i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6

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Extraordinarily high hydrogen-evolution-reaction

activity of corrugated graphene nanosheets derived
from biomass rice husks

Sankar Sekar a,b, Abu Talha Aqueel Ahmed a, Dae Hyun Sim a,
Sejoon Lee a,b,*
a
Department of Semiconductor Science, Dongguk University-Seoul, Seoul, 04620, Republic of Korea
b
Quantum-functional Semiconductor Research Center, Dongguk University-Seoul, Seoul, 04620, Republic of Korea

highlights graphical abstract

Corrugated graphene (CG) nano-

sheets were derived from biomass
rice husks.

KOH activation at 700  C led to the
high degree of graphitization in
biomass CG.

Biomass CG showed the meso-
porous characteristics (total pore
volume: 0.7566 cm3/g).

Biomass CG exhibited the extraor-
dinarily high HER activities.

A small overpotential of 9 mV and
a small Tafel slope of 31 mV/dec
were recorded.

article info abstract

Article history: The metal-free carbonaceous catalysts are one of the promising candidates for efficient
Received 29 December 2021 electrocatalytic hydrogen production. Aiming at demonstrating the high electrocatalytic
Received in revised form activity of the hydrogen evolution reaction (HER), we synthesized the biomass rice husk-
21 February 2022 derived corrugated graphene (RH-CG) nanosheets via the KOH activation. The 700  C-
Accepted 27 February 2022 activated RH-CG nanosheets exhibited the large specific surface area as well as the high
Available online 24 March 2022 electrical conductivity. When using the RH-CG nanosheets as a HER electrocatalyst in
0.5 M H2SO4, the excellent HER activities with a small overpotential (9 mV at 10 mA/cm2)
Keywords: and a small Tafel slope (31 mV/dec) were achieved. The results provide a new strategy for
Biomass

