MoC1−x and OMGC. S10
Figure S3. Porosity analysis of KIT-6, OMGC, and intermediate samples. S10
Figure S4. TEM image of the carbon product prepared from pure CH4 gas. S11
Figure S5. TEM images of carburization time-controlled samples. S12
Figure S6. SAXS patterns of carburization time-controlled samples. S12
Figure S7. TEM images of carburization temperature-controlled samples. S13
Figure S8. SAXS and XRD patterns of carburization temperature-controlled samples. S13
Figure S9. TEM images of Mo precursor content-controlled samples. S14
Figure S10. TEM and HR-TEM images of pore size-controlled OMGCs. S15
Figure S11. SAXS patterns of pore size-controlled OMGCs. S15
Figure S12. Porosity analysis of pore size-controlled OMGCs. S16
Figure S13. Structural characterization of hexagonal OMGC. S17
Figure S14. HR-TEM images of post-annealed OMGCs. S18
Figure S15. XRD patterns of post-annealed OMGCs. S18
Figure S16. TGA analysis of OMGC and post-annealed OMGCs. S19
Figure S17. BJH pore size distribution curves of OMGC, OMC_AT, and OMC_AR. S20
Figure S18. Porosity analysis of CNT and KB. S20
Figure S19. Major advances in the development of OMCs. S21
Figure S20. XRD patterns of carburization temperature-controlled MoC1−x@C samples. S22
Figure S21. TEM images of carbon products prepared with different transition metal S22
endo-templates.
Figure S22. Particle size distribution histogram of 20Ru/OMGC catalysts. S23
Figure S23. Compositional analysis of 20Ru/OMGC. S23
Figure S24. XRD patterns of 20Ru/OMGC, 20Ru/OMC_AT, and 20Ru/OMC_AR S24
catalysts.
Figure S25. STEM images of 20Ru/OMC_AT and 20Ru/OMC_AR. S25
Figure S26. Ru 3p XPS spectra of Ru-based electrocatalysts. S26
Figure S27. Nyquist plots of Ru-based electrocatalysts. S27
Figure S28. CVs of electrocatalysts. S28
Figure S29. TEM images of 20Ru/OMGC after the stability test. S29

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Figure S30. Ru 3p XPS spectra of 20Ru/OMGC and 20Ru/C after the stability test. S29
Figure S31. Schematic illustration of the AEMWE MEA. S30
Figure S32. SEM images of the AEMWE MEA. S30
Figure S33. Bar graph for electrical conductivity of carbon supports. S31
Figure S34. Charge storage behavior of the carbon-based anodes. S32
Figure S35. Cycle stability of the OMGC anode//Li metal half-cell. S33
Figure S36. Charge-discharge voltage profiles and CV curves of the OMGC S33
cathode//Li metal half-cell.
Figure S37. Charge storage behavior of OMGC cathodic cell. S34
Figure S38. Schematic illustration of the OMGC//OMGC LIC. S35
Figure S39. Charge storage behavior of OMGC//OMGC LIC. S35
Table S1. Elemental analysis results of OMGC, OMC_AT, and OMC_AR. S36
Table S2. N2 physisorption analysis results for KIT-6, OMGC, and intermediate S36
samples.
Table S3. Unit cell parameters and N2 physisorption analysis results for OMGC, S37
OMGC_130, and OMGC_150.
Table S4. Carbon framework structures and N2 physisorption analysis results for S37
OMGC, OMC_AT, OMC_AR, CNT, and KB.
Table S5. Electrical conductivity data for OMGC, OMC_AT, and OMC_AR. S38
Table S6. Ru contents in the Ru-based electrocatalysts. S38
Table S7. Comparison of alkaline HER activity of 20Ru/OMGC with those of S39
previously reported Ru-based electrocatalysts.
Table S8. Comparison of LIC performance of the OMGC-based electrode with those of S40
previously reported electrodes.

