Microporous and Mesoporous Materials 167 (2013) 249–253

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Microporous and Mesoporous Materials

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

Short Communication

In situ transformation of agave bagasse into activated carbon by use of an

environmental scanning electron microscope
Cesar Nieto-Delgado, Jose Rene Rangel-Mendez ⇑
Environmental Sciences Division, Instituto Potosino de Investigación Científica y Tecnológica, A.C, San Luis Potosí, S.L.P. 78216, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: The formation of ZnCl2 activated carbon from a lignocellulosic material such as agave bagasse fibers has
Received 8 July 2012 been characterized in situ, by environmental scanning electron microscopy. The carbonization process of
Received in revised form 3 September 2012 raw bagasse fibers showed the development of a macroporous structure, which was related to the fibers
Accepted 17 September 2012
chemical composition. In contrast, when fibers were activated with ZnCl2, a molten phase and a rapid
Available online 24 September 2012
evolution of gasses were observed. These results, which are recorded in a video, significantly contribute
to the understanding of the chemical activation process of lignocellulosic materials to form activated
Keywords:
carbon.
ZnCl2
Chemical activation
Ó 2012 Elsevier Inc. All rights reserved.
Pore formation
Molten phase

1. Introduction this study, the production of activated carbon from agave ba-
gasse fibers [7] was monitored in situ with an environmental
The production of activated carbon from lignocellulosic materi- scanning electron microscope (ESEM) to examine the structural
als with ZnCl2 is a widespread practice. Previous studies have changes accompanying the carbonization and activation of this
investigated the effect of ZnCl2 during the activation and have sug- lignocellulosic material.
gested the activation mechanism [1–5]: ZnCl2 promotes an acid
hydrolysis during the impregnation and during the thermal treat-
2. Materials and methods
ment acts as a dehydrating agent promoting the scission of glyco-
sidic bonds and the elimination of hydroxyl and carbonyl groups.
The experimental procedure is summarized as follows: bagasse
These reactions result in the aromatization of the carbon structure.
fibers and ZnCl2 (1:1 weight) were mixed in 30 mL of distilled
Finally, part of the pores are opened by the removal of the activat-
water. This mixture was equilibrated for 24 h and then heated to
ing agent that remains in the material after the carbonization. An
60 °C until dryness. Fibers were vertically aligned and placed in a
interesting characteristic of ZnCl2 activation of lignocellulosic
heating plate in order to obtain images of the transversal section
materials is the physical changes that occur after the activation
of the fibers during the thermal treatment. The ESEM FEI QUANTA
process. Previous studies have reported the formation of a plastic
200 was operated at 15 kV with a chamber pressure of 190 Pa. The
phase during the thermal treatment of the ZnCl2 impregnated
heating rate was 10 °C/min, and a series of micrographs were taken
material [6,7]. This transition from a solid to a rubbery state is
throughout the process. A set of carbons were produced to evaluate
characteristic of polymeric materials and is caused by the slippage
their pore structure: about 100 mg of ZnCl2 impregnated agave ba-
of polymer chains once these get enough kinetic energy [8]. This
gasse fibers (weight ration g ZnCl2 /g bagasse = 1) were activated in
effect is related directly to the catalytic effect of the ZnCl2 during
thermo gravimetric analyzer under N2. The heating rate was 10 °C /
the thermal treatment, since the pyrolysis of lignocellulosic mate-
min. After activation, samples were washed with deionized water.
rials in the absence of ZnCl2 follow a carbonization pathway rather
that the formation of the plastic phase.
Despite the broad characterization of ZnCl2 activated carbons 3. Results and discussion
from lignocellulosic materials, the reason why this plastic phase
is formed and the implications that this process may have on the Fig. 1 shows a snapshot sequence of the thermal degradation of
characteristics of activated carbon have never been evaluated. In a single agave bagasse fiber. The full process was recorded and ap-
pears as Video1 in complementary material. As observed in Fig. 1
⇑ Corresponding author. Tel.: +52 4448342010. during the early stages of the thermal treatment, the raw bagasse
E-mail address: rene@ipicyt.edu.mx (J.R. Rangel-Mendez). fibers do not exhibit any significant change. However, it should

1387-1811/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso. 2012.09.014
250 C. Nieto-Delgado, J.R. Rangel-Mendez / Microporous and Mesoporous Materials 167 (2013) 249–253

