RSC Advances

PAPER

N-doped mesoporous carbon nanosheets obtained

by pyrolysis of a chitosan–melamine mixture for
Cite this: RSC Adv., 2015, 5, 44969
the oxygen reduction reaction in alkaline media†
Maria K. Rybarczyk,* Marek Lieder and Milena Jablonska

By simple thermal decomposition of low-cost precursors (chitosan, melamine) in an inert atmosphere,

Received 31st March 2015
Accepted 12th May 2015
DOI: 10.1039/c5ra05725f
www.rsc.org/advances
nitrogen-doped porous carbonaceous materials were prepared. The samples pyrolyzed at 700
C are
composed of mainly mesoporous nitrogen-doped carbon nanosheets and partially graphitized carbon.
The nanosheets contain a disordered area due to the strain imposed by the presence of nitrogen and/or
oxygen groups in their structure. Some portion of the material is comprised of clean well crystallized
graphene sheets. They show an interlayer distance of about 0.359 nm. The average size of the visible
well-crystallized carbon is 8  8 nm, covering ca. 4% of the samples flat projection. Further, these
materials possess total specific areas up to ca. 285 m2 g1, and exhibit efficient electrocatalytic activity
(the onset potential of 0.735–0.761 V vs. RHE) for the oxygen reduction reaction (ORR) in alkaline media.
Our results show that besides the total nitrogen content and the type of nitrogen group (pyridinic or
graphitic), also the amount of carbon ‘kinks’ and/or surface roughness strongly influence the ORR activity.

nanosheet and doped carbon nanosheet for catalytic

Introduction
Recently, carbon nanosheets, two-dimensional graphene-like
nanostructures, have drawn considerable attention due to
their versatile physicochemical properties and prospects for
many industrial applications. The carbon sheets, apart from a
large specic surface area, also provide porosity, chemical
inertness, intrinsically low toxicity, long-term operation
stability or/and good electrical conductivity. These may facili-
tate adsorption, catalysis, sensing, ion or substance delivery,
e.g. for medical or environmental applications, and membrane
transportation.1–3 To extend the potential applications, chem-
ical and physical modication is commonly used to tailor, in
particular, the electronic properties and catalytic activity of
these carbonaceous structures. For example, electrocatalytic
activity of non-metal doped graphene-like or microporous
structures towards the oxygen reduction reaction brings hope
for future replacement of platinum-based catalysts in fuel cells
applications.4–7 These exciting chances have stimulated inten-
sive research on developing new methods for large-scale
synthesis of the carbon nanosheets and on their chemical
modication for catalytic, environmental or medical applica-
tions. Numerous synthesis technique (chemical, pyrolytic,
hydrothermal, mechanical, electrochemical and chemical
vapour deposition) have been devised to produce carbon
Gdansk University of Technology, Narutowicza Str. 11/12, 80-233 Gdansk, Poland.
E-mail: maria.rybarczyk@pg.gda.pl
† Electronic supplementary information (ESI) available.
10.1039/c5ra05725f
applications.
To date, carbon nanostructures have been synthesised
primarily based on the pyrolysis of plentiful raw material
sources (including eco-friendly and renewable biomass), which
has advantages such as low cost or the simple synthetic
conditions.8 Although high-temperature carbonization of
organic precursor provides an attractive route to prepare
nanosized carbon, the production of graphitic carbon with
uniform mesostructure, in any case, still remains a challenge.
For example, pyrolysis of hydrocarbons always leads to amor-
phous nanoparticles, whereas nitrogen-rich compounds (e.g.