* Corresponding author. Department of Semiconductor Science, Dongguk University-Seoul, Seoul, 04620, Republic of Korea.
E-mail address: sejoon@dongguk.edu (S. Lee).
https://doi.org/10.1016/j.ijhydene.2022.02.233
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
40318 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6
Rice husk materializing the superb biomass-derived electrocatalyst for highly efficient hydrogen
Graphene production.
Nanosheets © 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Electrocatalysts
Hydrogen evaluation reaction
Introduction
Hydrogen production via the electrocatalytic water electrol-
ysis is one of the auspicious methods to perform the mass
production of hydrogen energy resources, which can alternate
the fossil fuels in future green energy technology [1e3]. In
general, Pt and Pt-based alloys are the most widely used
electrocatalysts; however, their poor stability, high cost, and
low availability have restricted their practical applications in
hydrogen evolution reaction (HER) technology [4,5]. To replace
the Pt-based electrocatalysts, recently, various alternatives
have been reported as a potential candidate of the high-
performance HER electrocatalyst. For example, the transition
metal/metal oxide composites [6e8], single-atom catalysts
[4,9], and noble metal alloys [10,11] are the typical examples
that showed the outstanding electrocatalytic HER activities.
Due to their complicated synthesis procedures, poor stability,
and low productivity, however, it has been tried to evade the
usage of the metal-based electrocatalysts. Therefore, devel-
oping the acid-stable, high-efficient, and cost-effective metal-
free HER electrocatalysts is vital. In recent years, various
carbonaceous materials such as activated carbon [12e14],
porous carbon [15], carbon nanotube [16,17], carbon fiber [18],
graphene [19e22], graphitic carbon [23], and graphene oxide
[24] have been proposed as a metal-free high-performance
HER electrocatalyst. Among them, graphene is one of the
promising carbonaceous HER electrocatalysts because of its
high surface area, high electrical conductivity, large porosity,
and robust stability [25,26]. For the synthesis of high-quality
graphene, there are several well-known methods such as
chemical vapor deposition [27,28], epitaxial growth on SiC [29],
chemical reduction of graphene oxide [30], and exfoliation
from graphite [31]. Unfortunately, however, these techniques
not only require the expensive chemicals and the sophisti-
cated experimental facilities but also yield the low production
rate [32,33]. Different from the aforementioned methods, the
derivation of graphene from biomass and bio-waste materials
allows a cost-effective and facile approach for mass produc-
tion of high-quality graphene. Among various biomass re-
sources, rice husk (RH) can be used as an effective precursor
because of its huge abundance, low-cost, and environmental
friendliness [34e36]. When synthesizing biomass-derived
graphene, furthermore, the morphological and textural char-
acteristics could be effectively modified; for instance, meso-
porous graphene nanosheets from peanut shells [37],
nanoporous graphene nanosheets from jute sticks [38],
microporous graphene nanosheets from black sesames [39],
and microporous graphene aerogels from pears [40]. Such a
microstructural tunability is highly favorable for the
electrocatalytic HER process because the high porosity of the
highly-conductive graphene nanostructures could help in-
crease the active sites for the electrochemical reaction be-
tween the catalysts and the electrolytes. Despite all the above
benefits of biomass graphene, a study on the electrocatalytic
HER activities of RH-derived graphene has not been reported
yet.
To demonstrate the superb electrocatalytic HER perfor-
mances, we investigated the synthesis and the characteriza-
tion of the biomass rice husk-derived corrugated graphene
(RH-CG) nanosheets. The RH-CG nanosheets were synthesized
through the KOH activation at 600e700  C using the RH ashes;
and the synthesized RH-CG samples exhibited the extraordi-
narily high HER activities, compared to other carbonaceous
HER electrocatalysts. Herein, the material synthesis-to-
electrocatalytic performance analyses of the RH-CG nano-
sheets are systematically examined and discussed in detail.
Experimental
Synthesis of RH-CG nanosheets
Fig. 1 schematically represents the experimental procedures
for the synthesis of the RH-CG nanosheets. The raw biomass
sources of the red-rice husks were collected from Tamil Nadu,
India. Initially, the raw red-rice husks were cleaned in
deionized (DI) water and dried at 72 h in an air atmosphere.
Next, the dried RHs were carbonized at 400  C for 1 h in a
muffle furnace. After carbonization, 5 g of the RH ashes (RHAs)
was mixed with 20 g of KOH in a mortar. Thereafter, the KOH-
RHA mixture was transferred to the alumina crucible. After
encapsulating the crucible, the mixture was subsequently
activated at two different temperatures of 600 and 700  C for
2 h in an air atmosphere. The KOH-activated RHAs were stir-
red in 100 ml DI water to eliminate the potassium traces and
other precipitates. Finally, the powder type of the RH-CG
nanosheets was obtained through filtrating, cleaning, and
drying at 130  C for 20 h in an electric oven. For convenience,
we refer the RH-CG nanosheets prepared by KOH activation at
600 and 700  C as ‘RH-CG-600’ and ‘RH-CG-700’, respectively.
Material characterizations
The morphological, microstructural, and compositional
properties of the prepared materials were monitored by field-
emission scanning-electron microscopy (FE-SEM, Inspect-F50,
FEI, Mahwah, NJ, USA), transmission electron microscopy
(TEM, JEM 2100F, JEOL, Tokyo, Japan), and in-situ energy
dispersive X-ray (EDX) spectroscopy, respectively. X-ray
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6 40319

Fig. 1 e Schematic representation of the experimental procedures for the synthesis of the RH-CG nanosheets via the KOH
activation method using the biomass red-rice husks. (For interpretation of the references to color in this figure legend, the
reader is referred to the Web version of this article.)

