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Synthesis of Carbon Microspheres from Starch by Hydrothermal Process

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Sakhon Ratchahat Nawin Viriya-empikul

The Foundation Amano Institute of Technology in Collaboration to Shizuoka Univ… National Science and Technology Development Agency


Tawatchai Charinpanitkul Apinan Soottitantawat

Chulalongkorn University Chulalongkorn University


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SCIENCE JOURNAL Sci. J. UBU, Vol. 1, No. 2 (July – December, 2010) 40-45
Ubon Ratchathani University

Research Article

Synthesis of Carbon Microspheres from Starch by

Hydrothermal Process

S. Ratchahat1, N. Viriya-empikul2, K. Faungnawakij2,

T. Charinpanitkul1, A. Soottitantawat1,*
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


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 µm 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:

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 41

1. Introduction CMSs surface which can be immobilize

target reactive agents on the surface without
Since the significant finding of Buckminster- further surface modification. The uniform
fullerene (C60) [1] and carbon nanotubes CMSs can be determine particle morpho-
(CNTs) [2] considerable efforts have been logies and particle size distributions by scan-
made toward the synthesis of functional ning electron microscopy (SEM) and laser
carbonaceous materials with diverse morpho- diffraction method (Mastersizer 2000), resp-
logies and structures, such as colloidal ectively. The porous CMS particles were
spheres [3], nanofibers [4], coin-like hollow characterized by X-ray diffraction method
carbons [5], macroflowers [6], and so on. (XRD) to reveal their crystalline properties.
Among the different morphologies of carbon- They were determined their specific surface
iceous materials, carbon microspheres area both before and after carbonization
(CMSs) have attracted widespread interest, process to reveal the development of porous
owing to their potential properties in adsorb- structure using adsorption–desorption of
ents [7], catalyst supports [8], and anode nitrogen or the Brunauer, Emmett, Teller
material for lithium ion batteries [9] and method (BET method). Moreover, elemental
templates for fabricating core-shell or hollow components of the porous CMS particles
structures [10]. The CMS particles have been were determined by energy dispersive X-ray
synthesized by many techniques, such as method (EDX) to demonstrate carbon content
pressure carbonization [11], chemical vapor in their structure.
deposition [12], mixed-valence oxide-catal-
ytic carbonization [13], and reduction of 2. Materials and Methods
carbides with metal catalysis [5]. Accord-
ingly, various applications have been intens- Materials. Two types of modified starch, Hi-
ively developed [14]. Carbon microspheres CAP®100 and CAPSUL®, were obtained
(CMSs) with a perfect shape have the priority from National Starch and Chemical Ltd,
in catalyst support [15] and template (Bangplee, Thailand). These starches (HI-
utilization [16]. However, there are a few CAP®100 and CAPSUL®) were partially
reports of CMSs with a uniform size and hydrolyzed of waxy maize starch and then
perfect spherical morphology from various derivatized to impart lipophilic properties
types of starch. Consequently, in this study with n-octenyl succinic anhydride. They can
the synthesis of CMSs from various types be immediately dissolved in water. The
of starch was investigated via hydrothermal difference in structure of HICAP®100 and
process and following by carbonization pro- CAPSUL®, HICAP®100 is a straight chain
cess. The aim of this study is to investigate starch but CAPSUL® is a branch chain starch.
effects of types of starch on particle size and Therefore HICAP®100 has water-solubility
morphology of carbon microspheres. The more than CAPSUL®. Meanwhile, other
two main types of starch, modified starch and native starch or crystallized starch (corn,
native starch, were used to investigate differ- tapioca, wheat, rice, and sticky rice starch)
ences in particle size and morphology of the were obtained from a general commercial
obtained carbon microspheres. After hydro- resource. High purity nitrogen gas (99.999%)
thermal process, the dried CMSs had been was purchased from TIG.
carbonized under nitrogen atmosphere. The
carbonization process had highly developed Synthesis of the CMSs. In the hydrothermal
microporosity of CMSs but had removed the process, starch (5.0 g) was dispersed in 45.0
reactive functional group (-OH,-COOH) on mL of de-mineralized water and magnetically
their surface [17]. The porous CMSs have stirred at 60C for 30 min. The mixture was
highly microporosity and inert surface that filled in a 50 mL Teflon-lined stainless
can be used as adsorbents or gas storage autoclave. Subsequently, the autoclave was
materials. Without carbonization process, the put into an oven, which was heated at 180C
CMSs have the reactive functional group on

