Preparation and characterization of silica

nanoparticles from rice straw ash and its application

as fertilizer
Emas Agus Prastyo Wibowo1*, Khoironni Devi Maulana1, Adi Wahyu
Arzanto1, Ika Sri Hardyanti1, Dyan Septyaningsih. H. HP1, Alberto Krishna
Winning Kusuma1
1
Department of Chemistry, Faculty of Mathematic and Natural Science,
Semarang State University
Abstract: This study was carried out to investigate the characteristics of silica
extracted from rice straw obtained from rice farming region of Pekalongan. The
silica was obtained using a sol-gel method, which involves extraction of silica
using alkalis solution and gelation of the silica using acid solution. It was found
that the highest yield was obtained from the extraction using 5% KOH solution
with the extraction time of 60 minutes, and gelation pH of 7.0. The preparation
was successfully produced by heating rice straw at 10 °C/min and holding at
500°C to facilitate decomposition and gasification of the organics while avoiding
auto-ignition. The SiO2 chemical composition was confirmed by EDS and FTIR
and the amorphous nature by XRD. SEM analysis indicates the existence of
various particle sizes distributed irregularly, which reflects that homogeneous
sample has not been achieved in this study. Nanosilica powders with a 45,3869
nm average pore size and have specific surface (94,761 m2/g). Silica nanoparticle
fertilizer applied to various plants such as peanuts, tomato and soybean.
Berdasarkan penelitian dapat dilihat bahwa tinggi batang dan jumlah daun
tanaman dengan pupuk nanosilika lebih memperlihatkan pertumbuhan yang
sangat cepat.