melamine) result in orderly graphitic structures.9
The carbonization of polysaccharides have been reported
under mild10,11 and moderate temperature conditions.12–17 For
example, pyrolysis of chitosan lms under argon at 800
C
results in high-quality single layer N-doped graphene layer.18
Also recently it was developed a simple and scalable synthesis of
highly-porous N-doped carbon nanosheets by the pyrolysis of
chitosan and urea.19
The conversion of biomass into desired electrocatalyst found
to serve a promising approach for ORR catalysts from natural
and renewable resources. It was proven that can be used a
feedstock material, mostly carbohydrates, biopolymers or
biomass, for N-doped carbon catalysts. Metal free catalysts are
mainly carbon based materials, which aer chemical as well as
physical functionalization, tune electronic activity. In this
regard, S. A. Wohlgemuth et al. have synthesized sulfur and
See DOI:
nitrogen co-doped materials from glucose with electrochemical
activity towards the ORR.20 N-doped carbon aerogels, used as

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RSC Advances
well as ORR catalysts, can be easily manufactured from
carbohydrate-based derivatives, i.e. glucose, D-glucosamine.21
Recently, Meng et al. reported the production of a N-doped
carbon nanober aerogel with low mass density, continuous
porosity from a bacterial cellulose precursor. Due to their highly
porous and interconnected 3D structure, the obtained N-doped
carbon aerogel was used directly as a catalyst for the oxygen
reduction reaction.22
In this work, the nitrogen-doped carbon-nanosheet catalysts
were prepared by gelation of chitosan (a source of carbon and
nitrogen) with nitrogen-rich melamine precursor followed by
lyophilization and pyrolysis under nitrogen atmosphere. Mela-
mine (C3N6H6) is a low-cost industrial material with a honey-
comb atomic arrangement. Melamine possesses a three-
dimensional monoclinic structure which is similar to C3N4.23
Due to this specic structure, decomposition of melamine may
favor the incorporation of nitrogen in carbonaceous materials
obtained by pyrolysis. Inuence of melamine on morphology,
structure and nitrogen doping extent of carbonized chitosan
has not been reported. Linear sweep voltammetry was per-
formed to evaluate the activity of catalysts towards the oxygen
reduction reaction. The nature of the active sites of catalysts was
discussed based on various physical and chemical
characterizations.
Experimental
Materials
- Chitosan, medium molecular weight and deacetylation degree
81% (Sigma Aldrich).
- Melamine (Sigma Aldrich).
All reagents were used without further purication.
Methods and apparatus
Chitosan (0.4 g) was dissolved in aqueous acetic acid solution.
Solid melamine (0.02 g – designated 20 wt% of total doping in
the system) was added to the prepared solution. Then, it was
mixed thoroughly formed the liquid composite. The water
from the pores was removed by controlled freezing and
lyophilization followed by carbonization in an inert atmo-
sphere. A two step carbonization was used, involving material
heating to a temperature of 400
C and holding for 30 min,
before continued increasing up to 700
C with ramping rate of
5
C min1. The obtained N-doped carbon was treated using
KOH activation in order to increase the surface area. The
activation process was carried out at 700
C for 30 min under
N2 atmosphere with a heating rate of 5
C min1. Aerwards,
the samples were washed with 1 M HCl in order to get rid of the
potassium salts present in the carbonaceous material and then
with distilled water until the pH of the ltrate was neutral. The
nal nitrogen-doped carbon (CH-mel) was obtained aer
drying at 100
C for 24 h. Carbonized material was stored
under vacuum. CH-mel was further sonicated for one hour at
room temperature. According to the above described proce-
dure sample without melamine doping (called CH) was
prepared.
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The samples were characterized by scanning electron
microscope SEM-EDX Zeiss LEO 1430VP, transmission electron
microscope TEM Tecnai G20 X-TWIN (FEI Company) and
atomic force microscope AFM Veeco NanoScope V. Thermal
responses of the freeze-drying samples were performed using
thermal gravimetric analyzer NETZSCH TG 209F3 TGA209F3A-
0346-L. The measurements were set in the temperature range
of 40–900
C, at heating rate of 5
C min1 under nitrogen
atmosphere. An alumina crucible with a cover was used during
thermal analysis to prevent sublimation of melamine. The
Raman spectra were recorded on the Raman Scattering Spec-
troscopy (Renishaw 2000 system) with excitation by diode laser
(514 nm, laser power of 25 mW) in backscattering geometry.
The curve tting and data analysis soware Fityk was employed
to determine the peak locations.24 BET Micromeritics Gemini V
was assigned to measure the total surface area. The elemental
analysis was carried out on CHN Analyser 2400 (Perkin-Elmer,
Germany) by a conventional CHN combustion method. The UV-
Vis absorption spectra were recorded on UV-Vis spectropho-
tometer (Evolution 220, Thermo Scientic) at room tempera-
ture. The base-line was determined using distilled water as a
reference. X-ray photoelectron spectroscopy (XPS) analysis was
used to determine the nitrogen-containing functional groups
present on the carbon surface. The XPS analysis was performed
using a VG Scienta250Xi spectrometer (Prevac sp. z o.o.) with Al
Ka radiation (hn ¼ 1486.6 eV). The binding energy scale was
regulated by setting the C 1s transition at 284.6 eV. XRD
patterns were recorded with a Bruker-D8 apparatus with Cu
radiation. Each pattern was recorded with a step size of 0.03
.
