Active Edge-Site-Rich Carbon Nanocatalysts with Enhanced Electron Transfer for Efficient Electrochemical Hydrogen Peroxide Production

Article abstract of DOI:10.1002/anie.201812435

A highly efficient, metal-free carbon nanocatalyst is presented that possesses abundant active, oxygenated graphitic edge sites. The edge site-rich nanocarbon catalyst exhibits about 28 times higher activity for H₂O₂ production than a basal plane-rich carbon nanotube with a H₂O₂ selectivity over 90 %. The oxidative treatment further promotes the H₂O₂ generation activity to reach close to the thermodynamic limit. The optimized nanocarbon catalyst shows a very high H₂O₂ production activity, surpassing previously reported catalysts in alkaline media. Moreover, it can stably produce H₂O₂ for 16 h with Faradaic efficiency reaching 99 % and accumulated H₂O₂ concentration of 24±2 mm. Importantly, we find that the heterogeneous electron transfer kinetics of the carbon-based catalyst is closely related to the electrocatalytic activity, suggesting that first outer-sphere electron transfer to O₂ is an important step governing the H₂O₂ production rate.

Full text of DOI:10.1002/anie.201812435

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Accepted Article
Title: Active Edge Site-Rich Carbon Nanocatalysts with Enhanced
Electron Transfer for Efficient Electrochemical Hydrogen
Peroxide Production
Authors: Young Jin Sa, Jae Hyung Kim, and Sang Hoon Joo
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201812435
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COMMUNICATION
Active Edge Site-Rich Carbon Nanocatalysts with Enhanced
Electron Transfer for Efficient Electrochemical Hydrogen
Peroxide Production
Young Jin Sa, Jae Hyung Kim, and Sang Hoon Joo*
Abstract: Electrochemical hydrogen peroxide production enables
clean and on-site production of H , for which highly active and
and atomically dispersed Pt, have demonstrated excellent
catalytic activity and selectivity for H
production.[5] As low-
2
O
2
2 2
O
selective electrocatalysts are of crucial importance. Here, we report
a highly efficient, metal-free carbon nanocatalyst that possesses
abundant active, oxygenated graphitic edge sites. The edge site-rich
cost alternative electrocatalysts, metal-free carbon materials
have been recently received increasing attention, particularly for
2 2
H O production in alkaline media, where the reaction bath can
[
6]
nanocarbon catalyst exhibits ~22 times higher activity for H
2
O
O
2
be directly utilized in some applications. As pristine carbons
are inactive as electrocatalysts, it is important to activate the
inert carbon surfaces by creating defective carbon sites and
doping heteroatoms. Graphitic carbon edges have been
demonstrated to exhibit much superior (electro)catalytic
properties than those of basal carbons owing to the modified
local electronic structure.[7] In addition to the enhanced intrinsic
reactivity, the edge sites are subject to a facile chemical
modification owing to their more reactive nature than basal
carbons, enabling a rational design of doped carbons. However,
typical graphitic carbons, such as graphene and carbon
nanotube (CNT), have a large proportion of basal carbon planes.
Moreover, a top-down fabrication of edge-rich carbons from
these carbons can cause structural damages, leading to
deterioration of the materials properties.
production than a basal plane-rich carbon nanotube with a H
2
2
selectivity over 90%. The oxidative treatment further promotes the
generation activity to reach close to the thermodynamic limit.
The optimized nanocarbon catalyst shows very high
production activity, surpassing previously reported catalysts in
alkaline media. Moreover, it can stably produce H for 16 hours
with Faradaic efficiency reaching 99% and accumulated
concentration of 24 mM. Importantly, we find that the
2 2
H O
a
2 2
H O
2 2
O
2 2
H O
±
2
heterogeneous electron transfer kinetics of the carbon-based
catalyst is closely related to the electrocatalytic activity, suggesting
that first outer-sphere electron transfer to O
governing the H production rate.
