Beruflich Dokumente
Kultur Dokumente
A R T I C L E I N F O A B S T R A C T
Article history: Rice husk is a promising abundant bioresource for the production of high value-added silica materials
Received 1 May 2019 because it has the highest SiO2 content among all plant-based resources. In this study, ordered
Received in revised form 10 August 2019 mesoporous silica with various pore structures are synthesized from rice husk by combining acid
Accepted 30 August 2019
leaching, chemical dissolution, and co-assembly with additional surfactants. Depending upon the type of
Available online xxx
the surfactant used and the co-assembly conditions, various mesoporous silica that have controlled pore
structures (mesocellular forms and hexagonal nanochannel structures), pore sizes (3–60 nm), large
Keywords:
surface areas (297–895 m2 g 1), and pore volumes (0.81–1.77 cm3 g 1) are successfully synthesized from
Rice husk
High-purity silica
a sodium silicate solution, which was made from high-purity silica (99.8%) extracted from rice husk. The
Mesoporous structure synthesis of high value-added silica from an abundant bioresource can open up new avenues for
Biogenic material sustainable and environment-friendly industrial development.
© 2019 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering
Chemistry.
Introduction –SO3H. Chen et al. used rice husk ash as a support for loading
calcined eggshells to prepare a solid-base catalyst, which was
Silicon is an abundant element in soil, which helps plants tolerate further used in the conversion of palm oil to biodiesel [10]. Another
environmental stress [1]. Silicic acid in soil is taken up and study showed the use of rice husk ash to support a nickel–iron
transported via two Si transporters, OsLsi1 and OsLsi2, in plants catalyst for biomass pyrolytic gasification [11]. The rice husk
and converted into insoluble silica in leaves [2,3]. Silica (SiO2) is ash-supported nickel–iron catalyst was synthesized by incipient
accumulated mainly in the form of phytoliths in plants, e.g., in wetness impregnation and calcination with iron and nickel
dicots, monocots, conifers, and sphenophytes/scouring rushes [4]. precursors. For high value-added application, the silicon element
Typically, rice husk is the biomaterial with the highest SiO2 content. in rice husk was used to synthesize battery materials [12]. This
The content of SiO2 is averaging close to 10.6% [5]. Silica in rice husk process involved the reduction of rice husk ash to silicon. In
exists in hydrated amorphous form [6]. Rice husk is a byproduct of addition to these examples, various approaches have been studied
white rice production process; typically, 1 kg of white rice to develop advanced Si-based materials using the components of
production results in approximately 0.20–0.25 kg of rice husk [7]. rice husk [13–15].
Rice husk silica can be used as a low-cost precursor resource for The use of renewable resources for synthesizing high value-
the production of high value-added silica or silicon-based added materials is becoming increasingly important [16]. Rice
materials for future applications [6,8]. For example, rice husk husk-derived silica is not only economic, but also helps in miti-
silica was used to synthesize a catalyst after modifying the silica gating environmental issues [6]. The attractive application of rice
surface. Zeng et al. synthesized a nano-sized solid acid from rice husk silica is the synthesis of mesoporous silica, which in turn can
hull ash by acid activation [9]. After acid activation, amorphous be used in a variety of applications involving large molecules [17];
silica derived from rice hull was functionalized with OH and which would be infeasible using conventional microporous
materials [18]. Mesopores are useful for the encapsulation of
active ingredients and afford a high specific surface area, which is
* Corresponding author. beneficial for cosmetics and drug delivery applications [19]. For
E-mail address: leejinh1@kicet.re.kr (J.H. Lee). these reasons, there have been several efforts to synthesize
https://doi.org/10.1016/j.jiec.2019.08.064
1226-086X/© 2019 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
2 J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx
mesoporous silica using SiO2 component in rice husk [20–26]. Metals), sodium hydroxide (97%, Aldrich), acetic acid (99.7%,
While conventional methods using silicon alkoxide require Kanto Chemicals), 1-butanol (99.4%, Aldrich), Pluronic P-123
expensive reagents like silica sources, rice husk is used as an (EO20PO70EO20, Aldrich), cetyltrimethylammonium bromide
abundant and cheap resource to synthesize mesoporous silica. (CTAB; 99%, Aldrich), and trimethylbenzene (TMB; 98%, Aldrich)
Compared to other synthetic methods using sodium silicate were used as received without further purification.
chemicals as the silica sources, utilization of rice husk can provide
an additional advantage in terms of eco-friendly recycling of waste Preparation of ordered mesoporous silica from rice husk
biomass.
