Downloaded from https://iranpaper.

ir
https://www.tarjomano.com https://www.tarjomano.com

Diamond & Related Materials 104 (2020) 107740

Contents lists available at ScienceDirect

Diamond & Related Materials

journal homepage: www.elsevier.com/locate/diamond

Direct electrodeposition of hydrogenated reduced graphene oxide from T

unsonicated solution and its electrochemical response
R. Della Nocea, , S. Eugéniob,c, K.I. Siwekb, T.M. Silvab,d, M.J. Carmezimb,e, A.M.P. Sakitaf,
⁎

R.L. Lavallf,g, M.F. Montemorb

a
Faculdade de Química, Instituto de Ciências Exatas e Naturais, Federal University of Pará, Rua Augusto Corrêa, 1, 66075-110 Belém, PA, Brazil
b
Centro de Química Estrutural-CQE, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal
c
Universidade Atlântica, Fábrica da Pólvora de Barcarena, 2730-036 Barcarena, Portugal
d
Department of Mechanical Engineering, GI-MOSM, Instituto Superior de Engenharia de Lisboa, 1950-062 Lisboa, Portugal
e
ESTSetúbal, Instituto Politécnico de Setúbal, 1959-007 Setúbal, Portugal
f
Department of Chemistry/ICEx, Federal University of Minas Gerais (UFMG), Belo Horizonte, Brazil.
g
CTNano/UFMG, Rua Prof. José Vieira de Mendonça, 520, Engenho Nogueira, Belo Horizonte, MG, Brazil

ARTICLE INFO ABSTRACT

Keywords: Reduced graphene oxide (rGO) is successfully electrodeposited from a graphene oxide-containing suspension
Reduced graphene oxide under stirring and no sonication onto Ni foam by applying −1.5 V/SCE. The electrodeposited material is
Electrodeposition characterized by X-Ray Diffraction (XRD), Scanning electron microscopy (SEM), Raman spectroscopy, Fourier
Cyclic voltammetry Transform Infra-Red spectroscopy (FTIR) and Thermogravimetric analysis (TGA). FTIR and TGA results indicate
the formation of hydrogenated rGO after electrodeposition. In addition, the electrochemical response of the
rGO/Ni electrode is evaluated by cyclic voltammetry in 1 M potassium hydroxide solution. The results reveal
that the electrode possesses higher conductivity and lower polarization loss compared to bare Ni foam, opening
wider perspectives to design composites with improved electrochemical performance.

1. Introduction groups on their structures. Graphene and highly hydrogenated gra-

phene have attracted much attention due to their particular properties
Since the demonstration of graphene fabrication in 2004 [1], gra- that enable several applications in electronic and electrochemistry
phene and its derivatives (graphene oxide and reduced graphene oxide) [12,13]. Furthermore, the capacitive and electrochemical properties
have undoubtedly become the most studied materials in the current can be enhanced by controlling the content of hydrogen inserted in
state-of-art. Despite the extraordinary chemical and physical properties their structures [13].
(high surface area and mechanical strength, excellent thermal and Electrodeposition is most likely the simplest and cheapest method to
electrical conductivity) [2], and vast applications of graphene (nanoe- produce rGO in comparison to the other above-mentioned processes.
lectronics, sensors, electroanalysis, etc.) [3–5], graphene oxide (GO) Besides, it can be considered as green route, since neither toxic che-
and reduced graphene oxide (rGO) have also drawn an increasing at- micals (e.g. hydrazine or dimethylhydrazine) nor high temperatures are
tention from the scientific community in the last years. This is due, not employed during rGO electrodeposition.
only to their potential applications in different fields (e.g. electro- The direct electrodeposition of hydrogenated rGO, from a graphene
analytical chemistry, electrocatalysis and electrochemical sensors), but oxide-containing suspension under stirring and no sonication, onto Ni
also because they are considered efficient precursors for the graphene foam is reported. The fabrication of electrodeposited rGO has been
synthesis [2]. In this context, GO and rGO have been prepared by achieved by two main electrochemical routes: potentiostatic (constant
various chemical and physical methods including spin-coating [6], potential) and potentiodynamic (cyclic voltammetry) modes [14,15].
vacuum filtration [7], chemical vapor deposition (CVD) [8], chemical However, in most of these works, the GO colloidal suspension, used as
reduction [9], thermal reduction [10], and electrodeposition [11]. rGO precursor, is previously sonicated for long periods of time which in
Recently, a new frontier in bidimensional materials has been opened by some cases is superior to 1 h [16]. In fact, it has been reported that
graphene analogue materials, which have heteroatoms or functional excessive sonication might have detrimental effects, leading to a

