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Procedia Technology 24 (2016) 210 – 216

International Conference on Emerging Trends in Engineering, Science and Technology (ICETEST

- 2015)

Synthesis of Iron Oxide Nanoparticles Coated Sand by

Biological Method and Chemical Method

Raiza Rasheeda*, Meera Vb

a
PG Student, Dept. of Civil Engineering, GEC Thrissur,680009, India
b
Associate Professor, Dept. of Civil Engineering, GEC Thrissur, 680009, India

Abstract

Iron oxide nanoparticles can be prepared by physical, chemical and biological methods. Due to the practical difficulties in using
iron oxide nanoparticles for water treatment, these nanoparticles may be coated onto some supports. This paper focuses on the
preparation of iron oxide nanoparticles coated sand by biological method using polysaccharide templates and chemical method
i.e. sol-gel method. The synthesized particles were characterized using energy dispersive spectroscopy (EDS), scanning electron
microscope (SEM) and powder X-ray diffraction analysis (PXRD). From EDS analysis the highest percentage coating of iron on
the sand surface was obtained for the iron oxide nanoparticles coated sand synthesized using chitosan templates. The PXRD
analysis revealed the crystallite size of the synthesized particles as 42.8 nm. The SEM image showed the presence of almost
spherical shaped particles on the sand surface and the coating was discontinuous.

©©2016
2016The
TheAuthors. Published byby
Authors.Published Elsevier Ltd.Ltd.
Elsevier This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICETEST – 2015.
Peer-review under responsibility of the organizing committee of ICETEST – 2015
Keywords: Iron oxide nanoparticles; polysaccharide templates; sol-gel method.

1. Introduction

Iron oxide nanoparticles are gaining more attention now-a-days in environmental remediation due to their small
size, large surface area and magnetic property. Iron is one of the most widespread elements in the earth. Iron oxides

* Corresponding author. Tel.:+0 9037260526;

E-mail address:raizarasheed@gmail.com

2212-0173 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICETEST – 2015
doi:10.1016/j.protcy.2016.05.029
 Raiza Rasheed and V. Meera / Procedia Technology 24 (2016) 210 – 216 211

are chemical compounds composed of iron and oxygen. Altogether, there are sixteen known iron oxides and
oxyhydroxides. Previous studies showed that iron oxide coated sand has high efficiency for removing various
contaminants from water/wastewater [1,2,3,4,5,6]. Application of iron oxide based nanomaterial is more attractive
for removal of heavy metals contamination from the water because of their important features like small size, high
surface area, and magnetic property [7,8]. Magnetic property of iron oxide nanoparticles enables easy separation of
adsorbents from the system and could be reused for further application. Reusability of iron oxide based nanomaterial
leads to a decrease in the economic burden [9]. The facileness of resource and ease in synthesis render nanosized
ferric oxides (NFeOs) to be low-cost adsorbents for toxic metal sorption. Since elemental iron is environmentally
friendly, NFeOs can be pumped directly to contaminated sites with negligible risks of secondary contamination. The
iron oxide nanoparticles have been utilized in various promising applications, such as catalysis, electronic devices,
information storage, sensors, drug-delivery technology, biomedicine, magnetic recording devices, and
environmental remediation [10]. The intensively studied NFeOs for heavy metals removal from water/wastewater
include goethite, hematite, amorphous hydrous ferric oxides, maghemite, magnetite and nano zero valent iron.
Up to now there are several methods that can be used to synthesize iron-oxide-based nanomaterials. The
methods can be generally classified as physical, chemical and biological methods. Previous studies showed that
chemical methods are commonly used for the synthesis of iron oxide nanoparticles. The commonly employed
chemical methods include hydrothermal synthesis, thermal decomposition, co-precipitation, reverse micelles and
micro-emulsion technology, sol-gel synthesis, sonochemical reactions, hydrolysis and thermolysis of precursors,
flow injection synthesis, electrospray synthesis and colloidal chemistry method.
The major drawbacks of the chemical methods are the low dispersion in solvents, wide particle size distribution
and the uniformity of the size of the particle of these nanomaterials was rather poor [11]. These methods causes
aggregation of particles. So there is an increasing interest in the use of green resources for nanoparticle synthesis.
The distinct advantages that biological synthesis protocols have over the conventionally used physical and chemical
methods include [12]:
x clean and eco-friendly method, as toxic chemicals are not used.
x the active biological component like enzyme itself acts as a reducing and capping agent, thereby reducing the
overall cost of the synthesis process.
x small nanoparticles can be produced even during large-scale production.
x external experimental conditions like high energy and high pressure are not required, causing significant energy
saving.
For practical applications the iron oxide nanoparticles must be coated onto some supports such as sand,
bentonite, perlite etc due to agglomeration of particles, difficult separation, low hydraulic conductivity and
excessive pressure drops when applied in flow through systems.
Hence, this paper focuses on the preparation of iron oxide nanoparticles coated sand by biological method
employing polysaccharide templates and chemical methods i.e sol-gel method.