3. References S41

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1. Materials and Methods

Chemicals. Pluronic P123 (Mn=5,800), tetraethyl orthosilicate (TEOS, 98%), n-butanol (99.9%),
phosphomolybdic acid (PMA, ACS reagent grade), ruthenium chloride (RuCl3, 39%), aluminium chloride
(AlCl3, 98%), furfuryl alcohol (FA, 98%), polyvinyl alcohol (PVA, Mw=85,000–124,000, 99%
hydrolyzed), and isopropyl alcohol (IPA, 99.7%) were purchased from Sigma-Aldrich. Hydrochloric acid
(HCl, 35–37%), nitric acid (HNO3, 60%), sulfuric acid (H2SO4, 95%), ethanol (EtOH, 94.5%), anhydrous
EtOH (99.9%), n-hexane (96%), and sucrose were purchased from Samchun Chemicals. Hydrofluoric
acid (HF, 50%) was purchased from J. T. Baker. All chemicals were used as received, without further
purification. Deionized (DI) water was produced by a Millipore Milli-Q system (18.2 MΩ). Argon (Ar,
99.999%), nitrogen (N2, 99.999%), hydrogen (H2, 99.999%), H2/Ar (4/96 vol.%), methane (CH4,
99.999%), and CH4/H2/Ar (60.5/29.5/10 vol.%) gases were purchased from KOSEM and used as received,
without further purification.
Synthesis of OMGC. The ordered mesoporous silica (OMS) exo-template with cubic Ia3d symmetry,
KIT-6, was synthesized according to a previously reported method with some modifications. [1] Triblock
copolymer P123, n-butanol, and TEOS were used as the structure-directing agent, additive, and silica
source, respectively. The initial gel mixture was aged at 30 °C for 1 d and subsequently 100 °C for another
day. In the optimized OMGC synthesis, 3.2 g of PMA was dissolved in 0.8 mL of DI water to form a
concentrated molybdenum precursor solution. Separately, 2 g of KIT-6 was immersed in 20 mL of n-
hexane. Next, 4 g of aliquot of the concentrated molybdenum precursor solution was added dropwise to
the KIT-6/n-hexane suspension in a 250-mL beaker with vigorous magnetic stirring, and the mixture was
dried overnight at room temperature (RT). The PMA/KIT-6 mixture was then transferred to an alumina
crucible and carburized in a tube furnace by raising the temperature from RT to 650 °C at a ramping rate
of 10 °C min−1 and maintaining this temperature for 5 h under CH4/H2/Ar flow (200 sccm). After
carburization, the sample was cooled to RT under N2 flow (200 sccm). Next, the KIT-6 exo-template was
etched with a 1:1 (vol.%) EtOH:10 wt% HF solution and stirred for 30 min. The product was filtered and
washed with EtOH. The etching process was repeated once more to generate the MoC 1−x@C structure.
To further etch the MoC1−x endo-template, MoC1−x@C and 6 M HNO3 (500 mL HNO3/1 g MoC1−x@C)
were added into a polypropylene (PP) bottle and stirred at a 80 °C oven for 12 h. (Caution: owing to the
vigorous oxidation of molybdenum carbide species, 10 mL of HNO3 was pre-mixed with the MoC1−x@C
powder in a fume hood and the remaining amount of HNO3 was added after stabilization.) After cooling
to RT, the suspension was diluted with a large amount of DI water and the product was filtered and washed
with DI water until the filtrate reached pH of 7. After the washing step, the powder was moved to an oven

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at 60 °C and dried for 6 h. The etching step was repeated once more to completely etch the MoC 1−x,
yielding approximately 0.38 g of OMGCs. The syntheses of the porous carbon materials were extensively
explored by changing various experimental parameters, including the carburization conditions (gas,
duration, heating temperature, and the amount of precursor), type of metal used as the endo-template, and
pore size and pore structure of the silica templates.
Synthesis of OMC_AT and OMC_AR. The synthesis of OMC_AT was achieved by using Al
impregnated KIT-6 (AlKIT-6) and FA as the template and carbon source, respectively. 0.37 g of AlCl3
was dissolved in 60 mL of anhydrous EtOH in a 250-mL round bottom flask. 4 g of KIT-6 was added to
the AlCl3 solution followed by an additional 25 mL of anhydrous EtOH, and the mixture was stirred at
RT for 1 h. The solvent was completely evaporated using a rotary evaporator at 60 °C and further dried
in an oven at 60 °C for 24 h. The dried powder was then calcined at 550 °C for 5 h to afford AlKIT-6. 3
g of FA was added dropwise to 4 g of AlKIT-6 in a PP bottle and mixed using a vortex for 30 min. The
FA/AlKIT-6 composite sealed in a PP bottle was then maintained in a 95 °C oven for 24 h. The powder
was carbonized by heating at 350 °C for 3 h and subsequently at 900 °C for 6 h under N2 flow (60 sccm).
After cooling to RT, the AlKIT-6 template was etched by HF following the same procedure used for
OMGC. OMC_AR was synthesized using KIT-6 and sucrose as the template and carbon source,
respectively. 4.7 g of sucrose, 17 g of DI water, and 0.5 g of H2SO4 were added in a PP bottle. After
sucrose was completely dissolved, 4 g of KIT-6 was added to the solution, and the mixture was gently
agitated to make a homogeneous paste. The mixture was heated in a box furnace for 6 h at 100 °C and
subsequently at 160 °C for further 2 h. Next, a sucrose solution comprising 2.8 g of sucrose, 17 g of DI
water, and 0.3 g of H2SO4 was prepared, and the above polymerized sucrose/KIT-6 composite was added
to the sucrose solution. The polymerizing step was conducted again at 100 °C and 160 °C. The sample
was carbonized by heating at 400 °C for 4 h and subsequently heating at 900 °C for 2 h under N2 flow
(60 sccm). After cooling to RT, KIT-6 was etched by HF treatment.
Preparation of carbon supported Ru catalysts. The OMC supported Ru catalysts were prepared
by incipient-wetness impregnation and H2 reduction using RuCl3 as the precursor. To prepare the
Ru/OMGC, Ru/OMC_AT, and Ru/OMC_AR catalysts with 20 wt% Ru loading, 0.13 g of RuCl3 precursor
was dissolved in 0.6 mL of anhydrous EtOH. The precursor solution was then mixed with 0.2 g of carbon
support (OMGC, OMC_AT, or OMC_AR) by hand scrubbing. After drying in a fume hood overnight, the
RuCl3-impregnated OMC support was transferred to a tube furnace, heated to 200 °C at a ramping rate
0.6 °C min−1, and maintained at this temperature for 2 h under H2 flow (30 sccm) to reduce the Ru
precursor to Ru NPs. Subsequently, the hydrogen adsorbed on the Ru NPs was removed by heating the
sample from 200 to 350 °C at a ramping rate of 2.5 °C min−1 and maintaining it at 350 °C for 2 h under