⁎
Corresponding author.
E-mail address: dellanoce@ufpa.br (R.D. Noce).

https://doi.org/10.1016/j.diamond.2020.107740
Received 30 October 2019; Received in revised form 22 January 2020; Accepted 30 January 2020
Available online 31 January 2020
0925-9635/ © 2020 Elsevier B.V. All rights reserved.
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com https://www.tarjomano.com

R.D. Noce, et al. Diamond & Related Materials 104 (2020) 107740

decrease in lateral dimension and hole defects in the GO deposit [17]. 0

Here, we demonstrate that rGO can be successfully obtained by elec-
trodeposition from an unsonicated suspension by employing stirring to
avoid agglomeration of the GO sheets. As far as we know, this is a novel -5
procedure to electrochemically prepare hydrogenated rGO. In addition,
the electrochemical performance of electrodeposited rGO is evaluated

Current / mA
by cyclic voltammetry in 1 M KOH solution. -10

2. Experimental details
-15
Ni foam was used as substrate to improve the rGO adhesion, as
compared to stainless steel. Ni foam, with geometrical area of 1.79 cm2,
was galvanostatically deposited on stainless steel (AISI 304, -20
Goodfellow) from an electrolyte containing chemical grade 0.1 M NiCl2,
1 M NaCl and 1 M NH4Cl. The deposition process was carried out at
current density of 1 A cm−2 for 150 s using two electrodes electro-
-25
chemical cell connected to a power source (Sorensen LH110). Graphite
0 50 100 150 200 250 300 350
plate served as a counter electrode. And the Ni foam as working elec-
trode. Afterwards, the foam was rinsed with distilled water to remove Deposition time / s
excess of electrolyte and dried before rGO deposition. rGO was po-
Fig. 1. Current vs. time (I × t) profile for the electrodeposition of rGO onto Ni
tentiostatically obtained by applying potentials in the range −1.2 to
foam by applying −1.5 V (SCE) under stirring. Total deposition time: 300 s.
−1.5 V vs. Saturated Calomel Electrode (SCE). Even though the rGO Stirring speed: 500 rpm.
deposition at −1.2 V is possible, it takes long times (more than 15 min)
and for this reason the rGO deposition was optimized at −1.5 V for a
period of 5 min only. Higher deposition times lead to lower electro- conductivity values between 4 and 25 mS cm−1 for a bath containing
chemical activity as described below. The rGO deposits were produced 0.5 g L−1 GO plus 0.25 M NaCl.
from an unsonicated suspension containing 0.5 g L−1 GO (commercial The morphology of the rGO deposits has been analyzed by SEM at
monolayered GO) plus 0.1 M Na2SO4, used as supporting electrolyte, at different magnifications (Fig. 2). It is clearly observed that the Ni foam
pH 7 and under stirring of 500 rpm. At these concentrations, the sus- retains its original characteristic porosity, while the surface is covered
pension displays a conductivity of 22 mS cm−1 measured by a con- by nearly continuous nanosheets (Fig. 2b), characterisitc of graphene-
ductivity meter (Eutech Instruments model PC 700), previously cali- based materials, revealing the presence of electrodeposited rGO. Note
brated with commercial buffer solutions. The average deposited mass that the porosity and roughness of Ni foam allows better adhesion of the
was 0.4 mg obtained for several experiments carried out at −1.5 V and rGO sheets compared to flat substrates, e.g. stainless steel. To further
5 min of deposition. The rGO deposits were physically characterized by confirm the presence of electrodeposited rGO, XRD and Raman spec-
scanning electron microscopy (SEM, (JEOL model JSM-7001F)), X-ray troscopy have been employed (Fig. 3). The XRD pattern of the rGO
diffractometry (XRD, Bruker AXS D8 Advance), Raman (WiTec Alpha deposit (Fig. 3a) presents a broad peak located at ca. 25°, corresponding