2. Materials and methods

2.1. Preparation of sand

River sand of gradation between 2.36 mm and 0.85 mm was used. The sand was soaked in 8% nitric acid solution
for 24 hours, rinsed with de-ionized water to pH 7 and dried at 1050 C for 24 hours in preparation for surface
coating.

2.2. Synthesis of iron oxide nanoparticles coated sand

Iron oxide nanoparticles coated sand was prepared by biological methods using starch and chitosan templates and
chemical method by sol-gel method. Sol-gel method is the widely used chemical method for the synthesis of
nanoparticles. The methods employed are discussed below:
212 Raiza Rasheed and V. Meera / Procedia Technology 24 (2016) 210 – 216

x Using starch templates [11]

70 g of starch was dissolved in 1000 ml of de-ionized water. FeSO4.7H2O was added to the known volume of the
template solution such that the starch: Fe ratio is 1:4. 1000g sand was added to it. The resultant solution was stirred
for 30 minutes and then treated at 800 0C and maintained at that temperature for 120 minutes, after which it was
cooled to room temperature at a rate of 10 0C/minute. The coated sand was washed several times with de-ionized
water to remove loose precipitates. It was then dried and stored for future use.
x Using chitosan templates [11]
94 g of chitosan was dissolved in 2% acetic acid (1000 ml). 280 g of FeSO 4.7H2O was added to it. 1000 g of
sand was added to it. The resultant solution was stirred for 30 minutes. The template-iron-sand mixed solution was
treated at 8000C (heating rate of 50C/ minute) and maintained at that temperature for 120 minutes, after which it was
cooled to room temperature at a rate of 10 0C/ minute. The coated sand was washed several times with de-ionized
water to remove loose precipitates. It was then dried and stored for future use.
x Sol – gel method [13]
405 g of Fe(NO3)3.9H2O was dissolved in 1000 ml of de-ionized water and then stirred for 30 minutes. At this
stage, the pH of the solution should be approximately 1.4. On the other hand, 152 g of gelatin was dissolved in 1000
ml of de-ionized water and then stirred for 30 minutes at 600C inorder to get clear solution and the pH was around
5.6. Afterwards, the gelatin solution was added slowly to the iron nitrate solution with stirring. 1000 g sand was
added to it. The resulting solution was stirred for an hour and the solution turns to gel followed by drying in hot air
oven at 900C for 6 hours. The obtained product was calcined at 600 0C in air atmosphere for an hour using muffle
furnace.

3. Characterization

The synthesized iron oxide nanoparticles coated sand were characterized using Scanning Electron Microscope
(SEM), Energy Dispersive Spectroscopy (EDS) and Powder X-ray Diffraction (PXRD). SEM image gives the
morphology and structural characteristics of the synthesized materials. EDS analysis was carried out inorder to find
the elemental composition. PXRD analysis gives the crystallite size of the synthesized particles.
SEM and EDS were done at Centre for Scanning Microscopy, National Institute of Technology, Calicut. SEM
was done using Hitachi SU6600 Variable Pressure Field Emission Scanning Electron Microscope (FESEM).
Electron gun used was Tungsten Schottky emission electron source. EDS was done using Energy Dispersive
Spectroscopy Horiba, EMAX, 137 ev. PXRD analysis was carried out at C-MET, Attani, Thrissur (Bruker Germany
D5005).