2
is an important step
2
O
2
Hydrogen peroxide (H
most important chemicals in a high industrial demand. The
current production of H depends predominantly on the
2 2
O ) is a green oxidant and one of the
[
1]
In this work, we demonstrated that a graphitic carbon
nanocatalyst with exposed abundant edge sites could catalyze
2 2
O
anthraquinone process.[2] However, this process involves multi-
step reactions and separations, which require enormous energy
and produce organic wastes. In addition, the use of precious
2 2
H O production with a ~22 times higher mass activity than that
of a basal plane-rich CNT. Additional oxidative treatments of the
graphitic carbon nanocatalyst could preferentially generate
active oxygenated species at the carbon edge, which further
2
metal catalysts and high-pressure H in the hydrogenation step
further increase the production cost.[ These drawbacks have
triggered the investigation of alternative production
technologies. Electrochemical H generation via the oxygen
reduction reaction (ORR) is an appealing method that allows
low-cost, green, continuous, and on-site production of H
.[3]
However, H production from the ORR competes with the
complete reduction of O
2]
2 2
promoted the catalytic activity for H O production reaching
H
O
2 2
close to the thermodynamic limit. It was revealed that the activity
improvement through the edge-rich design and oxidative
promotion could be correlated to the heterogeneous electron
transfer (ET) rate, thereby suggesting that the first outer-sphere
2 2
O
2 2
O
O
2 2
2 2 2
ET to O was a critical step determining the H O
production rate.
for 16
–
to H
2
O via a four-electron (4e ) transfer, The optimized nanocarbon catalyst stably produced H O
2 2
2
and thus, requires efficient electrocatalysts that can selectively
promote the two-electron ORR.[4]
h
2 2
without activity loss. In addition, a significant H O
accumulation of 24 ± 2 mM was achieved, demonstrating its
tremendous potential for direct utilization in areas such as
bleaching and acidic waste treatments.
Precious metal-based catalysts comprising engineered
active sites, such as bimetallic Pt–Hg and Pd–Hg nanoparticles
Catalyst preparation consisted of the infiltration of an
aromatic carbon precursor into a mesoporous silica with a
hexagonal mesostructure, graphitization, and removal of the
silica template. The mesopores in the silica template acted as
nanoreactors within which confined graphitization generated
nano-sized graphite, whereas its silica frameworks transformed
into mesopores after the removal of the template. The resulting
graphitic ordered mesoporous carbon (GOMC) showed a CMK-
[
*]
Dr. Y. J. Sa, J. H. Kim, Prof. S. H. Joo
Department of Energy Engineering and School of Energy and
Chemical Engineering
Ulsan National Institute of Science and Technology (UNIST)
Ulsan 44919 (Republic of Korea)
E-mail: shjoo@unist.ac.kr
Dr. Y. J. Sa
-like mesostructure with graphitic frameworks.[8] The GOMC
3
Clean Energy Research Center
Korea Institute of Science and Technology (KIST)
Seoul 02792 (Republic of Korea)
retained the parental hexagonal periodic mesostructure of the
silica template as revealed by the small-angle X-ray diffraction
(
XRD) patterns (Figure S1). The transmission electron
Supporting information for this article is given via a link at the end of
the document.
microscopy (TEM) image of the GOMC shows a hexagonal
array of carbon nanorods with a diameter of ~9 nm (Figure 1a).
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COMMUNICATION
Figure 1. a) Side-view TEM image of the GOMC (inset: top-view TEM image, scale bar = 25 nm). High-resolution TEM image of b) the
GOMC and c) CNT with schematic models for each carbon. d) XRD patterns e) Raman spectra, and f) C 1s XPS spectra of the GOMC
and CNT.