The electrocatalytic performance of the chitosan-derived
samples towards oxygen reduction reaction (ORR) was
measured with a computer-controlled potentiostat (Atlas 0531
Electrochemical Unit & Impedance Analyser, Poland). A three-
electrode cell system was employed for all the measurements,
using the modied glassy carbon (GC) electrode as the working
electrode, Pt wire as the auxiliary electrode, and an Ag/AgCl
electrode (in sat. KCl) as the reference electrode. All poten-
tials in this report were converted into reversible hydrogen
electrode (RHE) scale by adding 0.965 V. The GC was polished
with 50 nm alumina slurry to a mirror-nish effect. The
working electrode was prepared by dropping a catalyst ink on
the surface of the GC (6 mm diameter), and drying at room
temperature. The catalyst ink was composed by dispersing
1 mg of sample into the mixture of 0.5 mL isopropanol and 9 mL
Naon (5 wt% in isopropanol, Sigma Aldrich) with sonication
for 30 min. For each experiment, the catalyst ink 7 mL was
casted onto the freshly polished GC, yielding a sample loading
of 0.487 mg cm2. A commercial Pt/C (5 wt% Pt on carbon,
Sigma Aldrich) catalyst was also measured for reference by
applying a catalyst loading of 0.487 mg cm2 using the same
procedure described above. Prior to the ORR measurements,
the modied GC was electrochemically cleaned in N2-saturated
0.1 M KOH in the potential range between 0 and 1.00 V for a
couple of cycles at a scan rate of 10 mV s1. Linear sweep vol-
tammetry (LSV) measurements for the ORR were performed at
the potential range from 1.0 to +0.2 V at the scan rate of 10 mV
s1. An O2-saturated 0.1 M KOH aqueous solution was used as
This journal is © The Royal Society of Chemistry 2015
Paper
the electrolyte. All the electrochemical experiments were
carried out at room temperature.
Results and discussion
The basic concept of our approach was to adjust the porosity of
the N-doped carbon surface since the main disadvantage of its
activated form is the incapability to control the porosity of the
nal carbon. Fig. 1a and b show TEM images, which were taken
to characterize the structure and the interlayer distance of the
nanosheets contained in the studied materials. Three major
features are present: graphitic region, high contrast disordered
regions, indicating areas of high oxidation, and lamellar
structure regions (marked with red ellipse), with approximate
area share of 4%, 82%, and 14%, respectively. Well-crystallized
(graphitic) area shows an interlayer distance of about 0.359 nm,
which is larger than that of graphite (0.335 nm). The increased
layer distance between graphene nanosheets may stem from
some imperfection in their two dimensional sp2 lattice, i.e. the
presence of small sp3 domains. By far largest area is composed
of disordered region, still featuring carbon nanosheets, though
highly distorted due to the strain imposed by the presence of
nitrogen and/or oxygen groups in their structure. The average
distance between these layers was measured as 0.462 nm (red
ellipse). The revealed by the TEM images large distance between
the carbon layers implies the presence of slit like micro- and
mesoporous texture of the synthesized materials.
The SEM images of Fig. 2a and b exhibit the texture of the
stack of carbon nanolayers. Clearly visible surface wrinkling
supports the view that the stacks comprise distorted graphene
sheets. Apart from this, the stack surface is featureless and lacks
macropores. The average thickness of the stacks was measured
as ca. 290 nm. Morphological changes to the carbonaceous
sheets as a result of blending the chitosan precursor with
melamine prior to pyrolysis were judged from AFM imaging,
Fig. 3a and b. Average surface roughness of the ca. 290 nm thick
samples, over a large area of 1 mm2, was found to be remarkably
higher of about 5.32 nm for the CH samples compared to that of
the CH-mel samples (ca. 0.335 nm).
Fig. 4 shows the XRD spectra of the KOH activated CH-mel
catalyst, and for comparison, the XRD spectra of graphite.
