CNTs For Water Treatment

CNTs For Water Treatment
 INTRODUCTION
The availability of safe and clean water is decreasing day by day, which is expected to
increase in upcoming decades. Water demand is growing rapidly as a result of increasing
population and rapid urbanization. However, water resources are limited in populated
areas and arid regions, such as North China and the Arabian Peninsula.
The shortage of water resources calls for efficient technologies for waste water
reclamation and seawater desalination. Meanwhile, pollution exacerbates the water
shortage problems. According to UN-Water statistics, 2 million tons of human waste are
disposed of in water courses every day; in developing countries, 70 percent of industrial
wastes are dumped untreated into waters where they pollute the usable water supply.
Various contaminants are entering water resources from anthropogenic activities: from
conventional pollutants such as heavy metals and distillates to emerging micropollutants
such as microcystins and antibiotics. Some of these pollutants could not be removed from
water efficiently via traditional water treatment methods. Moreover, more effective and
low-cost technologies to decontaminate and disinfect water for point-of-use purposes are
needed, especially in rural regions.
To address this problem, various water purification technologies have been

adopted. Among the various concepts proposed, CNTs based water treatment
technologies have found to be promising because of its large surface area, high aspect
ratio, greater chemical reactivity, lower cost, and energy, less chemical mass and impact
on the environment. Carbon nanotubes, owing to their tunable physical, chemical,
electrical and structural properties, inspire innovative technologies to address the water
shortage and water pollution problems. Carbon nanotube based nanotechnologies have
found water-treatment applications in many fields, such as sorbents, catalyst, filters or
membranes. Therefore, research development and commercial interests in CNT are
growing worldwide to treat water contaminants, which have huge impacts on the entire
living systems including terrestrial, aquatic, and aerial flora and fauna. Here we reviewed
most of the effective CNT based water purification technologies such as adsorption,
hybrid catalysis, desalination, disinfection, sensing and monitoring of three major classes
UDCT Amravati Page 1

such as organic, inorganic and biological water pollutants. Since the Nano biohybrid field
yet remains to be matured, special importance has been paid on its mediated water
purification technology. We have forayed into the deeper thoughts and compiled
promises, facts and challenges of the important water purification technologies.
Since water purification is a complex process; hydrologists, membrane technologists,

environmentalists and industrialists can design “ONE POT” combination where effective
water purification technologies would instate to tackle both the conventional and newly
emerging toxic pollutants effectively.
 HYDROLOGY
Hydrology is the study of the movement, distribution, and quality of water throughout
the Earth. The study of the distribution of water is hydrography. The study of the
distribution and movement of groundwater is hydrogeology, of glaciers is glaciology, of
inland waters is limnology and distribution of oceans is oceanography. Ecological
processes with hydrology are in focus of ecohydrology.
The collective mass of water found on, under, and over the surface of a planet is
called the hydrosphere. Earth's approximate water volume (the total water supply of the
world) is 1.338 billion cubic kilometers (321×106 cu mi).
Liquid water is found in bodies of water, such as an ocean, sea, lake, river,
stream, canal, pond, or puddle. The majority of water on Earth is sea water. Water is also
present in the atmosphere in solid, liquid, and vapor states. It also exists as groundwater
in aquifers.
Water is important in many geological processes. Groundwater is present in

most rocks, and the pressure of this groundwater affects patterns of faulting. Water in
the mantle is responsible for the melt that produces volcanoes at subduction zones. On
the surface of the Earth, water is important in both chemical and
physical weathering processes. Water, and to a lesser but still significant extent, ice, are
also responsible for a large amount of sediment transport that occurs on the surface of
the earth. Deposition of transported sediment forms many types of sedimentary rocks,
which make up the geologic record of Earth history.