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N2 flow (60 sccm). For 3Ru/OMGC, 0.008 g of RuCl3 was dissolved in 0.3 mL of anhydrous EtOH and
mixed with 0.1 g of OMGC. The subsequent drying, reduction, and hydrogen desorption steps were
carried out using the same procedures described for the 20 wt% Ru catalysts.
Characterization methods. The HR-TEM and HAADF-STEM images were taken using an FEI
Titan3 G2 60-300 microscope equipped with a double-side spherical aberration (Cs) corrector operating
at accelerating voltages of 80 and 200 kV, respectively. The particle size distributions of Ru NPs were
analyzed using Gatan Microscopy Suite 3 Software by counting at least 150 particles. The SAXS patterns
were obtained at a synchrotron facility (PLS-II 6D UNIST-PAL and 9A U-SAXS beamlines of at the
Pohang Accelerator Laboratory, Republic of Korea). The XRD patterns were obtained with a high-power
X-ray diffractometer (D/MAX2500V/PC, Rigaku) equipped with Cu Kα radiation and operating at 40 kV
and 200 mA. The sample porosities were determined using a N2 sorption analyzer (BELSORP-Max, BEL)
operated at −196 °C. Prior to measurement, the samples were evacuated at 150 °C under vacuum for 12
h to clean their surfaces. The specific surface areas of the samples were calculated using the BET equation,
while their pore size distributions were derived from the adsorption branches of the isotherms using the
BJH method. XPS spectra were acquired using an X-ray photoelectron spectrometer (ESCALAB 250XI,
Thermo Fisher Scientific) with a monochromatic Al Kα X-ray source (1,486.6 eV). For the XPS
measurements, 3 mg of each sample was pelletized into a wafer. Raman spectra were obtained using a
WITec alpha300R instrument coupled with a He–Ne laser of 532-nm exciting wavelength at a power of
1 mW. XPS and Raman spectra were deconvoluted using XPSPeak41 software with a mixed Gaussian
(70)–Lorentzian (30)-function after linear (Shirley)-type background correction. The Ru contents in the
catalysts were analyzed using an inductively coupled plasma optical emission spectroscopy analyzer
(700-ES, Varian), while their C, H, N, and O contents were measured using a combustion elemental
analyzer (Flash 2000, Thermo Fisher Scientific). The carbon combustion temperature and quantification
of the remnant species were investigated by thermogravimetric analysis (TGA Q50 from TA instruments),
under air at a scan rate of 5 °C min−1.
Electrical conductivity measurement. First, 20 wt% PVA was dissolved in DI water to prepare the
binder. A small amount of binder was then added to each carbon sample powder and each mixture was
kneaded to form a slurry. The slurries were then pressed at 1,000 kgf cm−2 to form pellets. The pellets,
placed in a ceramic boat, were calcined in a tube furnace by raising the temperature from RT to 550 °C
(ramping rate: 10 °C min−1) and maintaining this temperature for 2 h, followed by heating at 650 °C for
1 h under H2/Ar flow. The electrical conductivities of the carbon pellets were measured by the four-point
van der Pauw method (Keithley 2,400 multimeter controlled by Lab trace 2.0 software, Keithley