diffraction (XRD, D8-Advance system, Bruker, Madison, WI,
USA) and Raman scattering spectroscopy (LabRAM HR800
system, Jobin Yvon, Longjumeau, France) measurements were
performed to investigate the structural and vibrational prop-
erties, respectively. The pore characteristics of the samples
were evaluated through the Brunauer-Emmett-Teller (BET)
and Barrett-Joyner-Halenda (BJH) analysis methods by nitro-
gen adsorption-desorption isotherm measurements using the
BELSORP-mini II equipment (MicrotracBEL, Osaka, Japan).
Electrocatalytic measurements
and electrolyte, respectively. After constructing the three-
electrode system using above materials and electrodes, the
linear sweep voltammetry (LSV) measurements were con-
ducted at 5 mV/s. Additionally, the cyclic voltammetry (CV)
characteristics were measured at 0e0.8 V under various scan
rates (10e100 mV/s). Finally, to examine the impedance
characteristics of the prepared RH-CG-600 and RH-CG-700
working electrodes, the electrochemical impedance spec-
troscopy (EIS) measurements were carried out at a frequency
range of 1 Hze10 kHz.

The electrocatalytic HER measurements of RH-CG-600 and Results and discussion

RH-CG-700 were performed in a three-electrode configuration
by using a VersaSTAT 3 electrochemical system (Ametek
Scientific Instruments, USA). Here, we note that two different
types of working electrodes were fabricated by mixing the
prepared samples (i.e., either RH-CG-600 or RH-CG-700) with
the N-methyl-2-pyrrolidinone solution. Next, the mixture
slurries were coated on the stainless steel substrates (1 cm2)
and were subsequently dried at 180  C for 8 h. In addition, the
saturated calomel electrode (SCE), Pt mesh, and H2SO4 (0.5 M)
were prepared as the reference electrode, counter electrode,
Fig. 2 shows the FE-SEM images of the RH-CG-600 and RH-CG-
700 nanosheets. The RH-CG-600 sample displays the inter-
connected morphology of the wrinkled graphene nanosheets
(Fig. 2(a)and(b)). Similarly, the RH-CG-700 sample also exhibits
the interconnected topography of the corrugated graphene
nanosheets (Fig. 2(c)and(d)). The microstructural insights of
RH-CG-600 and RH-CG-700 could be further confirmed by TEM
(Fig. 3). The RH-CG-600 sample exhibits the wrinkled and/or
folded textures (Fig. 3(a)and(b)) and the overlapped wrinkle
40320 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6
Fig. 2 e (a) Low- and (b) High-magnification FE-SEM images of the RH-CG-600 nanosheets. (c) Low- and (d) High-
magnification FE-SEM images of the RH-CG-700 nanosheets.
edges (Fig. 3(c)) of the interconnected graphene nanosheets.
The selective-area electron diffraction (SAED) pattern of RH-
CG-600 (Fig. 3(d)) reveals the amorphous nature of multiple
graphene stacks. In the case of RH-CG-700, the corrugated
microstructural textures are also visible (Fig. 3(e)e(g)). However,
the RH-CG-700 sample displays the ring type of clear SAED
patterns, which are indicative of the disordered lattice ar-
rangements in corrugated few-layer graphene (Fig. 3(h)) [41,42].
Additionally, it was confirmed that, from the EDX analysis, both
samples were composed of high purity carbon species. Namely,
although the raw source of the RHA showed to contain various
constituents such as Si, Mg, K, and W (Fig. S1), both RH-CG-600
and RH-CG-700 revealed only their main species of C, except for
the small amount of Cu that was sprouted from the Cu grid
used for the TEM measurement (Fig. S2).
The graphitic natures of RH-CG-600 and RH-CG-700 could
be further elucidated by characterizing their crystallographic
structures and lattice vibrational properties. Fig. 4(a) shows
the XRD patterns of the RH-CG-600 and RH-CG-700 nano-
sheets. Both samples clearly exhibit the broad diffraction
pattern at the Bragg angle of 26.9 , which is attributable to the
(002) lattice plane of the few-layer corrugated graphene
nanosheets (JCPDS 41e1487) [36,41]. No other secondary
phases depict the samples to have a high purity, as confirmed
from the EDX analysis. By using the Scherrer formula [43,44],
the average numbers of graphene layers were determined to
be eight and five for RH-CG-600 and RH-CG-700, respectively.
Fig. 4(b) displays the Raman spectra of the samples, from
which the degree of graphitization could be examined by
comparing the ordered and the disordered lattice vibrations.
In both samples, three dominant Raman bands are clearly
observable at 1343, 1597, and 2772 cm1, as denoted by D, G,
and 2D, respectively. The G band originates from the E2g vi-
bration mode (i.e., CeC stretching) of the sp2 hybridized hon-
eycomb carbon lattices [45], and the 2D band arises from the
second-order in-plane vibration mode from the graphitized
layer stacks [36]. The D band is known to come from the dis-
order, edge, and defect natures of graphene [20]. Hence, the
intensity ratios of D to G (ID/IG) and 2D to G (I2D/IG) are typically
used to evaluate the degree of graphitization and the number
of layers in the graphene, respectively [46e54]. For RH-CG-600
and RH-CG-700, the magnitudes of I2D/IG were determined to
be 0.26 and 0.22, respectively, which correspond to those of
the few-layer graphene nanosheets [53,54]. In the case of ID/IG,
RH-CG-600 and RH-CG-700 recorded 1.02 and 0.94, respec-
tively, which are in a good agreement with those of well-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6 40321

