Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 515–520

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Agricultural waste as a source for the production of silica nanoparticles

Vineet Vaibhav a, U. Vijayalakshmi a,⇑, S. Mohana Roopan b,⇑
a
Materials Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, India
b
Chemistry Research Laboratory, Organic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Silica nanoparticles have been

reported in green manner.
 A feasibility of producing pure silica
from waste materials by alkali/acid
treatment.
 Acidic extraction, high purity 98% has
been obtained.
 Ash obtained from waster materials
would be promising low cost raw
material.

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

Article history: The major interest of the paper deals with the extraction of silica from four natural sources such as rice
Received 15 July 2014 husk, bamboo leaves, sugarcane bagasse and groundnut shell. These waste materials in large quantities
Received in revised form 4 November 2014 can create a serious environmental problem. Hence, there is a need to adopt proper strategy to reduce the
Accepted 17 December 2014
waste. In the present investigation, all the waste materials are subjected to moisture removal in a hot
Available online 27 December 2014
plate and sintered at 900 °C for 7 h. The sintered powder was treated with 1 M NaOH to form sodium sil-
icate and then with 6 M H2SO4 to precipitate silica. The prepared silica powders were characterized by FT-
Keywords:
IR, XRD and SEM-EDAX analysis. The silica recovered from different sources was found to vary between
Silica
Nanoparticles
52% and 78%. Magnesium substituted silica was formed from the groundnut waste and further treatment
Rice husk is required to precipitate silica.
Groundnut Ó 2014 Elsevier B.V. All rights reserved.
Sugarcane bagasse
Bamboo leaves

Introduction
Nano science is one of the major interdisciplinary are in the cur-
rent focus of research [1–4]. Silica nanoparticles are used in many
fields such as ceramics, chromatography, and anticorrosion agent
and in catalysis [5–7]. The sources such as rice husk, groundnut
shell, bamboo leaves and sugarcane bagasse are considered as a
⇑ Corresponding authors. Tel.: +91 98656 10356, +91 04162 202352; fax: +91 416
224 5544/5766.
E-mail addresses: lakesminat@yahoo.com, vijaya_lakshmi_u@yahoo.com
(U. Vijayalakshmi), mohanaroopan.s@vit.ac.in, mohanaroopan.s@gmail.com
(S.M. Roopan).
waste material. At harvesting time, these waste materials are burnt
to release nutrients for the next growing season and to get rid of
the huge quantity of it. During burning, carbon, oxygen and
hydrogen elements which are present in these waste materials
are converted into flammable gases such as carbon monoxide,
hydrogen, methane and ash. This ash is rich in silica and carbon
and it has no exploitation yet.
Extraction of silica from rice husk is an emerging trend in the
current research field. Large amount of rice husk (RH) are treated
as waste and disposed off at the landfill site. These waste materials
can also cause fire, which may lead to severe environmental
pollutions. The airborne particles produced from dust may induce
respiratory disease to human beings [8]. The burning of rice husk

http://dx.doi.org/10.1016/j.saa.2014.12.083
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
516 V. Vaibhav et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 515–520