Fig. 1 Representative TEM images of the CH-mel catalyst (a and b).
This journal is © The Royal Society of Chemistry 2015
RSC Advances
Fig. 2 Representative SEM images of the CH-mel catalyst (a and b).
Two broad peaks appearing at 24.55
and 43.89
indicate that
the CH-mel carbon can be treated as the combination of a lot of
small domains that consist of a few graphene sheets in parallel.
The lateral extent of the graphene layers was calculated as La ¼
31.9 A by applying Scherrer's equation to (101) diffraction peak,
while mean stack height of crystallite was calculated as 9.09 A by
applying Scherrer's formula to (002) diffraction peak. Interlayer
spacing (d002) was measured to be 3.62  A using Bragg's law. An
empirical parameter (R), dened as the (002) peak-to-
background ratio,25 was estimated as R ¼ 1.46. It has previ-
ously been demonstrated that R can be used as a measure of the
number of carbon sheets arranged as single layer. It decreases
as the single-layer content of the carbon increases, such that
when R ¼ 1, all graphene layers are randomly distributed as
single layers while larger (>1) values of R indicate a higher
percentage of graphene sheets stacked in parallel.26
N2 adsorption–desorption isotherms were performed to
examine the structure characteristics of the samples. The plots
feature a distinct hysteresis loop in the range of ca. 0.1–1.0 P/P0,
indicating the presence of slit like pores in the materials
(Fig. S1†). This type can be associated with plate-like structure.27
The assumption, based on the isotherm classication recom-
mended by the IUPAC, is consistent with our TEM and SEM
results. The Brunauer–Emmett–Teller (BET) specic surface
area (SSA) of CH-mel (ca. 285 m2 g1) is much higher than that
of CH (ca. 3 m2 g1). Moreover, the CH material contains
negligible amount of pores, whereas the CH-mel SSA stems
mainly from meso- and micropores. The area of the former type
is 40 times larger than that of the latter one (Table 1).
The thermal and gravimetric behaviour of chitosan during
pyrolysis in dynamic nitrogen atmosphere was analyzed up to
900
C. The representative TG and c-DTA curves are shown in
Fig. 3 AFM surface topography images of the CH (a) and CH-mel (b)
samples (3D projection).
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Fig. 4 Powder XDR spectra of CH-mel and graphite. Bragg peaks
(002) and (101) are indicated in the CH-mel sample. Spectra are
y-offset for clarity.
Fig. 5a. The initial weight loss of about 19% in the range from
20 to 195
C, usually attributed to evaporation of physically
adsorbed water (2.2% below 100
C), is followed by endothermic
release of strongly hydrogen-bonded water (3.0% below 140
C).
Then, further dehydration, or preliminary deacetylation, follows
coupled with exothermic cross-linking reactions without the
main chitosan chain degradation (13.2% below 195
C). The
second stage of degradation from 195 to 400
C presents a
moderate endothermic peak followed by a small exothermic
peak in the c-DTA curve and a rapid mass loss (50%) in the TG
curve. This weight loss may be ascribed to a series of complex
chemical reactions, leading to the disintegration of intra-
molecular forces and the breaking of the molecular structure
accompanied by the exclusion of small molecular gases, such as
hydrogen, ammonia etc. Specically, the process includes
depolymerisation of chitosan chains, decomposition of pyra-
nose rings through dehydration and deamination and nally
ring-opening reaction.28–30 The decomposition process is visu-
alized in c-DTA by the endothermic peak at 220
C. The pyrolytic
degradation of chitosan involving homolytic bond scissoring
(generating radicals) results in the immediate new bond
formation and crosslinking (the exothermic peak at 255
C).
These bond scissoring and cross-linking reactions results in
structures composed of fused-ring which have nitrogen atoms
substituted in the pentagonal or hexagonal lattices of the cyclic
carbon. These cyclized and crosslinked fused-ring structures are
thermally stable and may be able to withstand high tempera-
tures. Thus, in the higher temperature range, from 400 to 900

from the hydrogen bonding with water molecules upon drying.
C, the third step of degradation, there is no distinct weight loss
region in the TG curve, which implies that the carbon residue in
this region is thermostable and rigid owing to the dominance of
the good p-conjugated structure of the polycyclic-type fused
Table 1 Surface and pore structures of CH and CH-mel
Total area Micro-pore Meso-pore area
Catalyst m2 g1 area m2 g1 m2 g1
CH 3.064 n.a. n.a.