The high-resolution TEM image exhibits a vertical stacking of
slightly wrinkled graphitic nanosheets with nanopores present
between the graphitic rods (Figure 1b). This characteristic
nanostructure of the GOMC enables a high degree of utilization
of the graphitic edges in the carbon nanorods. For comparison,
we prepare an acid-leached CNT mainly comprising of graphitic
basal planes (Figure 1c). We note that acid-leaching is an
important step for removing the iron impurities from the original
CNT, which can otherwise catalyze the Fenton reaction causing
The electrocatalytic performances of the GOMC and CNT for
2 2
H O production via ORR were examined in 0.1 M KOH using
the rotating ring disk electrode (RRDE) technique. The
polarization curves of the catalysts presented in Figure 2a reveal
that the GOMC exhibits a much higher ORR activity than that of
the CNT, indicated by a positive shift of the onset potential by 65
mV in the GOMC (0.78 V vs. reversible hydrogen electrode;
2 2
RHE). The kinetic current of the GOMC for H O production at
0.75 V is 22 times higher than that of the CNT (Figure 2b). In
addition, the GOMC and CNT have similar Brunauer-Emmett-
underestimation of the
H
O
2 2
production capability of the
CNT.[6d,9] The XRD pattern of the GOMC exhibits a broader and
negatively shifted peak for the (002) plane of graphite than that
of the CNT, indicating a smaller grain size and larger interplanar
distance in the GOMC (Figure 1d). The defective nature of
GOMC was verified by Raman spectroscopy. The Raman
spectrum of the GOMC shows a broad D band peak, indicative
of the presence of a large portion of defective carbons, along
with a sharp G band (Figure 1e).[ In contrast, the CNT exhibits
sharp Raman peaks for both the D and G bands. Carbon 1s X-
ray photoelectron spectroscopy (XPS) further suggests that the
GOMC has more defective carbon sites than those in the CNT,
Teller (BET) surface areas of 279 and 187 m g , respectively
(Figure S3 and Table S1). The most dramatic structural
difference between the GOMC and CNT is the density of edge
sites. Therefore, the graphitic carbon edges in the GOMC seem
2
−1
to be the major active sites for the electrochemical H
generation. Furthermore, the GOMC exhibits a high selectivity
for H of >90% over the entire potential range investigated,
2 2
O
2 2
O
10]
whereas the CNT is less selective than the GOMC, particularly
close to the onset potential (Figure 2c). The Koutecky-Levich
2 2
analyses also indicate a high two-electron (H O ) selectivity of
the GOMC (Figure S4).
2
[6e]
evidenced by the wider peak for sp C (Figure 1f). The higher
XPS signals for the oxygenated carbon species in the GOMC
are presumably due to O-doping, which may originate from the
silica template (Figure S2). The oxygen content of the catalysts
determined by combustion analysis were 2.4 wt% for the GOMC
and 1.0 wt% for the CNT.
2 2
We next explored the possibility of further promoting H O
production via doping of the oxygenated species in the high-
performing GOMC. For this purpose, the GOMC was acid-
treated in nitric acid, and the oxidation degree was controlled by
adjusting the treatment time from 1 hour to 8 hours.
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COMMUNICATION
a) 0.6
the generation of abundant O species after the acid-treatment,
the periodic nanoporous structure and graphitic nature of the
GOMC were retained. This is indicated by the similar XRD
iperoxide
0.4
0.2
0.0
2
patterns and N physisorption isotherms of the GOMC and o-
GOMCs (Figures S3, S6, and Table S1). Incorporation of O
atoms into the carbon is verified via XPS analyses, wherein the
intensities of C–O, C=O, and O–C=O increase on increasing the
treatment duration (Figure S7). It is noteworthy that the C 1s
XPS intensity for the –* shake-up (Figure S7a) and Raman
spectra (Figure S8) of the o-GOMCs are preserved even after
the acid treatments. The Raman and XPS results indicate that O
atoms are mainly incorporated at the carbon edge sites. We
note that the O dopants at the carbon edge were suggested as
active sites for the two-electron ORR.[6d,6e] Therefore, this unique
structural feature of o-GOMCs is expected to be favorable for
-0.2
-0.4
-0.6
CNT
GOMC
0
.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
E − iR (V vs. RHE)
b) 0.85
electrochemical H
2 2
O production.
0
0
0
0
0
0
.80
.75
.70
.65
.60
.55
The ORR activities and H
2
2
O selectivities of the o-GOMCs
GOMC
are presented in Figure 3. The oxidative modification of the
GOMC can further improve the ORR activity, as indicated by the
positively shifted polarization curve of o-GOMC-1 compared with
GOMC (Figure 3a). It should be noted that the onset potential of
0.81 V (vs. RHE) is almost close to the thermodynamic limit of
the two-electron ORR.[ Therefore, the o-GOMC-1 catalyst with
abundant O-containing carbon edges is highly active for
CNT
6e]
2 2
electrochemical H O production. However, as the oxidation time
is increased, the ORR activity deceases (Figure 3a). This
indicates that the ORR activity of the GOMC follows a volcano-
like trend with the O-doping level. In contrast, the acid-treatment
does not affect the reaction mechanism, as revealed by the
0
.001
0.01
0.1
1
ik,peroxide (mA)
c) 100
2 2
similar H O selectivities and Tafel slopes (Figure 3b and
GOMC
Figures S9, S10). Therefore, O-doping at the carbon edge
boosts the reaction rates while maintaining a high selectivity of
over 90%.