Fig. 1. Micrographs of the thermal degradation of agave bagasse fiber. Magnification was set at 600X. See Video1 in supporting information.

be mentioned that in this step the chamber pressure slightly in- are caused by the carbonization of cellulose and hemicelluloses lo-
crease, presumably by the moisture released from the sample. cated in the center of the bagasse fibers. To support this assump-
The most important physical changes were observed at a temper- tion, bagasse fibers were carbonized at 400 °C for 20 min under
ature higher than 230 °C, when small pores were formed on the N2 atmosphere, with the aim of decompose the most labile compo-
transversal section of the fiber. This process continue at higher nents of the bagasse fiber. The analysis of the carbonized sample
temperatures, widening the pores previously formed. Finally at reveals a honey comb structure formed by the remaining middle
about 450 °C the fiber shrank, collapsing the pores formed. These lamella layer and the carbonized cellulose and hemicellulose
physical changes observed during the thermal degradation of the (Fig. 3). Finally, it is worthy to mention that the carbonized fiber
bagasse fiber can be related with the structure and disposition of does not have any significant micro and mesopore structure, since
their constituents. The fiber analysis shows that the agave bagasse its BET surface area was less than 3 m2/g.
is composed of 12.8% Hemicelluloses, 47.3% Cellulose, 10.1% Lignin On the other hand, the pyrolysis of ZnCl2 impregnated agave
and 29.8% of extractives that can be waxes, salts, starch, tannin, bagasse fibers exhibit a different transformation. Fig. 4 shows the
soluble sugars and proteins [9]. These components are distributed
onto different biopolymers layers according to Fig. 2: the middle
lamella are mainly constituted by lignin, and the cell walls are
formed by cellulose and hemicelluloses chains that form threadlike
aggregates known as microfibrils [10]. Studies concerning the ther-
mal degradation of biopolymers have found that lignin has a high
degradation temperature (280–500 °C) compared to cellulose
(240–350 °C) and hemicelluloses (200–260 °C) [11]. Therefore,
the developed pores in bagasse fibers during the thermal treatment

Fig. 2. Morphological structure of the agave bagasse fiber, performed by diverse Fig. 3. Honey comb structure developed by the agave bagasse fiber after its
wall structures. carbonization at 400 °C under N2 atmosphere.
 C. Nieto-Delgado, J.R. Rangel-Mendez / Microporous and Mesoporous Materials 167 (2013) 249–253 251

Fig. 4. Micrographs of the thermal degradation of ZnCl2 impregnated agave bagasse fiber. Magnification was set at 600X. See Video2 in supporting information.

Fig. 5. Micrographs of ZnCl2 activated agave bagasse after removal of the remaining activating agent.

