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Materials Today: Proceedings 4 (2017) 12321–12327 www.materialstoday.com/proceedings

ICNANO 2016

Synthesis and Characterization of Activated Carbon Coated

Alumina as Nano Adsorbent
K.R.Sree Harshaa, Murthy Mb, L.Udayasimhaa, Dharmaprakasha, Dinesh Rangappab*
a
BMS College of Engineering Bangalore,
b
Dept. Of Nanotechnology VTU CPGSB Muddenahalli*

Abstract

High surface area of Activated carbon and Nano alumina have attracted researchers in Environmental remediation application as
nano adsorbents for removal of heavy metal ions from the industrial waste water. Activated carbon is coated on Alumina by
hydrothermal method at relatively low temperature of 1200C. In our present work, we have synthesised nano alumina coated
activated Carbon as adsorbent for heavy metal removal application. Activated carbon coated Alumina is characterised by X-ray
Diffractometer (XRD), Scanning Electron microscope (SEM), Energy Dispersive Spectroscopy (EDX), Fourier Transform
Infrared Spectroscopy (FTIR). The obtained XRD results confirmed the formation of corundum phase alumina with well
crystallinity with an average particle size of about 50 nm as calculated by Debey Scherer’s equation. The SEM image confirmed
the carbon particles coated with alumina nanoparticles, FTIR shows the presence of Al-O stretching vibrations below 600 cm-1,
EDX confirms the presence of all Al, O and Carbon Elements Showing purity of the sample, activated carbon coated Nano
Alumina was used as adsorbent for removal of heavy metals. Batch mode adsorption was carried out by varying the contact time
of adsorbent. The results showed excellent removal of Ni(II) and Cu(II) ions.
© 2017 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON NANOTECHNOLOGY (ICNANO-
2016).

Keywords: Nanoparticles, Heavy metals removal, pH, contact time, rotation speed, adsorption isotherm

1. Introduction

In the last few decades, heavy metals like Ni(II), Zn(II),Cr(VI),Cu(II) etc,.are producing in larger amount by
electroplating, galvanizing, pigments, mining industries and textile industry. These industrial and textile effluents are
responsible for the contamination of water bodies [1-6]. Particularly, presence of Cu(II) in higher concentration in

*
Email:sreeharsharamaswami@gmail.com, dineshrangappa@gmail.com

2214-7853© 2017 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON NANOTECHNOLOGY (ICNANO-2016).
12322 K.R. Sree harsha et al./ Materials Today: Proceedings 4 (2017) 12321–12327

water bodies are causing allergies, alopecia, anaemia, anorexia, anxiety, arthritis (osteon & rheumatoid), autism,
cancer etc presence of NI+ ions in higher concentration can cause anorexia, kidney dysfunction, apathy, disruption of
hormone and lipid metabolism [7]. These metal bearing effluents demand for efficient treatment methodologies to
reduce the metal ion concentration permissible levels before its discharge. Nanotechnology offers the potential route
for the treatment of surface water, groundwater and wastewater contaminated by toxic metal ions, organic and
inorganic solutes and micro-organisms. [8-12].
There are many methods available for the removal of heavy metal ions from waste water by means of adsorption
[13-14], photo-degradation [15–17], ion exchange [18], oxidation [19], etc. Among these methodologies, adsorption
is simple, low cost and effective method [20]. When the particle scale down to nano size, there is drastic change in
chemical, physical, mechanical and optical properties. The surface to volume ratio increases, hence the adsorption
capacity of nano material also increases [13]. This makes the nanomaterial suitable for heavy metal adsorption
process.
Recently, carbon based materials such as Single-Walled Carbon Nanotubes(SWCNTs), Multi-Walled Carbon
Nanotubes (MWCNT), Gold, Silver, Iron oxide, Titanium oxide, and alumina-based nanoparticles, etc. were used as
a Nano adsorbent [13,20]. The functionalized Carbon Nanotubes (CNTs) with activated neem bark was used as
adsorbent for the adsorption of a chromium (6+) [4, 20]. Carbon nanotube coated magnesium and alumina-coated
carbon nanotubes were employed for the removal of Pb(II) [22]. The nickel oxide nanomaterials were used for the
removal of Zn(II), Co(II) and Cd(II) [23], Cu(II) and Zn(II) from aqueous solution [25]. Zinc oxide nanoparticles
(ZnO) for the adsorption of Zn(II), Cd(II) and Hg(II) [26], clay minerals were used in surficial sediment samples for
the removal of Cu(II) and Zn(II) [27]. Activated Carbon coated Aluminum composite showed excellent adsorption
of phenol and potassium dichromate removal (28). These report shows the reduction of carbon coated alumina
particle size will in turn increase the adsorption capacity.
In the present study, an effort is made to study the behaviour of carbon coated aluminum nanoparticles in removal
of Cu and Ni heavy metal ions from industrial waste water. A comparative study is also been made with the Nano
Alumina which is prepared by simple combustion method with respect to the Activated carbon coated Alumina
synthesised by low temperature Hydrothermal method. Removing Cu and Ni heavy metals from Waste water was
performed by batch adsorption experiment with varying the contact time of Nano particles.