3000 with laser wavelength 532 nm), Fourier-transform infrared (FTIR, to the (002) diffraction line of rGO. This feature is characteristic of non-
Perkin Elmer Frontier) spectroscopy, and thermogravimetric analysis graphitic carbon materials with highly disordered nanocrystalline
(TGA, TA instruments Q5000). The rGO electrochemical response was structure [18].
evaluated in 1 M KOH solution by cyclic voltammetry (Voltalab PGZ Raman spectroscopy is a powerful and non-destructive technique
100 potentiostat/galvanostat). used to reveal the structural information of carbon-based materials
[19]. The Raman spectrum of rGO (Fig. 3b) depicts two well-defined
3. Results and discussion bands at about 1345 and 1585 cm−1, corresponding to the typical D
and G bands for carbon materials [20]. The ID/IG ratio is often em-
Fig. 1 displays the current vs. time (I × t) profile for the potentio- ployed to describe the sp2 sp3 hybridized carbons on the graphitic
static electrodeposition of rGO onto Ni foam by applying −1.5 V/SCE structures. For GO is observed an ID/IG ratio of 0.99 whereas its elec-
under stirring. It is seen that the current increases as the deposition time trochemically reduced form is 0.96, suggesting a decrease of the defects
increases, nearly reaching a plateau at the end of the deposition pro- upon the graphene lattice after reduction. Evenly several authors have
cess. This means that the Ni foam surface was completely covered by shown that after the reduction of GO to rGO the ID/IG increases sug-
the rGO deposit in this condition. The coverage of Ni by rGO inhibits gesting that the sp2 domains are restored by reducing the functional
the hydrogen evolution reaction (HER) decreasing the total current groups and forming defects [21]. However, here it is possible to have
density observed in the I vs. t plot. Moreover, the surface pH increases reduction and hydrogenation, which lead to the decrease of functional
due to the reduction of water molecules producing OH– which suppress groups and insertion of hydrogen keeping the sp3 domains. Sofer's
the HER current. Potentials lower than −1.5 V have been employed, group studied the exfoliation of graphite oxide in hydrogen plasma and
nevertheless, the high HER damages the rGO deposit leading to low also observed the decreasing of D and G bands ratio after the reduction
carbon content upon the electrode surface. Similar behavior was ob- [22,23]. The decreasing of the ID/IG ratio observed here suggests: First,
served by Ambrosi and Pumera [15] in the preparation of rGO de- the unsonicated suspension allows obtaining less defective rGO and
posited at −1.5 V upon a carbon screen printed electrode that shows a second, the graphitic structure is not well affected by the proposed
lower catalytic activity for HER. This fact suggests the possibility of rGO reduction mode and most of the functional groups are replaced by
entrapment in the porous and rough Ni foam surface even with higher hydrogenated one, which does not permit the formation of defects near
catalytic activity for HER. Also, it is important to highlight that the rGO sp2 domains.
deposition only takes place in presence of Na2SO4 (supporting elec- FTIR has been also employed to investigate the chemical structure
trolyte) in solution. Indeed, it has been reported that the supporting of the electrodeposited rGO and is shown in Fig. 3c. Graphene oxide
electrolyte plays an important role on the rGO deposition, along with spectrum depicts a strong wide band at 3000–3750 attributed to OeH
the conductivity and pH of the solution [11]. Specifically, the rGO vibrational mode of C-OH from oxidized groups of GO. This band is not
deposition occurs in a wide range of pH from 1.5 to 12.5 and observed on rGO spectrum (red line), suggesting that OH groups were

