3098 CARBON 5 0 ( 2 0 1 2 ) 3 0 9 2 –3 1 1 6

Acknowledgments [2] Ryoo R, Joo SH, Jun S. Synthesis of highly ordered

carbon molecular sieves via template-mediated
structural transformation. J Phys Chem B 1999;103(37):
These studies were partially financially supported by the DFG
7743–6.
(project KL 1202/7-1) and the European Regional Development
[3] Xia Y, Yang Z, Mokaya R. Templated nanoscale porous
Funds. carbons. Nanoscale 2010;2:639–59.
[4] Klepel O, Strauss H, Garsuch A, Böhme K. Several ways to
Appendix A. Supplementary data produce porous carbon monoliths by template assisted routes.
Mater Letters 2007;61:2037–9.
[5] Garsuch A, Michaud X, Wagner G, Klepel O, Dahn JR.
Supplementary data associated with this article can be found,
Templated Ru/Se/C electrocatalysts for oxygen reduction.
in the online version, at doi:10.1016/j.carbon.2012.02.039.
Electrochim Acta 2009;54:1350–4.
[6] Merlino S, Bonaccorsi E, Armbruster T. Tobermorites: their
structure and order-disorder (OD) character. Am Mineral
R E F E R E N C E S 1999;84:1613–21.

[1] Kyotani T, Ma Z, Tomita A. Template synthesis of novel porous

carbons using various types of zeolites. Carbon
2003;41:1451–9.

A microporous and high surface area active carbon obtained

by the heat-treatment of chitosan

Anna Kucinska, Aleksandra Cyganiuk, Jerzy P. Lukaszewicz *

Faculty of Chemistry, Nicholas Copernicus University, 87-100 Toruń, Poland

A R T I C L E I N F O A B S T R A C T

Article history:
Received 30 October 2011
Accepted 14 February 2012
Available online 23 February 2012
A method is described for converting chitosan into a high surface area and porous active
carbon using a Na2CO3 solution impregnated into a partly depolymerized, protonated
and water soaked chitosan. The wet chitosan paste is heat treated and transformed into
a nonporous solid i.e. a carbon-rich matrix with uniformly suspended Na2CO3 nanocrystal-
lites. Subsequent HCl etching opens cavities in the matrix due to the removal of the
Na2CO3. The active carbon is high surface area (above 400 m2/g), microporous (below
1 nm) and nitrogen-rich (above 6% atomic).
Ó 2012 Elsevier Ltd. All rights reserved.

Chitosan is a biopolymer obtained by deacetylation of an-
other commonly accessible biopolymer, chitin. Chitin can be
obtained as a by-product during processing of Euphausia
superba, known by the name of Antarctic krill (annual fishery
ca. 100 000 ton in year 2000 with evident decrease tendency),
and other crustaceans (crabs, shrimps, etc.). Chitosan struc-
ture is characteristic because of amino groups linked to the
chain of six-member saccharide rings i.e. poly-(D)glucosamine
(Fig. 1). Thus, the polymer is naturally rich of nitrogen and
possesses specific acid–base properties and chelation abilities
directly resulting from the presence of NH2– groups. In gen-
eral, chitosan structure resembles the structure of cellulose
(Fig. 1), in which hydroxyl groups are present instead of ami-
no groups. The similarity apparently suggests that chitosan,
as cellulose, can be transformed in an active carbon by a sim-
ple heat-treatment in oxygen-free conditions. The procedure
if applied to lignin-cellulose materials like wood of different
kinds (pine, oak, bamboo, etc.) yields active carbons of well-
developed surface area and pore structure [1]. These parame-
ters may achieve more spectacular values provided an addi-
tional activation procedure is applied prior to or after the
carbonization. However, carbonization of pure cellulose is a
more complex case since the achievement of more advanced
surface parameters (total pore volume, specific surface area)

* Corresponding author.
E-mail address: lukaszju@chem.uni.torun.pl (J.P. Lukaszewicz).
0008-6223/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2012.02.042
 CARBON 5 0 ( 20 1 2 ) 3 0 9 2–31 1 6 3099

Fig. 1 – The structure of chitosan (a) and cellulose (b).