Fig. 3 e Microstructural properties of the RH-CG nanosheets. (a, b) Bright-field TEM images, (c) High-resolution TEM image,
and (d) SAED pattern of RH-CG-600. (e, f) Bright-field TEM images, (g) High-resolution TEM image, and (h) SAED pattern of RH-
CG-700.

Fig. 4 e (a) XRD patterns, (b) Raman spectra, (c) Nitrogen adsorption-desorption isotherm characteristic curves, and (d) Pore
size distributions of the RH-CG-600 and RH-CG-700 nanosheets.

graphitized carbon nanosheets [36]. As a result, one can After confirming the graphitization of the samples, the
expect the RH-CG nanosheets to have a higher degree of textural properties were examined by the BET and BJH
graphitization, which is necessary for both high conductivity analysis methods. Fig. 4(c) shows the nitrogen adsorption-
and high porosity of the HER electrocatalyst. desorption isotherm characteristic curves of RH-CG-600
40322 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6
and RH-CG-700. Both samples clearly exhibit the Type-IV
physisorption isotherm characteristics with the Type-H4
hysteresis loops (classified from IUPAC), indicating an
obvious signature of the mesoporous texture [41,55,56].
Through the BET analysis, the specific surface areas were
calculated to be 972 and 1154 m2/g for RH-CG-600 and RH-G-
700, respectively. From BJH analysis (Fig. 4(d)), additionally,
the pore surface areas were determined to be 343 and 398 m2/
g for RH-CG-600 and RH-CG-700, respectively. Furthermore,
the total pore volume (0.7566 cm3/g) and the average pore
size (2.62 nm) of RH-CG-700 were estimated to be larger and
smaller, respectively, in comparison with those of RH-CG-
600 (total pore volume: 0.6102 cm3/g, average pore size:
3.51 nm). These specify that the RH-CG-700 nanosheets have
a higher porosity than RH-CG-600, which is favorable for the
high electrocatalytic HER activity, as mentioned earlier.
Based upon all the above results, one can conjecture that
the biomass RH-CG nanosheets are eligible for the electro-
catalytic HER application because they possess the highly-
conductive graphene nature as well as the high textural
porosity. We therefore assessed the electrocatalytic HER ac-
tivities of RH-CG-600 and RH-CG-700. Fig. 5(a) and (b) show
the CV curves at various scan rates (v) of 10e100 mV/s for RH-
CG-600 and RH-CG-700, respectively. From both samples, the
quasi-rectangular shapes of the CV curves are observed at
low v of 10 mV/s. As the magnitude of v increases, the CV
windows become larger and the current values become
greater. These behaviors are much clearer and stronger in
RH-CG-700, compared to RH-CG-600. Such a substantial HER
activity of RH-CG-700 could be explained by its large
electrochemically-active surface area (ECSA), in which the
electrochemical reaction occurs during the electrocatalytic
HER process. In other words, hydrogen production takes
Fig. 5 e CV curves of the (a) RH-CG-600 and (b) RH-CG-700 electrodes. Non-Faradaic current density recorded from the CV
curves at 0.45 V for the (c) RH-CG-600 and (d) RH-CG-700 electrodes. JCC as a function of the scan rate for the (e) RH-CG-600
and (f) RH-CG-700 electrodes.
place at the ECSA through the chemical reaction between the
acidic solution (e.g., H2SO4) and the electrocatalyst (e.g., RH-
CG) via ‘RH-CG þ 2Hþ þ 2e / H2’ [57,58]. The ECSA can be
estimated by using the following equations:
ECSA ¼ CNF =CE (1)
JCC ¼ CNF  v (2)
2