CH-mel 285.3 4.267 172.187
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Fig. 5 Gravimetric (TGA) and thermal (c-DTA) decomposition spectra
of CH (blue) and CH-mel (red). The black plots represent heat flow.
rings. It seems that the thermal characteristic is similar in both
samples, especially for DTA curves which can be explained by
chitosan degradation. The difference in weight loss between
both samples is equal 16%. It suggests the melamine conden-
sation with increasing N content in the nal product. At the
same time, the concentration of residual hydrogen and nitrogen
reduces to small level (these processes are endothermic, huge
peak at 750
C) and the carbon content increases accordingly to
the elemental analysis results shown in Table 2. This indicates
that the nitrogen-containing rings of chitosan are decomposed
by the pyrolysis process and carbonization occurs. Pyrolysis of
chitosan gives a char residue yield of ca. 18% at 900
C. Func-
tionalization chitosan polymer with melamine becomes effec-
tive due to the strong interaction between the pyranose units
and the amine groups, which results in the crosslinked
networks. The relevant TG and c-DTA thermographs (see
Fig. 5b) clearly show three major changes in the decomposition
run. The initial mass loss (up to 195
C), ascribed to water
evaporation, is 5% lower than the one for chitosan. It seems,
that it can be accounted for by the lower water content in the
composite due to melamine bearing, which prevents chitosan
The decomposition of chitosan that commences at higher
temperatures proceeds much slower (50% mass reduction
needs 110
C higher temperature), what might be ascribed to
Total pore volume Micropore volume Mesopore volume
cm3 g1 cm3 g1 cm3 g1
0.0014 n.a. n.a.
0.275 0.039 0.236
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Paper
Table 2 Elemental analysis from CHN combustion method and XPS data
CH
Element Precursor CHNa [%mass]
C 38.3 [67.7] 69
H 6.7 [5.4] 2.5
N 5.9 [1.9] 4.5
O 49.1 [25] 23
a
Data in brackets concern the samples as withdrawn from the pyrolytic oven, i.e. without alkali activation.
intermolecular stabilization of the composite structure exerted
by melamine. The third difference between the thermographs
concerns the melamine conversion and degradation. Melamine
has been reported to be stable up to 250
C under nitrogen
atmosphere. At higher temperatures a series of reaction associ-
ated to the decomposition of triazine rings, followed by some
condensation process proceeds.31,32 In another study, it has been
shown that melamine thermally treated at 450
C yielded melem
(s-heptazine derivative). A postulated mechanism predicts that
melamine molecules decompose into cyanamide H2N–CN at
about 300–320
C followed by condensation of cyanamide with
melamine, resulting in melem formation under simultaneous
release of ammonia gas.33 Other authors proposed the direct
thermal condensation of melamine to melem, i.e. without
cyanamide formation, accompanied with deammonation
process.34 Although, melamine sublimes between 297–345
C, it
has not been resolved to what extent this process prevents
melting, or condensation reactions.35 The c-DTA thermograph in
Fig. 3b shows a weak thermic effect between 420 and 500
C. It
well corresponds with ndings of Lotsch and Schnick that at
temperature around 380
C melem is formed, and it is stable up
to 507
C.35 Pyrolysis of chitosan–melamine composite gives a
char residue yield of ca. 34% at 900
C.
XPS has been used for quantitative assessment of individual
nitrogen- and oxygen-containing functional groups on the
surface of the CH and CH-mel materials aer deconvolution of
the N 1s (Fig. 6a and b) and O 1s (Fig. S2 and S3†) spectra. The N
1s spectra of CH has been deconvoluted as three peaks at
binding energies of 398.5, 400.3 and 401.7 eV. The rst is
attributed to pyridinic-N, the second and dominant one is oen
assigned to pyridone or pyrrole-like nitrogen or both of them. In
Fig. 6 N 1s XPS spectra of CH (a) and CH-mel (b).