However, only silica with limited mesoporous structures have Rice husk was washed with deionized water three times to
been prepared thus far from rice husk; the sizes of ordered remove the physically adhered impurities and was dried in an air-
mesopores were less than 10 nm [20–23,25,26], and only irregu- circulating oven at 80 C overnight. The dried rice husk (100 g) was
larly formed large-sized pores were observed [20,21,24]. Moreover, treated with 72% H2SO4 (1000 mL) for 1 h, followed by slow
many researchers have used non-purified ash as a silicate source addition of distilled water to adjust the concentration of H2SO4 to
[20–23], which can cause undesired side effects arising from 4%. The rice husk ash in 4% H2SO4 was reacted at 121 C for 1 h. The
residual metal traces present in the non-purified ash. Therefore, purpose of this procedure was to remove the flux materials, such as
the development of mesoporous silica with various pore sizes and alkaline and alkaline earth oxides, in the rice husk [32]. After
a uniform, ordered structure using purified SiO2 from rice husk is decanting H2SO4, the sample was washed with water and dried at
still highly required for a number of potential value-added 80 C for 24 h. The diluted sulfuric acid wastewater was collected
applications, such as bioimaging, biomolecule delivery, heteroge- and treated by a professional waste treatment company. Rice husk
nous catalysis, cosmetic ingredients, and additives for energy ash was burned at 900 C for 12 h under air to obtain white silica.
storage devices [27–31]. The white silica was poured in 5 M NaOH solution to obtain a
In this study, we synthesized ordered and pore size-controlled 0.5 g SiO2 per mL of NaOH. The solution was heated at 150 C inside
mesoporous silica using high-purity silica extracted from rice husk. a reflux flask to obtain a sodium silicate solution. From the sodium
The process involves removal of organic components and metallic silicate solution, ordered mesoporous silica particles (OMS series)
impurities in the rice husk, obtaining a sodium silicate solution, and were synthesized following previously reported procedure [33,34].
formation of a mesoporous structure through self-assembly with In a typical synthesis of OMS-1, 9.8 g of P-123 and an amount of
additional surfactants (Fig. 1). Various mesoporous silica with acetic acid (~4.5 mL) equivalent to the hydroxide content in the
controlled pore structures (mesocellular forms and hexagonal silicate solution were mixed in 400 mL of distilled water. After
nanochannel structures), pore sizes (3–60 nm), large surface areas complete dissolution of P-123, 11.2 mL of TMB was added at 60 C.
(297–895 m2 g 1), and pore volumes (0.81–1.77 cm3 g 1) were Then, 16 mL of the silicate solution diluted in 400 mL of distilled
successfully synthesized via the co-assembly of additional surfac- water was added and stirred for 12 h. The resulting solution was
tants with the sodium silicate solution, which was made from high- aged at 100 C for 24 h. After aging, the product was filtered and
purity (99.8%) silica extracted from rice husk. The ordered calcined at 550 C for 4 h. The overall synthetic procedure of OMS-2
mesoporous structures of silica were investigated by transmission was similar to that of OMS-1, except that the amount of silicate
electron microscopy and small-angle X-ray scattering analysis. We solution was 32 mL (diluted in 400 mL of distilled water) and TMB
expect that the development of various ordered mesoporous silica was not used. For the synthesis of OMS-3, CTAB was used instead of
from an abundant bioresource can open up new avenues for P-123. A mass of 1.6 g of CTAB was dissolved in 8 mL of distilled
sustainable and environment-friendly industrial development. water. Then, 0.8 mL of 1-butanol, 6.5 mL of silicate solution, and 10
mL of 1.2 M H2SO4 were added sequentially. The resulting solution
Experimental was stirred vigorously for 12 h at room temperature. After aging at
100 C for 24 h, the product was filtered and calcined at 550 C for
Materials 4 h. In contrast to OMS-1, 2, and 3, a sodium silicate solution with a
concentration of 0.1 g SiO2 per mL of NaOH was used to synthesize
Rice husk was provided by a rice mill factory located in OMS-4. Therefore, the amounts of additives were adjusted for the
Gyeongnam, Korea. Sulfuric acid (72%, Daejung Chemicals & synthesis of OMS-4 to compensate for the difference in SiO2
Fig. 1. Schematic of the procedure to obtain ordered mesoporous silica from rice husk.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx 3
Table 1 Table 2
Composition of pristine rice husk. Inorganic chemical compositions of pristine rice husk, RH-SiO2, and OMS-1.
