pubs.acs.

org/JPCC Article

Enhancing Reactivity of SiC-Supported Graphene by Engineering

Intercalated Metal Atoms at the Interface
Kah-Meng Yam, Na Guo, Zhuoling Jiang, Shulong Li, and Chun Zhang*
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ABSTRACT: Controlling the reactivity of graphene with effective yet practical

physical/chemical methods has been known to be the key for many applications of
graphene including graphene-based solid-state catalysis. Here, by state-of-art ab initio
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modeling, we present a new avenue to enhance reactivity and catalytic activity of

graphene that is supported on a SiC substrate. We show that intercalated metal atoms
(e.g., Ru atoms) at the SiC−graphene interface form a self-assembled two-dimensional
monolayer with hexagonal lattice, and by controlling the concentration of the metal
atoms, the reactivity of the supported graphene could be greatly enhanced, resulting in
the chemisorption of O2 molecule on graphene. Detailed analysis revealed that the O2
chemisorption originates from the charge transfer of nearly one electron from the
activated graphene to the O2 2π* orbital. We further show that the activated graphene
can be an excellent catalyst toward CO oxidation reaction.

1. INTRODUCTION homogeneous epitaxial graphene.15 While graphene can grow

It has been convincingly shown that graphene has great
potential in applications in both solid-state physics (as an
excellent electronic material)1−3 and solid-state chemistry (as
an excellent catalyst)4−10 owing to its peculiar electronic
properties and the ease of modulating it.4 Graphene is gapless
and chemically inert so that certain types of “preprocessing” of
graphene are necessary in both electronics (for band gap
opening) and catalysis (to catalytically activate graphene)
applications, for which an efficient yet practical way of
controlling the reactivity of graphene often plays a key role.
Many ways of controlling graphene reactivity have been
proposed in the literature such as applying a moderate
mechanical strain,8 introducing vacancy defects11 or impurity
atoms,7,12 and decorating with functional groups.9,13 Very
recently, it was shown that the reactivity of graphene can be
greatly enhanced by engineering the underlying metal substrate
for which the direct treatment of graphene can be avoided, and
then graphene can be turned into an excellent solid-sate
catalyst.10,14 Here, by state-of-art first-principles calculations,
we present a novel way of controlling the graphene reactivity
that is supported on a nonmetal substrate by engineering the
intercalated metal atoms at the interface. We show that the
system can be an excellent catalyst with greatly reduced
amount of Ru atoms compared with the previously proposed
Ru-supported graphene catalyst,10 which may have the
potential to impact future applications of graphene-based
solid-state catalysis.
Besides chemical vapor deposition over appropriate metal
substrates, graphitization via high-temperature annealing of
hexagonal silicon carbide (SiC) is another promising method
employed to realize industrial production of large-area,
on either the silicon-terminated SiC(0001) surface or carbon-
terminated SiC(0001), growth on the SiC(0001) surface is
more extensively studied between the two and can allow better
control of the process and therefore produce graphene of
higher quality. Thus, in this study, the SiC(0001) surface is
chosen for which graphene is deposited on.
During the graphitization on either 4H- or 6H-SiC(0001),
surface thermal decomposition takes place where Si in various
moieties sublimes away from the sample surface in an inert
ultrahigh vacuum (UHV) condition. A (6 3 × 6 3 )R 30°
(6R3) surface reconstruction was observed during the process,
where the 6R3 reconstruction corresponds to the first single
layer of carbon atoms with the atomic arrangement similar to
graphene, commonly known as the buffer layer (BL).16−19 In
previous computational studies, it has been shown that the so-
called R3 model16,20 with a 2 × 2 supercell of graphene and a
( 3 × 3 )R 30° supercell of SiC is able to correctly
reproduce the structure and electronic properties of the BL
on SiC(0001). The model was then widely used in the
literature to study SiC−graphene-based systems.17,21,22 Here,
we employed the same model in our calculations. To model
hexagonal SiC substrate, the 4H-SiC polytype structure is
chosen with four bilayers of SiC, and a flat graphene layer was
Received: June 10, 2020
Revised: July 16, 2020
Published: July 29, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jpcc.0c05286