where CNF (mF), CE (0.035 mF/cm for 1 M H2SO4), and JCC (mA/
cm2) are the non-Faradaic capacitance, the acidic electrolyte
capacitance, and the non-Faradaic current density, respec-
tively. To estimate the ECSA values, firstly, the JCC values were
taken from the non-Faradic CV curves at 0.45 V (Fig. 5(c)
and(d)), and the CNF values were extracted from the slopes of
the ‘JCC vs. v’ curves (Fig. 5(e)and(f)). Then, the ECSA values
were estimated to be 73 and 150 cm2 for RH-CG-600 and RH-
CG-700, respectively, by fitting the extracted parameters to
the above equations. Therefore, one can ascribe the higher
HER activity of RH-CG-700 to the larger magnitude of ECSA,
when comparing it with RH-CG-600.
The enhanced electrocatalytic HER activity could be further
explained by observing the LSV polarization characteristics.
According to the Nernst equation [6,59,60], the potential value
of the reversible hydrogen electrode (ERHE) corresponds to the
overpotential (h) for the HER; and this relation can be
described as follows:
ERHE ¼ ESCE þ 0:059,pH þ E0SCE (3)
ERHE ¼ h (4)
h ¼ sT  log JCC þ c (5)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6
where E0SCE is the standard potential values of the SCE at room
temperature; pH is the molar concentration of the electrolyte;
sT and c are the Tafel slope and the fitting parameter,
respectively. Fig. 6(a) shows the LSV polarization character-
istics of the RH-CG-600 and RH-CG-700 electrodes. RH-CG-700
exhibits a steeper slope in its LSV curve than that of RH-CG-
600. Accordingly, a smaller overpotential of 9 mV (at 10 mA/
cm2) was achieved from RH-CG-700, in comparison with that
of RH-CG-600 (h ¼ 33 mV). In addition, we here notice that the
obtained overpotential values from RH-CG-600 and RH-CG-700
are much smaller than literature values ever reported (see
Table S1). This represents the biomass-derived RH-CG nano-
sheets could deliver the superior HER activity than other
carbonaceous materials. The superior catalytic activity could
also be linked with the favorable HER kinetics. Namely, the
values of sT were determined from the ‘ERHE vs. log JCC’ curves.
As represented in Fig. 6(b), RH-CG-700 possesses a smaller
Tafel slope of 31 mV/dec, compared to RH-G-600 (67 mV/dec).
The smaller sT value is associated with the faster electro-
chemical reaction kinetics. In other words, the efficient elec-
tron/ion transport occurs at the electrode/electrolyte interface
because of high porosity and high conductivity of the well
graphitized textures in RH-CG-700, as confirmed in Fig. 4.
The superb HER activities of the samples can be further
verified by examining the chronopotentiometric characteris-
tics. Fig. 6(c) shows the ERHE plots as a function of time, during
which the current density was increased from 10 to 100 mA/
cm2 at each time period. For example, the working electrode
Fig. 6 e (a) LSV polarization curves, (b) Tafel slope curves, (c) Multi-chronopotentiometric profiles at different current
densities (from ¡10 to ¡100 mA/cm2), and (d) HER stability for the RH-CG-600 and RH-CG-700 electrodes.
40323
was polarized to 10 mA/cm2 for 10 min at the initial period,
and the current density was increased stepwise up to 20, 30,
40, 50, and 100 after every 10 min. At every time duration (i.e.,
under each current density), both samples exhibit the static
ERHE responses. As can be expected from the above results
(Fig. 6(a)and(b)), compared to RH-CG-600, the RH-CG-700