Keyword: Rice straw; Silica nanoparticles, fertilizer

Introduction
Nutrient is needed by plants and nitrogen, phosphorus and potassium
(NPK) are included in the soil nutrient. If the nutrient deficiency, especially NPK,
occurred to the plant, then the quality and quantity of peanuts decreased. NPK in
the soil were limited and they would decrease gradually, because of plant growth,
harvesting, washing, vaporization and erosion. Fertilization was needed to fulfill
the deficiency of NPK. The suitable fertilizer to fulfill those nutrients was
Phonska that contain 15% N, 15% P and 15% K (Sitorus, 2004).
Silica was included nutrient that never added to soil. Because the
information about the advantages of silica for rice had not lacked enough and
precursors to made silica fertilizer were expensive. Japan had applied this silica
fertilizer with dosage 1.5-3.0 tons/ha field. Those dosages were still expensive to
apply in Indonesia. So, it was necessary to look for an alternative source of silica
that easy to get and cheap.
 Nanotechnology has attracted considerable scientific interest due to the
new potential uses of particles in 1-100 nanometer scale (Stone et al. 2010). At
the nanoscale, physical, chemical, and biological properties differ from the
properties of individual atoms and molecules of bulk matter. Therefore, it
provides opportunity to develop new classes of advanced materials which meet
the demands from high-tech applications (Kharisov et al. 2010).A quickly
growing range of applications of nanomaterials in many fields has been observed
in recent years (Kharisov et al. 2010). Among them, nanosilica is a widely used
nanomaterial with applications in polymer, adhesives, fiber optic strands, sealants,
inks, paints, coatings, cosmetics, food additive and in cement-based building
materials (Hessien et al., 2009). Nanosilica is one of the most common nanofillers
used in the preparation of nanocomposites (Dorigato et al. 2012). Low valued
silica bearing natural resources are converted into value added marketable types of
silica by various processes (Zaky et al. 2008). The resulting silica products are
generally classified based on their properties and include nanosilica, fumed silica,
precipitated silica, colloidal silica and silica gels (Jal et al. 2004). The applications
of nanosilica ultimately depend on the surface chemistry, molecular structure,
morphology and porosities (Sun et al. 2004). Therefore, the modification of silica
nanoparticles to enhance the surface chemical and physical properties is the key
for the successful applications of the material (Guo et al. 2008).
The best solution could be done to produce silica nanoparticle was the
reuse of agricultural waste i.e. rice straw. Rice straw is torched after the rice
product is collected, which is due to the increase in soil nutrition elements for the
next year of cultivation, as well as removing the necessity for straw storage. In the
developed countries however, the concept of "waste material" is no longer valid,
as all waste materials are considered as sources for the production of new
products and increasing of added value. Studies have proven that rice straw, the
waste material of agricultural processes, may be a potential candidate (Hessien et
al., 2001). But a major problem is the pile up of rice straw ash (RSA) which is
rich in silica (Hessien et al., 2009; Agbagla et al., 2001; Husnain, 2011). The
content of silica collected in rice straw is much greater than other plants as the
organic constitutes of rice straw as follows: Cellulose: 32-47%, Hemi
cellulose:1927%, Lignin: 5-24%, Ash: 13-20 % (Zaky et al., 2008). Rice straw
ash has around 60% of silica (Santos et al., 2010) which, of course, is reported to
be different in different climatic conditions, depending On the type of soil, the
season of rice cultivation, weather conditions and geography.
The advantages of silica source from agricultural waste than mined source
silica were (1) value added to agricultural waste, (2) its structure were amorph,
reactive and easy to transformed to cristobalite, so it was suitable to used as
starting material in silica production and (3) easy to separated from impurities;
from the separation we got silica with high purity. Rice straw also could produce
activated carbon with specific surface area 1517 m2/g and it had the good ability
to adsorp phenol, heavy metals and ammonia-nitrogen (Kim and Choi, 1998,
Karyasa, 2014).
To improve the availability of silica in soil, silica absorption by plants and
its function to paddy, we had attempted size diminution of silica molecule from
rice straw until it could be categorized as nanoparticle. The use of nanoparticle
silica were expected to have significant advantages than a regular silica. This
research could give information about nanotechnology application especially
silica nanoparticle in Indonesian agriculture.
2. Experimental methods
2.1. Materials
Rice straw from Pekalongan City were used as silica source. Potassium
hydroxide, hydrochloric acid, sulfuric acid, ammonium hydroxide and aquadest
were used in this research. Hot plate, stirer, burner, laboratory glassware, oven,
XRD, FTIR, SAA, TGA, and SEM-EDX were instruments that we were used.
2.2 Rice Straw Preparation
Rice straw was cleaned from impurities and dried under the sunlight. After
dried, rice straw were heated at 700 oC for 4 hours until the ash formed. Rice
straw ash crushed and sifted 200 mesh (Agung et al., 2013).
2.3 Silica Extraction from rice straw ash
About 20 gr of rice straw ash were dissolved in 160 ml potassium
hydroxide 3 M; 3.5 M and 4 M. The solution were covered then be heated; stired
at 85 oC for 3 h. Solution were filtered. Residue were washed with 40 ml
aquadest. After it was cold at room temperature, the solution were added
hydrochloric acid 1 M slowly while it were stirred; til neutral. The result were
kept at room temperature for 3.5 h. Solution were filtered and got residu. Residu
were dried (Kalapathy et al., 2000).
Pure silica refluxed using hydrochloric acid 6 M for 4 h then washed until
neutral. The solution were disolved in sodium hydroxide 2.5 N then stired for 6 h.
Sulfuric acid was added until pH 8. Residue were washed until neutral. The result
were dried (Rafiee et al., 2012).
2.4. Characterization
To determine the structure, X-ray diffraction (XRD) experiments were
performed using Phillips PW1800 diffractometer. Phillips PW1480 apparatus was
also used to determine the chemical composition of RSA and purity of silica
synthesized through Energy-dispersive X-ray spectroscopy (EDS). In order to
study the morphology of silica with Scanning electron microscopy (SEM). To
study stability thermal of silica use a thermogravimetric analyzer (TGA-50,
Shimadzu, Japan), respectively. Samples were heated at a ramping rate of 10
°C/min from 30 to 600 °C in air flowing at a 30 mL/min rate. Finally, BET test
was performed to determine the specific surface area.
3. Result and Discussion
3. Characterization with FTIR

Figure 1. Silica FTIR spectrum were got from rice straw

Silica were got from rice straw with extraction, were analized with FTIR
and figure 1 had shown the spectrum. Main peak at wave number 3448.72 cm-1
were showed the typical for stretching vibration for –OH (Hydroxyl group).
Therefore, silica were used as sample, had hydroxyl group. It showed Si-OH bond
or silanol (Lin et al., 200; Lai, 2013; Mourhly et al., 2015), although that vibration
were not only silanol bond but also –OH from water which could not be ignored
(Daifullah et al., 2003). Second peak at 1103.28 cm-1 showed silica group. It
showed siloxane group Si-O-Si (Daifullah et al., 2003, Adam et al., 2006;
Nandiyanto et al., 2016; Lu and Hsieh, 2012; Rafiee et al., 2012). Siloxane group
were made sure with peak at 470.63 cm-1 (Lin et al., 2001; Lu and Hsieh, 2012)
and deformation of Si-O bond for SiO4 (Liou, T.H, 2004; Liu et al., 2011;
Rahman et al., 2009).
Other peak with high intensity was shown at 1635.64 cm-1. It showed
carbonyl vibrational stretch from hemicellulose. It might be disolved when
extractrion process and adsorbed by silica also H-O-H bond. Other weak peak
were shown at 972.12 cm-1, that showed bond between Si-O and metal. This IR
data interpetation were consistent with functional analysis by Kamath and Proctor
(1998). The shoulder appeared at 3750 cm indicating the presence of hydrogen
bonds that resulted from interaction between the silanol groups (Si-OH) located at
the surface of the nanosilica material (Yang and Wang, 2006).

