SCIENCE JOURNAL

Ubon Ratchathani University

Sci. J. UBU, Vol. 1, No. 2 (July December, 2010) 40-45

http://scjubu.sci.ubu.ac.th

Research Article

Synthesis of Carbon Microspheres from Starch by

Hydrothermal Process
S. Ratchahat1, N. Viriya-empikul2, K. Faungnawakij2,
T. Charinpanitkul1, A. Soottitantawat1,*
1

Center of Excellence in Particle Technology, Department of Chemical Engineering,

Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand.

National Science and Technology Development Agency, 130 Thailand Science Park,
Paholyothin Rd., Klong Luang, Pathumthani 12120, Thailand.
Received 10/03/10; Accepted 22/12/10

Abstract
This study showed a facile catalyst-free method to synthesize carbon microspheres (CMSs) via
hydrothermal and carbonization process using various types of starch as starting materials. In
hydrothermal process, starch was hydrolyzed, dehydrated, and polymerized to form carbon
microspheres in water as a medium without involving any hazardous solvents. After hydrothermal
process, the dried products were treated by heat in carbonization process under nitrogen atmosphere to
develop their pore system of carbon microspheres. The two main types of starch, modified starch and
native starch, were employed to address differences in particle size and morphology of resulting
carbon microspheres. The SEM images clearly illustrated that the carbon microspheres have their
perfect spherical morphology and smooth surface. The particle size distributions of the products with a
size range of 0.4-4.0 m were determined by laser diffraction technique (Mastersizer). The particle
size and particle size distribution of carbon microspheres strongly depended on types of starch. In
other words, carbon microspheres from modified starch tended to smaller in particle size than carbon
microspheres from native starch because of water-solubility of modified starch higher than native
starch. After carbonization process, structural CMSs characterization performed by X-ray diffraction
technique (XRD) indicated semi-hexagonal graphite structures which would be suitable for secondary
lithium ion application. Elemental compositions of the carbonaceous products determined by energy
dispersive X-ray spectroscopy (EDX), indicated that a main component was carbon being inert to
many chemical reactions. Furthermore, these carbon materials have specific BET areas in the range of
400-500 m2/g which were formed during carbonization process. All N2 adsorption-desorption
isotherms of these carbon materials have type I isotherm regarding to IUPAC classification that
indicated micropore system.
Keywords: Carbon microspheres, Starch, Porous carbon, Hydrothermal process.
*Corresponding author. E-mail address: apinan.s@chula.ac.th

Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.

S. Ratchahat et al., Sci. J. UBU, Vol. 1, No. 2 (July December, 2010) 40-45

1. Introduction
Since the significant finding of Buckminsterfullerene (C60) [1] and carbon nanotubes
(CNTs) [2] considerable efforts have been
made toward the synthesis of functional
carbonaceous materials with diverse morphologies and structures, such as colloidal
spheres [3], nanofibers [4], coin-like hollow
carbons [5], macroflowers [6], and so on.
Among the different morphologies of carboniceous materials, carbon microspheres
(CMSs) have attracted widespread interest,
owing to their potential properties in adsorbents [7], catalyst supports [8], and anode
material for lithium ion batteries [9] and
templates for fabricating core-shell or hollow
structures [10]. The CMS particles have been
synthesized by many techniques, such as
pressure carbonization [11], chemical vapor
deposition [12], mixed-valence oxide-catalytic carbonization [13], and reduction of
carbides with metal catalysis [5]. Accordingly, various applications have been intensively developed [14]. Carbon microspheres
(CMSs) with a perfect shape have the priority
in catalyst support [15] and template
utilization [16]. However, there are a few
reports of CMSs with a uniform size and
perfect spherical morphology from various
types of starch. Consequently, in this study
the synthesis of CMSs from various types
of starch was investigated via hydrothermal
process and following by carbonization process. The aim of this study is to investigate
effects of types of starch on particle size and
morphology of carbon microspheres. The
two main types of starch, modified starch and
native starch, were used to investigate differences in particle size and morphology of the
obtained carbon microspheres. After hydrothermal process, the dried CMSs had been
carbonized under nitrogen atmosphere. The
carbonization process had highly developed
microporosity of CMSs but had removed the
reactive functional group (-OH,-COOH) on
their surface [17]. The porous CMSs have
highly microporosity and inert surface that
can be used as adsorbents or gas storage
materials. Without carbonization process, the
CMSs have the reactive functional group on