2
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com https://www.tarjomano.com

R.D. Noce, et al. Diamond & Related Materials 104 (2020) 107740

rGO sheets
Fig. 2. SEM images of rGO potentiostatically electrodeposited onto Ni foam by
applying −1.5 V (SCE) under stirring. Total deposition time: 300 s. Stirring
speed: 500 rpm.

efficiently removed from GO during the electrodeposition process [24].

Characteristic bands at 1049 and 1222 cm−1, assigned to CeO
stretching vibration and CeO breathing vibration from epoxide, re-
spectively, are also seen. A band at 1350 cm−1 attributed to OeH de-
formations in C-OH, a 1617 cm−1 band from C]C groups from GO
layer and a band at 1720 cm−1 from C]O stretching vibration in ke-
tone and carboxyl acids groups are all related to GO layer. All of these
bands were mostly suppressed after the reduction of GO, remaining
only two weak bands at 2913 cm−1 from CH2 stretching modes and ca.
1550–1350 cm−1 from C]C skeletal vibration from graphene domain.
The CH2 stretching mode indicates a highly hydrogenated rGO which is Fig. 3. XRD pattern (a), Raman spectrum (b) and FTIR spectrum (c) precursor
in agreement with hydrogen evolution during the rGO electrodeposi- GO and rGO potentiostatically electrodeposited onto Ni foam by applying
tion process [25,26]. Two strong bands at 1200 and 1150 cm−1 are also −1.5 V (SCE) under stirring. Total deposition time: 300 s. Stirring speed:
observed and attributed to the sulfate vibrational modes from re- 500 rpm.
maining Na2SO4 (supporting electrolyte) [27]. Thermogravimetric
analysis (TGA) in air environment has been performed to assess the about 100–250 °C assigned as the decomposition of remained oxyge-
thermal stability of the electrodeposited rGO and the results are dis- nated functional groups of GO yielding CO, CO2, and H2O steam;
played in Fig. 4. For comparison, the TGA curves of GO have been also second ca. 350–550 °C related to the thermal decomposition of sp2-
recorded. Obviously, the TGA curves of GO and rGO are different. For hybridized carbon atoms. The highly hydrogenated rGO shows high
GO a massive weight loss between 150 and 450 °C is related to the stability related to the thermal decomposition of functional groups in-
dehydration, decomposition of oxygen-containing function groups [28]. dicating that the main product of the electrodeposition process is
TGA curves of rGO can be divided in two main events: the first one completely reduced. Moreover, the hydrogenation of electrodeposited