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The Journal of Physical Chemistry C
Figure 1. Relative formation energy of the intercalated Ru atoms as a function of concentration (number of atoms) of Ru atoms (n). The lowest-
energy configuration for each concentration is imposed. Ru is in yellow. Then the formation energy of the the most stable concentration (16 Ru
atoms in the supercell) is set as the reference. Note that from the lowest to highest concentrations shown in the figure, the number of Ru atoms in
the supercell increases from 14 to 18.
placed on top of the SiC(0001) surface while the dangling
bonds on the SiC(0001) surface were passivated with
hydrogen atoms. The bottom two bilayers were fixed to
simulate the bulk. A vacuum layer of at least 12 Å was included
to prevent significant interactions between the periodic images
in the [0001] direction.
After structural optimization, it was observed the formerly
flat graphene buckled to give the BL. It is evident that there are
two types of carbon atoms in this BL: the first type is one with
a Si atom directly underneath, and the second type is without.
The first type (1Cgr) forms covalent bonds with the underlying
Si atoms resulting in sp3 hybridization, relaxed toward the
substrate with a 1Cgr−Si bond length of 2.0 Å. On the other
hand, the average vertical distance of the second type (2Cgr)
away from the substrate is about 2.5 Å, and these atoms retain
their sp2 hybridization. Furthermore, the average binding
energy of graphene on SiC(0001) is 0.34 eV per graphene unit
cell. The calculated structure parameters and the electronic
energy band structure (as shown in Figure S1) that we
obtained agree very well with previous reports.17,20,21
2. COMPUTATIONAL DETAILS
All first-principles calculations are carried out under the
ground-state spin-polarized density functional theory (DFT)
formalism implemented in the Vienna ab initio simulation
package (VASP).23,24 Activation barriers of the catalyzed CO
oxidations were determined by the climbing image nudged
elastic band (cNEB) method.25 The generalized gradient
approximation (GGA) in the Perdew−Burke−Ernzerhof
(PBE) format26 and the projector augmented-wave (PAW)
method27 are employed in all calculations. A plane wave basis
with the cutoff kinetic energy of 400 eV is used. The energy
and force convergence criteria are set to 10−4 eV and 0.02 eV/
Å respectively for all structural optimizations.
3. RESULTS AND DISCUSSIONS
Intercalation at the gr−SiC interface using different metal
atoms has been extensively studied both experimentally and
theoretically,28−36 but the implications of such system in
applications of graphene-based catalysis have not been
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discussed. In this paper, we perform ab initio calculations to
provide a comprehensive understanding of the two-dimen-
sional (2D) monolayer formed by intercalated Ru atoms and
then propose that the intercalated metal atoms at the interface
could be used as an effective tool to tune the catalytic activity
of graphene. We show that by controlling the concentration of
interaction of Ru atoms, the reactivity and the catalytic activity
of the supported graphene could be greatly enhanced, leading
to O2 chemisorption and a low reaction barrier of CO
oxidation. Ru was chosen as the intercalating species because
previous studies have shown that Ru−graphene interaction can
be used as an excellent tool to activate graphene.10 We start by
investigating how the concentration of Ru atoms affects the
atomic and electronic structures of intercalated atoms at the
interface. We found that when the concentration is not too
high, the intercalated Ru atoms form a 2D self-assembled
monolayer at the interface, similar to other metal species that
were observed in experiments.