Water Ash Cellulose Hemicellulose Organic Lignin Rice husk (wt%) RH-SiO2 (wt%) OMS-1 (wt%)
content extract
SiO2 94.7 99.8 99.4
wt% 4.93 14.52 29.97 10.61 10.76 20.32 K2O 1.70 <0.01 0.01
CaO 1.42 0.02 <0.01
P2 O 5 1.14 0.01 <0.01
MgO 0.54 0.01 <0.01
content in the sodium silicate solution. First, 7.8 g of P-123 and an MnO 0.18 0.01 <0.01
Na2O 0.09 0.01 0.52
amount of acetic acid (~17 mL) equivalent to the hydroxide content
Al2O3 0.08 0.04 0.05
in the silicate solution were mixed in 160 mL of distilled water. Fe2O3 0.06 <0.01 0.01
After complete dissolution of P-123, 4.5 mL of TMB was added at ZnO 0.02 <0.01 <0.01
60 C. Then, 45 mL of the silicate solution diluted in 130 mL of
distilled water was added and stirred for 12 h. The resulting
solution was aged at 100 C for 24 h. After aging, the product was SiO2 in ash (13.75 g), other inorganic components in ash (0.77 g),
filtered and calcined at 550 C for 4 h. organic components (cellulose, hemicellulose, organic extract,
The mass balances of rice husk and extracted rice husk ash are and lignin; 71.66 g), water content (4.93 g), and other organic
as follows: rich husk (100 g) used in this study was composed of components (e.g. protein, lipid, non-structured sugars, etc.; 8.89 g).
Fig. 2. SEM-EDS results of (a) pristine rice husk and (b) RH-SiO2.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
4 J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx
Extracted rice husk ash (12 g) after thermal treatment at 900 C rate of 0.6 mL/min. To measure the contents of acid insoluble lignin
was composed of SiO2 (11.98 g) and other components (0.02 g). and ash, the solids were transferred to a crucible and placed in the
The synthesized OMS (11.16 g) from rich husk ash was composed muffle furnace at 575 C for 24 h. The contents of ash and acid
of SiO2 (11.09 g) and other components (0.07 g). Considering insoluble lignin were calculated according to the National
these mass balances, the final yield of OMS from the pristine Renewable Energy Laboratory Procedure [35,37].
rice husk was 80.68%. The detailed analysis methods and The inorganic chemical composition of silica was determined
discussion are described in “Material characterizations” and by using an inductively coupled plasma-optical emission spec-
“Result and discussion”. trometer (ICP-OES; Optima 5300DV, PerkinElmer, USA). X-ray
diffraction (XRD) patterns were obtained with a Rigaku D/Max
Material characterizations 2500/PC diffractometer (Japan). The material morphologies were
investigated using a scanning electron microscope (SEM; Oxford,
The rice husk composition was analyzed according to the X-Max T50) and a transmission electron microscope (TEM; JEOL,
National Renewable Energy Laboratory Procedure [35–38]. JEM-2000EX, Japan). An energy dispersive spectrometer (EDS)
The water content of the rice husk was measured using Moisture attached to the SEM instrument was used for elemental analysis.
analyser (50–3C, Kern & Sohn GmbH, Germany). The rice husk was The nitrogen (N2) physisorption isotherms were obtained at 77 K
dissolved in H2SO4 and carbohydrates, acid soluble lignin, and using an ASAP 2420 system (Micromeritics Inc., USA). The surface
extractives were determined by high pressure liquid chromatog- areas of materials were calculated from the measured isotherms
raphy (HPLC) using an Agilent 1200 series HPLC fitted with a according to the Brunauer–Emmett–Teller (BET) method, and the
refractive index detector (Agilent Technologies, USA) and an pore volumes were taken at the P/P0 =~0.995 single point. The pore
Aminex HPX-87P and HPX-87H column (BioRad, USA). The solvent size distributions of materials were calculated by the Barrett–
was 0.5 wt% H2SO4 for HPX-87H and water for HPX-87P at a flow Joyner–Halenda (BJH) method from the adsorption branches of the
Fig. 3. (a) XRD, (b) SEM, (c–d) TEM, (e) N2 physisorption isotherms, and (f) pore-size distribution of RH-SiO2.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx 5
isotherms. Small angle X-ray scattering (SAXS) measurements products completely removed the residual lignin and organic
were carried out on the 4C SAXS beamline at the Pohang Light components and yielded the white silica powder (Fig. 1). The purity
Source II. of resulting rice husk-derived silica (RH-SiO2) was as high as
99.8% (Table 2). Previous studies burned rice husk at 700 C for
Results and discussion 2 h to remove organic compounds [25,26]. Originally, the thermal
removal conditions of organic compounds depend upon the
Extraction of high-purity SiO2 from rice husk combination of furnace performance and volume of sample to
furnace’s inner space beside of organics thermal properties. This
Table 1 presents the components of pristine rice husk used in study used higher temperature and longer thermal treatment time
this study. The rice husk was analyzed according to the National for completely removing the organic compounds from rice husk.
