FIRST PART

PROPOSSEMENT OF THE PROBLEM

In chemistry, nanotubes are called tubular structures (cylindrical) with a
diameter of nanometer size. There exists nanotubes of many materials, such
as silicon or boron nitride, but generally, the term applies to carbon
nanotubes. The nanotubes have unusual properties, which are valuable for
nanotechnology, electronics, optics and other fields of materials science and
technology.
Carbon nanotubes (NTC) are an allotrope of carbon, such as diamond,
graphite or fullerenes. Its structure can be considered from a graphite sheet
rolled on itself. Depending on the degree of curl, and how the original sheet
is formed, the result can lead to nanotubes of different diameters and
internal geometry. These are formed as if the ends of a sheet were united at
their ends forming the said tube, they are called single wall or monolayer
nanotubes. There are also nanotubes whose structure resembles a series of
concentric tubes, one inside the other, logically increasing diameters from
the center to the periphery. These are the multilayer nanotubes. There are
known derivatives in which the tube is closed by half fullerene sphere, and
others that are not closed
They are being actively studied, for their fundamental interest for chemistry
and for their technological applications. It is, for example, the first material
known to mankind theoretically capable of sustaining its own weight
suspended indefinitely on our planet.
This work is done in order to solve a problem, which is to determinate the
use of carbon nanotube for water treatment.

OBJECTIVES
General Objective
The capability of carbon nanotubes (CNTs) to adsorb lead (Pb) in aqueous
solution.
Specific Objectives
1.
2.
3.
4.

Determinate
Determinate
Determinate
Determinate

the
the
the
the

effects of pH on the uptake of lead.

effect of agitation speed on the uptake of lead.
effects of CNTs dosage on the uptake of lead.
effects of contact time on the uptake of lead.

VARIABLE
1.
2.
3.
4.
5.
6.

pH
Agitation speed
CNTs dosage
Contact time
Temperature
Wavelenghts for lead

THEORICAL FRAMEWORK
Carbon nanotubes are molecular-scale tubes of graphitic carbon with
outstanding properties. They are among the stiffest and strongest fibres
known, and have remarkable electronic properties and many other unique
characteristics. For these reasons they have attracted huge academic and
industrial interest, with thousands of papers on nanotubes being published
every year. Commercial applications have been rather slow to develop,
however, primarily because of the high production costs of the best quality
nanotubes
1. History
The current huge interest in carbon nanotubes is a direct consequence of
the synthesis of buckminsterfullerene, C 60, and other fullerenes, in 1985. The
discovery that carbon could form stable, ordered structures other than
graphite and diamond stimulated researchers worldwide to search for other
new forms of carbon. The search was given new impetus when it was shown
in 1990 that C60 could be produced in a simple arc-evaporation apparatus
readily available in all laboratories. It was using such an evaporator that the
Japanese scientist Sumio Iijima discovered fullerene-related carbon
nanotubes in 1991. The tubes contained at least two layers, often many
more, and ranged in outer diameter from about 3 nm to 30 nm. They were
invariably closed at both ends. A transmission electron micrograph of some
multiwalled nanotubes is shown in the figure 1. In 1993, a new class of
carbon nanotube was discovered, with just a single layer. These singlewalled nanotubes are generally narrower than the multiwalled tubes, with
diameters typically in the range 1-2 nm, and tend to be curved rather than
straight. The image on the right shows some typical single-walled tubes. It
was soon established that these new fibres had a range of exceptional
properties, and this sparked off an explosion of research into carbon
nanotubes. It is important to note, however, that nanoscale tubes of carbon,
produced catalytically, had been known for many years before Iijimas

discovery. The main reason why these early tubes did not excite wide
interest is that they were structurally rather imperfect, so did not have
particularly interesting properties. Recent research has focused on
improving the quality of catalytically-produced nanotubes.

Figure 1

2. Structure
The bonding in carbon nanotubes is sp, with each atom joined to three
neighbours, as in graphite. The tubes can therefore be considered as rolledup graphene sheets (graphene is an individual graphite layer). There are
three distinct ways in which a graphene sheet can be rolled into a tube, as
shown in figure 2.

Figure 2

The first two of these, known as armchair (top) and zig-zag (middle)
have a high degree of symmetry. The terms "armchair" and "zig-zag" refer
to the arrangement of hexagons around the circumference. The third class
of tube, which in practice is the most common, is known as chiral, meaning
that it can exist in two mirror-related forms. An example of a chiral nanotube
is shown at the bottom.
The structure of a nanotube can be specified by a vector, (n,m), which
defines how the graphene sheet is rolled up. This can be understood with
reference to figure 3. To produce a nanotube with the indices (6,3), say, the
sheet is rolled up so that the atom labelled (0,0) is superimposed on the one
labelled (6,3). It can be seen from the figure that m = 0 for all zig-zag tubes,
while n = m for all armchair tubes.