2. Experimental details

2.1. Materials

The analytical grade Aluminum Nitrate, Urea, Glycine Activated carbon are all obtained from vasa chemicals. Ni
and Cu ion containing waste water was collected from electroplating industry situated near Bangalore district and
diluted it with distilled water to get 300ppm concentration.

2.2. Synthesis of Al2O3 nanoparticles

A solution containing 10m moles of Al2(NO3)2 was taken in a 10ml distilled water. 5m Moles of urea and 06g of
glycine was added to this solution. This mixture was kept for heating at 4000C until self-ignition take place. The
resultant product was collected and grinded using Mortar for 30 min.

2.3. Synthesis of Activated carbon coated Al2O3 nanoparticles

Activated carbon coated Nano Al2O3 (C-Al2O3) was produced by simple and low temperature Hydrothermal
method. In a typical synthesis 1g of Alumina and 0.2g (20 wt%) of commercial activated carbon were added in to 50
ml of distilled water then sonicated for 20 min. The solution was placed in a stainless steel autoclave for 3 h at
1300C. After the reaction the sample were collected by repeated washing with Distilled water and product was
dried in hot air oven.
 K.R. Sree harsha et al./ Materials Today: Proceedings 4 (2017) 12321–12327 12323

2.4. Sample characterization

The sample were characterized using following method. Powder X-ray diffraction (XRD) patterns were collected
from 20 to 700 in 2-theta with 0.020steps/s using a Rigaku Ultima -IV X-ray diffractometer with Cu Kα as radiation
source (l ¼ 0.15406 nm) at 40 kV and 30 mA to know the crystal structure and average crystallite size of the
prepared material. The surface morphology was analysed by using scanning electron microscopy (SEM, Hitachi).
The elemental composition and sample purity was studied by Energy dispersive spectroscopy (EDX, Thermofisher).
The surface functional groups on the sample were identified using Fourier transform infrared spectroscopy (FTIR,
Perkin Elmer). The thermal properties were analysed by Thermo gravimetric and differential thermal analyser (STA
8000, Perkin Elmer).

2.5. Batch mode Adsorption Studies

Adsorption studies were carried out by conducting batch experiments using Ni (II) and Cu(II) solution, which
was diluted to 300 ppm by adding appropriate amount of distilled water. A 20 mg of synthesized Al2O3 and C-Al2O3
adsorbent were added in to 50 ml of 300 ppm Ni and Cu stock solution and mixed well by shaking. After every 30
min the samples were collected through syringe filtration and perform the adsorption studies by measuring
concentration by UV visible spectroscopy. Adsorption capacity is calculated based on the equation as following
Adsorption Capacity(%)= (initial concentration – final concentration *100)/Initial concentration.

3. Results and Discussions

3.1. Characterisation of Al2O3 and C-Al2O3

XRD pattern measured for the Al2O3 and C- Al2O3 is shown in figure 1. The diffraction peaks of both Al2O3 and C-Al2O3
appeared at 25.530, 35.090, 37.710, 43.30, 52.500, 57.60, 61.160, 66.460, and 68.130 which can be indexed to (012),
(101), (110), (113), (024), (116),(302),(204) and (300) planes of the Corundum phase with good crystallinity. The
sharp peaks indicate good crystallinity of the prepared Al2O3. The peaks are well matched with D.B Card NO:
90058085. The average crystallite size was calculated by Debye Scherer’s equation which was found to be 50 nm
and The inter layer spacing 2.56 nm. The intensity of the C-Al2O3 compared to Al2O3 nanoparticles decreased due
to reduction in the particle size during hydrothermal reaction and deposition of activated carbon.

Figure 1. XRD pattern of a) Al2O3 synthesised by solution combustion method calcinated at 7000C. b) Al2O3 coated activated carbon (20 wt.%)
by Hydrothermal method.