In Figure 1, we plotted the relative formation energy per Ru
atom of the monolayer as a function of the concentration of Ru
atom. Different concentration corresponds to different number
of Ru atoms (n) in the supercell. The most stable (lowest
formation energy) configuration is found to be 23.6 g/cm2 (or
n = 16). In the figure, the formation energy of the most stable
case is set to zero. Note that other than n = 16, there are
actually a few different stable configurations for each
concentration or each n. The structures shown in the figure
are the energetically most stable ones at each n. The top view
of those structures can be found in Figure S2 in the Supporting
Information. When n > 17, Ru atoms start to form clusters,
breaking the 2D structure. We picked the n = 16 case as the
model system for further investigations. In this case, Ru atoms
are underneath the C−C bridge sites (Figures 2a and 2b) and
form a 2D pattern with a hexagonal lattice (see Figure S3 in
the Supporting Information for details). The average Ru−Ru
bond length is around 2.67 Å, very close to the lattice constant
of 2.71 Å of bulk Ru, which is why this case gives the lowest
formation energy. The supported graphene is more planar than
the case without intercalation. To further confirm the
structure, we performed calculations with the minima hopping
algorithm as implemented in the atomistic simulation environ-
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Figure 2. (a) Top and (b) side view of the optimized gr/SiC system
with 16 intercalated Ru atoms (one unit cell). The sites of the four
inequivalent Ru atoms in the unit cell are labeled as 1, 2, 3, and 4 in
red in (a). (c) Calculated band structure and DOS of the system. The
color bar for the band structure indicates the contribution of Ru states
to the bands. We see that around the Fermi energy, the bands are
mainly from Ru.
ment (ASE) interfaced with VASP as the external calcu-
lator.37,38 The main results are shown in Figure S5 in the
Supporting Information where we can see that the same
interfacial structure is refound.
In Figure 2c, the calculated band structure and the projected
density of states (DOS) of the whole system (gr/SiC with 16
intercalated Ru atoms) are plotted, where we can see that now
the system is very metallic, with the states near the Fermi level
originating mainly from the interfacial 2D Ru monolayer. Since
there is still a low number of states around the Fermi level
coming from graphene, it is expected that after intercalation
graphene is still not reactive. Indeed, our calculations show that
in this case, the O2 molecule still does not bind onto graphene,
which is consistent with the previous report that the epitaxial
graphene grown on pristine Ru substrate remains inert toward
the chemisorption of O2.10 This also indicates that the R3
model used in calculations is able to predict a reliable reactivity
of graphene toward O2 adsorption in the case under study.
Next, we consider tuning the reactivity of graphene by
engineering the underlying Ru monolayer.
We shall abbreviate the Ru intercalated system of gr/SiC as
gr/Ru/SiC from this point onward. We will show that the
defect-engineered intercalated Ru layer at the interface could
greatly improve the reactivity of graphene. The defect here
refers to a single vacancy in the Ru layer. Single vacancies can
be introduced by controlling the concentration of Ru atoms.
There are four inequivalent sites for Ru atoms in one unit cell,
labeled as 1, 2, 3, and 4 in red in Figure 2a. Consequently,
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there are four different types of single vacancies in the Ru layer.
Note that the formation energies of those four single vacancies
are close to each other with the lowest-energy vacancy
appearing at site 3 (corresponding to the structure of n = 15