results in the formation of rice husk ash (RHA) with major SiO2 Determination of structure and elemental composition of powder
content with 10–20% of carbon and traces of other organic compo- sample
nents depending on the burning conditions, the furnace type, the
rice variety, the climate and the geographical area [9]. Morphological and elemental characterizations were carried
Moreover, the commonly used silica precursor like tetra ethyl out by using a scanning electron microscope (SEM-EDAX) device
orthosilicate is more expensive, and hence rice husk ash (RHA) (FEI Quanta FEG 200 High Resolution Scanning Electron Micro-
and other waste sources having silica are used as an alternative scope). The analyzer was previously calibrated with a multi-min-
[10,11]. Acid leaching of the rice husk ash was carried out to eral sample.
remove soluble elemental impurities and hence it increases the
purity of the silica content. The organic compounds in rice husk Results and discussion
and other waste materials can be decomposed under sintering con-
ditions. The metallic impurities can be transferred to soluble ions The waste materials are converted to ash by sintering at 900 °C
by simple acid treatment [12,13]. With the aforementioned and the % of silica from the ash can varies from 55% to 80% depend-
method, sintering the sources at high temperature requires high ing on the elemental composition of the ash which is taken for the
energy and the utilization of acid especially the volatile hydrochlo- alkali and acid treatment. The various waste materials and its
ric acid not only corrupts the reaction equipment but also brings an treatment processes followed by characterization are summarized
extra financial cost and pollutes environment. Hence, sulfuric acid in Fig. 1.
treatment was selected for acid treatment and the purification
treatment was done in two steps. The first step is leaching with
Analysis of functional group by FT-IR spectroscopy
acid solution to remove the soluble metallic impurities and the
second one is sintering the leached sample in order to reduce the
The IR spectra of sodium silicate gels obtained from the alkali
total carbon content. The expected results of these two unit pro-
treatment are shown in Fig. 2. The broadband at 3400–
cesses are an overall increase in the purity of the silica content.
In continuation of our earlier work [14–16], in the present
investigation, silica glass was prepared from different waste mate-
Natural Source
rial such as rice husk (RH); bamboo leaves (BL), sugarcane bagasse
(Rice Husk, Sugarcane Bagasse,
(SB) and groundnut shell (GN). The obtained powder was charac- Bamboo Leaves, Groundnut Shell)
terized by FT-IR and XRD analysis to confirm the functional group
and purity of silica. The morphological changes occurred during
the alkali and acidic treatment was observed from SEM analysis
and the elemental composition of the obtained powder was further Sintered at
900 oC for 7 h
analyzed by EDAX spectra.

Experimental details Treated with

1 M NaOH
All the four samples such as rice husk (from rice mill), sugar-
cane bagasse (from juice shop), groundnut shell and bamboo
leaves are collected from Vellore district (Katpadi), Tamil Nadu, Na2SiO3
India and are subjected to moisture removal using a hot plate. After pH=11.8
moisture removal, it was sintered at 900 °C for 7 h in order to
remove the volatile gases and converted to respective ash powders.
Silica nanoparticles have been prepared through dissolution and Acid Treatment
precipitation process. The dissolution of silica was carried out (6M H2SO4 )
using an alkali leaching process using 1 M sodium hydroxide to
partially dissolve carbonaceous materials. The obtained sodium sil- Ageing for 12 h.
icate was filtered and dried in an oven for 24 h at 100 °C. The pre-
cipitation of silica from sodium silicate solution was carried out
using 6 M sulfuric acid at the pH of 7 and left for aging for 24 h.
The precipitate was centrifuged and washed with hot water and Centrifuge and washing the
dried at 80 °C for 24 h. precipitate with hot water

SiO2 þ 2NaOH!Na2 SiO3 þ H2 O

Dried at 80 oC for 24 h
Na2 SiO3 þ H2 SO4 !SiO2 þ Na2 SO4 þ H2 O

Silica Xerogel
Determination of functional group and phase formation of the powder
sample

The chemical bond in the prepared powder was studied by Characterization

using Fourier infrared spectroscopy using SHIMADZU instrument.
The study was carried out in the wave number of 400–
4000 cm1. The XRD measurement was taken at the step size of FT-IR XRD SEM/EDA
0.02 deg/min by using BRUKER D8, Advance X-ray Diffractometer
using Cu Ka (1.5406 Å), and Ni filtered radiation. Fig. 1. Schematic representation of silica extraction from the waste materials.
 V. Vaibhav et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 515–520 517

Fig. 2. FT-IR spectrum for sodium silicate gels obtained from the NaOH treated ash Fig. 3. FT-IR spectrum for the acid treated sodium silicate glass.
of different waste materials.