This journal is © The Royal Society of Chemistry 2015
RSC Advances
CH-mel
XPS Precursor CHNa [%mass] XPS
71.6 36.4 [66] 78 73.4
2.3 18.6 [19] 3.3 3.6
4.6 5.7 [2] 3.3 3
21.5 39.3 [13] 15.4 20
the literature this peak is more oen correlated with the pyrrolic
nitrogen.36 However, it is hard to envisage a mechanism that
converts 6-membered, and reach in oxygen, chitosan rings into
pyrrolic rings. The formation of pyridone-N (pyridinic-N next to
an OH group), indistinguishable from pyrrolic-N within the
accuracy of XPS measurements, is the alternative. Upon pro-
longed pyrolysis at temperatures above 600
C, pyridine and
pyridone (also pyrrole, if present) rings undergo condensation
into structures containing graphitic nitrogen. Available reports
indicate that the rate of this conversion is relatively low,37,38
therefore the third peak at 401.7 eV, attributed to the graphitic
nitrogen, is relatively small. The proportion of each of the
previous N atoms has been quantied as 31.68, 55.8 and 12.53%
at. conc., respectively. The N 1s spectra of CH-mel has been
deconvoluted as four components at binding energies of 398.5,
400.4, 401.8 and 403.6 eV. The latter peak can be ascribed to the
N-oxides of pyridine, which results from the reaction between
oxygen-containing groups in chitosan and nitrogen in
melamine-based species during the thermal synthesis of the
CH-mel material. The proportion of each of the previous N
atoms has been quantied as 28.65, 51.13, 11.84 and 8.39% at.
conc., respectively. Table 2 summarizes the elemental compo-
sition of the pyrolyzed materials, as determined with XPS and by
the elemental analysis, confronted with the elemental compo-
sition of the chitosan and chitosan–melamine precursors. The
data show that upon pyrolysis of chitosan or chitosan–mela-
mine, the remaining carbonaceous solid gains on content of
carbon at the expense of other elements. Obviously, it does not
mean that CO2 and/or CO have not evolved during thermal
decomposition of the precursors. We have recalculated the
values from Table 2 (column 3) by taking into account the
results of our TGA studies, which show that only 18% of the
initial mass of chitosan remains solid aer pyrolysis. It turns
out that carbon, nitrogen, hydrogen and oxygen content drops
by 68%, 85%, 95%, and 91%, respectively. In the case of the
chitosan–melamine precursor the remaining carbonaceous
mass was measured as 34% of the initial dose, accordingly the
recalculated (Table 2, column 7) composition of the char yielded
the mass drop of 38%, 65%, 88%, and 89% for carbon, nitrogen,
hydrogen and oxygen, respectively. The results may lead to the
following conclusions. Firstly, as expected both precursors
mostly loose on content of hydrogen and oxygen. Secondly, both
precursors loose uniformly on content of oxygen. This is exactly
what one expects since melamine itself contains no oxygen
groups, and its nitrogen atoms should not interact specically
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RSC Advances Paper

with the chitosan oxygens what might render these oxygen

groups less prone to separate from chitosan during pyrolysis.
Thirdly, the CH-mel precursor looses less of the nitrogen atoms
than CH does. We assume that amine groups of chitosan and
melamine get quite easily volatilized, whereas the melamine
nitrogens composing, with carbons, of six-membered rings are
more likely to undergo polymerization, e.g. forming melem, as
analysis of our TGA results indicate. Finally, both carbonaceous
materials dramatically loose of nitrogen upon KOH activation
which followed the pyrolysis. The activation is generally bene-
ciary, since it results in greater specic area of the carbona-
ceous material, but at the expense of some mass loss (carbon
gets partly volatilized). In the case of N-doped carbon materials
losses of nitrogen were also reported, however they seemed to
be correlated with the losses of carbon. Our data indicate lack of
such correlation.
The UV-Vis spectra show two visible transitions: two sharp
peaks occurred in the UV region wavelength about 210 nm and
246 nm (Fig. 7). The rst at 210 nm has been attributed to the p
/ p* transition of aromatic C–C bond in partially restored
C]C bonds.39–41 The second one at about 246 nm is assigned to
n / p* transitions in C]O bonds in nonconductive species,
sp3 hybrid regions. One additional wave can be seen at the
wavelength around 317 nm and corresponds to the moved n /
p* transitions, the same as the previous one, from aromatic Fig. 8 Raman spectra of the CH (a and b – before and after activation,
system with heteroatoms C]O. This shi may be due to respectively) and CH-mel samples (c and d – before and after acti-
inductive inuence of the adjacent nitrogen atoms.42 vation, respectively).
