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Research Article
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
Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.
42
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
(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
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
2 (degree)
Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.
44
4. Conclusions
530
546
520
457
444
415
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Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.
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45
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Copyright 2010 Faculty of Science, Ubon Ratchathani University. All rights reserved.