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 shell growth formation plays an important
temperature naturally. Dark precipitates were role than nucleate formation. On the other
collected and washed with de-mineralized hand, if native starches (unmodified starches)
water several times and dried in an oven at were used as starting material, the CMSs
100C for 24 h. The obtained powders were became larger and some of CMSs became
carbonized in a tube furnace under N2 aggregates with diameters ranging from 1.0
atmosphere. The N2 flow rate, final temper- to 7.0 μm (Figure 1f-h). In this work, it
ature and heating rate of the furnace were 100 appears that HI-CAP®100 could provide
ml/min, 600C and 1C/min, respectively. 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: JSM-
5410LV, Japan). The specific BET surface
area was measured by N2 adsorption-
desorption at -196C (BEL: BELSORP-mini,
Japan). The carbonaceous products were
confirmed by energy-dispersive X-ray spectra

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-CAP®100 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-CAP®100 can be hydrolyzed
carbonization: (a) HI-CAP®100; (b) HI-
immediately to form simultaneous nucleates
CAP®100 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 43

distributions directly related to SEM observ- In addition, the XRD patterns of some CMSs
ations. The particle size distribution of CMSs after carbonization are shown in Figure 3.
from HICAP®100 has the narrowest because There are the presences of two broad peaks at
HICAP®100 has its high water-solubility. 2 = 24.8 and 43.5 which are reflections from
Contradictory, particle size distributions of the (002) plane and the (101) plane,
carbon microspheres from native starch respectively. The peaks can be indexed to a
tended to broaden distributions that confirm- hexagonal graphite lattice. The broadening of
ed from SEM observations. the peaks suggests the presence of an
amorphous carbon phase within the CMSs
[19]. These semi-hexagonal graphite struct-
ures 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
Intensity (a.u.)

after carbonization which are ()HICAP-
®100, ()CAPSUL, ()Tapioca, ()Corn, HI-CAP® 100
()Rice, ()Wheat, ()Sticky rice.
Table 1. The elemental components of Sticky rice
CMSs from energy dispersive X-ray.
Types of Elemental components 2 (degree)
starches Carbon (%) Oxygen (%)
HICAP®100 71.08 28.92 Figure 3. X-ray diffraction patterns of
CAPSUL® 68.15 31.85 CMSs after carbonization at 600 oC.
Tapioca 69.11 30.89
Corn 66.67 33.33
Rice 68.44 31.56
All N2 adsorption-desorption isotherms of
Wheat 67.72 32.28 CMSs after carbonization process were
Sticky rice 69.01 30.99 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
The energy-dispersive X-ray (EDX) analyses
[20]. The Brunauer–Emmett–Teller (BET)
of carbon microspheres from various types of
surface areas of CMSs before and after
starch after carbonization process are shown
carbonization were also summarized in Table
in Table 1. These results showed that carbon
2. The CMSs surface areas were dramatically
is the main component of the CMSs in the
increased after carbonization process. The
range of 66-71wt%. However, the oxygen
release of H, O and C during carbonization
component in carbon microspheres might
process increased large quantities of micro-
mainly come from the absorbed water
pores throughout the bulk of the samples [7].
molecules in pore structure [18].

Copyright  2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.
44 Synthesis of Carbon Microspheres from Starch by Hydrothermal Process

4. Conclusions

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 HICAP®100
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
Figure 4. N2 adsorption-desorption isotherm hydrothermal process to grow shell of CMSs.
of CMSs after carbonization which are This mechanism came from their water-
()HI-CAP®100, ()CAPSUL, ()Tapioca, insolubility of native starch. Furthermore,
()Corn, ()Rice, ()Wheat, ()Sticky rice. 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,
Table 2. Specific BET surface area of the CMSs also increased their carbon
CMSs. contents by losing oxygen and hydrogen
atoms during carbonization process. There-
Specific BET surface area, fore, the rearrangement of carbon atom in
Types of SBET [m2/g] CMSs to form grapheme sheets took place.
starches Before After
carbonization carbonization
HI- 4.32 560 Acknowledgements
CAPSUL® 3.41 530 This work was financially supported by
Tapioca 3.23 546 the Centennial Fund of Chulalongkorn
Corn 3.57 520 University for Center of Excellence in
Rice 2.89 457 Particle Technology (CEPT) and Department
Wheat 1.23 444
Sticky rice 3.12 415
of Chemical Engineering, Faculty of Engi-
neering, Chulalongkorn University.


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