needs additional treatments (preliminary oxidation) [2] and/

or specific carbonization conditions (hydrothermal carboniza-
tion) of pure cellulose [3].
In the literature there is lack of work describing successful
transformation of chitosan to an active carbon of satisfactory
surface parameters. However, the carbonization mechanism
has been investigated in detail [4]. Such a carbon could poten-
tially find several important applications since carbonization
of nitrogen-rich raw materials frequently results in a high
content of nitrogen in the carbonizate, mostly in the form
of nitrogen-containing base-type functional groups.
If the concept of a direct chitosan carbonization could
really yield high surface-active carbons it would have been
realized a long time ago, but in practice no satisfactory results
have been achieved so far. We have assumed that proper sur-
face parameters are achievable provided the carbonization of
the considered raw material (chitosan) is supported by an
additional activating procedure, as in the case of pure cellu-
lose carbonization [2,3]. In fact, the known measures support-
ing carbonization of cellulose (hydrothermal method and
cellulose pre-oxidation) are chemical in nature since they
partly destroy the original chemical structure of the cellulose.
We intended to avoid any severe chemical intervention in the
structure of chitosan before its transformation to a carbon
matrix during heat-treatment. Therefore, we turned our
attention towards a less aggressive procedure involving the
application of a bulge agent, which should help the develop- Fig. 2 – SEM images of Na2CO3-enriched chitosan
ment of a porous sponge-like structure of a chitosan driven carbonizate before HCl-etching sample CH-8 (a), after HCl-
active carbon. Past experience in the fabrication of carbon etching sample CH-8–HCl (b) and pure chitosan carbonizate
films [5] for chemical sensing applications proves that inor- sample CH-0.
ganic carbonates like Na2CO3 and/or K2CO3 act as bulge
agents when added to the carbon matrix precursor (bicarbon-
ates are added too). In that case, the authors mixed furfuryl CAS Number: 9012-76-4). In this form chitosan has limited
alcohol (carbon matrix precursor) with a water solution of ability to absorb water and water solutions, therefore HCl
the carbonates. A similar procedure was applied in the cur- was used to partly depolymerise chitosan chains and proton-
rent study. Literature [6] describes sodium and other alkali ate NH2- groups [7,8]. Both phenomena help to solubilize the
metal carbonates application for activation of carbons but polymer. Ten gram of chitosan was mixed with 45–100 cm3 of
this method involves a burn-off carbon matrix due to the di- water and neutral pH of the slurry was noticed. Then, 3 cm3 of
rect chemical reaction of alkali metals with carbon atoms. As 1 M HCl water solution was added, but surprisingly the pH of
a side product the evolution of CO2 and CO is observed. There- the slurry did not change. Only the consistency of the slurry
fore this kind of activation does not resemble the currently altered since after HCl addition it became more uniform
described one. and sticky and resembled a thick paste. The pH did not
A series of carbon samples (CH0–CH16) were prepared in a change because, as expected, protons in the acid solution
similar manner. Dry chitosan powder was provided by Sigma chemically bonded to the NH2– groups in the polymer. Neutral
Aldrich (75–85% deacetylation, medium molecular weight, pH let to admit carbonate solution (4–17% Na2CO3) and no
3100 CARBON 5 0 ( 2 0 1 2 ) 3 0 9 2 –3 1 1 6

spectacular reaction results were visible i.e. CO2 was not re-
leased due to direct reaction of sodium carbonate with the
strong acid. The concentration of sodium carbonate in the
modifying solution and in the paste was low enough to avoid
its instant precipitation. The chitosan-based paste was
placed in a tubular stove and subsequently subjected to a
heat-treatment: heating from 20 to 600 °C (10 °C/min), 600 °C
(1 h), cooling from 600 °C to room temperature (free cooling).
The obtained black active carbon was subjected to several
chemical analyses:
o SEM /SEM-EDX – morphology, elemental composition;
o XRD wide angle – crystallographic structure;
o XPS – chemical structure of the surface;
o Low temperature adsorption of nitrogen in properly equil-
ibrated conditions – surface area.
After the analysis, the samples of chitosan which origi-
nated from virgin carbon were treated with 0.1 M HCl. A
spectacular evolution of a gas in form of fine bubbles after
immersing the carbon in acid solution was observed. After
the HCl treatment and careful rinsing, such samples of etched
carbon were again subjected to the above-mentioned instru-
mental analysis.
SEM investigations revealed that the active carbon consists
of a carbon matrix in which nano-sized Na2CO3 crystallites
are suspended and uniformly distributed (Fig. 2a). The crys-
tallites disappear after HCl etching (Fig. 2b) and resemble pure
chitosan carbonized without the addition of carbonates
(Fig. 2c). Also, XRD measurements proved the presence of
Na2CO3 in the non-etched carbon and its disappearance after
etching. Fig. 3 presents low temperature ( 196 °C) nitrogen
adsorption/desorption isotherms recorded for an example
etched activated carbon sample CH-11. It is evident that
etched activated carbon takes up high quantities of nitrogen,
proving the presence of a well-developed surface area and
pore structure. BET surface area increases after etching from
ca. 1 to 440 ± 17 m2/g (Table 1). Less developed surface area of
HNO3-etched sample should be attributed to the oxidative
properties of the acid which cause a partial dissolution the
carbon matrix and high oxygen content on the surface (XPS
measurements). The shape of adsorption/desorption iso-
therms (I – type according to IUPAC classification) suggest that
the active carbons under investigation are strictly micropo-
rous with a little contribution of mesopores (no adsorption/
desorption hysteresis is visible). Carbon CH-11 has been used
as molecular sieve for the separation of Ne, Kr and N2 in chro-
matographic conditions. Successful separation has been
achieved in the temperature range 30–70 °C. Elemental com-
position of the surface (XPS measurement) proves that the re-
moval of sodium is almost complete while the surface
nitrogen level exceeds 6% atomic (Fig. 4). The nitrogen in
the surface layer is chemically accessible and may reveal its
presence in some surface processes. High-resolution N1s
spectrum (Fig. 4) interpretation allows us to state that most
of the nitrogen atoms are constituents of NH2– groups (local

Fig. 3 – Nitrogen adsorption/desorption isotherms for a

chitosan carbonizate (CH-11–HCl sample): Na2CO3-enriched Fig. 4 – XPS N1s BE profile for a chitosan carbonizate (CH-11–
and HCl-etched. HCl sample): Na2CO3-enriched and HCl-etched.