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Instrument, Inc.). The sheet resistance was determined from the current–voltage relation, while the
electrical conductivity was calculated from the pellet thickness.
Electrochemical measurements. Electrochemical measurements were conducted on an
electrochemical workstation (CHI760E, CH Instruments) under atmospheric pressure. A three-electrode
system was built with a rotating ring−disk electrode (RRDE, AFE7R9GCPT, Pine Research
Instrumentation), graphite rod, and Hg/HgO electrode as the working, counter, and reference electrodes,
respectively. All potentials were converted to the potential scale of the reversible hydrogen electrode
(RHE), unless otherwise noted. This was achieved with a two-electrode setup comprising Pt wire and the
reference electrode to be measured. The open circuit voltage (OCV) was then monitored, following
sparging of the electrolyte with H2 gas. In this setup, the Pt wire serves as the RHE, as H+/H2 equilibrium
is established. A stable OCV, i.e. the potential difference between the RHE and reference electrode, was
obtained within 20 min and used as the conversion value. Prior to each measurement, the RRDE was
sequentially polished with aqueous suspensions of 1.0 and 0.3 μm alumina powder on a micro-cloth to
generate a mirror finish. The catalyst ink was prepared by mixing 3.5 mg of catalyst, 100 μL of DI water,
28 μL of 5% Nafion solution (D521, DuPont), and 1072 μL of anhydrous EtOH and homogenizing the
mixture in an ultrasonic bath (Branson) for at least 30 min. A 6-μL portion of the catalyst ink was deposited
onto a glassy carbon (GC) disk (diameter, 5.61 mm) using a micro syringe (Hamilton) and subsequently
dried at RT to attain a PGM loading of 14 μgPGM cm−2. Prior to the electrochemical measurements, the
catalyst-coated RRDE was immersed in Ar-saturated 1 M KOH and the catalyst was cleaned by cycling
the potential between 0.05 and 1.05 V for 100 cycles at a scan rate of 500 mV s−1. The CV curves were
obtained under the same conditions, but with a scan rate of 50 mV s−1 for three cycles instead. The ECSAs
were estimated using the hydrogen underpotential deposition (ECSAHupd). The ECSAHupd was estimated
by the integrated charge from the Hupd peak, which was in the range of 0.05–0.35 V in the CV. The alkaline
HER activities of the catalysts were evaluated in H2-saturated 1 M KOH solution. To measure the solution
resistance for iR-correction, EIS measurements were conducted at −0.01 V in the frequency range of 10
kHz–1 Hz and an amplitude of 10 mV with a rotation speed of 1,600 rpm. The LSV curves were recorded
by sweeping the potential from −0.2 to 0.6 V at a scan rate of 10 mV s−1 with a rotation speed of 1,600
rpm. Each LSV measurement was performed in triplicate and the averaged value was used. The catalytic
activities were presented in three difference metrics. The geometric current density (j, mA cm−2) was
calculated by dividing the measured current by the geometric area of the GC electrode. The specific
activity was estimated by normalizing the geometric current density with ECSAHupd. For turnover
frequency (TOF) calculation, the number of active sites (n) of catalysts was quantified using the Hupd
desorption charge (QHupd) with the following equation.

