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Oxidized few layer graphene and graphite as metal-free

catalysts for aqueous sulfide oxidation†
Cite this: J. Mater. Chem. A, 2013, 1,
9491
~o P. de
Bruno R. S. Lemos,a Ivo F. Teixeira,a Bruno F. Machado,b Marcos R. A. Alves,b Joa
Mesquita,a Ronny R. Ribeiro,c Revathi R. Bacsa,b Philippe Serp*b and Rochel M. Lago*a

Received 4th February 2013
Accepted 3rd April 2013
DOI: 10.1039/c3ta10541e
www.rsc.org/MaterialsA
Few layer graphene and natural graphite were chemically modified by oxidation with HNO3 at 80 and 140
C
and used to promote the oxidation of sulfide ions in aqueous solutions. TEM, potentiometric titration, XRD,
BET and Raman spectroscopy show that HNO3 treatment even at 140
C did not modify the graphene and
graphite morphologies but produced significant amounts of different oxygen surface groups. The
presence of these groups on few layer graphene and graphite strongly increased the Saq2 oxidation,
showing activities comparable to a high surface area activated carbon with a similar amount of oxygen
surface groups. The obtained results suggest that the sulfide oxidation efficiency requires a balance
between two important effects, i.e. the presence of oxygen functionalities to initiate the Saq2 oxidation
and the electrical conductivity that is important to further transfer the electrons removed from sulfide.

Introduction
Modern industrial processes in the paper, natural gas, coal-
mining, chemical and petroleum rening industries result in
the production of gases and aqueous waste streams containing
varying amounts of hydrogen sulde and/or sulde ions asso-
ciated with different cations such as sodium or ammonium.
Concern for the environment1 and applicable regulations
preclude the discharge of such sulde-containing water to
receiving bodies of water such as rivers, lakes or estuaries.
Additionally, these waste streams can be corrosive to equipment
and constructions.2 For waste water streams containing rela-
tively large amounts of suldes, it is conventional to treat the
waste water containing sulde with acid and large amounts of
steam to convert the sulde into hydrogen sulde gas. The H2S
gas can be recovered and converted, inter alia, to elemental
sulfur. With increasing energy costs, the expense of generating
the steam needed to implement this procedure can be prohib-
itive. Such expense is exacerbated when only small or trace
amounts of sulde are present in relatively large streams, but
nevertheless large amounts of steam must be used to remove
the sulde that is present. Consequently, there has been a
considerable interest in the last few years in the development of
a
Chemistry Department, Universidade Federal de Minas Gerais, UFMG, Belo
Horizonte, Brazil. E-mail: rochel@qui.ufmg.br; Fax: +55 34095700; Tel: +55 34095719
b
Laboratoire de Chimie de Coordination, Composante ENSIACET, UPR CNRS 8241,
Université de Toulouse UPS-INP-LCC, 4 allée Emile Monso, BP 44362, 31432
Toulouse Cedex 4, France. E-mail: philippe.serp@ensiacet.fr; Fax: +33 534323596;
Tel: +33 534323572
c
Chemistry Department, Universidade Federal do Paraná, UFPR, Curitiba, PR, Brazil
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3ta10541e
efficient and low cost systems for the removal of sulde from
gas and aqueous phases.3
The removal of hydrogen sulde from the gas phase has
been studied by different processes such as adsorption, bio-
logical processes and catalytic oxidation. Several studies have
investigated the removal of gaseous H2S using different adsor-
bents such as activated carbon,4 alumina,5 silica6 and zeolite.7
Catalytic oxidation of H2S using air has been proposed using
different catalysts such as vanadium,8 iron oxides9 or carbon
materials.10 Various biological processes to remove hydrogen
sulde gas have also been proposed, e.g. biolters11 and
microorganisms supported on activated carbon.12,13
The removal of H2S from aqueous media has been investi-
gated using different methods such as precipitation,14 adsorp-
tion,15 ultrasonic irradiation,16 electrochemical processes17 or
chemical oxidation using hydrogen peroxide.18 For this latter
process, catalysts may be used to favor the reaction towards
sulfate or elemental sulfur formation. Catalytic removal of
sodium sulde from aqueous solutions by catalytic aerobic
oxidation with hydroquinone/ferric salts19 or with carbon
materials or carbon materials/ferric salts has also been repor-
ted.20,21 Microorganisms can also be used to oxidize sulde into
sulfur-containing species (mainly elemental sulfur, poly-
suldes, thiosulfates, thionates and sulfates).22 Several studies
have suggested that these sulde oxidizing bacteria are based
on a sulde-quinone reductase enzyme.23,24 These enzymes
show two main features, i.e. the presence of quinone redox
groups and a facile electron transportation system. Such char-
acteristics can also be present in some carbon materials.
This has inspired us to modify an activated carbon in order
to introduce some of the properties of the enzymatic systems for
the aqueous phase oxidation of sulde.25 It has been shown that