The Raman spectra of alkali-treated, and the as-prepared
chitosan based carbon nanomaterials are shown in Fig. 8. The
peak at ca. 1350 cm1 is assigned to the A1g breathing mode of carbon nanomaterials with and without alkali activation was
disordered graphite structure (the D band), and the high- evaluated by means of deconvolution of the raw spectroscopic
frequency peak at ca. 1580 cm1 assigned to the E2g stretch- data. The ID/IG ratios are 0.55, and 0.54 for the as-prepared CH,
ing mode of graphite (the G band). The G band reects the and CH-mel respectively, 0.86 and 0.76 for the activated
structure of the sp2 hybridized carbon atom.43 The D band is samples. Furthermore the Raman spectra reveal one additional
due to defect sites in the hexagonal framework of graphite band around 1200 cm1, which can be associated with
materials. The height of the D peak usually increases upon conductive sp2 carbon species outside of perfectly planar
chemical modication of carbon nanomaterials.44 carbon network. In correlation with the later discussed XRD
The extent of the defects in carbonaceous materials upon data and also from TEM images, the analysis reveal the pres-
surface modication can be quantied by the intensity ratio of ence of sp2 hybridized carbon atom within amorphous C-
the D to G bands (ID/IG). The intensity ratios of ID/IG for studied species. A clear trend can be seen that the ID/IG ratio
decreases for both carbon nanomaterials upon alkali treatment,
and the etched carbon nanomaterials have a lower ID/IG ratio (or
less structural damage) than that for the corresponding as-
prepared carbon nanomaterials. This trend is consistent with
the elemental analysis and the XPS study results shown in Table
2. Alkali activated carbon material contains higher mass
percentage of carbon atoms and much lower content of
nitrogen, that is, nitrogen containing structures, which are
partly responsible for the D band intensity, are more prone to be
etched. 2D band Raman (2700 cm1) is active for crystalline
graphitic materials and it is sensitive to the p band in the
graphitic electronic structure or number of layers.45 The
combination mode of D + G is induced by disorder 2 D and D +
G bands are normally ignored on the studies of carbon mate-
rials because of the weak intensity.
The electrochemical activity of the CH and CH-mel samples,
Fig. 7 UV-Vis spectra of a colorless dispersion of CH-mel in water. as well as Pt/C as a reference, for ORR was characterized by the

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Paper
LSV scan in the alkaline solution saturated with either N2 or O2.
As shown in Fig. 9, in the presence of N2, no distinguished
current peaks can be seen on the curves. However, the back-
ground current, which arises from the capacitive, non-faradaic
charge transfer (curves 1 and 2), underlines the large surface
area, the high electronic conductivity as well as good charge
propagation throughout the carbonaceous catalytic materials.
Accordingly, the better performance of CH-mel well correlates
with presented data of the surface area and slit like porosity
measurements. In contrast, a well-dened cathodic peak at
0.544 V for CH and at 0.504 V for CH-mel appears in the O2-
saturated solution, clearly demonstrating the electrocatalytic
activity for ORR. On the other hand, the peak current on Pt/C is
more than twice as large as those on CH and CH-mel materials.
The results are summarized in Table 3 alongside with half-wave
potentials and onset potentials, also derived from the polari-
zation curves of Fig. 9.
Good ORR activity was also demonstrated in literature for N-
doped carbon nanotubes or graphene derived from melamine
without assistance from metal atoms.46–51 Wang et al. have
established that the surface nitrogen content and nitrogen–
carbon ratio strongly affect ORR activity of a carbon black-
supported melamine-treated vitamin B12 catalyst.52 Lee et al.
have studied the N-doped Ketjenblack incorporated into Fe/
Fe3C-functionalized melamine foam as a highly efficient ORR
electrocatalyst in alkaline solution.53
The CH-mel nanomaterial exhibits the higher current
density compared with the CH catalyst, the latter however,
shows better performance in terms of Eonset and E1/2. These
results indicate that it is not the surface areas, but the nitrogen
content, the nitrogen bonding congurations, and textural
structure play key roles in the catalysis for the reduction of
oxygen. The ORR activity performance of these nanocarbon
samples is still not as good as that of commercial Pt/carbon in
terms of the onset potential and current density at the peak
Fig. 9 LSV plots of the ORR at the GC electrodes covered with the CH
(1, 1a), CH-mel (2, 2a), and Pt/C (3, 3a) catalysts in a 0.1 M KCl solution;
deoxygenated (dotted lines) or saturated with oxygen (solid lines). Scan
rate 10 mV s1.