Figure 3

3. Synthesis
The arc-evaporation method, which produces the best quality nanotubes,
involves passing a current of about 50 amps between two graphite
electrodes in an atmosphere of helium. This causes the graphite to vaporise,
some of it condensing on the walls of the reaction vessel and some of it on
the cathode. It is the deposit on the cathode which contains the carbon
nanotubes. Single-walled nanotubes are produced when Co and Ni or some
other metal is added to the anode. It has been known since the 1950s, if not
earlier, that carbon nanotubes can also be made by passing a carboncontaining gas, such as a hydrocarbon, over a catalyst. The catalyst consists
of nano-sized particles of metal, usually Fe, Co or Ni. These particles
catalyse the breakdown of the gaseous molecules into carbon, and a tube
then begins to grow with a metal particle at the tip. It was shown in 1996
that single-walled nanotubes can also be produced catalytically. The
perfection of carbon nanotubes produced in this way has generally been
poorer than those made by arc-evaporation, but great improvements in the
technique have been made in recent years. The big advantage of catalytic
synthesis over arc-evaporation is that it can be scaled up for volume
production. The third important method for making carbon nanotubes
involves using a powerful laser to vaporise a metal-graphite target. This can
be used to produce single-walled tubes with high yield.

4. Properties
The strength of the sp carbon-carbon bonds gives carbon nanotubes
amazing mechanical properties. The stiffness of a material is measured in
terms of its Young's modulus, the rate of change of stress with applied
strain. The Young's modulus of the best nanotubes can be as high as 1000
GPa which is approximately 5x higher than steel. The tensile strength, or
breaking strain of nanotubes can be up to 63 GPa, around 50x higher than
steel. These properties, coupled with the lightness of carbon nanotubes,
gives them great potential in applications such as aerospace. It has even
been suggested that nanotubes could be used in the space elevator, an
Earth-to-space cable first proposed by Arthur C. Clarke. The electronic
properties of carbon nanotubes are also extraordinary. Especially notable is
the fact that nanotubes can be metallic or semiconducting depending on

their structure. Thus, some nanotubes have conductivities higher than that
of copper, while others behave more like silicon. There is great interest in
the possibility of constructing nanoscale electronic devices from nanotubes,
and some progress is being made in this area. However, in order to
construct a useful device we would need to arrange many thousands of
nanotubes in a defined pattern, and we do not yet have the degree of
control necessary to achieve this. There are several areas of technology
where carbon nanotubes are already being used. These include flat-panel
displays, scanning probe microscopes and sensing devices. The unique
properties of carbon nanotubes will undoubtedly lead to many more
applications.

SECOND PART

ABSTRACT
The capability of carbon nanotubes (CNTs) to adsorb lead (Pb) in aqueous
solution was investigated. Batch mode adsorption experiment was
conducted to determine the effects of pH, agitation speed, CNTs dosage and
contact time. The removal of Pb (II) reached maximum value 85% or 83% at
pH 5 or 40 mg/L of CNTs, respectively. Higher correlation coefficients from
Langmuir isotherm model indicates the strong adsorptions of Pb (II) on the
surface of CNTs (adsorption capacity Xm = 102.04 mg/g). The results
indicates that the highest percentage removal of Pb (96.03%) can be
achieved at pH 5, 40 mg/L of CNTs, contact time 80 min, and agitation speed
50 r/min.

INTRODUCTION
Carbon nanotubes (CNTs), a new member of the carbon family, have good
anion and catin adsorption materials for water treatment, as they exhibit
exceptionally large specific Surface area. In addition to the remarkable
mechanical properties, their hollow and layered nanosized structures make
them a good candidate as absorbers.
Various technologies are currently employed in industry to deal with heavy
metals such as chemical precipitation, reverse osmosis (Ahalya et al., 2007)
and adsorption or ion
exchange (Lu et al., 2007).
In wastewater treatment, nanomaterials especially CNTs have been
developed in remediation and end-of-pipe treatment technologies
(Masciangioli and Zhang, 2003). Lead in wastewater comes mainly from the
discharge of battery manufacturing, printing, dying and other industries
(Li et al., 2002). Other major sources of lead in the environment include
lead-based paint, household dust and food containers. Lead has been found
to be acute toxic to human beings when present in high amounts in water.
Studies have shown that young children, infants and pregnant women are
particularly susceptible to unsafe lead levels (http://www.safe-drinkingwater.com). For adults, increased levels of lead have been linked to high
blood pressure and damaged hearing. Drinking, eating, inhaling even at low
level of lead can cause other serious health effects. The aim was to study
the removal of lead from synthetic water using CNTs by optimizing the
process parameters to maximize the removal.