Renewable Energy Laboratory Procedure [35–38]. The ratio of ash The main purpose behind this step was to completely remove
corresponding to the inorganic components of rice husk is~14.5 wt organic compounds, and not to optimize the conditions of
%. In particular, almost 95% of ash is composed of silica (Table 2); temperature and treatment time. However, the thermal treatment
therefore, it can be used as a precursor for silicon-based materials temperature and time should be optimized to save energy
efficiently. In this study, cellulose, hemicellulose, and inorganic consumption in industrial processes. SEM-EDS analysis also shows
compounds except the silica in rice husk were dissolved and the removal of other impurities in rice husk after purification
removed by sulfuric acid treatment. Subsequent pyrolysis of solid (Fig. 2). This indicates that the high-purity silica was successfully
Fig. 4. TEM images of (a–c) OMS-1, (d–f) OMS-2, (g–i) OMS-3, and (j–l) OMS-4.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
6 J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx
obtained by the chemical treatment of rice husk using sulfuric acid structure, particle shape, and overall size to OMS-1, but has tens of
followed by pyrolysis. nanometers larger pore size than OMS-1. The average pore size of
The XRD pattern of RH-SiO2 only exhibits a broad diffraction at OMS-4 estimated from Fig. 4l is around 60 nm, which is slightly
near 20 , which is typical for amorphous silica (Fig. 3a). The larger than the upper limit (50 nm) of the definition of mesopores.
morphology of RH-SiO2 was investigated by electron microscopes The main difference in experimental conditions between the
and N2 physisorption isotherms. RH-SiO2 had an irregular bulk synthesis of OMS-1 and OMS-4 was the amount of NaOH and acetic
shape and there was no specific microstructure or nanostructure acid. Compared to the reactant solution for OMS-1, relatively large
(Fig. 3b–d). The small-sized nanoparticles formed large particles amounts of sodium and acetate ions were contained in the reactant
upon aggregation with sizes of a few hundred nanometers. The solution of OMS-4. In a previous study, Boissière et al. showed that
poorly defined random mesopores were observed in RH-SiO2, the pore size of mesoporous silica increases with increasing the
which mostly originate from the removal of organic components or amount of sodium fluoride (NaF). Fluoride can promote the
inorganic impurities. Such properties are also reflected in the oxolation reaction and considerably increase the hydrophobicity of
shape of isotherms and the pore size distribution (Fig. 3e–f). N2 silica. As a result, silicate oligomers cannot incorporate into the
physisorption isotherm of RH-SiO2 shows type H3 hysteresis loop inner region of the PEO shell, leaving silicate-free internal PEO
at P/P0 = 0.4–0.99, which is typically observed in the particulate which adds with the hydrophobic core to contribute to larger pores
aggregates having irregular slit-shaped pores. The pore size was [41]. Likewise, the large amount of acetate would play a similar
broadly distributed from 2 to 30 nm, which is in good agreement role, as it can promote the condensation of silica (i.e., increase the
with TEM observation. The surface area and pore volume of hydrophobicity of silica), thereby leading to the pore expansion in
RH-SiO2 were 88 m2 g 1 and 0.18 cm3 g 1, respectively. Although OMS-4.