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n (mol) = QHupd / F (1)
where F represents the Faraday constant. It is approximated that one electron is required for the Hupd
desorption. Finally, the TOFs of catalysts can be calculated as follows.
TOF (s−1) = id / (2 × n × F) (2)
where id is the disk current of HER, n is the number of active sites, and F is the Faraday constant. The
factor ½ is based on the approximation that two electrons are transferred for the H2 evolution reaction.
A long-term stability test was conducted by performing chronopotentiometry measurements at −10
mA cm−2 with a rotation speed of 1,600 rpm. To avoid carbonate poisoning of the GC electrode, a Pt wire
electrode was used as the counter electrode instead of a carbon rod.
AEMWE single-cell tests. Electrodes for the AEMWE MEAs were fabricated using the catalyst-
coated substrate (CCS) method. The catalyst ink slurry was prepared with IrO2 (Premion®, Alfa Aesar)
as the anode catalyst and 20Ru/OMGC, 20Ru/OMC_AT, or 20Ru/OMC_AR as the cathode catalyst. Each
catalyst was mixed with IPA, a Sustainion® XB-7 alkaline ionomer (5% in EtOH, dioxide material), and
DI water. The amount of ionomer in the electrode was 30 wt% of the total solid weight. The prepared
anode and cathode inks were homogenized in an ultrasonic bath for 1 h and then cast onto titanium paper
(Bekaert) and a gas diffusion layer (SGL-39BC, SIGRACET®), respectively. For the membrane, a
Sustainion® alkaline anion exchange membrane (X37-50 grade T, Dioxide material) was used, and was
pretreated in 1 M KOH solution for 10 h prior to loading. The pretreated membrane was sandwiched
between the two electrodes by pressing under approximately 30 Nm. The single cells for AEMWE, which
were square-shaped with an area of 6.25 cm2, were filled with 0.5 M KOH solution during operation. The
KOH solutions were preheated to 50 °C and fed to the anode side with a flow rate of 3 mL min−1. During
cell testing, the cell temperature was maintained at 80 °C. The AEMWE cell performance was determined
using the voltage sweep method, from 1.35 to 2.0 V at a scan rate of 10 mV s−1, using a water electrolysis
test station and potentiostat (HCP-803, Bio-Logic). EIS was performed to examine the resistance of the
AEMWE MEA at 1.8 V with an amplitude of 10 mV and a frequency range of 50 mHz–50 kHz.
LIC performance measurement. The LIC performances were measured using a CR2032 type coin
cell (Wellcos Co.), battery tester (Wonatech, WBCS3000S), and multichannel potentiostat (BioLogic
VSP-300). The anode and cathode were prepared by pasting the slurry (active material-to-poly(vinylidene
fluoride)-to-super P weight ratio, 80:10:10) onto an 18-μm copper foil or 20-μm aluminium foil, using the
doctor blade method, followed by overnight drying in a vacuum oven at 120 °C. The loadings of the
circular carbon anode and cathode were approximately 1.0 and 3.0 mg cm–2, respectively. The half-cell
was constructed using 300-μm Li metal/PE separator (Celgard2400, Celgard®)/OMGC with an aprotic
electrolyte [1.3 M LiPF6 in ethylene carbonate and diethyl carbonate (EC/DEC, 3/7 in volume) with 10

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wt% fluorinated ethylene carbonate (FEC)]. The galvanostatic charge–discharge measurements were
performed under various current densities and voltage ranges of 3.00–0.005 and 2.5–4.5 V for the anode
and cathode, respectively. The Nyquist plots were recorded in the frequency range of 2.0×10 5–1.0×10–1
Hz with an amplitude voltage of 10 mV. For the preparation of full-carbon LIC cell, the OMGC anode
was pre-lithiated (pre-cycled twice at 0.05 A g–1; last cutoff at 0.005 V) before the LICs were assembled.
The optimized weight ratio between the anode and cathode was 1:3. The LIC energy and power densities
were calculated based on the galvanostatic discharge curves and total weight of anode and cathode active
materials using the following equations.
E = ∫ IV dt / m (3)
P = E / ∆t (4)
where E is the energy density, I is fixed current (A), V is the cell voltage (V), t is the discharge time, m is
the total weight of the anode/cathode active material (kg), P is the power density, and Δt is the total
discharge time (h).

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2. Supplementary Figures and Tables

Figure S1. a) Low- and b) high-magnification TEM images of MoC1−x synthesized in the absence of KIT-
6 template. Scale bars: 10 nm.

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Figure S2. Wide-angle XRD patterns of MoC1−x@C and OMGC. The dark grey vertical lines indicate
the peak positions of α-MoC1−x (JCPDS # 89–2868).

Figure S3. a) N2 adsorption isotherms of KIT-6, MoC1−x@C/KIT-6, MoC1−x@C, and OMGC. The
isotherms of MoC1−x@C/KIT-6, MoC1−x@C, and OMGC are upward-shifted to 600, 900, and 1,200 cm3
g−1, respectively, for clarity. b) BJH pore size distribution curves obtained from the adsorption branches
of the isotherms in a).

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Figure S4. TEM image of the carbon product prepared from pure CH4 gas. Scale bar: 10 nm.

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Figure S5. TEM images of the carbon products prepared with different carburization times of a) 1 h, b)
5 h, and c) 9 h. Low- and high-magnification images are presented in upper and lower panels, respectively.
The sample carburized for 5 h corresponds to OMGC. Scale bars: 10 nm.

Figure S6. SAXS patterns of the carbon products prepared with different carburization times of 1 h, 5 h,
and 9 h. The sample carburized for 5 h corresponds to OMGC.

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Figure S7. TEM images of the carbon products prepared with different carburization temperatures of a)
650 °C, b) 750 °C, and c) 850 °C. Scale bars: 10 nm. The sample carburized at 650 °C corresponds to
OMGC.

Figure S8. a) SAXS and b) wide-angle XRD patterns of the carbon products prepared with different
carburization temperatures of 650 °C, 750 °C, and 850 °C. The sample carburized at 650 °C corresponds
to OMGC. The dark grey vertical lines indicate the peak positions of α-MoC1−x (JCPDS # 89–2868).