electrode maintains the lower ERHE responses at all current
densities. Fig. 6(d) displays the chronopotentiometric HER
stability, which was measured under 10 mA/cm2 for 10 h. At
the beginning stage, the value of ERHE suddenly decreases
presumably due to the initial activation of the electrochemical
reaction in the electrode system. However, ERHE becomes
stable soon after the initial activation stage, and then the
samples retain their stable ERHE states throughout the whole
measurement time. Furthermore, the samples clearly
revealed the almost identical polarization curves before and
after the stability test (Fig. S3). Hence, one can deduce that the
samples have the robust HER activities in acidic medium.
Such a robustness can be corroborated by the electro-
chemical impedance characteristics. Fig. 7 shows the EIS
Nyquist plots of RH-CG-600 and RH-CG-700, which were
measured before and after the chronopotentiometric HER sta-
bility test. Both samples show only the straight lines in the low
frequency region with no semi-circles in the high frequency
region. This depicts that the electrochemical reaction is domi-
nant at the electrolyte/electrode (i.e., acid solution/catalyst
surface) rather than the charge transport throughout the inte-
rior of the electrolyte-electrode material system. Along the
40324 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 3 1 7 e4 0 3 2 6
Fig. 7 e Nyquist plots of the (a) RH-CG-600 and (b) RH-CG-700 electrodes before and after the HER stability test.
straight EIS line, the intersection at the Z'-axis represents the
solution resistance (Rs), attributing to both the ionic and the
electronic resistances [61,62]. Compared to RH-CG-600
(Fig. 7(a)), RH-CG-700 possesses a steeper slope (Fig. 7(b)),
which is indicative of lower Rs. Such a steep slope is maintained
even after the stability test for 10 h; and this result is consistent
with the LSV polarization characteristics before and after the
stability test (Fig. S2). As a consequence, all the results obtained
here sturdily suggest the biomass-derived RH-CG nanosheets
to hold huge potential and great benefit as a high-performance
HER electrocatalyst for future green energy technology.
Conclusions
Biomass RH-CG was successfully synthesized through the
KOH activation of the red-rice husk ashes. The 700  C-acti-
vated RH-CG sample displayed the interconnected
morphology with the corrugated graphene nanosheets and
exhibited the high porosity. Due to the higher degree of
graphitization with the mesoporous texture of RH-CG, the
sample showed the extraordinarily high HER activities with a
substantially low overpotential (9 mV at 10 mA/cm2) and a
very smaller Tafel slope (31 mV/dec). Consequently, the RH-
CG nanosheets could be of good use for hydrogen produc-
tion via the highly-active electrocatalytic HER process.
Author's contribution statement
Sankar Sekar: Investigation; Methodology; Writing - original
draft. Abu Talha Aqueel Ahmed: Data curation; Validation. Dae
Hyun Sim: Formal analysis. Sejoon Lee: Conceptualization;
Supervision; Funding acquisition; Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This research was supported by the National Research Foun-
dation of Korea through the Basic Science Research Programs
(2016R1A6A1A03012877 and 2019R1A2C1085448) funded by
the Korean Government.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2022.02.233.
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