41

CMSs surface which can be immobilize

target reactive agents on the surface without
further surface modification. The uniform
CMSs can be determine particle morphologies and particle size distributions by scanning electron microscopy (SEM) and laser
diffraction method (Mastersizer 2000), respectively. The porous CMS particles were
characterized by X-ray diffraction method
(XRD) to reveal their crystalline properties.
They were determined their specific surface
area both before and after carbonization
process to reveal the development of porous
structure using adsorptiondesorption of
nitrogen or the Brunauer, Emmett, Teller
method (BET method). Moreover, elemental
components of the porous CMS particles
were determined by energy dispersive X-ray
method (EDX) to demonstrate carbon content
in their structure.
2. Materials and Methods
Materials. Two types of modified starch, HiCAP100 and CAPSUL, were obtained
from National Starch and Chemical Ltd,
(Bangplee, Thailand). These starches (HICAP100 and CAPSUL) were partially
hydrolyzed of waxy maize starch and then
derivatized to impart lipophilic properties
with n-octenyl succinic anhydride. They can
be immediately dissolved in water. The
difference in structure of HICAP100 and
CAPSUL, HICAP100 is a straight chain
starch but CAPSUL is a branch chain starch.
Therefore HICAP100 has water-solubility
more than CAPSUL. Meanwhile, other
native starch or crystallized starch (corn,
tapioca, wheat, rice, and sticky rice starch)
were obtained from a general commercial
resource. High purity nitrogen gas (99.999%)
was purchased from TIG.
Synthesis of the CMSs. In the hydrothermal
process, starch (5.0 g) was dispersed in 45.0
mL of de-mineralized water and magnetically
stirred at 60C for 30 min. The mixture was
filled in a 50 mL Teflon-lined stainless
autoclave. Subsequently, the autoclave was
put into an oven, which was heated at 180C

Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.

42

Synthesis of Carbon Microspheres from Starch by Hydrothermal Process

for 12 h. The autoclave was cooled to room

temperature naturally. Dark precipitates were
collected and washed with de-mineralized
water several times and dried in an oven at
100C for 24 h. The obtained powders were
carbonized in a tube furnace under N2
atmosphere. The N2 flow rate, final temperature and heating rate of the furnace were 100
ml/min, 600C and 1C/min, respectively.

shell growth formation plays an important

role than nucleate formation. On the other
hand, if native starches (unmodified starches)
were used as starting material, the CMSs
became larger and some of CMSs became
aggregates with diameters ranging from 1.0
to 7.0 m (Figure 1f-h). In this work, it
appears that HI-CAP100 could provide
monodisperse CMSs when compared with
other carbon sources. However, some of
Characterization. The particle size distribut- unmodified starches (corn and tapioca starch)
ions of synthesized carbon microspheres can also result in the monodisperse CMSs
were determined by laser diffraction techn- (Figure 1d, e).
ique (Mastersizer 2000: Malvern, United
Kingdom). The samples were characterized
by X-ray powder diffraction (XRD,
SIEMENS D5000, Japan) using CuK
radiation. The morphology observation of the
samples was examined with scanning
electron microscopy (SEM, JEOL: JSM5410LV, Japan). The specific BET surface
area was measured by N2 adsorptiondesorption at -196C (BEL: BELSORP-mini,
Japan). The carbonaceous products were
confirmed by energy-dispersive X-ray spectra
(EDX).
3. Results and Discussion.
Figure 1 shows the typical morphology of the
synthesized CMSs from hydrothermal
process. Perfect spherical shape and smooth
surface can be observed in CMSs from all
types of starch. These spherical particle
formations are generally patterns in particle
formation because they can keep the lowest
their surface energy in spherical formation.
When HI-CAP100 was used as a carbon
precursor, the smallest size and highly
uniform CMSs were obtained (Figure 1a, b)
because of its high water-solubility.
Figure 1. SEM images of CMSs after
Therefore HI-CAP100 can be hydrolyzed
carbonization: (a) HI-CAP100; (b) HIimmediately to form simultaneous nucleates
CAP100 at 10,000 magnification; (c)
of carbon microspheres. Nonetheless, the
CAPSUL; (d) corn; (e) tapioca; (f) sticky
CMSs obtained from CAPSUL showed the
rice; (g) wheat; and (h) rice starch.
big particle size more than carbon

microspheres from HI-CAP 100 because

CAPSUL which is a branch modified starch Based on our experimental results, CMS
can continuously be hydrolyzed to form a particle size and its distribution depended on
shell after nucleates forming. In other words, types of starch (Figure 2). These particle size

Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.