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Figure S9. TEM images of the carbon products prepared with different Mo/Si molar ratios of a) 0.32, b)
0.63, c) 0.95, and d) 1.26. The sample with 0.63 of Mo/Si ratio corresponds to OMGC. Scale bars: 20 nm.

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Figure S10. a) TEM and b) HR-TEM images of OMGC_130. c) TEM and d) HR-TEM images of
OMGC_150. Scale bars: 20 nm and 5 nm for the TEM and HR-TEM images, respectively.

Figure S11. SAXS patterns of OMGC, OMGC_130, and OMGC_150.

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Figure S12. a) N2 adsorption isotherms of OMGC, OMGC_130, and OMGC_150. The isotherms of
OMGC_130 and OMGC_150 are upward-shifted to 800 and 1,600 cm3 g−1, respectively, for clarity. b)
BJH pore size distribution curves obtained from the adsorption branches of the isotherms in a). Inset:
magnified BJH pore size distribution curves of OMGC, OMGC_130, and OMGC_150.

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Figure S13. a) TEM and b) HR-TEM images of hexagonal OMGC [OMGC(S)]. Scale bars: 20 nm and
5 nm for TEM and HR-TEM, respectively. c) Small-angle XRD patterns of SBA-15 and OMGC(S). d)
N2 adsorption isotherm of OMGC(S) and (inset) the corresponding BJH pore size distribution curve.

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Figure S14. HR-TEM images of the OMGCs after post-annealing treatments under different gases and
temperatures: a) Ar and 800 °C, b) Ar and 1,000 °C, and c) H2 and 600 °C. Scale bars: 5 nm.

Figure S15. a) Small- and b) wide-angle XRD patterns of OMGC and OMGCs post-annealed under
different gases and temperatures. The dark grey vertical lines indicate the peak positions of α-MoC1−x
(JCPDS # 89–2868).

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Figure S16. TGA traces of OMGC and OMGCs post-annealed under different gases and temperatures.

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Figure S17. BJH pore size distribution curves of OMGC, OMC_AT, and OMC_AR. The curves were
obtained from the adsorption branches of the isotherms. Inset: magnified BJH pore size distribution
curves of OMGC and OMC_AT.

Figure S18. a) N2 adsorption isotherms of OMGC, CNT, and KB. The isotherms of CNT and KB are
upward-shifted to 1,000 and 2,000 cm3 g−1, respectively, for clarity. b) BJH pore size distribution curves
obtained from the adsorption branches of the isotherms in a).

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Figure S19. Diagram illustrating major advances in the development of OMCs. The developed OMC
materials together with the synthesis strategies and template materials used for the corresponding carbons
are presented.

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Figure S20. Wide-angle XRD patterns of MoC1−x@C products prepared with different carburization
temperatures of 550 °C, 650 °C, 750 °C, and 850 °C. The dark grey and pink vertical lines indicate the
peak positions of α-MoC1−x (JCPDS # 89–2868) and MoO2 (JCPDS # 74–7913), respectively.

Figure S21. TEM images of the products prepared using different transition metal endo-templates and
carburization temperatures: a) Fe and 950 °C, b) Co and 650 °C, and c) Ni and 650 °C. Scale bars: 10 nm.

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Figure S22. Particle size distribution histogram of 20Ru/OMGC, which is based on counting the size of
150 Ru particles. APS, average particle size.

Figure S23. a) HAADF-STEM image of 20Ru/OMGC and the corresponding elemental mapping images
for b) C and c) Ru. Scale bar: 10 nm.

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Figure S24. Wide-angle XRD patterns of 20Ru/OMGC, 20Ru/OMC_AT, and 20Ru/OMC_AR. The dark
grey vertical lines indicate the peak position of Ru (JCPDS # 06–0663).

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Figure S25. a) HAADF-STEM and b) bright-field STEM images of 20Ru/OMC_AT. c) HAADF-STEM

and d) bright-field STEM images of 20Ru/OMC_AR. Scale bars: 20 nm and 5 nm for the HAADF-STEM
and bright-field STEM images, respectively.

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Figure S26. Ru 3p XPS spectra of 20Ru/OMGC, 20Ru/OMC_AT, and 20Ru/OMC_AR catalysts.

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Figure S27. Nyquist plots of 20Ru/OMGC, 20Ru/OMC_AT, and 20Ru/OMC_AR at −0.01 V vs. RHE.

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Figure S28. CV curves of the catalysts in 1 M KOH for estimating their ECSAHupd values: a)
20Ru/OMGC, b) 20Ru/OMC_AT, c) 20Ru/OMC_AR, d) 20Ru/C, and e) 20Pt/C. ECSA values of the
catalysts are given in the plots.

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Figure S29. a) Low- and b) high-magnification TEM images of 20Ru/OMGC after the stability test. Scale
bars: 20 nm and 5 nm, respectively.