snapshot sequence of this activation process. The complete process ted material is transformed into a rigid solid whose shape and vol-
was recorded at two different magnifications, and appears as Vi- ume are maintained at temperatures as high as 600 °C. This fiber
deo2 (600 magnification) and Video3 (1400 magnification). was carefully washed to eliminated the remaining activating agent
Comparing Figs. 1 and 4 we can notice that a partial degradation and analyzed in a scanning electron microscope. After washed,
of the inner layers of the bagasse fiber occurs during the impregna-
tion. This fragmentation of the botanic precursor has previously
been linked with the cellulose dissolution at the low pH, that is gi- Table 1
ven by the ZnCl2 in water solution [1]. There is no a significant Pore size distribution and surface area of ZnCl2 activated carbons.
change in the morphology of the impregnated fiber at tempera- Activation Micropore Mesopore BET surface
tures below 180 °C. However, above this temperature and up to Temperature (°C) volume (cm3/g) volume (cm3/g) area (m2/g)
240 °C, some macropores started to form in all over the fiber. 160 0.018 0.012 10.6
Above this temperature, the impregnated fiber start to melt, while 240 0.040 0.017 103.3
gas bubbles start to evolve and permeate the viscous molten mate- 320 0.157 0.234 511.3
rial over a temperature range of 280–350 °C. At higher tempera- 400 0.242 0.404 1281.8
600 0.149 0.378 650.7
tures, the gas bubble generation starts to slow down until no
additional bubbling is observed. At the end of this process the trea- Activation time: 20 min; Weight ration ZnCl2/Bagasse = 1.
252 C. Nieto-Delgado, J.R. Rangel-Mendez / Microporous and Mesoporous Materials 167 (2013) 249–253
Fig. 6. Micrographs of the thermal degradation of ZnCl2 impregnated agave bagasse fiber. Magnification was set at 1400X. See Video3 in supporting information.
some of the nodules formed onto the fiber surface during the acti-
vation were broken, showing that within them exists a foamy
microporous structure (Fig. 5).
Based on the above observations, we can infer some of the
process that are happening during the bagasse activation. First,
the main difference of the physical changes between the impreg-
nated and raw bagasse fibers are the formation of the molten
phase at temperatures around 260 °C, that can be related with
the fusion of ZnCl2 (melting point = 290 °C). Based on the previ-
ously proposed activation mechanism, once the ZnCl2 is fused, it
starts to react with the precursor, promoting dehydration reac-
tions [1,3,5]. This dehydration mechanism breakdown the bio-
polymer, generating short biopolymer chains that have a
weaker interaction with other polymer chains, making easier
the slippage of the polymer chains and form the fluid phase [8].
The close interaction between the ZnCl2 and the low molecular
weight biopolymer chains promote the condensation of the car-
bonaceous structure, but mean while this consolidation of the
carbonaceous structure happen, the gasses generated inside the
fiber try to emerge through the molten phase. The diffusion of
gasses develop pathways through the fluid phase which at certain
point of the activation become solid and are the responsible of
the pore structure of the activated carbon.
It is worthy noticing that the development of pore structure and
as consequence, the increase of the carbons surface area become
significant at temperatures between 200 and 350 °C (Table 1)
which corresponds with the formation of the molten and the later
evolution of gasses. Particularly, all the carbons have a mixture of
micro and mesopores as reported in Table 1. According to previous
reports, at low impregnation ratios (less than 40%), the porosity
generated during ZnCl2 activation is due to the spaces left by this
chemical after washing, since the carbons pore volume is com-
pared with the volume of ZnCl2 used during the impregnation
[3]. In these cases a homogeneous pore structure is formed mainly
in the micropore range. Also, during activation at low impregna-
tion ratios, the precursor keeps its initial structure [1,3,6]. However
at higher impregnation ratios as the employed here (g precursor /
g ZnCl2 = 1), the activation comes with an intense degradation of
the precursor (Fig. 4), leading to the formation of a heterogeneous
material with a mixture of micro and mesopores, as appears in
Table 1.
As previously mentioned, it is assumed that the molten phase is
formed by both ZnCl2 and part of the biopolymers, since this blister
structure that is formed at the end of the activation remains after
the removal of the remaining ZnCl2 by acid water washing (Fig. 5).
An additional effect that is observed during the activation of the
bagasse fibers is the consolidation of the carbonaceous materials
since it promotes the fusion of the diverse tissues present in the
lignocellulosic material (Fig. 6).
4. Conclusion
In conclusion, in situ characterization of the carbonization and
activation processes of precursors (i.e. agave bagasse fibers) by
ESEM allows us to acquire additional information to suggest, sup-
port and/or compliment activation mechanisms. It is also impor-
tant to mention that the results of this study are in close
agreement with the carbonization mechanisms reported in the lit-
erature. During the carbonization of agave bagasse, the biopolymer
chains that compose the fibers coalesce among them. The presence
of numerous polar hydroxyl groups and a high molecular weight
result in very strong intermolecular forces, that cause a fiber
decomposition before it begins to soften and melt, as observed.
In contrast, during the activation of the bagasse fibers with ZnCl2,
the formation of a molten phase is observed. This is possible by
the chain cleavage promoted by the dehydration reaction catalyzed
by the ZnCl2. The elimination of the polar groups and the genera-
tion of low molecular weight units reduce the intermolecular
forces forming a molten phase, that has a relevant implication in
the pore structure, and the physical properties of the activated
carbon.
Acknowledgements
We would like to thank to FOMIX-SLP (FMSLP-2008-C02-
99664), Ciencia Básica (SEP-CB-2008-01-105920) and to CONACYT
(fellowship 204158) for the financial support. Also to LINAN and
LANBAMA national laboratories by allowing the use of their facili-
ties. The authors gratefully acknowledge Dulce Partida, Guillermo
Vidriales, Carmen Rocha, Gladis Labrada, Beatriz Rivera and Andrea
Pavlick (Peace Corps) for their technical support.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.micromeso.2012.
09.014.
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