3
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com https://www.tarjomano.com

R.D. Noce, et al. Diamond & Related Materials 104 (2020) 107740

8
100
6 rGO/Ni foam
Ni foam

Current density / A g-1

80 4
Weight / %

60
2
0
40
-2
20 -4
GO
rGO -6
0
100 200 300 400 500 600 700 800 -8
-0.2 0.0 0.2 0.4 0.6 0.8
Temperature / °C
E / V vs. SCE
Fig. 4. TGA curves of GO and electrodeposited rGO.
Fig. 5. Cyclic voltammogram of Ni foam and rGO/Ni foam in 1 M KOH solution
obtained at 20 mV s−1.
rGO gives rise to lower thermal stability than that of chemically rGO
(with low hydrogen content). Bousa et al. [25] also observed lower
glassy carbon electrode (GCE) exhibits a current increase in the CV from
thermal stability as the hydrogen content on rGO increases. The for-
50 μA to ca. 150 μA, by employing 0.1 M KOH as electrolyte, in com-
mation of highly hydrogenated reduced graphene was reported by
parison to the CV of bare GCE [35]. For comparison, it is important to
Krishna et al. [29] who produced it by electrochemical reaction of Ni
stress that although GO acts as the most suitable precursor for gra-
nanoparticles and HCl. By wet chemistry, some reports have shown the
phenic-like materials, its pure form is an insulating material showing
production of highly hydrogenated graphene by nascent hydrogen in
conductivity values about 10−8 S m−1 [36]. Thus, its application on
acid medium [30,31] and the mechanism is regarded to Clemmensen
electrochemical purposes is not common due to its poor electro-
reduction. Jankovsky et al. [32] studied the reduction and hydro-
chemical activity. The GO and rGO electrochemical behavior has been
genation of graphene oxide employing aluminum powder in alkaline
demonstrated by Basu et al. [37] who observed low current density
deuterated solutions nascent hydrogen formed during Al oxidation.
values for GO electrodes in aqueous [Fe(CN)6]3−/4− system. A similar
Indeed, the metal mediated nascent hydrogen reveals to be efficient for
result has also been obtained by Strong and co-workers [38] for GO
reduction/hydrogenation of graphene oxide to more reduced species.
deposited onto flexible substrates.
However, in electrodeposition the oxidation step that generates metal
Besides a current increase, the CV of rGO/Ni foam electrode depicts
ions on the reacting surface does not exist on the cathode. Thus, the
an expansion in the positive potential range, where the oxygen evolu-
mechanism for hydrogenation should be quite different than that pro-
tion reaction (OER) is shifted to more positive values, increasing the
posed for nascent hydrogen mediated by metal oxidation. In a recent
operating potential window approximately 250 mV. Lai and co-workers
work, Quezada-Renteria et al. [33] studied the electroreduction of
produced NiO/Ni composites and evaluated their electrochemical per-
graphene oxide in aqueous and organic medium evaluating its chemical
formance. The higher content of metallic nickel on the mesostructured
structure and electrochemical behavior. The authors suggest that elec-
composite increases the electrical conductivity and decreases the po-
trochemical reduction of GO in presence of H+ occurs via consecutive
larization loss [39]. Here, rGO acts like the metallic nickel of Lai's work
hydrogenation of oxidized groups, leading to higher content of sp3
by connecting the nanostructured nickel particles and increasing the
hybridized carbons (high content of CeH bonds). For instance, at pH 12
conductivity of the resulting rGO/Ni electrode. Moreover, the change
(low proton content) a higher sp2/sp3 ratio in comparison to pH 2
on the electronic structure of hydrogenated rGO also changes the ca-
(higher proton content), was observed when the applied potential is
pacitance in the case of its charge storage. Jiang et al. [13] evaluated
sufficiently negative to produce hydrogen bubbles coming from water
the hydrogenation of CVD graphene and found higher capacitances for
reduction. It must be noted that the working electrode used in this case
the hydrogenated product compared to those of pristine. These char-
(AISI 1045) have less catalytic activity for hydrogen adsorption/evo-
acteristics are important, for example, in energy storage applications. In
lution than nanocrystalline nickel and, additionally, does not exhibit
particular, in the case of electrochemical capacitors (ECs) a current
oxide formation during cathodic overpotential imposition. Daniels et al.
increase in the CV may lead to higher capacitance values of the re-
[34] attributed the electrochemical hydrogenation to the defect density
sulting material. Likewise, an augment in the working potential
of pristine graphene which enhances the surface area and allows hy-
window may result in higher energy density values. Considering that
drogen to adsorb onto additional sites in the graphene structure. Thus,
the energy density in ECs is obtained by E = CV2/2, where C is the total
in neutral medium and high applied overpotentials (−1.5 V vs. SCE)
capacitance and V is the operating voltage, expanding V leads to a
the high hydrogen evolution leads to the production of defective rGO
considerable increase in their energy density [40]. Another application
[16] which is more susceptible to hydrogenation.
of rGO and its hydrogenated form is in the field of electrochemical
To evaluate the electrochemical response of electrodeposited rGO,
sensing. In this context, they have been remarked as a promising plat-
cyclic voltammetry has been employed in 1 M KOH aqueous solution.
form for biomark detection [41]. Also, rGO has been used as sensor in
Fig. 5 depicts the cyclic voltammograms (CVs) of Ni foam and rGO/Ni
the detection of glucose in conjunction with metal oxides to form
foam obtained at 20 mV s−1. The current density is increased about
composites electrodes [42,43]. In this case, the rGO-based sensor dis-
three times in the case of the rGO/Ni foam electrode compared to the
plays high electrochemical activity for electrocatalytic oxidation of
bare Ni foam. This is because rGO possesses high electrical conductivity
glucose in alkaline medium which is attributed to an increase in the
and is a more active host, with large interlayer distances and a dis-
electrical conductivity of the composite due to the rGO presence.
ordered structure that also facilitate the electrolyte penetration into the
Note that our findings have been attained for an rGO mass loading
electrode [18]. In fact, Wang et al. reported that rGO deposited onto