Figure S30. Ru 3p XPS spectra of a) 20Ru/OMGC and b) 20Ru/C before and after the stability test.

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Figure S31. Schematic illustration for the structure of an AEMWE MEA.

Figure S32. a) Low- and b) high-magnification SEM images of the AEMWE MEA employing
20Ru/OMGC and IrO2 as the cathode and anode catalysts, respectively. Scale bars: 50 µm.

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Figure S33. Bar graph comparing the electrical conductivity of OMGC, Vulcan, OMC_AT, and
OMC_AR.

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Figure S34. Carbon anode//Li metal half-cell discharge–charge voltage trajectories and CV curves: a,b)
OMGC, c,d) OMC_AT, and e,f) OMC_AR anodes, respectively. The galvanostatic charge–discharge was
conducted at 0.05 A g−1 for the 1st cycle and 0.10 A g−1 for the 2nd cycle.

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Figure S35. Cycle stability of the OMGC anode//Li metal half-cell. Inset: voltage trajectory at the specific
cycle numbers.

Figure S36. a) Performance of an OMGC cathode/Li metal half-cell evaluated by the galvanostatic
charge–discharge voltage profiles with various current densities and the voltage range of 2.5–4.5 V. Inset:
schematic illustration of the OMGC cathode//Li metal half-cell architecture. b) CV curves of the OMGC
cathode//Li metal half-cell. Voltage range: 2.5–4.5 V.

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Figure S37. Electrochemical performances of the OMGC cathode//Li metal half-cell: a) rate capability
with current densities in the range of 0.5–10.0 A g−1 and b) long-term stability at the fixed current density
of 2.0 A g−1.

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Figure S38. Schematic illustration for the structure of the OMGC//OMGC LIC.

Figure S39. a) CV curves of the full-carbon LIC. b) Galvanostatic charge–discharge voltage curves at
various current densities based on the total weight of OMGC in the LIC (OMGC mass loadings: 1.0~1.2
and 3.0~3.3 mg cm–2 for anode and cathode, respectively). c) Long-term cycle life of OMGC//OMGC at
a fixed current density of 4.0 A g–1.

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Table S1. Elemental analysis results of OMGC, OMC_AT, and OMC_AR.

C[a] H[a] O[a] N[a] Mo[b]

Sample
(wt%) (wt%) (wt%) (wt%) (wt%)
OMGC 78.2 0.6 11.7 0.2 0.1
OMC_AT 92.1 0.8 5.4 - -
OMC_AR 93.8 1.0 4.6 - -
[a]
Determined by elemental analysis.
[b]
Determined by ICP-OES analysis.

Table S2. BET surface areas, pore volumes, and pore sizes of KIT-6, OMGC, and the intermediate
samples.

BET surface area[a] Pore volume[b] Pore size[c]

Sample
(m2 g−1) (cm3 g−1) (nm)
KIT-6 630 0.9 6.8
MoC1−x @C/KIT-6 230 0.3 6.8
MoC1−x@C 100 0.8 4.4, 24.4
OMGC 1,000 2.2 3.8, 4.3, 18.5
[a]
Calculated in the relative pressure range of 0.05–0.2.
[b]
Calculated at a relative pressure of 0.98–0.99.
[c]
Determined from the adsorption branch of the corresponding isotherm using the BJH method.

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Table S3. Unit cell parameters, BET surface areas, pore volumes, and pore sizes of the pore-size-
controlled OMGCs.

Unit cell parameter[a] BET surface area[b] Pore volume[c] Pore size[d]
Sample
(nm) (m2 g−1) (cm3 g−1) (nm)
OMGC 21.51 1,000 2.2 3.8, 4.3, 18.5
OMGC_130 22.77 960 3.3 4.5
OMGC_150 23.22 940 3.4 4.5, 5.1
[a]
Calculated by Bragg equation with cubic symmetry.
[b]
Calculated in the relative pressure range of 0.05–0.2.
[c]
Calculated at a relative pressure of 0.98–0.99.
[d]
Calculated from the adsorption branch of the corresponding isotherm using the BJH method.

Table S4. Framework structures, BET surface areas, pore volumes, and pore sizes of OMGC,
OMC_AT, OMC_AR, CNT, and KB.

Framework BET surface area[b] Pore volume[c] Pore size[d]

Sample
structure[a] (m2 g−1) (cm3 g−1) (nm)
graphitic
OMGC 1,000 2.2 3.8, 4.3, 18.5
tube
amorphous
OMC_AT 1,440 1.9 3.3, 3.8, 14.0
tube
amorphous
OMC_AR 1,120 1.2 3.8
rod
graphitic
CNT 300 1.7 -
tube
graphitic
KB 800 1.3 -
nanosphere
[a]
Labelled as graphitic and amorphous according to their crystallinity, and tubes, rods, and nanospheres
according to their morphology.
[b]
Calculated in the relative pressure range of 0.05–0.2.
[c]
Calculated at a relative pressure of 0.98–0.99.
[d]
Calculated from the adsorption branch of the corresponding isotherm using the BJH method.