4. Results and discussions

4.1.EDS analysis

x Using starch templates

Fig.1 shows the EDS spectrum and the elemental composition is given in table 1.

Fig.1. EDS Spectrum of iron oxide nanoparticles coated sand synthesized using starch templates.
 Raiza Rasheed and V. Meera / Procedia Technology 24 (2016) 210 – 216 213

Table 1. Elemental composition

Element Weight % Atomic %
OK 52.80 67.12
Si K 43.58 31.56
Fe K 3.62 1.32
Total 100 100

x Using chitosan templates

Fig.2 shows the EDS spectrum and the elemental composition is given in table 2.

Fig.2. EDS spectrum of iron oxide nanoparticles coated sand synthesized using chitosan templates.

Table 2. Elemental composition

Element Weight % Atomic %
OK 55.06 70.68
Al K 1.51 1.15
Si K 33.57 24.55
Fe K 9.85 3.62
Total 100 100

x Sol-gel method
Fig.3 shows the EDS spectrum and table 3 gives the elemental composition.

Fig.3. EDS spectrum of iron oxide nanoparticles coated sand synthesized using sol-gel method.
214 Raiza Rasheed and V. Meera / Procedia Technology 24 (2016) 210 – 216

Table 3. Elemental composition

Element Weight % Atomic %
OK 56.33 70.90
Al K 1.03 0.77
Si K 36.35 26.06
Fe K 6.29 2.27
Total 100 100

The Y-axis in the spectrum shows the counts i.e. number of X-rays received and processed by the detector and X-
axis shows the energy level of those counts. The iron (Fe) peaks in the spectrum confirms the presence of iron in the
synthesized particles. The highest percentage coating of iron was obtained for the iron oxide nanoparticles coated
sand synthesized using chitosan templates. So the SEM image and PXRD analysis was carried out for iron oxide
nanoparticles coated sand synthesized using chitosan templates.

4.2. SEM analysis

The SEM image of iron oxide nanoparticles coated sand synthesized using chitosan templates is shown in fig.4.
Fig.4 shows that the surface is rough and almost spherical shaped particles can be seen from the image. Due to
deposition of iron oxide nanoparticles on the sand surface, the coated sand has microspores and its specific surface
area may be high.

Fig.4. SEM image

4.3. PXRD analysis

The PXRD analysis was carried out for the iron oxide nanoparticles coated sand synthesized using chitosan
templates. The X-ray diffraction spectrum is given in fig.5.
The crystallite size can be calculated using Debye-Scherrer equation:
D = 0‫ڄ‬9λ /(β cos θ)
Where, D is the particle size,
λ is the wavelength of the X-ray used,
β is the full width at half maximum
θ is the half diffraction angle of 2θ
2θ is the mid-point value of the two extremes of the peak and β is the half of the distance between the two
extremes of the peak. The values of λ ,β and 2θ were obtained from the spectrum as 0.1541 nm, 0.204 0 and 40.4490
respectively. The crystallite size was calculated as 42.8 nm.
 Raiza Rasheed and V. Meera / Procedia Technology 24 (2016) 210 – 216 215

Fig.5. X-ray Diffraction Spectrum

5. Conclusions

Iron oxide nanoparticles coated sand was prepared by chemical method and biological methods. The results of
the EDS analysis shows that the iron content on the sand surface varies with the method of synthesis. The highest
percentage coating of iron was obtained for the iron oxide nanoparticles coated sand synthesized by biological
method i.e. using chitosan templates. The PXRD analysis gave the crystallite size of the particles synthesized as
42.8 nm. The SEM image revealed almost spherical shaped particles and the coating was discontinuous. The iron
oxide nanoparticles coated sand has high potential in removing various contaminants especially heavy metals from
water/wastewater.

Acknowledgement

The author wishes to thank Centre for Nanomaterials, Govt. Engineering College, Thrissur, under CERD for
rendering the financial support and its co-ordinator Dr. Manjith Kumar. B for his whole- hearted co-operation in this
endeavour.

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