the surface area of RH-SiO2 is comparable to that of silica The pore structures of OMS series were further analyzed by N2
(~110 m2 g 1) obtained from specific rice husk (Almaty in physisorption isotherms (Fig. 5) and small angle X-ray scattering
Kazakhstan) [39], this value is lower than that for conventional (SAXS) (Fig. 6). All OMS samples exhibit type IV isotherms typical
mesoporous silica. Therefore, although we confirmed that high- for mesoporous materials, as classified by IUPAC (Fig. 5a). They also
purity RH-SiO2 could be obtained from rice husk, an additional show characteristic SAXS patterns for ordered mesoporous
process is required to synthesize high value-added silica which has materials (Fig. 6a–d), which are in stark contrast to disordered
well-defined nanostructures and high specific surface area. RH-SiO2 with no scattering peaks (Fig. 6e). The isotherms of OMS-1
and OMS-4 show a type H1 hysteresis at high P/P0, which is
Synthesis of various ordered mesoporous silica using the associated with a mesocellular foam structure with large-size
extracted SiO2
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx 7
Fig. 6. SAXS patterns of (a) OMS-1, (b) OMS-2, (c) OMS-3, (d) OMS-4, and (e) RH-SiO2.
pores >30 nm [42]. The SAXS results of OMS-1 are well matched The surface areas and pore volumes of OMS series are
with the simulated scattering pattern from uniform and monodis- summarized in Table 3. All OMS powders have high surface areas
perse spheres, which are typical for mesocellular form silica with of more than 250 m2 g 1 and large pore volumes of more than
well-defined mesopores (Fig. 6a). OMS-4 shows relatively less- 0.8 cm3 g 1. The adsorption volume at a low relative pressure
defined scattering peaks (Fig. 6d) because of its nonuniform and (P/P0 < 0.1) is closely related to the micropore volume of OMS. The
broad size distribution of the spherical cells [43], as confirmed in micropores can contribute to the surface area more significantly
TEM image (Fig. 4l) and pore size distribution (Fig. 5b). OMS-2 than mesopores and macropores, and they are highly responsible
exhibits a type H1 hysteresis at a medium P/P0 owing to its for large surface area. Fig. 5a shows that as the main pore size of
relatively small-size pores. The type H4 hysteresis of the isotherms OMS increases, the adsorbed N2 volume at P/P0 < 0.1 decreases.
of OMS-3 indicates the existence of narrow slit pores [44]. Both This tendency is well-matched with the surface area series of
OMS-2 and OMS-3 have well-resolved SAXS peaks, which can be OMS (OMS-3 > OMS-2 > OMS-1 > OMS-4). On the other hand, as
indexed to highly ordered hexagonal (p6mm) mesostructures expected, OMS with large pores (OMS-1 and OMS-4) have
(Fig. 6b–c) [33,45]. Pore size distributions calculated from the significantly larger pore volumes calculated at P/P0 ~0.99 than
adsorption branches of isotherms show that the main pore sizes OMS with small pores (OMS-2 and OMS-3).
are ~30 nm, ~8 nm, and ~3 nm in OMS-1, OMS-2, and OMS-3, Additional analysis was conducted to investigate the material
respectively (Fig. 5b). These results are almost consistent with composition of OMS.
the observed pore structures and sizes in the SAXS results (Fig. 6) All OMS powders were made from the sodium silicate solution
and TEM images (Fig. 4). In the case of OMS-4, adsorption volumes and the principles of their synthetic methods were not very
are abruptly increased at very high P/P0 > 0.97 (Fig. 5b), which different. Therefore, we chose OMS-1 as a representative sample to
indicates the presence of macropores >50 nm. Macropores cannot analyze the material composition of OMS series. Similar to RH-
be fully assessed by N2 physisorption as they are in the size range SiO2, OMS-1 had an amorphous nature in its structural
that cannot be completely filled with gas adsorbate at atmospheric
pressure [46]. This makes the exact calculation of pore size Table 3
from the adsorption isotherms difficult and induces a slight Specific surface area and pore volume of OMS series and RH-SiO2.
deviation from the TEM images (Fig. 4j–l). However, there is no
OMS-1 OMS-2 OMS-3 OMS-4 RH-SiO2
doubt that the TEM and N2 physisorption isotherms analyses of
OMS-4 demonstrate the existence of large mesopores and even Surface area (m2 g 1) 337 648 895 297 88
Pore volume (cm3 g 1) 1.77 0.81 0.90 1.62 0.18
macropores.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
8 J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx
Declaration of interest
None
Acknowledgements
References
[1] M.E.F. Abdel-Haliem, H.S. Hegazy, N.S. Hassan, D.M. Naguib, Ecol. Eng. 99
(2017) 282.