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Journal of Materials Chemistry A
aqueous sulde oxidation is strongly promoted by the presence
of oxygen surface groups. However, activated carbon has a poor
electrical conductivity. In the present work, we investigate the
sulde oxidation promoted by three different chemically
modied carbonaceous materials, i.e. few layer graphene and
graphite with different concentrations of oxygen supercial
groups and a reference commercial activated carbon.
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Experimental
Materials
Few layer graphene powder was prepared by a catalytic chemical
vapor deposition method using a ternary oxide catalyst and
ethylene as the carbon source in a uidized bed reactor at
650
C.26 The carbon deposited at the end of the reaction was
puried by dissolving the catalyst in acid. The average thickness
of the particles was in the range of 6–8 nm as estimated from
the line broadening of (002) reection in the X-ray powder dif-
fractograms. High resolution TEM showed thin akes of varying
thicknesses from 2–8 nm with domain sizes in the 200 nm
range. Electron diffraction of the akes showed highly crystal-
line graphene layers (Fig. 1). Raman spectra were taken aer
sonication of the powders in ethanol and drying the suspension
on a substrate. The spectra conrmed the presence of graphene
layers with IG0 /IG ratios >1 (see ESI, Table S2†).
The modication of the graphene surface was carried out by
nitric acid oxidative treatment at 80 and 140
C for 3 hours. These
samples were named GN80 and GN140, respectively. The
graphite (GT) (Micrograf: high purity micronized grades with
average particle size (d50) between 3 and 60 microns; from
Nacional de Grate) was functionalized by the same method with
HNO3 at 80 (GT80) and 140
C (GT140). Aer the acid treatment,
both the graphene and graphite samples were extensively washed
to obtain pH ca. 7 and dried (80
C) for 24 hours.
Activated carbon (AC) made from coconut shell (Sulfal) was
used for comparison and was pre-treated with concentrated HCl
under reux for 30 min to remove soluble metals, extensively
washed with distilled water and dried in an oven at 80
C
overnight.
Characterization
The samples were characterized by transmission electron
microscopy – TEM (JEM 1011 electron microscope of JEOL
Fig. 1 Transmission electron microscopy images of few layer graphene
produced by ethylene CVD. Image on the right shows the high resolution image
of a thin flake (shown by arrow) and the corresponding diffraction pattern.
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operating at 100 kV), thermogravimetric analysis – TGA (Shi-
madzu TGA-60H, with a constant heating rate of 10
C min1 in
an air ow of 50 mL min1), X-ray diffraction – XRD (Seifert XRD
3000T using Cu Ka radiation and l ¼ 0.15418 nm). Raman
spectra were obtained on a HR800 One Labram Jobin Yvon, l ¼
632.82 nm. For each sample, between 5 and 10 spectra were
recorded at different spots and an average representative spec-
trum was obtained. The surface area values were obtained by
the BET method on Quantachrome Autosorb 1 Equipment. The
measurements were carried out using nitrogen with 41 cycles of
adsorption and desorption. The number of oxygen surface
groups was determined by potentiometric titration (Metrohm
670). The pH data and the volume of titrant were adjusted by a
nonlinear regression program developed in MATLAB 6.5.27,28 The
oxygen group density was calculated by dividing the number of
oxygen groups (obtained from titration) by the specic surface
area of the material. X-band Electron Paramagnetic Resonance
(EPR) spectra from solid samples at room temperature were
recorded on a Bruker Elexsys E500 spectrometer equipped with a
Bruker ER4122SHQE resonator. Semi-quantitative measure-
ments were performed using a non-calibrated chromium (3+)
doped magnesium oxide powder sample.
Electrochemical measurements
Cyclic voltammograms were obtained with a potentiostat (Palm-
Sens) at room temperature using a conventional three electrode
arrangement with a Pt wire counter electrode, a Ag/AgNO3
reference electrode (3.0 M KCl), and a carbon paste electrode as
the working electrode. The carbon paste electrodes were
prepared by mixing 45 mg of graphite powder with 5 mg of
mineral nujol oil for 10 minutes. The resulting paste was packed
into a glass tube of 2 mm internal diameter and 10 cm length.
Electrical contact was made through a copper wire cleaned in a
solution of 10% HNO3. The surfaces of the electrodes were
polished on paper to produce a at reproducible working
surface. All electrochemical experiments in this work were
carried out in a 1 mM Na2S–0.1 M KCl solution which is used as
an electrolyte.
Kinetic studies of sulde oxidation
Kinetic studies of sulde oxidation in aqueous solution were
performed using different carbon catalysts. The reactions were
carried out using 30 mg of the materials in 6 mL of Na2S$9H2O
(8.8 g L1). During the experiments, the formation of polysulde
was monitored by measuring the absorbance of the aqueous
solution at a wavelength of 290 nm, using a Shimadzu UV
spectrophotometer 2550.
Results and discussion