MATERIALS AND METHODS

Experimental
The production of carbon nanotubes was conducted in two horizontal
tubular reactors, using chemical vapor deposition (CVD) technique, which
has been developed from Muataz (2005) technique. The horizontal reactors
are a ceramic tube of 50 mm in diameter and 1200 mm in length and
heated by silicon carbide heating element.
The ferosine (C10H10Fe) catalyst of 100 mg was fixed at the first reaction
chamber at 150C for 10 min, while the second reaction chamber was used
for the reaction with H2O2 and for growth processes at 800C for 30 min.
Hydrogen was used as a reacting gas and the argon was used for flushing
the air from the system. Both of them were controlled by a flow meter.
Batch mode adsorption experiment
Experiments were conducted at 25C to study the effects of initial solution
pH, CNTs dosage, contact time, and agitation speed on the adsorption of Pb
(II). Each test was conducted in volumetric flask and the initial and final
concentration of Pb (II) were analyzed using atomic adsorption spectrometer
(AAS) (AAnalyst 400, Elemer Precise, USA) at wavelengths of 283.3nm for
lead. The final concentration of each study was use to determine the Pb (II)
removal percentage. The run orders for complete batch mode adsorption
experiment were determined using matrix analysis (Levine, 2001).

RESULTS AND DISCUSSIONS

Efect of pH on the uptake of lead
The differences in percentage removal indicate that the initial pH would play
a vital role in Pb (II) removal as shown in Figure 4, where the percentage
uptake of Pb (II) varied at different pH values (37). Previous study has
stated that the adsorption of Pb (II) increases with an increase in solution pH
from 3 to 7. This is because oxidation of CNTs with oxidized acid can
introduce many functional groups such as hydroxyl, carbonyl and carboxyl
on the surface of CNTs (Li et al., 2002).

Figure 4: Effect of pH on the uptake of lead. Conditions: contact time 20min;

adsorbent 20 mg/L; pH 3, 5, and 7.

The decrease in percentage removal at pH 7 reflects a reduction of negative

surface charge density on CNTs. Therefore, the presences of a negative
charge on CNTs surface over the pH range were the main reason for Pb
adsorption. H+ should be considered as competitive ones in ion-exchange
processes and consequently, ion Exchange of metals favored by high
acidity, which should, however, be lower than the minimum acidity of
precipitation.

+(1)
X 1
C++ H 2 O (M ( H 2 O ) ) (OH )C1 + H 3 O
(M ( H 2 O ) X )

Consequently, the above equilibrium (Reaction (1)) metal complexes are

formed. This fact is beneficial for the exchange. Therefore, very low
adsorption of the metal takes place from highly acidic solutions (Inglezakias
et al., 2007). The white crystal structure in the image was analyzed as Pb
(II). This was supported by energy dispersive X-ray (EDX) analysis in Figure
5, where CNTs at pH 5 obtained the highest peak.

Figure 5: Energy dispersive X-ray analysis of CNTs for pH 3 (a), 5 (b), and 7 (c).

The distribution of Pb at pH 5 was the highest (10.91%) compared to pH 3

(0.45%), and pH 7 (1.74%). Therefore, it can be concluded that Pb (II) have
been adsorbed on the surface of CNTs. The maximum adsorption can be
achieved at pH 5 with removal percentage of 84.78% (Figure 4). The result
agreed with the result by Bismarck and Wuertz (1999), that acidic surface
sites give a negative zeta-potential, whereas basic sites give a positive
zetapotential.
This implies that at low pH, a significant amount of basic groups which are
able to induce a positive surface charge, are present on the surface.
Efect of agitation speed on the uptake of lead
As shown in Figure 6, the removal percentage of lead is decreasing as the
speed increases. The removal of lead reach to 37.76% at 50 r/min, while at
150 r/min only 3.49% of Pb (II) was removed from the solution.
It can be concluded that the effects of agitation speed on the uptake of lead
are not significant for Pb (II) removal. As the speed increases, the
suspension may not become homogeneous due to the rapid agitation. This
will increase the boundary layer between the solid and liquid phase.
Thus, the removal of Pb (II) could achieve maximum value at 50 r/min.