[2] J.F. Ma, N. Yamaji, N. Mitani, K. Tamai, S. Konishi, T. Fujiwara, M. Katsuhara, M.
Yano, Nature 448 (2007) 209.
[3] S. Yamanaka, H. Takeda, S. Komatsubara, F. Ito, H. Usami, E. Togawa, K. Yoshino,
Appl. Phys. Lett. 95 (2009)123703.
[4] D.M. Hart, Australia Aust. J. Bot. 36 (1988) 159.
[5] T.P. Ding, G.R. Ma, M.X. Shui, D.F. Wan, R.H. Li, China Chem. Geol. 218 (2005) 41.
[6] Y. Shen, Renew. Sust. Energ. Rev. 80 (2017) 453.
[7] D. An, Y. Guo, Y. Zhu, Z. Wang, Chem. Eng. J. 162 (2010) 509.
[8] P. Chen, H. Bie, R. Bie, Korean J. Chem. Eng. 35 (2018) 1911.
[9] D. Zeng, S. Liu, W. Gong, H. Chen, G. Wang, RSC Adv. 4 (2014) 20535.
[10] G. Chen, R. Shan, J. Shi, B. Yan, Fuel Process Technol. 133 (2015) 8.
[11] Y. Shen, P. Zhao, Q. Shao, F. Takahashi, K. Yoshikawa, Appl. Energy 160 (2015)
808.
[12] D.S. Jung, M. Ryou, Y.J. Sung, S.B. Park, J.W. Choi, PNAS 110 (2013) 12229.
Fig. 7. (a) XRD pattern and (b) SEM-EDS result of OMS-1.
[13] N. Soltani, A. Bahrami, M.I. Pech-Canul, L.A. González, Chem. Eng. J. 264 (2015)
899.
[14] S. Hossain, L. Mathur, P.K. Roy, J. Asian Ceram. Soc. 6 (2018) 299–313.
characteristics; only a broad single peak was observed in the XRD [15] H.B. Dizaji, T. Zeng, I. Hartmann, D. Enke, T. Schliermann, V. Lenz, M. Bidabadi,
Appl. Sci. 9 (2019) 1083.
pattern (Fig. 7a). Excluding ignition loss of residual carbon [16] Biomass Research and Development Technical advisory Committee, Roadmap
components originating from the structure-directing agents, for Bioenergy and Biobased Products in the United States, (2007) .
SiO2 comprised 99.4 wt% of OMS-1 (Table 2). Only a small amount [17] B. Özbek, S. Ünal, Korean J. Chem. Eng. 34 (2017) 1992.
[18] J.Y. Ying, C.P. Mehnert, M.S. Wong, Angew. Chem. Int. Ed. 38 (1999) 56.
(0.52 wt%) of unwashed sodium compounds originating from [19] A. Watermann, J. Brieger, Nanomaterials 7 (2017) 189.
sodium silicate was observed in OMS-1. The SEM-EDS result shown [20] T. Witoon, M. Chareonpanich, J. Limtrakul, Mater. Lett. 62 (2008) 1476.
in Fig. 7b also supports that the main component of OMS-1 is SiO2. [21] O. Jullaphan, T. Witoon, M. Chareonpanich, Mater. Lett. 63 (2009) 1303.
[22] H.T. Jung, Y. Park, Y.S. Ko, J.Y. Lee, B. Margandan, Int. J. Greenh. Gas Con. 3 (2009)
These results indicate that the OMS synthesized in this work was
545.
composed of high-purity silica. [23] M. Bhagiyalakshmi, J.Y. Lee, R. Anuradha, H.T. Jang, J. Hazard. Mater. 175 (2010)
This study used rice husk as a resource to extract silica. Because 928.
natural resources are complex mixtures of various compounds, [24] H.A. Alyosef, D. Schneider, S. Wassersleben, H. Roggendorf, M. Weiß, A. Eilert,
R. Denecke, I. Hartmann, D. Enke, ACS Sustain. Chem. Eng. 3 (2015) 2012.
using natural resources could affect conversion reactions in [25] S. Suyanta, A. Kuncaka, Indo. J. Chem. 11 (2011) 279.
unexpected manners. For example, the sodium silicate synthesized [26] N.K. Renuka, A.K. Praveen, K. Anas, Mater. Lett. 109 (2013) 70.
in this study showed different color compared to that of the [27] Y. Wang, Q. Zhao, N. Han, L. Bai, J. Li, J. Liu, E. Che, L. Hu, Q. Zhang, T. Jiang, S.