Characterization with XRD (X-Ray Diffraction)

Figure 2. Silica from rice Figure 3. Nanosilica standard straw
straw (Prematne et al., 2013)
Silica crystal structure analysis were done by using X-ray difraction
method. Detected phase in next chromatogram were identified by ploting method
using Origin software. Figure 3 showed the spectrum. The resulting pattern
showed amorphous silica, with additional phase at 2θ = 31.46 and 50.16. There
was no phase that appeared at 2θ = 22. Based on the table, main peak from the
cristobalite difractogram and quartz polymorphy appeared as companion phase
and polymorph tridimit did not appear. This result was similar with previous
research (Karsaya, 2014). Standard nanosilica in Figure (2θ) 1(d) showed strong
board peaks at 22.14 which is characteristic of amorphous silica (Singh et al.
2008; Kalapathy et al. 2000). Crystal size of silica nanoparticle based the equation
was 45,3869 nm.

3.3. Morphology and Chemical Components

Figure 4. Silica morphology Figure 5. Silica morphology

magnifications 10000 x magnifications 20000 x
Silica surface structure characteristic was shown in figure 4 and figure 5. Figure 4
showed unarranged surface and The structural characteristics of the silica surface
studied addressed by the SEM results in Figure 4 for magnification of 10000x and
Figure 5 for magnification 20000x. From Figure 4 it was clear that the sample
surface is uneven and consists of clumps (clusters), which indicates the grain size
is quite diverse with an uneven distribution on the surface. The separation
between the clumps were also seen quite clearly, namely in the form of micro-
cracking that occur between clusters. Analyses with greater magnification (Figure
5) shows that the cluster is actually made up of particles with a size relatively
similar to the relatively even distribution as well, but was interrupted by
microcracking fairly wide and deep.
 Fig 6. EDS spectrum and chemical components
The chemical composition of silica was confirmed by EDS (Fig. 6) that showed Si
and O at a calculated 1:2 atomic ratio. The absence of other elements, such as C,
K, Na,Cl , reported in rice straw (Wu et al., 2009), also confirmed that extensive
washing of the ground rice straw powders with water before heating was effective
in removing these earth metals. Metal impurities have also been reported to be
carried away with the volatiles during thermal decomposition of rice straw (Liou,
2004). Strategic pausing at these critical temperatures and lengthening the heating
process may have enhanced this efficacy.
3.4. Characterization with TGA

Fig.7. Thermal decomposition of silica from rice straw

The thermal characteristics of rice straw were studied first to determine the
heating process to generate ash without affecting the amorphous state of silica
(Fig. 1a). Ground (to pass through 20 mesh) and water-washed (to get rid of dirt
and water soluble substances) rice straw powders were heated in air at 10 °C/min
to 500 °C. Three major thermal transitions were observed in DSC and TGA
thermograms: 6.0% moisture loss at up to 100 °C, two significant oxidative
decomposition exotherms between 260 and 500 °C, and the completion of thermal
decomposition in the 500°C region. The exothermic peak at 200°C coincided with
the end of a sharp 5,893% mass loss from 50 to 200°C while the second
exothermic peak at 500 °C happened in the latter part of a more gradual 2,607%
 mass loss between 200 to 500 °C. The residues from TGA analyses appeared gray
in color, indicating the presence of carbon from incomplete oxidative
decomposition of the organics and possibly over-heating. This observation
suggests heating in stages according to these thermal transitions may be
beneficial.