Few layer graphene, graphite and activated carbon were modi-
ed by a well-known chemical oxidation method with HNO3 at
different temperatures, i.e. 80 and 140
C, in order to yield
different amounts of oxygenated surface groups.29,30
The nature and concentration of the oxygen surface groups
produced by the oxidation was determined by potentiometric
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titration.27 Fig. 2 shows the concentration of oxygen surface
groups according to their pKa for the samples studied.
An increase in the concentration of oxygen groups can be
observed for GN aer treatment with HNO3. This increase is
more pronounced at 140
C compared to 80
C due to the more
aggressive oxidation conditions. The presence of sites with
pKa < 5 conrms the formation of carboxylic groups, especially
aer oxidation at 140
C. Lactone and lactol groups show pKa
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between 5 and 9 and were observed mainly for graphene
samples (especially for GN140). Phenols and quinones with pKa
greater than 9 were observed for all the samples. This high
degree of oxidation is conrmed by XPS analysis that showed an
oxygen content of 17% for GN140, whereas it was less than 4%
for GN. On the other hand, the oxidation of GT at 80
C (GT80)
did not produce a signicant change in the oxygen surface
group concentration compared to the initial GT. Only for the
GT140 sample, there was an increase in the number of oxygen
sites. A commercial sample of activated carbon containing a
similar number of oxygen groups to GN140 and GT140 was
selected for comparison.
FTIR spectra in KBr (ESI, Fig. S1†) conrmed the presence of
carbonyl groups on the surface of GT140 and GN140, the latter
showing a broader band. The band due to the C–C stretching is
also shied with respect to graphite.
XRD powder analyses (ESI, Fig. S2†) for the graphite samples
showed intense peaks at 2q ¼ 26.5
related to the (002) graphitic
planes. The graphitic crystallites were characterized by the
distance between graphene planes (d002) and the average sizes
of the crystallites, La and Lc (see ESI, Table S1†). For GT, d002
(0.335–0.336 nm), La (42–44 nm), and Lc (20–21 nm) values did
not change signicantly before and aer treatment at 80 and
140
C, showing that the HNO3 treatment did not affect the
graphite crystallite structure signicantly. GN also showed a
peak at 2q ¼ 26.3
conrming the presence of graphitic
ordering. There also, d002 (0.338–0.339 nm), La (21–23 nm), and
Fig. 2 Number of oxygen functional groups formed on few layer graphene and
graphite after treatment with HNO3 at 80 and 140
C and a commercial activated
carbon.
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Lc (10–11 nm) values did not change signicantly before and
aer the nitric acid treatment.
The Raman spectra of GT (Fig. 3) showed three bands, i.e. an
intense band centered at 1590 cm1 (G band) related to the well-
organized graphite layered structure, a band at ca. 1300 cm1
related to defective carbon structures (D band) and the one at
ca. 2700 cm1 (G0 band).31 Aer treatment with HNO3 the rela-
tive intensity of the D band strongly increased causing an
increase in the ID/IG ratio from 0.55–0.60 for GT and GT80 to
1.36 for GT140. This increase in the relative intensity of the D
band is related to the creation of defects on the graphite
structure (mainly on the edges) due to the extensive oxidation by
HNO3 at 140
C. GN showed a Raman spectrum with an ID/IG
ratio of 0.86 that did not change much aer functionalisation.
The higher ID/IG ratio in GN can be attributed to the smaller
domain sizes of the FLG akes with defects associated with a
larger number of edges. As these defects are oxidized prefer-
entially by HNO3, the increase in the ID/IG ratio was not so
pronounced as observed for GT. The G0 band intensity is
increased aer functionalization.
For the GN sample, the increase in G0 band intensity upon
functionalization (see ESI, Table S2†) could arise from a partial
exfoliation of the graphene sheets. The narrowing of the G0
band is also in accordance with this observation. These results
suggest that nitric acid treatment leads to the exfoliation of few
layer graphene.32
Nitrogen adsorption experiments at 196
C showed a low
surface area for GT and GT80 (2–3 m2 g1). Functionalization
with HNO3 at 140
C produced a small increase in the surface
area to 10 m2 g1. As expected, GN showed a higher surface area
when compared to graphite, i.e. 54 m2 g1, which increased to
65 and 71 m2 g1 aer treatment with HNO3 at 80 and 140
C,
respectively. This increase in specic surface areas is likely to be
related to an exfoliation process induced by the introduction of
oxygenated groups between the layers of graphene. The AC used
in this work showed a much higher surface area of 866 m2 g1.
TEM images of the few layer graphene samples showed the
presence of sheets with sizes varying between 0.1 and 1 mm
(Fig. 4). Curling and wrinkling of the sheets was also observed.
Fig. 3 Raman spectra of GN and GT before and after treatment with HNO3.
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GT showed in general larger particles/aggregates and smaller