case shown in Figure 1), and the highest-energy one appears at
site 1. The difference in formation energy between these two
sites is around 0.05 eV per Ru. The system with the vacancy-
engineered Ru layer will be abbreviated as gr/sv-Ru/SiC.
The vacancy-engineered Ru layer at the interface greatly
enhances the reactivity of the supported graphene. Our
calculations show that after introducing a single vacancy, O2
binds onto the graphene with a side-on configuration, forming
bonds with two C atoms right above the vacancy in the Ru
monolayer. The O2 adsorption energies for different types of
single vacancies, the Oads−Oads bond length of adsorbed O2
(abbreviated as O2*) on graphene, and the electrons O2*
gained and the underneath C atoms lost after adsorption from
Bader charge analysis39,40 are all tabulated in Table 1. For all
Table 1. O−O Bond Length of O2* in Å on Graphene
(r(O2*)), Corresponding Adsorption Energy in eV
(Eads(O2)), Number of Electrons Gained by the O2*, and
the Number of Electrons Lost by the Binding C Atoms
underneath the O2* Moleculea
Eads(O2*)/ e− gained by O2*/| e− lost by the C
site r(O2*)/Å eV e| atoms/|e|
1 1.48 0.30 0.93 0.89
2 1.49 0.58 1.00 0.89
3 1.49 0.79 1.02 0.95
4 1.49 0.80 1.02 0.97
a
Electron transfer is calculated by Bader charge analysis.
four types of vacancies (sites 1−4), O2* gained about one
electron, which are lost by the two binding C atoms
underneath, indicating the Ru vacancy induced charge transfer
from graphene to O2, thus resulting in the reasonably strong
chemisorption for all cases.
To further show the origin of the high reactivity of graphene
after intercalation, we calculated the charge redistribution
caused by the interaction between graphene and the 2D Ru
monolayer with a single vacancy for all cases (site 1 case is
shown in Figures 3a and 3b; the other three sites can be seen
in Figure S4 in the Supporting Info). The charge redistribution
in this case is defined as δρ = ρgr/sv‑Ru/SiC − (ρgr + ρsv‑Ru/SiC).
We see that the vacancy weakens the local interaction between
the Ru 2D monolayer and the two C atoms in graphene right
above the vacancy (circled by a red dotted line in Figure 3a−
b), making the local part of the graphene not as planar as
before. The vacancy induced changes in local bonding
symmetry and electron distribution, causing the different
reactivity of two C atoms right above the vacancy from other
parts of inert graphene.
To see more clearly how those two activated C atoms
interact with the O2 molecule, we plotted in Figures 3c and 3d
the charge redistribution caused by the O2 adsorption, defined
as δρ = ρO2@gr/sv‑Ru/SiC − (ρgr + ρsv‑Ru/SiC + ρO2) (see Figure S4
for the other three vacancy sites). The figure clearly shows that
there are significant charges transferred from two activated C
atoms to the antibonding 2π* orbital of O2*. The density of
states projected onto O2* and the two activated C atoms in
graphene before and after O2 adsorption (Figure 3e)
confirmed the charge transfer from binding C atoms to O2*.
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Figure 3. (a) Top view and (b) side view for the optimized structure of gr/sv-Ru/SiC with the defect at site 1 superimposed with the charge
redistribution. The site of the defect is circled in red with a dashed line in (a). The charge redistribution is defined as δρ = ρgr/sv‑Ru/SiC − (ρgr +
ρsv‑Ru/SiC), and green (blue) represents the electron accumulation (depletion). (c) Top view and (d) side view of the O2 adsorption configuration
with the isosurfaces of charge redistribution caused by the O2 adsorption. Here, the charge transfer is defined as δρ = ρO2@gr/sv‑Ru/SiC − (ρgr +
ρsv‑Ru/SiC+ ρO2) with the same color scheme as above, and the isosurface is set at 0.003 |e| Å−3. (e) Projected density of states of O2 and two binding
C atoms in graphene before/after adsorption.