4
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com https://www.tarjomano.com

R.D. Noce, et al. Diamond & Related Materials 104 (2020) 107740

of 0.4 mg. Under the proposed experimental conditions, mass loadings chemical sensors from chemically derived graphene, ACS Nano 3 (2009) 301–306,
up to 2 mg are achieved; however, an increase in the rGO mass loading https://doi.org/10.1021/nn800593m.
[7] G. Eda, G. Fanchini, M. Chhowalla, Large-area ultrathin films of reduced graphene
does not increase the electrochemical performance of the resulting oxide as a transparent and flexible electronic material, Nat. Nanotechnol. 3 (2008)
electrode. Most likely the electrolyte penetration is hindered in this 270–274, https://doi.org/10.1038/nnano.2008.83.
case. Also, our results are for a dilute GO concentration bath (0.5 g L−1) [8] V. López, R.S. Sundaram, C. Gómez-Navarro, D. Olea, M. Burghard, J. Gómez-
Herrero, F. Zamora, K. Kern, Chemical vapor deposition repair of graphene oxide: a
that exhibits lower viscosity compared to concentrated ones and allows route to highly conductive graphene monolayers, Adv. Mater. 21 (2009)
entry of GO into the foam structure for reduction as well. Faster rGO 4683–4686, https://doi.org/10.1002/adma.200901582.
deposition times, e.g. 10 s, have been proposed by potentiostatic fab- [9] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu,
S.B.T. Nguyen, R.S. Ruoff, Synthesis of graphene-based nanosheets via chemical
rication; nevertheless, much higher GO concentrations (up to 12 g L−1) reduction of exfoliated graphite oxide, Carbon N. Y. 45 (2007) 1558–1565, https://
are utilized in those works [44,45]. doi.org/10.1016/j.carbon.2007.02.034.
[10] X. Gao, J. Jang, S. Nagase, Hydrazine and thermal reduction of graphene oxide:
reaction mechanisms and design, J. Phys. Chem. C 114 (2010) 832–842, https://
4. Conclusions
doi.org/10.1021/jp909284g.
[11] M. Hilder, B. Winther-Jensen, D. Li, M. Forsyth, D.R. MacFarlane, Direct electro-
In summary, the direct electrodeposition of hydrogenated rGO, from deposition of graphene from aqueous suspensions, Phys. Chem. Chem. Phys. 13
a graphene oxide-containing suspension under stirring and no sonica- (2011) 9187–9193, https://doi.org/10.1039/c1cp20173e.
[12] M. Pumera, Z. Sofer, Towards stoichiometric analogues of graphene: graphane,
tion, onto Ni foam has been demonstrated. The proposed approach of fluorographene, graphol, graphene acid and others, Chem. Soc. Rev. 46 (2017)
employing unsonicated suspension is novel, facile, fast, cost-effective, 4450–4463, https://doi.org/10.1039/c7cs00215g.
environmentally friendly and scalable as well, since potentiostatic or [13] L. Jiang, W. Fu, Y.Y. Birdja, M.T.M. Koper, G.F. Schneider, Quantum and electro-
chemical interplays in hydrogenated graphene, Nat. Commun. 9 (2018), https://
galvanostatic deposition can be employed to directly obtain rGO unlike doi.org/10.1038/s41467-018-03026-0.
the potentiodynamic method (cyclic voltammetry) which has been [14] V.H. Pham, T. Gebre, J.H. Dickerson, Facile electrodeposition of reduced graphene
widely reported in the last years. These results open the door to the oxide hydrogels for high-performance supercapacitors, Nanoscale 7 (2015)
5947–5950, https://doi.org/10.1039/C4NR07508K.
production of electrodeposited hydrogenated rGO which is a promising [15] L. Chen, Y. Tang, K. Wang, C. Liu, S. Luo, Direct electrodeposition of reduced
material with a myriad of applications such as energy storage and graphene oxide on glassy carbon electrode and its electrochemical application,
harvesting, sensing, biosensing, and many others. Electrochem. Commun. 13 (2011) 133–137, https://doi.org/10.1016/j.elecom.
2010.11.033.
[16] A. Ambrosi, M. Pumera, Precise tuning of surface composition and electron-transfer
Declaration of competing interests properties of graphene oxide films through electroreduction, Chem. - A Eur. J. 19
(2013) 4748–4753, https://doi.org/10.1002/chem.201204226.
[17] S. Yongchao, T. Samulski Edward, Synthesis of water soluble graphene, Nano Lett. 8
The authors declare that they have no known competing financial
(2008) 1679–1682, https://doi.org/10.1021/nl080604h.
interests or personal relationships that could have appeared to influ- [18] Y.-X. Wang, S.-L. Chou, H.-K. Liu, S.-X. Dou, Reduced graphene oxide with superior
ence the work reported in this paper. cycling stability and rate capability for sodium storage, Carbon N. Y. 57 (2013)
202–208, https://doi.org/10.1016/j.carbon.2013.01.064.
[19] A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec,
CRediT authorship contribution statement D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Raman spectrum of graphene and
graphene layers, Phys. Rev. Lett. 97 (2006) 1–4, https://doi.org/10.1103/
R. Della Noce:Conceptualization, Methodology, Formal analysis, PhysRevLett.97.187401.