vibration. The decrease in the absorption peak at 3405 cm1 was

3700 cm1 is due to the absorption of hydrogen bonded silanol attributed to the decrease in the amount of Si–OH due to the
groups. The band at 3437 cm1 and a band at 1632 cm1 are corre- condensation of silanol [23]. As compared with other sources, rice
sponds to the stretching and bending vibration of H2O molecules husk have increased in silanol formation with respect to the inten-
[17,18]. The strong and broad band at 1111 cm1 with a weak sity of the peak at 3405 cm1. Hence, the presence of bands at 470,
shoulder at 1188 cm1 is assigned to the TO and LO modes of 810, 954, 1032 and 1086 cm1 have confirmed the formation of sil-
Si–O–Si asymmetric stretching vibrations. The intense bands at ica during acid treatment.
800 cm1 and 474 cm1 are due to symmetric stretching and bend-
ing vibrations of Si–O–Si. Bock and Su [8] have recorded the IR XRD Spectra for the ash sample sintered at 900 °C for 7 h
spectrum of fused silica and compared it with the results of vibra-
tional calculations. They found that the bands such as 465, 800, Fig. 4 represents the XRD spectra of the waste materials sin-
950, 1100 and 1190 cm1 are related to fused silica. Generally, tered at 900 °C for 7 h. All the major peaks around 22°, 27° and
these IR bands are appeared in various forms of silica such as 40° have shown the presence of quartz and cristobalite phases
quartz, cristobalite and tridymite respectively. Also, the absorption respectively. The formation of phase was confirmed based on the
bands at 1390 cm1 and 890 cm1 are observed in all the FT-IR literature [24,25]. In addition to silica, the peak around 30° and
spectra of alkali treated samples, which confirms the formation 40.5° is also observed in the sugarcane bagasse ash which indi-
of sodium silicate. cated the presence of calcite (CaCO3).
The alkali treated rice husk powder have shown a peak at The XRD spectra of bamboo leaves and groundnut shell ash
1388 cm1, which is due to the formation of Si–O–Na bond, have confirmed the presence of silica along with the mixture of
whereas the sample prepared from the other three sources such compounds such as microcline (KAlSi3O8) at 28°, potassium car-
as sugarcane, bamboo leaves and groundnut have shown an addi- bonate (K2CO3) at 31°, and calcium silicate (Ca2SiO4) at 41°. In
tional peak at 815 cm1 that indicated the formation of Si–O–Al addition to the above mentioned peaks, the presence of tridymite
phase. Bands near 567 cm1 for the groundnut sample and at (SiO2), sylvite (KCl) and peridase (MgO) are also observed in
472 cm1 for the bamboo sample are assigned to weak and strong
stretching vibrations of Mg–O in the silicate network [19–21]. This
is because of higher magnesium content in groundnut (26.17 wt%)
and bamboo leaves (5.32 wt%), which is further examined by EDAX
spectrum. The peak at 1090 cm1 is split into two separate bands
such as 1060 and 1180 cm1 in the hybrid gel structures. This is
due to the functionalizations of silanol through siloxane bridges
by methyl groups. Also, the ash except rice husk has shown the
band at 500–610 cm1 represents the appearance of Na–Al–Si
rings [22].
Hence, the formation of sodium silicate was observed for the
rice husk sample and the additional phase such as Si–O–Mg and
Si–O–Al was observed for the groundnut and bamboo leaves
respectively. In the entire IR spectrum, we observed the band at
2400 cm1, that corresponds to artefacts due to air contamination.

Development of silica by acid treatment

All the samples were subjected to sulfuric acid treatment to

precipitate silica particles and its FT-IR spectra are recorded in
Fig. 3. The vibrational bands of the Si–O ions at 810, 954 and
1032 cm1 are observed in all the samples. The bands at 470 and
810 cm1 are attributed to the ring structure of the SiO4 tetrahe-
dral and the band at 1080 cm1 is assigned to Si–O–Si stretching Fig. 4. XRD spectrum for the waste materials sintered at 900 °C for 7 h.
518 V. Vaibhav et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 515–520

groundnut shell ash which have been attributed to inorganic ele-

ments present in the ash [26,27]. The above phases are further con-
firmed by EDAX analysis.