S. Ratchahat et al., Sci. J. UBU, Vol. 1, No. 2 (July December, 2010) 40-45

In addition, the XRD patterns of some CMSs

after carbonization are shown in Figure 3.
There are the presences of two broad peaks at
2 = 24.8 and 43.5 which are reflections from
the (002) plane and the (101) plane,
respectively. The peaks can be indexed to a
hexagonal graphite lattice. The broadening of
the peaks suggests the presence of an
amorphous carbon phase within the CMSs
[19]. These semi-hexagonal graphite structures took place during carbonization process
at high temperature. In carbonization process,
carbon atom in CMSs would be rearranged to
form graphene sheets and partially collapsed
to yield pore structures. This structure would
be suitable for any substances storage which
have their molecule sizes less than micropore
(< 2 nm).

Figure 2. Particle size distribution of CMSs

after carbonization which are ()HICAP100, ()CAPSUL, ()Tapioca, ()Corn,
()Rice, ()Wheat, ()Sticky rice.

(101)

(002)

distributions directly related to SEM observations. The particle size distribution of CMSs
from HICAP100 has the narrowest because
HICAP100 has its high water-solubility.
Contradictory, particle size distributions of
carbon microspheres from native starch
tended to broaden distributions that confirmed from SEM observations.

Intensity (a.u.)

43

HI-CAP 100
Tapioca

CAPSUL
Sticky rice

Table 1. The elemental components of

CMSs from energy dispersive X-ray.
Types of
starches
HICAP100
CAPSUL
Tapioca
Corn
Rice
Wheat
Sticky rice

Elemental components
Carbon (%)
Oxygen (%)
71.08
68.15
69.11
66.67
68.44
67.72
69.01

28.92
31.85
30.89
33.33
31.56
32.28
30.99

The energy-dispersive X-ray (EDX) analyses

of carbon microspheres from various types of
starch after carbonization process are shown
in Table 1. These results showed that carbon
is the main component of the CMSs in the
range of 66-71wt%. However, the oxygen
component in carbon microspheres might
mainly come from the absorbed water
molecules in pore structure [18].

2 (degree)

Figure 3. X-ray diffraction patterns of

CMSs after carbonization at 600 oC.
All N2 adsorption-desorption isotherms of
CMSs after carbonization process were
shown in Figure 4. These isotherms indicated
that the carbonized CMSs exhibited type I
adsorption isotherm due to its micropore
structure regarding to IUPAC classification
[20]. The BrunauerEmmettTeller (BET)
surface areas of CMSs before and after
carbonization were also summarized in Table
2. The CMSs surface areas were dramatically
increased after carbonization process. The
release of H, O and C during carbonization
process increased large quantities of micropores throughout the bulk of the samples [7].

Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.

44

Synthesis of Carbon Microspheres from Starch by Hydrothermal Process

4. Conclusions

Figure 4. N2 adsorption-desorption isotherm

of CMSs after carbonization which are
()HI-CAP100, ()CAPSUL, ()Tapioca,
()Corn, ()Rice, ()Wheat, ()Sticky rice.

Table 2. Specific BET surface area of

CMSs.
Types of
starches
HICAP100
CAPSUL
Tapioca
Corn
Rice
Wheat
Sticky rice

Specific BET surface area,

SBET [m2/g]
Before
After
carbonization carbonization
4.32
560
3.41
3.23
3.57
2.89
1.23
3.12

530
546
520
457
444
415

High micropores and monodisperse CMSs

were synthesized via a facile hydrothermal
process without any catalysts. The low-cost
starting materials and moderate reaction
temperature provide an efficient way to
fabricate solid CMSs. Furthermore, the
particle size distribution of the CMSs
strongly depended on types of starch. In other
words, the smallest particle size of CMSs
could be synthesized from HICAP100
because it can be hydrolyzed immediately to
form nucleates of CMSs. On the other hand,
broaden particle size distributions of CMSs
from some types of native starch because
they were continuously hydrolyzed during
hydrothermal process to grow shell of CMSs.
This mechanism came from their waterinsolubility of native starch. Furthermore,
high porosity of CMSs could be developed
by treating the dried CMSs in carbonization
process. The BET surface area of CMSs after
carbonization process dramatically increased
from 1-5 m2/g to 400-500 m2/g. In addition,
the CMSs also increased their carbon
contents by losing oxygen and hydrogen
atoms during carbonization process. Therefore, the rearrangement of carbon atom in
CMSs to form grapheme sheets took place.
Acknowledgements
This work was financially supported by
the Centennial Fund of Chulalongkorn
University for Center of Excellence in
Particle Technology (CEPT) and Department
of Chemical Engineering, Faculty of Engineering, Chulalongkorn University.

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