[20] L. Tang, Y. Wang, Y. Li, H. Feng, J. Lu, J. Li, Preparation, structure, and electro-
Investigation, Writing - original draft, Writing - review & editing.S. chemical properties of reduced graphene sheet films, Adv. Funct. Mater. 19 (2009)
Eugénio:Investigation, Data curation.K.I. Siwek:Methodology, 2782–2789, https://doi.org/10.1002/adfm.200900377.
Formal analysis, Investigation.T.M. Silva:Visualization.M.J. [21] S. Eigler, C. Dotzer, A. Hirsch, Visualization of defect densities in reduced graphene
oxide, Carbon N. Y. 50 (2012) 3666–3673, https://doi.org/10.1016/j.carbon.2012.
Carmezim:Visualization.A.M.P. Sakita:Methodology, Formal analysis, 03.039.
Investigation, Writing - review & editing.R.L. Lavall:Supervision.M.F. [22] A.Y.S. Eng, Z. Sofer, P. Šimek, J. Kosina, M. Pumera, Highly hydrogenated graphene
Montemor:Project administration, Writing - review & editing. through microwave exfoliation of graphite oxide in hydrogen plasma: towards
electrochemical applications, Chem. - A Eur. J. 19 (2013) 15583–15592, https://
doi.org/10.1002/chem.201303164.
Acknowledgments [23] O. Jankovský, A. Libánská, D. Bouša, D. Sedmidubský, S. Matějková, Z. Sofer,
Partially hydrogenated graphene materials exhibit high electrocatalytic activities
related to unintentional doping with metallic impurities, Chem. - A Eur. J. 22
The authors would like to acknowledge FCT (Fundação para a
(2016) 8627–8634, https://doi.org/10.1002/chem.201600811.
Ciência e a Tecnologia, Portugal) for financial support under the pro- [24] Y. Gong, D. Li, Q. Fu, C. Pan, Influence of graphene microstructures on electro-
jects M-ERA.NET/0002/2012, M-ERA.NET/0004/2014 and PEst-OE/ chemical performance for supercapacitors influence of graphene microstructures on
QUI/UI0100/2013. We are grateful to Prof. Teresa Duarte and Prof. electrochemical performance for supercapacitors, Prog. Nat. Sci. Mater. Int. 25
(2015) 379–385, https://doi.org/10.1016/j.pnsc.2015.10.004.
Luis Santos (CQE/IST) for XRD and Raman facilities, respectively. [25] D. Bouša, J. Luxa, D. Sedmidubský, Š. Huber, O. Jankovský, M. Pumera, Z. Sofer,
AMPS and RLL also thank CNPq, CAPES, FAPEMIG, and INCT Carbon Nanosized graphane (C 1 H 1.14) n by hydrogenation of carbon nanofibers by birch
Nanomaterials. reduction method, RSC Adv. 6 (2016) 6475–6485, https://doi.org/10.1039/
C5RA22077G.
[26] Q. Miao, L. Wang, Z. Liu, B. Wei, J. Wang, X. Liu, W. Fei, Effect of defects controlled
References by preparation condition and heat treatment on the ferromagnetic properties of
few-layer graphene, Sci. Rep. 7 (2017) 1–9, https://doi.org/10.1038/s41598-017-
06224-w.
[1] K.S. Novoselov, Electric field effect in atomically thin carbon films, Science (80-.)
[27] C.H. Wilkins, F.A. Miller, Infrared spectra and characteristic frequencies of in-
306 (2004) 666–669, https://doi.org/10.1126/science.1102896.
organic lons their use in qualitative analysis, Anal. Chem. 24 (1952) 1253–1294
[2] D. Chen, H. Feng, J. Li, Graphene oxide: preparation, functionalization, and elec-
https://pubs.acs.org/sharingguidelines.
trochemical applications, Chem. Rev. 112 (2012) 6027–6053, https://doi.org/10.
[28] W. Liao, S. Yang, S. Hsiao, Y. Wang, S. Li, C.M. Ma, H. Tien, S. Zeng, Effect of octa
1021/cr300115g.
(aminophenyl) polyhedral oligomeric silsesquioxane functionalized graphene oxide
[3] D. Li, M.B. Müller, S. Gilje, R.B. Kaner, G.G. Wallace, Processable aqueous disper-
on the mechanical and dielectric properties of polyimide composites, ACS Appl.
sions of graphene nanosheets, Nat. Nanotechnol. 3 (2008) 101–105, https://doi.
Mater. Interfaces 6 (2014) 15802–15812, https://doi.org/10.1021/am504342j.
org/10.1038/nnano.2007.451.
[29] R. Krishna, E. Titus, O. Okhay, J.C. Gil, J. Ventura, E. Venkata Ramana,
[4] D.R. Dreyer, S. Park, C.W. Bielawski, R.S. Ruoff, The chemistry of graphene oxide,
J.J.A. Gracio, Rapid electrochemical synthesis of hydrogenated graphene oxide
Chem. Soc. Rev. 39 (2010) 228–240, https://doi.org/10.1039/B917103G.
using ni nanoparticles, Int. J. Electrochem. Sci. 9 (2014) 4054–4069.
[5] F. Tahernejad-Javazmi, M. Shabani-Nooshabadi, H. Karimi-Maleh, 3D reduced
[30] Z. Sofer, O. Jankovský, A. Libánská, P. Šimek, M. Nováček, D. Sedmidubský,
graphene oxide/FeNi3-ionic liquid nanocomposite modified sensor; an electrical
A. MacKová, R. Mikšová, M. Pumera, Definitive proof of graphene hydrogenation
synergic effect for development of tert-butylhydroquinone and folic acid sensor,
by Clemmensen reduction: use of deuterium labeling, Nanoscale 7 (2015)
Compos. Part B Eng. 172 (2019) 666–670, https://doi.org/10.1016/j.compositesb.
10535–10543, https://doi.org/10.1039/c5nr01356a.
2019.05.065.
[31] V.H. Pham, H.D. Pham, T.T. Dang, S.H. Hur, E.J. Kim, B.S. Kong, S. Kim, J.S. Chung,
[6] J.D. Fowler, M.J. Allen, V.C. Tung, Y. Yang, R.B. Kaner, B.H. Weiller, Practical
Chemical reduction of an aqueous suspension of graphene oxide by nascent