XRD results for sodium hydroxide treated ash samples

Fig. 5 shows the XRD spectrum of NaOH treated ash samples

sintered at 900 °C for 2 h. All the samples except rice hush have
shown the presence of sodium silicate with other accompanying
phases such as aluminum and magnesium in the silicate network.
The NaOH treated rice husk (RH) explains the presence of sodium
silicate and sodium silicate hydrate peaks around 22° and 24°
respectively. The NaOH treated sugarcane (SC) and bamboo leaves
samples have shown a major phase as sodium silicate and sodium
aluminum silicate as accompanying phase. As observed from the
FT-IR results of sugarcane and bamboo leaves the presence of
sodium silicate and sodium aluminum silicate was further con-
firmed. In addition to the major sodium silicate phase, the presence
of other phases such as sodium aluminum silicate and sodium
magnesium silicate was observed in the ash derived from ground-
nut shell [28]. This was confirmed by the FT-IR spectra of NaOH
treated powder and was shown in Fig. 2.
Fig. 6. XRD spectrum of sulfuric acid treated sample.
XRD results for sulfuric acid treated samples
investigated the possibility of producing high purity silicon from
Fig. 6 shows the XRD spectra of acid leached sodium silicate
rice husk. The authors concluded that purified RHA could be a
glass produced from the waste materials such as rice husk, sugar-
potential silica source for high purity silicon production. Hence,
cane, bamboo leaves and groundnut shell. All the natural sources
we obtained pure silica with amorphous structure from the waste
except groundnut shell have shown pure silica glass without any
materials which was considered as environmental contaminants.
Na and Mg contaminants [29]. Whereas, the groundnut shell
requires further acid leaching process at higher/other acidic med-
ium to eliminate Mg–O form silica network. This insoluble salt EDAX analysis of ash sample sintered at 900 °C for 7 h
adheres to the silicon particles and is then retained during filtra-
tion. Thus, it is better to maintain a slightly acidic medium during To determine the % of element present in the ash sample EDAX
the rinsing action after leaching. Subsequently, Hunt et al. [11] analysis was carried out. Fig. 7 shows the EDAX spectra of ash

Fig. 5. XRD spectrum of sodium hydroxide treated ash sample.