Table 1 – Preparation of selected samples and their surface area measured by BET method.
Sample Chitosan [g] Water [cm3] 1 M HCl [cm3] Na2CO3 volume [cm3] Na2CO3 Etching BET surface
concentration [%] area [m2/g]

0 10 5 3 None None None <10

CH-8 10 5 3 20 7.8 None <10
CH-8/HCl 10 5 3 20 7.8 HCl 24
CH-9 10 5 3 20 7.8 None <10
CH-9/HNO3 10 5 3 20 7.8 HNO3 19
CH-11 10 5 3 20 16.9 None <10
CH-11/HCl 10 5 3 20 16.9 HCl 440
CH-11/HNO3 10 5 3 20 16.9 HNO3 213
 CARBON 5 0 ( 20 1 2 ) 3 0 9 2–31 1 6 3101

maximum at 402.5 eV BE). Surprisingly, the content of proton-
ated NH2– groups is low (ca. 11% atomic of all nitrogen atoms
in the surface region). This means that the heat-treatment
and subsequent careful rinsing after HCl etching reversed
the protonisation process of the amino groups.
In conclusion, we propose application of a bulge agent (so-
dium carbonate) in order to obtain a high surface area, micro-
porous and high nitrogen content activated carbon from a
biopolymer chitosan. The bulge agent forms Na2CO3 nano-
crystallites uniformly distributed in the carbon matrix. Their
etching with hydrochloric acid leaves empty cavities in the
matrix, which contribute significantly to the total pore vol-
ume and surface area. The procedure allows a high level of
nitrogen content to be retained in the surface region. Nitrogen
is mostly present in the form of amino groups as in the pre-
cursor polymer i.e. chitosan.
R E F E R E N C E S
[2] Norton FJ, Love GD, Mackinnon AJ, Hall PJ. Mechanisms of char
production from oxidized cellulose. J Mater Sci
1995;30(30):596–600.
[3] Sevilla M, Fuertes AB. The production of carbon materials by
hydrothermal carbonization of cellulose. Carbon
2009;47(9):2281–9.
[4] Zawadzki J, Kaczmarek H. Thermal treatment of chitosan in
various conditions. Carbohydr Polym 2010;80(2):394–400.
[5] Lukaszewicz JP, Skompska M. A novel carbon-based ionic
conductor for humidity sensors. Sens Actuators B
2006;113(2):970–7.
[6] Addouna A, Dentzerb J, Ehrburger P. Porosity of carbons
obtained by chemical activation: effect of the nature of the
alkaline carbonates. Carbon 2002;40(7):1131–50.
[7] Osorio-Madrazo A, David L, Trombotto S, Lucas JM, Peniche-
Covas C, Domard A. Kinetics study of the solid-state acid
hydrolysis of chitosan: evolution of the crystallinity and
macromolecular structure. Biomacromolecules
2010;11(5):1376–86.
[8] Allan GG, Peyron M. Molecular weight manipulation of
chitosan. I: kinetics of depolymerization by nitrous acid.
Carbohydr Res 1995;277(2):257–72.

[1] Lukaszewicz JP, Wesołowski R, Cyganiuk A. Enrichment Salix

viminalis wood in metal ions by means of phytoextraction.
Polish J Environ Stud 2009;18(3):507–11.

Continuous preparation of multiscale reinforcement

by electrophoretic deposition of carbon nanotubes
onto carbon fiber tows
a,b a,*
Jinhai Guo , Chunxiang Lu
a
National Engineering Laboratory for Carbon Fiber Technology, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001,
China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, China

A R T I C L E I N F O A B S T R A C T

Article history:
Received 4 November 2011
Accepted 14 February 2012
Available online 23 February 2012
The simple and continuous deposition of carbon nanotubes onto the surface of carbon fiber
tows, using ethanol as a dispersive medium, was achieved by the electrophoretic process.
The resulting materials showed a uniform distribution of carbon nanotubes on the fiber
surface. Such a continuous process provides industrial potential for preparing a multiscale
carbon nanotube-carbon fiber reinforcement.
Ó 2012 Elsevier Ltd. All rights reserved.

Multiscale carbon nanotube-carbon fiber reinforcement fiber-reinforcement [1]. The interface between fiber and
has raised great interest due to the combination the excellent matrix could be strengthened by the nanotubes, which in
properties of carbon nanotubes (CNTs) with conventional turn improve the global performance of the composites mate-

* Corresponding author: Fax: +86 351 4166 215.

E-mail address: chunxl@sxicc.ac.cn (C. Lu).
0008-6223/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2012.02.044