3.5. Surface area and porosity

The Brunauer–Emmett–Teller (BET) surface area of silica powders is
509.5 m2/g (Table 1). These specific surfaces are much lower than the 326.9 m2/g
for the commercial silica.
Table 1
Surface area and pore characteristics of as-prepared silica powders by BET from
nitrogen adsorption isotherm, the data of commercial silica is also provided for
comparison
Sample BET surface area (m2/g)
Silica from rice straw 94,761
Commercial silica 326,9

3.6. Application nanosilica to grow the variety of plant

Based on the results of research influence nanoslilia use of fertilizers, compost, fertilizers
ZA, and without fertilizer to the growth of peanut plants (Arachis hypogaea L.), soybean,
and tomatoes which data is retrieved plant height and number of leaves for 14 days. This
research was conducted with watering every day for 14 days. In general, with the addition
of fertilizer, the plants will be faster growing and more fertile than plants that are not
fertilized at all. Provision of fertilizer makes plants grow faster

Table 1 Data of observation various types of fertilizers on crop growth peanuts

Fertilizer Fertilizer Fertilizer Nothing

Days SiO2 ZA Compost Fertilizer
Height Leaves Height Leaves Height Leaves Height Leaves
(cm) (cm) (cm) (cm)
1 - - - - - - - -
4 3,8 - 3,2 - 0,7 - - -
7 8,5 8 8 8 4,2 - 2 -
11 17,5 12 12 12 16,3 12 13,5 8
14 23 16 16 - 21 16 19 16
 Table 2. Data observations of various types of fertilizer on plant growth of tomatoes
Fertilizer Fertilizer Nothing
Fertilizer ZA Compost Fertilizer
Days SiO2
Height Leaves Height Leaves Height Leaves Height Leaves
(cm) (cm) (cm) (cm)
1 - - - - - - - -
4 - - - - - - - -
7 4 2 3,75 2 5 2 3 1
11 4,5 3 5 2 5 3 3 2
14 5,3 5 5 2 5,3 3 5 2

Tabel 3. Data pengamatan berbagai jenis pupuk terhadap pertumbuhan tanaman kedelai
Hari ke Fertilizer Fertilizer Nothing
Fertilizer ZA Compost Fertilizer
SiO2
Height Leaves Height Leaves Height Leaves Height Leaves
(cm) (cm) (cm) (cm))
1 - - - - - - - -
4 7,0 2 4,0 2 5,5 2 3,5 2
7 16,4 2 14,1 2 13,6 2 11,5 2
11 20,0 4 18,0 2 19,5 5 18,1 2
14 22,9 5 19,1 2 21,0 5 19,0 2

According to Table 1.2, and 3 can be seen that the plant height and number
of leaves of plants with fertilizers nanosilika more show very rapid growth. This is
in accordance with the opinion of Arryanto (2012) which states that the use of
manure fertilizer nano has advantages compared to regular size because it is more
reactive which can directly reach the target or targets because the size is very
smooth and is only required in smaller amounts. Needs fewer very helpful in the
application use of silica in the field while doing cultivation. Some studies explain
that the influence monosilikat acid on soil properties focused in its interaction
with the elements of phosphate (P). According Sudibyo (2008) award Andisol Si
on the ground can significantly increase the availability of soil P dama. The
addition of Si in the soil will go through two processes. The first process is the
increase of acid concentration monosilikat on the ground which will result in the
conversion of P does not dissolve into the P available to plants. Phosphorus is not
available for plants to stop on the side of the pin causes the P pinned becomes
available to plants. This is because 𝑆𝑖𝑂44− has electronegativity take more than 𝑃𝑂43− so
as 𝑆𝑖𝑂44− iO (4-) can replace 𝑃𝑂43− . The second process is Si can bind P So leaching P
reduced by about 40-90%. The equation is as follows (Matichenkov and Calvert, 2002):
CaHPO4 + Si(OH)4 CaSiO3 +H2O +H3PO4
2 Al(H2PO4)3 +2Si (OH)4 +5H+ Al2Si2O5 + 5H3PO4 + 5H2O
2FePO4 + Si (OH)4 +2H+ Fe2SiO4 +2H3PO4
 Silva (1981) suggests that the mechanism of land by Si in improving plant growth
is by increasing the solubility of P from P terfikasai, lowering the binder P by
components of the soil such as Al and Fe, improve soil CEC and lower concentrations of
Al, Fe, and Mn in the soil. The use of nano-sized Si will lead to uniformity in the spread
of Si into the soil and plant tissue is more secure because of the very small size. Besides,
with the very small size of the rice plant's ability to absorb Si through the roots or the
leaves will get bigger, so it will be more of Si is absorbed. This is in accordance with the
opinion of Ranjbar and Shams (2009) which states that the nano fertilizer is more easily
absorbed by plants and more efficient than conventional chemical fertilizers.

Conclusion
Pure amorphous silica was successfully extracted through base dissolution-acid
precipitation of rice straw ash, EDS analysis confirmed that the as derived product
contained Si and O. The FTIR of as-derived silica matched that of pure silica
available commercially. Furthermore, the amorphous nature of the silica was
affirmed by XRD. These freeze-dried amorphous silica powders with an average
pore size of 45,3869 nm.

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