 V. Vaibhav et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 515–520
(a)
(b)
Fig. 7. EDAX spectrum for the waste materials sintered at 900 °C for 7 h.
obtained from the natural sources sintered at 900 °C for 7 h. Except
groundnut ash all the other samples have shown higher % of silica
and small amounts of other trace elements such as magnesium,
potassium, calcium as impurities. The formation of magnesium
substituted silica from the acid treated groundnut sample was
due to the excessive % of magnesium content.
SEM Analysis of ash sample before and after sulfuric acid treatment
From the SEM analysis, it was found that all the ash samples
have its own shape and size arrangement. Bamboo leaves sample
sintered at 900 °C have agglomerated cluster like particles,
whereas the groundnut shell ash have shown uniform spherical
sized particles. Rice hush ashes have fiber like appearance,
whereas, the sugarcane Bagasse have agglomerated particles with
some pores on the structure (Figs. S1–S4). After acid treatment,
the particle size and shape of the particle was found to be altered
and all the samples have shown nanosized particles which confirm
the formation of silica glass and leach out of other impurities. The
formation of magnesium substituted silica from the groundnut
sample was further evidenced from the EDAX analysis, where the
% of magnesium and silica was found to be 26.17 wt% and
5.52 wt% respectively. All the other sources have shown higher %
of silica with a lower % of magnesium content in the ash powder.
Fig. S5 represents the % of silica recovered from each source. The
maximum of 78% and a minimum of only 12% were recovered from
the rice hush and groundnut shell ash. Jesionowski [30] have inves-
tigated the precipitation of silica from sodium metasilicate and sul-
furic acid emulsions. The properties of precipitated SiO2 depend
519
(c)
(d)
strongly on the conditions, such as the alkali treatment, nature of
acid used for the precipitation, pH and the mode of washing and
drying.
Conclusion
The feasibility of producing high purity silica from waste mate-
rials was studied by alkali and sulfuric acid treatment. The ash par-
ticles are subjected to sodium hydroxide treatment and showed
the presence of sodium silicate with other accompanying phases
such as Al, Na and Mg in the silica network. All the sources except
groundnut shell results in the formation of pure silica. The results
obtained from SEM have shown a reduction in size of the particles
with the diameter of 20–40 nm. After acidic extraction, the high
purity of 98% (wt%) of SiO2 was obtained with the yield of 78% from
rice husk, 71% from sugarcane bagasse and 52% from bamboo
leaves respectively. All these results suggest that the ash obtained
from different waste materials would be a promising low cost raw
material for the preparation of superfine silica. Further study is in
progress to improve the purity of silica from groundnut ash by
leaching with other organic acids such as acetic and citric acids.
Acknowledgments
Dr. S. Mohana Roopan thankful to DBT-RGYI, INDIA (No. BT/
PR6891/GBT/27/491/2012) for providing financial support to carry
out the research. Authors thank to management of VIT University,
Vellore, India for their encouragement and support.
520 V. Vaibhav et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 515–520
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.saa.2014.12.083.
References
[1] S.M. Roopan, T.V. Surendra, G. Elango, S.H.S. Kumar, Appl. Microbiol.
Biotechnol. 98 (2014) 5289–5300.
[2] G. Madhumitha, S.M. Roopan, J. Nanomater. 951858 (2013) 1–12.
[3] A. Bharathi, S.M. Roopan, A. Kajbafvala, R.D. Padmaja, M.S. Darsana, G.N.
Kumari, Chin. Chem. Lett. 25 (2014) 324–326.
[4] A. Kajbafvala, M.R. Shayegh, M. Mazloumi, S. Zanganeh, A. Lak, M.S.
Mohajerani, S.K. Sadmezhaad, J. Alloy. Compd. 469 (2009) 293–297.
[5] F. Adam, A.E. Ahmed, S.L. Min, J. Porous Mater. 15 (2008) 433–444.
[6] G.K. Angelos, Bull. Mater. Sci. 34 (2011) 299–303.
[7] S.N. Azizi, M. Yousefpour, J. Mater. Sci. 45 (2010) 5692–5697.
[8] J. Bock, G.J. Su, J. Am. Ceram. Soc. 53 (1970) 69–73.
[9] G.W. Brindley, J. Zussman, Am. Mineral. 44 (1959) 185–188.
[10] J.B. De Caillerie, M. De la Kermarec, O. Clause, J. Phys. Chem. 99 (1995)
17273–17281.
[11] L.P. Hunt, J.P. Dismukes, J.A. Amick, A. Schei, K. Larsen, J. Electrochem. Soc. 131
(1984) 1683–1686.
[12] N. Ikram, M. Akhter, J. Mater. Sci. 23 (1988) 2379–2381.
[13] T. Jesionowski, Colloids Surf. A Phys. Chem. Eng. Aspects 190 (2001) 153–165.
[14] R. Kumar, S.M. Roopan, A. Prabhakarn, V.G. Khanna, S. Chakroborty,
Spectrochim. Acta A 90 (2012) 173–176.
[15] S.M. Roopan, Rohit, G. Madhumitha, A. Rahuman, C. Kamaraj, A. Bharathi, T.V.
Surendra, Ind. Crops Prod. 43 (2013) 631–635.
[16] S.M. Roopan, A. Bharathi, A. Prabhakarn, A.A. Rahuman, K. Velayutham, G.
Rajakumar, R.D. Padmaja, M. Lekshmi, G. Madhumitha, Spectrochim. Acta A 98
(2012) 86–90.
[17] O. Jullaphan, T. Witoon, M. Chareonpanich, Mater. Lett. 63 (2009) 1303–1306.
[18] U. Kalapathy, A. Proctor, J. Shultz, Bioresour. Technol. 72 (2000) 99–106.
[19] S.G. Lee, Y.S. Jang, S.S. Park, B.S. Kang, B.Y. Moon, H.C. Park, Mater. Chem. Phys.
100 (2006) 503–506.
[20] Z. Li, J. Zhang, J. Du, B. Han, J. Wang, Colloids Surf. A Phys. Chem. Eng. Aspect
286 (2006) 117–122.
[21] T.H. Liou, Carbon 42 (2004) 785–794.
[22] W. Mozgawa, M. Sitarz, J. Mol. Struct. 614 (2002) 273–279.
[23] Y. Shinohara, N. Kohyama, Ind. Health 42 (2004) 277–285.
[24] S. Smriti, C. Ram, E. Reginald, M. Santosh, K. Verma, Int. J. Coal Geol. 87 (2011)
112–120.
[25] K. Sun, K. Gong, Ind. Eng. Chem. Res. 40 (2001) 5861–5877.
[26] H.W. VanderMarel, H. Beutelspacher, Atlas of Infrared Spectroscopy of Clay
Mineral and Their Admixtures, Elsevier, Amsterdam, 1976, pp. 20–45.
[27] C.G. Vassileva, S.V. Vassilev, Fuel Process. Technol. 87 (2006) 1095–1116.
[28] U. Vijayalakshmi, A. Balamurugan, S. Rajeswari, Trends Biomater. Artif. Organs
18 (2005) 101–110.
[29] U. Vijayalakshmi, S. Rajeswari, Metall. Mater. Trans. A 43 (2012) 4907–4919.
[30] T. Jesionowski, Powder Technol. 127 (2002) 56–65.