The morphology and size of the samples were studied using SEM. The result shown in the figure 2 reveals that the
spherical shaped Al2O3 nanoparticles coated on the surface of activated carbon. The SEM images recorded at
different magnification shows that Al2O3 nanoparticles are uniformly coated in the surface of the activated carbon.
This improves the active sites on the surface of the activated carbon
12324 K.R. Sree harsha et al./ Materials Today: Proceedings 4 (2017) 12321–12327

Figure 2. SEM images of Al2O3 coated Activated Carbon (20 wt.%) by Hydrothermal method at 1300C for 3h.

The figure 3 shows the elemental analysis results of the sample measured by EDAX. The Approximate elemental
weight of the C- Al2O3 samples was found to be 7.12 wt%, Oxygen 11.94% and Aluminium 65.42 wt% as shown in
Table1. From this Figure it is confirmed that the sample is pure and not having any other impurity except the peak
for Gold which is coated by sputtering, during preparation of sample for SEM analysis.

Figure 3. Activated Carbon (20 wt.%) coated Al2O3 by Hydrothermal method.

C-K O-K Al-K Au-M

Base(61)_pt1 7.12 11.94 65.42 15.52

Table 1: weight % distribution of . Activated Carbon (20 wt.%) coated Al2O3 by Hydrothermal method

FTIR analysis of Al2O3 and C-Al2O3 nanoparticles is shown in Fig 4. The strong absorption band at 500-600 cm-1 is
due to Al-O stretching vibration (21). The Absorption peaks at 1400-1600 cm-1 is due to single and double bond
vibrations of C-O and C=O which may due to bonding of coated Activated carbon on Alumina. This result indicates
Al2O3 not only deposited on the surface of the activated carbon but also there is increase in the active site. This will
influence the absorption behaviour of the materials.
 K.R. Sree harsha et al./ Materials Today: Proceedings 4 (2017) 12321–12327 12325

Figure 4. FTIR analysis of Nano Al2O3 synthesised by solution combustion method calcinated at 7000c and Activated Carbon (20 wt.%) coated
Al2O3 by Hydrothermal method.

3.2. Batch Adsorption studies

The absorption properties of Al2O3 and C-Al2O3 samples were studied using industrial waste solution containing
Ni2+ and Cu2+ ions with 300ppm concentration under different contact time. The efficiency of the sample were
presented as below

3.2.1. Ni Adsorption study

The figure 5. Shows the plot of removal percentage against contact time. It is observed that up to 60mins initial time
adsorption behaviour of both the sample were similar i.e., only about 20% Ni2+ ion was removed from the solution.
However, after 60 min the removal of Ni ions increased for the C-Al2O3 sample when compared to pristine Al2O3.
The C-Al2O3 sample shows about 80% removal of Ni2+ ion after 180 min and became constant after reaching 82%
whereas pristine Al2O3 sample shows only 20-30% removal even after 180mins. This results shows that activated
carbon Al2O3 sample shows better adsorption capacity due to synergetic effect at activated carbon and Al2O3
compound to only Al2O3 nanoparticles. Further adsorption capacity also depends on the contact time of the solute
with adsorbent. Adsorption rapidly increase after 60min for the same sample.

Figure 5. The effect of contact time on the removal of (Ni2+) by both Al2O3 and C-Al2O3
12326 K.R. Sree harsha et al./ Materials Today: Proceedings 4 (2017) 12321–12327

3.2.2. Cu Adsorption study

The removal of Cu2+ ions by C- Al2O3 and Al2O3 sample were presented in figure 6. The plot shows that C- Al2O3.
There is about 60% removal of Cu2+ ions in 150min for C- Al2O3 when compared to Al2O3 of about 10%. The time
dependent adsorption behaviour is not dominant in case of Cu2+ removal as there is a gradual increase in the
adsorption of Cu2+ from the beginning unlike in the Ni2+ removal where adsorption rapidly increased after 60mins.
Even in this case also C- Al2O3 sample shows better adsorption behaviour compared to pristine Al2O3

Figure 6. The effect of contact time on the removal of (Cu2+) by both Al2O3 and C-Al2O3

4. Conclusion

An alumina-coated Activated carbon was synthesized using combustion and hydrothermal method. The C-Al2O3
sample were found to be an effective adsorbent for the removal of Ni and Cu ions from aqueous solution. With an
increase contact time removal efficiency was increased. This study shows that the C-Al2O3 composite can be used in
an industrial wastewater treatment for removal of Ni and Cu ions.

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