Wang, Nanomed. Nanotechnol. Biol. Med. 11 (2015) 313.
synthetic one (see Fig. 1). However, this study proved that the [28] P. Singh, K. Sen, J. Porous Mater. 25 (2018) 965.
difference between natural and synthetic resources did not affect [29] J. Liang, Z. Liang, R. Zou, Y. Zhao, Adv. Mater. 29 (2017)1701139.
the synthesis of ordered mesoporous silica, when rice husk was [30] X. Ji, S. Evers, R. Black, L.F. Nazar, Nat. Commun. 2 (2011) 325.
[31] N.Ž Kneževi c, N. Ili
c, V. Doki c, R. Petrovi
c, D. Jana ckovi
c, ACS Appl. Mater.
used. Interfaces 10 (2018) 20231.
[32] V.P. Della, I. Kuhn, D. Hotza, Mater. Lett. 57 (2002) 818.
Conclusions [33] S.S. Kim, T.R. Pauly, T.J. Pinnavaia, Chem. Commun. (2000) 1661.
[34] Y.S. Lin, H.P. Lin, C.Y. Mou, Microporous Mesoporous Mater. 76 (2004) 203.
[35] A. Sluiter, B. Hames, R. Ruiz, C. Scarlata, J. Sluiter, D. Templeton, D. Crocker,
Ordered and pore size-controlled mesoporous silica was suc- Determination of Structural Carbohydrates and Lignin in Biomass, NREL/TP-
cessfully synthesized using the high-purity silica extracted from rice 510-42618, National Renewable Energy Laboratory, Colorado, 2008.
[36] A. Sluiter, R. Ruiz, C. Scarlata, J. Sluiter, D. Templeton, Determination of
husk. Acid leaching and pyrolysis of rice husk provided high-purity
Extractives in Biomass, NREL/TP-510-42619, National Renewable Energy
(99.8 wt%) silica powder, which was subsequently used as a Laboratory, Colorado, 2008.
precursor for mesoporous silica. Through a co-assembly process [37] A. Sluiter, B. Hames, R. Ruiz, C. Scarlata, J. Sluiter, D. Templeton, D. Crocker,
of additional surfactants with a silica precursor, mesoporous silica Determination of Ash in Biomass, NREL/TP-510-42622, National Renewable
Energy Laboratory, Colorado, 2005.
powders with controlled pore structures (mesocellular forms and [38] J.H. Lee, J.H. Kwon, J.H. Lee, H.S. Lee, J.H. Chang, B.I. Sang, J. Ind. Eng. Chem. 50
hexagonal nanochannel structures), pore sizes (3–60 nm), large (2017) 79–85.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064
G Model
JIEC 4759 No. of Pages 9
J. Chun et al. / Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx 9
[39] S. Azat, A.V. Korobeinyk, K. Moustakas, V.J. Inglezakis, J. Clean. Prod. 217 (2019) [43] P. Schmidt-Winkel, W.W. Lukens, P. Yang, D.I. Margolese, J.S. Lettow, J.Y. Ying,
352. G.D. Stucky, Chem. Mater. 12 (2000) 686.
[40] P. Schmidt-Winkel, W.W. Lukens Jr., D. Zhao, P. Yang, B.F. Chmelka, G.D. Stucky, [44] Z.A. Alothman, Materials 5 (2012) 2874.
J. Am. Chem. Soc. 121 (1999) 254. [45] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
[41] C. Boissière, M.A.U. Martines, M. Tokumoto, A. Larbot, E. Prouzet, Chem. Mater. 710.
15 (2013) 509. [46] K.A. Cychosz, R. Guillet-Nicolas, J. García-Martínez, M. Thommes, Chem. Soc.
[42] M. Yao, Y. Dong, X. Feng, X. Hu, A. Jia, G. Xie, G. Hu, J. Lu, M. Luo, M. Fan, Fuel 123 Rev. 46 (2017) 389.
(2014) 66.
Please cite this article in press as: J. Chun, et al., Synthesis of ordered mesoporous silica with various pore structures using high-purity silica
extracted from rice husk, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.08.064