9
8
7
6
0
0
0
0
The long-term stability of o-GOMC-1 was tested via
chronoamperometry (average of three repetitions) at 3 mA for 16
h using an H-type electrochemical cell. After a prolonged
operation, ~96% of the initial current is retained, demonstrating
its excellent stability (Figure 3c). To determine the Faradaic
CNT
efficiency for H
electrolyte was analyzed using iodometric titration.
quantification result indicates that the H Faradaic efficiency
of o-GOMC-1 is 99%, which corresponds to H accumulation
2 2 2 2
O production, the amount of H O in the tested
[
6e]
The
0
.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
2 2
O
E − iR (V vs. RHE)
2 2
O
of 24 ± 2 mM. This concentration is sufficiently high for direct
Figure 2. a) Polarization curves of the GOMC and CNT for the ORR
solid lines) and H production (dashed lines) measured in O
saturated 0.1 M KOH at an electrode rotation speed of 1600 rpm and
b) corresponding Tafel plots for the H production. The peroxide
current was calculated by the correction of the ring current with the
usage in some applications such as bleaching.[2,4b]
(
2
O
2
2
-
It is also worthwhile to note that the o-GOMC-1 catalyst did
not deteriorate in the presence of the oxidizing chemical (i.e.,
2
O
2
H
2 2
O )
and did not further catalyze the reduction or
collection efficiency of the RRDE. c) H
using the RRDE method.
2 2
O selectivity determined
decomposition of H during the reaction. This can be ascribed
2 2
O
to the robust graphitic carbon framework, which is, however,
active owing to the presence of oxygenated edges. These
excellent electrochemical performances of o-GOMC-1 surpass
those of most the other reported carbon nanocatalysts in
The resulting catalysts were denoted as o-GOMC-X (X:
oxidation time). The oxygen content was increased from 2.4 to
[
6]
10.1–16.2 wt% after oxidation for 1–8 hours (Figure S5). The
alkaline
media
(Figure
S11
and
Table
S2).
edge-rich structure of the GOMC could facilitate the oxygen
incorporation into carbon, leading to O content increase by 7.7
wt% after just 1 h of oxidative treatment. We noted that despite
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COMMUNICATION
a)
b) 100
0
0
0
0
.6
.4
.2
.0
i
peroxide
95
90
85
80
75
GOMC
-
-
-
-
0.2
0.4
0.6
0.8
o-GOMC-1
o-GOMC-3
o-GOMC-8
GOMC
o-GOMC-1
o-GOMC-3
o-GOMC-8
70
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
E − iR (V vs. RHE)
E − iR (V vs. RHE)
c)
0
1
2
3
4
o-GOMC-1
-
-
-
-
Faradaic efficiency = 99%
0
2
4
6
8
10
12
14
16
Time (h)
Figure 3. a) Polarization curves of the GOMC and o-GOMCs for the ORR (solid lines) and H production (dashed lines) measured in
2
O
2
O
2
-saturated 0.1 M KOH at an electrode rotation speed of 1600 rpm and b) corresponding H O selectivity determined using the RRDE
2 2
method. The peroxide current was calculated from the correction of the ring current with the collection efficiency of the RRDE. c)
Chronoamperometic response of o-GOMC-1 in O -saturated 0.1 M KOH in an H-type electrochemical cell.
2
The enhanced ORR activity of doped carbon materials to
production has been predominantly substantiated by
materials and further supports that the rate-determining step is
the first outer-sphere ET to O . The ability of the catalyst for the
H
O
2 2
2
computational methods that provide free energies of the reaction
intermediates, which are, however, hardly determined
ET was further confirmed by electrochemical impedance
spectroscopy (EIS), which provides the charge transfer
resistance (Rct). The Nyquist plots of the EIS spectra at 0.75 V
[
6d,6g]
empirically.