fragments, which were analyzed by TEM. The images of these
fragments showed packs of at graphitic layers with dimen-
sions of 0.3–1.5 mm. Upon nitric acid treatment at 140
C, the
FLG edges were found to be damaged due to acid etching,
whereas no modication of texture was seen for GT (Fig. 4).
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Sulde oxidation studies

The sulde oxidation was monitored by UV/Vis spectroscopy. A
typical evolution of the UV/Vis spectra during the reaction with
aqueous sulde is shown in Fig. 5.
Previous works25,33 have shown that the reaction of sulde
initially produces polysuldes, e.g. S22, S32 and S42, which
can be identied by absorptions in the UV/Vis spectrum at 267,
290 and 375 nm, respectively.
These polysuldes are further oxidized to form complex Fig. 5 Typical UV/Vis spectral evolution during the disodium sulfide oxidation at
mixtures of oxygenated sulfur species.34 The kinetic measure- 25
C (using AC).
ments were carried out by measuring the evolution of the pol-
ysulde (UV band at 290 nm). The results obtained for GN,
GN80, GN140, GT, GT80, GT140 and AC are shown in Fig. 6.
It can be observed that AC is the most efficient material
showing an increase in the 290 nm band intensity up to 45 min
that remains stable thereaer. The sample GT140 shows a nal
activity similar to AC, whereas GT and GT80 show very low
polysulde production. The sample GN140 also shows fairly
high activity for the oxidation of sulde that decreases for GN80
and GN. It is interesting to observe that GT140 and more
particularly GN140 show signicantly faster production of pol-
ysulde compared to AC in the rst 15 min of reaction. Even
though the exact nature of the active functional groups is not

Fig. 6 Polysulfide formation (band at 290 nm) during the reaction of aqueous
Na2S with different carbonaceous materials.

well understood, this high initial activity of GN140 may arise

from the presence of a higher concentration of acidic surface
groups (pKa < 5, Fig. 2). The data show that the HNO3 treatment
on GT and GN signicantly increases the sulde oxidation
activity, in agreement with previous results.25 If the reaction
data are normalized by the number of oxygen sites, the sample
GT140 still shows very good results comparable to AC (Fig. 7).
On the other hand, some important changes are observed for
the GN samples. The non-oxidized GN sample shows the best
result whereas the activity of GN140 strongly decreases (Fig. 7).
Although the reasons for these changes are not clear, one can
speculate that it could be related to the severe attack of the
graphene structure by the HNO3 oxidation. As suggested by
previous work,35–37 the activity of sulde oxidation depends on
the oxygen surface groups but also on the electrical conductivity
of the material. Although the HNO3 oxidation introduces oxygen
surface groups which are supposed to improve the activity of
Fig. 4 TEM images of GN and GT before and after HNO3 oxidation at 80 and 140
C. sulde oxidation, it also introduces a large number of defects in