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Table S5. Electrical conductivity data for OMGC, OMC_AT, and OMC_AR.

Thickness[a] Resistivity[b] Conductivity[b] Sheet resistance[b]

Sample
(mm) (Ω·m) (S m−1) (Ω m−2)
OMGC 1.2 1.9E−03 590 ± 64 1.55
OMC_AT 1.3 7.7 E−02 12.6 ± 0.3 60
OMC_AR 1.0 1.5E−01 7.6 ± 0.8 150
[a]
Measured for each pelletized carbon.
[b]
Measured by the four-point van der Pauw method.

Table S6. Ru contents in the carbon supported Ru-based electrocatalysts.

Sample Ru content[a] (wt%)

20Ru/OMGC 16.6
20Ru/C 16.8
20Ru/OMC_AT 16.9
20Ru/OMC_AR 17.2
[a]
Determined by ICP-OES analysis.

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Table S7. Comparison of alkaline HER activity of 20Ru/OMGC with those of previously reported,
Ru-based electrocatalysts in terms of Ru loading, overpotential at −10 mA cm−2 (η10), and Tafel
slope. Unless otherwise noted, all catalysts were tested in 1 M KOH.

Ru loading η10 Tafel slope

Sample Ref.
(μgRu cm−2) (mV) (mV dec−1)
20Ru/OMGC 14 30 30 This work
Sr2RuO4 9.4 61 51 [11]
Ru/N-Porous C 4 26 36 [12]
Ru/N-C 7.4 32 53 [13]
Ru/CQD 15.8 10 47 [14]
Ru/Ni@Ni2P 10.9 31 41 [15]
Ru/CoP hybrid 60 23 37 [16]
Ru/Meso TiO2* 12.8 150 113 [17]
RuCo@NC 9.8 28 31 [18]
Ru@C2N 81.8 17 38 [19]
Ru NPs/Cu2−xS 25.5 82 48 [20]
RuP2/NPC 233 52 69 [21]
Ru/C3N4/C* 2 79 - [22]
* The sample was tested in 0.1 M KOH.

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Table S8. Comparison of electrochemical performance of the OMGC-based LIC device with those
of previously reported electrodes.

Energy Power
Voltage Cycle number (n) /
density density
LIC structure window Capacity retention (%) / Ref.
(Wh kg−1) (W kg−1)
(V) Current density (A g−1 or C)
(max ~ min) (min ~ max)
OMGC//OMGC 0.005 – 4.5 312 ~ 58 1,139 ~ 12,168 10,000 / 86.9 / 4 A g−1 This work
AC//graphite 1.5 – 4.5 104 (max) 10,000 (max) 10,000 / 86 / 0.65 A g−1 [23]
AC//hard carbon 1.5 – 3.9 96 (max) 7,400 5,000 / 96 / 2 C [24]
AC//Li4Ti5O12 1.0 – 2.5 30 ~ 15 1,000 ~ 4,000 10,000 / 71 / 10 C [25]
AC//Li3VO4N 1.0 – 4.0 136 ~ 24 532 ~ 11,020 1,500 / 87 / 2 A g−1 [26]
APDC//VN-rGO 0.0 – 4.0 162 ~ 64 200 ~ 10,000 1,000 / 83 / 2 A g−1 [27]
AC//V2O5/CNT 0.1 – 2.7 38 ~ 7.5 140 ~ 5,000 10,000 / 80 / 60 C [28]
M-Nb2O5//C 1.0 – 3.5 74 ~ 15 100 ~ 18,510 1,000 / 90 / 1 A g−1 [29]
AC//T-Nb2O5/Gr 0.8 – 3.0 47 ~ 15 393 ~ 18,000 2,000 / 93 / 0.25 A g−1 [30]
AC//TiO2/rGO 1.0 – 3.0 42 ~ 8.9 800 ~ 8,000 10,000 / 80 / 4 A g−1 [31]
3DGr//Fe3O4/Gr 1.0 – 4.0 147 ~ 86 150 ~ 2,587 1,000 / 70 / 2 A g−1 [32]
ANCS//ANCS 0 – 4.5 208 ~ 115 225 ~ 22,500 10,000 / 86 / 4 A g−1 [33]
BNC//BNC 0 – 4.5 220 ~ 104 225 ~ 22,500 5,000 / 81 / 2 A g−1 [34]

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