We here provide the experimental evidence
elucidating the volcano-like ORR activity trends of the
nanocarbon catalysts. Tafel slopes ranging from 48 to 64 mV
dec are obtained for the GOMC, o-GOMCs, and CNT, where
the Tafel slope close to 59 mV dec−1 suggests that the ORR rate
(vs. RHE) show smaller semicircles for o-GOMC-1 and o-
GOMC-3 than that for GOMC (Figure 4c). Smaller semicircles
−
1
indicate a lower
Rct, and thus, a more facile ET in o-GOMC-1
and o-GOMC-3 than that in the GOMC. In contrast, o-GOMC-8
is limited by the first ET to the O
2
molecule under the Temkin
and the CNT exhibit higher
analysis results are highly consistent with the
activity trends (Figure S14 and Table S4). The reciprocal of
R
ct than that for the GOMC. The EIS
adsorption conditions (Figure S9).[ This kinetic insight gives
rise to an assumption that the ET ability of the carbon is a prime
determinant of the ORR activity. To evaluate the ET rate of the
11]
k
obs and ORR
0
ct
R ,
related to the charge transfer rate, also matches well with the
]3−/4− was
k
obs and ORR activity (inset of Figure 4c).
0
carbons, an outer-sphere redox system of [Fe(CN)
6
exploited. Cyclic voltammograms, independently measured at
least five times, show redox peaks, and the interval between the
peaks determines the observed heterogeneous electron rate
In conclusion, we demonstrated highly selective and active
electrochemical H O production via the ORR using carbon
2 2
nanomaterials that are rich in oxygenated carbon edges. The
experimental evidence suggested that the faster heterogeneous
outer-sphere ET was responsible for the higher ORR activity of
the oxidized and edge-rich carbon nanocatalysts. This kinetic
insight into the ET, which has thus far been largely neglected,
was revealed to play a crucial role, providing an important
guideline for the design of carbon-based electrocatalysts.
Furthermore, the large H O accumulation by the GOMC and its
2 2
excellent stability during the prolonged operation shed light on
the feasibility of our carbon nanocatalysts in the electrochemical
0
constant (
k
obs ) obtained from the Nicholson equation (see the
[
12]
Supporting Information for details, Figure S12 and Table S3).
0
The
k
obs values and ORR mass activity (at 0.75 V vs. RHE)
show a similar trend in which the maximum appears at
approximately between 5–8 wt% of the O-doping level (Figure
0
4
a). The
k
obs values plotted versus the mass activities clearly
display a linear relationship (Figure 4b). The similar trend and
correlation are also clearly seen in the specific activity-based
comparison (Figure S13). This correlation reveals that the ET
capability governs the ORR activity of the doped carbon
2 2
H O production technology.
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COMMUNICATION
a)
b)
c)
1
1
1
1
6
4
2
0
8
6
4
2
0
800
600
400
CNT
4
3
2
1
0
0
0
0
0
5
6
4
2
0
0
4
8
12 16
O (wt%)
1
1
o-GOMC-3
1 Hz
o-GOMC-1
0
5
0
200
o-GOMC-8
GOMC
0.1 Hz
0
0
2
4
6
8 10 12 14 16 18
0
5
10 15 20 25 30 35
0
200
400
600
800
kobs0 × 10 (cm s )
3
−1
Zʹ (Ω)
O Contents (wt%)
Figure 4. a) Trends of the mass activity at 0.75 V (vs. RHE) (bottom) and heterogeneous ET rate constant (top) with the change in the O
content. b) Relationship between the mass activity at 0.75 V (vs. RHE) and heterogeneous ET rate constant. c) Nyquist plots of the
GOMC, o-GOMCs, and CNT measured at 0.75 V (vs. RHE) with an electrode rotation of 1600 rpm in O
trends of the reciprocal of the charge transfer resistance value with the O content).
2
-saturated 0.1 M KOH (inset:
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Angewandte Chemie International Edition
10.1002/anie.201812435
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Young Jin Sa, Jae Hyung Kim, Sang
Hoon Joo*
Page No. – Page No.
Active Edge Site-Rich Carbon
Nanocatalysts with Enhanced
Electron Transfer for Efficient
Electrochemical Hydrogen Peroxide
Production
Active edge site-rich carbon nanocatalyst is developed, which is highly active
and selective for electrochemical hydrogen peroxide production. The optimized
nanocarbon catalyst shows excellent H
reported catalysts in alkaline media, and can sustainably produce H
2
O
2
production activity, surpassing previously
for 16 h with
2 2
O
Faradaic efficiency reaching 99%. The superior activity can be correlated to the
enhanced electron transfer capabilities of the (oxygenated) edge-rich carbon.
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