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Fig. 7 UV absorption (at 290 nm) normalized by the oxygen sites concentration
showing polysulfide formation during the reaction of aqueous Na2S with
different carbonaceous materials.
the graphene layer. These defects should strongly decrease the
electrical conductivity of the graphene layers, which leads to a
decrease in the activity for sulde oxidation. As graphite is a
more compact structure (as shown by the Lc values), the HNO3
oxidation should take place more on the edges of the graphitic
layers and affect less the conductive structure (Fig. 8).38–40
In fact, EPR spectra of the samples GT, GT80 and GT140
showed a strong signal related to the spin of electrons origi-
nating on the graphite bulk and surface.41 As graphite is
oxidized by HNO3 at 80 and 140
C the relative number of these
spins does not change dramatically, e.g. the spin relative
concentrations decrease to 80% of the original values (see ESI,
Fig. S3†). It can also be observed by the asymmetry of the EPR
line A/B ratio (between 1.1809 and 1.3088)42 that the graphite
electrical conductivity is not signicantly affected by the
Fig. 8 Schematic representation of the oxidation and creation of oxygen surface
groups and defects on GN and GT.
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oxidation with HNO3 even at 140
C. The GN samples did not
show any signicant EPR signal. These results combined with
the XRD data suggest that the graphite oxidation takes place
mainly on the surface and on the edges/borders of the material.
It is also interesting to compare the polysulde production
kinetic curves normalized by the surface area of the materials
(Fig. 9).
It can be observed that GT samples, especially treated at
140
C with HNO3, showed the highest activities for the oxida-
tion of sulde per m2. This result is apparently related to the
combination of two features of graphite, i.e. the high electrical
conductivity with a high density of oxygen groups present on the
surface of the materials. For example, the sample GT140 has an
oxygen group density of 14 mmol m2, which is potentially active
for sulde oxidation. Although AC shows a very high surface
area, which is supposed to improve sulde oxidation, the
oxygen surface group density is low, ca. 0.2 mmol m2, and oen
located in low electrical conductivity domains inside the pore
structure.
Results of recent works have shown that graphite has a very
high conductivity, generally higher than 103 S m1,43–45 while
few layer graphene and particularly activated carbon have
conductivities usually lower than 102.45–48
Cyclic voltammetry (CV) of the samples GT, GT80 and GT140
was carried out to investigate the redox processes on the surface
of these samples. CV proles suggest that the conductivity of
these materials did not change signicantly even aer oxidation
at 140
C. CV studies of GN samples did not give reliable data
due to the low electrical conductivity of the samples. The elec-
trocatalytic activity of the samples GT, GT80 and GT140 (in the
presence and absence of Na2S) with different sweeping veloci-
ties is shown in the ESI (Fig. S4–S6†). In all the voltammograms
an anodic peak current in potentials near 0.4 V is observed. A
linear correlation between the anodic peak current and
the square root of scan rate (see ESI, Fig. S7†) suggests that the
redox reactions are controlled by the diffusion of the
Fig. 9 Polysulfide formation monitored at 290 nm during the reaction of
aqueous Na2S with different carbonaceous materials normalized by the BET
surface area.
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Fig. 10 Cyclic voltammetry for the oxidation of sulfide in the presence of
graphite samples, GT, GT80 and GT140.
electroactive species (Saq2, HSaq) to the carbon surface.
Furthermore, an increase in the scan rate shis the anodic peak
potential to a more positive value indicating a kinetic limitation
in the reaction and so it appears that the surface of the carbon
catalyst plays an important role in sulde oxidation.49 When the
different graphite samples are compared, it can be clearly
observed that the oxidation potentials shied to lower values,
from 0.46 to 0.41 and 0.36 V as graphite is functionalized by
oxidation with HNO3 at 80 and 140
C, respectively (Fig. 10).
These results clearly show that the oxygen groups have a
catalytic effect on the sulde oxidation.
Conclusions
Both few layer graphene and graphite promote sulde oxidation
in an aqueous medium. Chemical modication of these mate-
rials by oxidation with HNO3 introduced oxygen surface groups,
which strongly improved the activity of sulde oxidation.
Comparison of sulde oxidation activities based on the
concentration of oxygen groups and surface area shows that for
graphite, the activity per site or per m2 increases upon oxidation
whereas these activities decrease for graphene. These results are
discussed in terms of a balance between two effects: the pres-
ence of oxygen functionality and the electrical conductivity.
Upon oxidation, the number of oxygen groups increases
favoring the reaction. On the other hand, in the case of gra-
phene, the HNO3 oxidation results in a severe attack of the
graphene pi electron structure, which leads to a decrease of the
specic activities for aqueous S2 oxidation.
Acknowledgements
BRSL, IFT and RML are grateful to Centro de Microscopia
UFMG, CNPq, CAPES, FAPEMIG and UFMG. BFM, RRB and PS
thank Pierre Lonchambon for technical help in the preparation
of GN and Lucien Datas (TEMSCAN, Toulouse University) for
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the high resolution TEM images of GN. Funding from the
CAPES-COFECUB program (Ph715/11) is also acknowledged.
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