Before adsorption (an isolated O2 and the gr/sv-Ru/SiC), the

paramagnetic O2 molecule has a spin-down 2π* orbital as its
lowest unoccupied molecular orbital (LUMO). After adsorp-
tion, electrons transfer from the states of the binding C atoms
near the Fermi level to the O2 LUMO, pulling the LUMO
below the Fermi level.
The significant elongation of the O−O bond from 1.23 Å in
the gas phase to around 1.48 Å (Table 1) implies that the O2*
molecule is ready for catalyzed chemical reactions. We now use
the CO oxidation reaction to probe the catalytic activity of gr/
sv-Ru/SiC. We pick the site 1 case in Table 1 as a test since the
site 1 adsorption gives the shortest O−O bond length so shall
be the most nonreactive one among all four cases. According
to our calculations, the CO molecule does not adsorb onto the
supported graphene, so the catalyzed reaction should happen
in the Eley−Rideal (ER) mechanism. We investigate the ER
type of CO oxidation catalyzed by gr/sv-Ru/SiC via the cNEB
method.30 As such, a complete cycle of the catalyzed CO
oxidation consists of two steps: (1) CO (g) + O2 (ads) → CO2
(g) + O (ads) and (2) CO (g) + O (ads) → CO2 (g). The
calculated energy profiles of the two-step reaction along the
reaction path are shown in Figure 4. In the first step, the CO
molecule approached the adsorbed O2 molecule from 2.63 to
1.90 Å away to reach the transition state (TS), resulting in the
r(O2*) to increase from 1.48 to1.52 Å. In the second step, the Figure 4. cNEB calculations for the two reaction steps of catalyzed
CO molecule approached the adsorbed O atom to be only 1.72 CO oxidation by gr/sv-Ru/SiC with the defect at site 1 in the ER
Å away to reach the TS. Both steps have low reaction barriers, mechanism: (a) CO (g) + O2 (ads) → CO2 (g) + O (ads) and (b)
CO (g) + O (ads) → CO2 (g). Atomic structures of the initial state
0.35 eV for the first step and 0.47 eV for the second step, (IS), the transition state (TS), and the final state (FS) are also shown
indicating the high activity of the catalyst. It is worth with the same color scheme as before.
mentioning here that other reaction mechanisms (e.g., the
CO insertion mechanism41) may also be possible for the
catalyzed CO oxidation. interface with single vacancies (which can be done by
controlling the concentration of Ru atoms), the reactivity of
the supported graphene can be greatly enhanced, leading to
4. CONCLUSION reasonably strong chemisorption of O2 molecules. Using the
As a summary, by ab initio calculations, we find that the CO oxidation reaction as a probe, we show that with the
intercalated Ru atoms at the graphene and SiC interface form a underlying vacancy-engineered 2D Ru monolayer, graphene
self-assembled 2D monolayer with hexagonal lattice, and we exhibits high catalytic activity. Compared with previously
then propose that by engineering the 2D Ru layer at the proposed graphene catalyst supported on Ru substrate, the
D https://dx.doi.org/10.1021/acs.jpcc.0c05286
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
catalyst we suggest here has a greatly reduced amount of Ru,
which is important for real applications. These results provide a
new way for the controlling the reactivity and catalytic activity
of graphene, which may have potential for future applications
of graphene-based solid-state catalysis.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.0c05286.
Band structure of gr/SiC; top view of the optimized
structures of lowest-energy gr/Ru/SiC of different
concentrations of interfacial Ru atoms in the cell,
corresponding to different concentrations; the optimized
2d structure of interfacial Ru monolayer; the top view of
the optimized structure of various of gr/sv-Ru/SiC
systems superimposed with the corresponding charge
redistribution; results from the minima hopping
calculations (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Chun Zhang − Department of Physics and Centre for Advanced
2D Materials and Department of Chemistry, National
University of Singapore, Singapore 117542; orcid.org/
0000-0002-1581-5806; Email: phyzc@nus.edu.sg
Authors
Kah-Meng Yam − Department of Physics and Centre for
Advanced 2D Materials and Department of Chemistry,
National University of Singapore, Singapore 117542
Na Guo − Department of Physics and Centre for Advanced 2D
Materials, National University of Singapore, Singapore 117542
Zhuoling Jiang − Department of Physics and Centre for
Advanced 2D Materials, National University of Singapore,
Singapore 117542
Shulong Li − Department of Physics and Centre for Advanced
2D Materials, National University of Singapore, Singapore
117542
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.0c05286
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We acknowledge the support from the NUS academic research
fund (R-144-000-410-114), NUS green energy program (R-
143-000-A63-114), and Ministry of Education of Singapore
(R-723-000-029-112). Computational works were performed
at the Graphene Research Centre computing cluster facilities.
■
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