This journal is © The Royal Society of Chemistry 2015
RSC Advances
Table 3 Electrochemical kinetic parameters for the oxygen reduction
reaction assisted by CH, CH-mel, and Pt/C catalytic materials
Catalyst Ep [V] Eonset [V] E1/2 [V] b/V dec1 an
CH 0.544 0.735 0.615 0.250 0.23
CH-mel 0.504 0.761 0.595 0.172 0.34
Pt/C 0.49 0.821 0.577 0.149, 0.181 0.39, 0.32
potential. The more positive onset potential of Pt/C indicates
lower overpotential for the oxygen reduction on the platinum
catalyst. However, the ORR peak and E1/2 potentials of the
carbonaceous catalysts are more positive than those of the
Pt/C commercial catalyst. To gain insight into the oxygen
reduction kinetics on the catalysts, Tafel analysis was con-
ducted (Fig. 10 and Table 3). The corresponding Tafel plots
have a slop of 172 mV dec1 for CH-mel and 250 mV dec1 for
CH. The black plot is related to commercial Pt catalyst.
Generally, the Tafel plot for ORR has two liner regions, one
corresponding to the low overpotential region where the
oxygen reaction is controlled by the kinetics of the surface
charge transfer and the other to the high overpotential region
where the reaction rate is dominated by the diffusion limita-
tion inside the material. Fig. 10 presents the Tafel curves
which were derived from the polarization curves of Fig. 9. It
can be seen that different catalysts will lead to different Tafel
slope values. The smaller Tafel slope of CH-mel catalyst than
that of the CH may indicate the faster reaction kinetics for
ORR. In the case of the Pt/C catalyst the variation in Tafel slope
can be seen. It is known that the smaller Tafel slope corre-
sponds to the ORR at the Pt surface covered with an oxide, and
the large slope corresponds to that at a clean Pt surface. A
change in the adsorption energy of oxygen from Temkin-type
to Langmuir-type due to a reduction of the surface oxide was
also proposed for that variation.54
Fig. 10 Tafel plots of the ORR at the GC electrodes covered with the
CH (blue), CH-mel (red), or Pt/C (black) catalysts by using the corre-
sponding LSV data from Fig. 9.
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RSC Advances
This observation indicate that besides the type of nitrogen
site (pyridinic or graphitic), also other properties like amount of
carbon ‘kinks’ (e.g. inuenced by the organic synthesis of
carbon catalyst), the total content, the surface area and the
degree of graphitization might inuence the ORR activity.55–59
Moreover, it seems the best ORR activity could be achieved if an
optimal balance of surface area, active site density, and electron
conductivity were found.
Conclusions
We have demonstrated a facile methodology for the production
of the layered carbon structures with the surface area of 285
m2 g1 without the template approach. The nanosheets contain
disordered area due to the strain imposed by the presence of
nitrogen and/or oxygen groups in their structure. Some portion
of the materials is comprised of clean well crystallized graphene
sheets. They show an interlayer distance of about 0.359 nm. The
average size of the visible well-crystallized carbon is 8  8 nm,
covering ca. 4% of the sample at projection. To examine the
surface quality of the nanosheets, AFM has been employed to
provide the average surface roughness over a larger area
(1 mm2), which was found to be 5.32 nm and 0.335 nm for the
samples derived from chitosan and chitosan–melamine
mixture, respectively. Further, these materials exhibit efficient
electrocatalytic activity (the onset potential of 0.735–0.761 V vs.
RHE) for oxygen reduction reaction (ORR) in alkaline media.
Our results show that besides the total nitrogen content and the
type of nitrogen group (pyridinic or graphitic), also an amount
of carbon ‘kinks’ and/or surface roughness strongly inuence
the ORR activity.
Acknowledgements
Acknowledgements are made to Dr Robert Tylingo for his
precious help in freeze drying of our samples and to Dr Michal
Strankowski for TG analysis, and to Dr Miroslaw Sawczuk for
Raman spectra.
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