Figure 6: Effect of agitation speed on the uptake of lead. Conditions: contact time
120 min; adsorbent 40 mg/L; agitation speed 50, 100, and 150 r/min.

Efect of CNTs dosage on the uptake of lead

As shown in Figure 7, the highest percentage removal (82.54%) occurred at
high dosage (10 mg). The reason is that the high CNTs dosage provided
more adsorption site for the attachment of Pb (II) and this accessibility
greatly enhanced the adsorption of lead.
EDX analysis was conducted to verify the effect of dosage on the Pb (II)
removal from aqueous solution (Figure 8). It was observed that the high

dosage of CNTs obtained a high peak. The Pb (II) distribution was 15.90% at
10 mg of CNTs compared to 1.74% at 5 mg. This verified Pb (II)
have been adsorbed on the surface of CNTs.

Figure 7: Effect of dosage on the uptake of lead. Conditions: adsorbent 20 and 40

mg/L; contact time 20120 min.

Figure 8: EDX analysis of CNTs with different dosages. (a) 5 mg; (b) 10 mg

Efect of contact time on the uptake of lead

The equilibrium time was measured from 20 to 120 min and the effect of
contact time is determined by plotting the percentage uptake of Pb (II)
against contact time (Figure 9). It was observed that the removal rate was
very fast for the first 40 min, but it gradually becomes slower until reached
a maximum at 80 min. It was also detected that the percentage uptake of
Pb (II) became saturated from 80 to 120 min.

Figure 9: Effect of contact time on the uptake of lead. Conditions: adsorbent 40

mg/L; pH 5; contact time 20 to 120 min.

Optimum conditions for the removal of Pb (II) using CNTs

The highest predictive percentage removal is 96.03%. The parameters that
contribute to these optimal conditions are pH 5, 10 mg dosage of CNTs in
250 mL Pb (II) solution, agitation speed at 50 r/min and contact time of 80
min. The control of carbon surface chemistry through the exclusive
introduction of a certain surface group is a natural goal for the lead removal
using carbon structures. It is highly challenging, as most methods give a
surface covered with a mixture of acidic and basic groups. Moreover, the
properties of each group are again dependent on its neighbors (Schlogl,
1999). Therefore, the deposition of metal particles is usually achieved
through multistep and time-consuming procedures.
Comparative analysis of various adsorbents
In comparison with the adsorption kinetics of the various adsorbents, it was
concluded that most of the removal process occurred very fast within the
first 40 min. It can be concluded that the adsorption capability of the
adsorbent is highly dependent on many factors such as surface functional
groups, the specific surface area and the solution components (Table 1).

Table 1: Comparison of various adsorbents and its percentage uptake of

Pb (II)

CONCLUSIONS
The optimum pH is 5 in which gave 85% removal of Pb (II) from aqueous
solution. The percentage uptake decreased with an increase in agitation
speed from 50 to 150 r/min, in which 50 r/min gave 37.76% removal.
The percent removal of Pb (II) was observed to be optimal for higher dosage
of CNTs, in which 10 mg contribute to 82.54% removal of Pb (II). The
Langmuir model fitted best, in which the highest adsorption capacity is
102.04 mg/g. The effect of contact time experiment indicated that higher
fraction of the Pb (II) migrates from the bulk solution through the adsorbent
boundary layer onto the active sites of the adsorbent. The overall adsorption
rate demonstrated that the kinetics of the adsorption of Pb (II) on the CNTs
was best described by pseudo second-order model. The results obtained
from these analyses proved that this method of adsorption of Pb (II) using
CNTs are promising for further development of water and wastewater
treatment.

REFERENCES
1. Adesola N A, Babalola J O, Sanni R A, 2006. Biosorption of lead ions
from aqueous solution solution by maize leaf. International Journal of
Physics Science, 1(1): 2332.
2. Adeyiga A A, Liang H U, Greer T, 2006. Removal of metal ions from
wastewater with natural wastes. Hampton University, Hampton.
3. Ahalya N, Ramachandra T V, Kanamadi R D, 2007. Biosorption of
heavy
metals.
http://www.ces.iisc.ernet.in/energy/water/paper/biosorption/biosorptio
n.htm, accessed November 10 2007.
4. Akhnazaroza S, Kefarov V, 1982. Experiment Optimization
Chemistry and Chemical Engineering. Moscow: Mir Publishers.

in

5. Augustine A A, Orike B D, Edidiong A D, 2007. Adsorption kinetics and

modeling of Cu (II) ions sorption from aqueous solution by
mercaptoacetic acid modified cassava wastes. Electronic Journal of
Environmental, Agricultural and Food Chemistry, 6(4): 22212233.