5
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com https://www.tarjomano.com

R.D. Noce, et al. Diamond & Related Materials 104 (2020) 107740

hydrogen, J. Mater. Chem. 22 (2012) 10530–10536, https://doi.org/10.1039/ Patterning and electronic tuning of laser scribed graphene for flexible all-carbon
c2jm30562c. devices, ACS Nano 6 (2012) 1395–1403, https://doi.org/10.1021/nn204200w.
[32] O. Jankovský, P. Šimek, M. Nováček, J. Luxa, D. Sedmidubský, M. Pumera, [39] H. Lai, Q. Wu, J. Zhao, L. Shang, H. Li, R. Che, Z. Lyu, J. Xiong, L. Yang, X. Wang,
A. Macková, R. Mikšová, Z. Sofer, Use of deuterium labelling - evidence of graphene Z. Hu, Mesostructured NiO/Ni composites for high-performance electrochemical
hydrogenation by reduction of graphite oxide using aluminium in sodium hydro- energy storage, Energy Environ. Sci. 9 (2016) 2053–2060, https://doi.org/10.
xide, RSC Adv. 5 (2015) 18733–18739, https://doi.org/10.1039/c4ra16794e. 1039/C6EE00603E.
[33] J.A. Quezada-Renteria, C.O. Ania, L.F. Chazaro-Ruiz, J.R. Rangel-Mendez, Influence [40] R. Della Noce, S. Eugénio, T.M. Silva, M.J. Carmezim, M.F. Montemor, α-Co(OH)2/
of protons on reduction degree and defect formation in electrochemically reduced carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V
graphene oxide, Carbon N. Y. 149 (2019) 722–732, https://doi.org/10.1016/j. in aqueous medium, J. Power Sources 288 (2015) 234–242, https://doi.org/10.
carbon.2019.04.109. 1016/j.jpowsour.2015.04.131.
[34] K.M. Daniels, S. Shetu, J. Staser, J. Weidner, C. Williams, T.S. Sudarshan, [41] M. Pumera, Heteroatom modified graphenes: electronic and electrochemical ap-
M. Chandrashekhar, Mechanism of electrochemical hydrogenation of epitaxial plications, J. Mater. Chem. C 2 (2014) 6454–6461, https://doi.org/10.1039/
graphene, J. Electrochem. Soc. 162 (2015) E37–E42, https://doi.org/10.1149/2. c4tc00336e.
0191504jes. [42] X. Zhang, Z. Zhang, Q. Liao, S. Liu, Z. Kang, Y. Zhang, Nonenzymatic glucose sensor
[35] Y. Wang, Y. Wan, D. Zhang, Reduced graphene sheets modified glassy carbon based on in situ reduction of Ni/NiO-graphene nanocomposite, Sensors
electrode for electrocatalytic oxidation of hydrazine in alkaline media, (Switzerland) 16 (2016) 1–10, https://doi.org/10.3390/s16111791.
Electrochem. Commun. 12 (2010) 187–190, https://doi.org/10.1016/j.elecom. [43] B. Yuan, C. Xu, D. Deng, Y. Xing, L. Liu, H. Pang, D. Zhang, Graphene oxide/nickel
2009.11.019. oxide modified glassy carbon electrode for supercapacitor and nonenzymatic glu-
[36] H.J. Shin, K.K. Kim, A. Benayad, S.M. Yoon, H.K. Park, I.S. Jung, M.H. Jin, cose sensor, Electrochim. Acta 88 (2013) 708–712, https://doi.org/10.1016/j.
H.K. Jeong, J.M. Kim, J.Y. Choi, Y.H. Lee, Efficient reduction of graphite oxide by electacta.2012.10.102.
sodium borohydride and its effect on electrical conductance, Adv. Funct. Mater. 19 [44] K. Sheng, Y. Sun, C. Li, W. Yuan, G. Shi, Ultrahigh-rate supercapacitors based on
(2009) 1987–1992, https://doi.org/10.1002/adfm.200900167. eletrochemically reduced graphene oxide for ac line-filtering, Sci. Rep. 2 (2012)
[37] J. Basu, A. Baral, N. Samanta, N. Mukherjee, C. Roychaudhuri, Low noise field 3–7, https://doi.org/10.1038/srep00247.
effect biosensor with electrochemically reduced graphene oxide, J. Electrochem. [45] Y. Li, K. Sheng, W. Yuan, G. Shi, A high-performance flexible fibre-shaped elec-
Soc. 165 (2018) B3201–B3207, https://doi.org/10.1149/2.0261808jes. trochemical capacitor based on electrochemically reduced graphene oxide, Chem.
[38] V. Strong, S. Dubin, M.F. El-Kady, A. Lech, Y. Wang, B.H. Weiller, R.B. Kaner, Commun. 49 (2013) 291–293, https://doi.org/10.1039/C2CC37396C.