Earth water—a generous gift from the almighty God, and is the major constituent for all
living organisms. Water has covered around 71% of the Earth’s surface area. Figure shows
three pie charts of total water volume, and its distributions on Earth’s surface.
Pie charts of total water volume on, in and above the Earth. The figure is adapted with
permission from the Earth-Forum
According to Fig, water can exist in different forms such as gaseous (cloud vapors
and atmospheres), liquids (seas and oceans, rivers, lakes), and solid waters (ice and
glaciers). Although a higher percentage of water exists as saline water in the sea and
oceans (97%) (Fig. top chart), it cannot be used for drinking purpose due to its salinity
and impurities.
Only (3%) freshwater exists as 79, 20 and 1% of the frozen, ground and accessible
fresh surface waters, respectively (Fig. middle chart). This accessible fresh water (1%)
covers 53% in the rivers and streams; and the remaining percentages are in the forms of

vapor, moisture, and biological (Fig. down chart). These clearly indicate the
unavailability of pure fresh water facilities for drinking which are necessary for sustaining
and growing of all living organisms on Earth. While limited fresh water availability is so
obvious, many persistent pollutants have been simultaneously added into the world water
bodies through both point and nonpoint origins. This leads to a global decrease in the
availability of clean and safe water forms of water resources.
Three major classes of water pollutants such as organic, inorganic, and biological
contaminants have been dwindled the finite fresh water resources. Moreover, climate
change due to persistent global warming could bring variation in natural systems, leading
to ice-melting, sea level rise, soil, an fresh water submergence, increase evaporation and
so on, which have collectively been contaminated the oceans. While it is difficult to
control or significantly reduce water pollution, the lack of cost-effective water purification
technology has accelerated the problems. At some places, polluted water is not treatable
for recycling especially in developing countries because of lacking cost effective, but Fig.
Pie charts of total water volume on, in and above the Earth. The figure is adapted with
permission from the Earth-Forum. Carbon Nanotube in Water Treatment sensitive water
purification technology. Therefore, a novel, sensitive and cost-effective water purification
technology is an urgent need, and the failure to develop such a system might further
endanger the life processes and eco-friendly human existence.
 WATER SCARCITY AND ITS CONSEQUENCES

Increasing world population with water demands is highly interlinked and
interdependent with each other. World population has been increasing day by day (80
million/year), which could directly increase water demand in the near future. Figure 1.
represents the trends of population growths and their water demands from 1950 to 2025.
This alarms the looming crisis of water can be seen, if corrective steps are not taken at
right time.
Figure 2. represents the water scarcity of different areas on Earth. It shows many
countries have encountered with little, physical and economical water scarcities, while
some are waiting to reach. In the last century, water usages have been more than twice the
rate of population growth, resulting in global water shortages. Such fresh water crisis

brings problems not only to human, but also to the eco-systems. It has already been
affected many continents, mainly developing countries, which accommodate almost 40%
populace of our planet. People in the developing countries depend mainly on the ground
water facility due to the lack of expensive water purification techniques. Approximately
30% of the fresh and clean water accumulated in aquifers have commonly been utilized
for irrigation to cultivate food grains, vegetables and fruits, leading to a water depletion
of about 12 billion m3/year, endangering biodiversities, flora and fauna.
Fig. 1 Schematic representation of population growth (outer plot) and their

corresponding water demand (inner plot) from 1950 to 2025.
A mere 0.014% of all water on Earth is both fresh and easily accessible. Of the
remaining water, 97% is saline and a little less than 3% is hard to access. Technically,
there is a sufficient amount of freshwater on a global scale. However, due to unequal
distribution (exacerbated by climate change) resulting in some very wet and some very
dry geographic locations, plus a sharp rise in global freshwater demand in recent decades
driven by industry, humanity is facing a water crisis. Demand is expected to outstrip
supply by 40% in 2030, if current trends continue.

World population is increasing at a rate of 80 million/year, putting an additional

demand of 64 billion cubic meters of potable water per annum. Around the world, 780
million people can't access to safe and clean drinking water to use. It has been forecasted
that by 2025; about 3 billion people will be forced to survive under water scarcity as
estimated by World Water Council. Almost 1.1 billion people don't have facility to
improve drinking water bodies throughout the world, and 2.6 billion are under sanitation.
Water scarcity can affect economic growth and human health, since this jeopardizes the
industrial production and shrinks the availability of hygienic foods, and drinks and causes
various epidemic diseases such as diarrhea. Deficiency of clean and safewater counts for
almost 3.1% of death worldwide, which is forecasted to rise over the years. Drinking of
contaminated water has become the biggest killer of children under five years of age.
According to World Health of Organization (WHO) and the United Nations International
Children's Emergency Fund (UNICEF), one child is dying every 15 s due to the direct or
indirect consumption of unsafe water. Further, water crisis causes poverty especially in
developing countries, which weakens the Millennium Development Goal (MDG) that
depends on the major improvements in access to water.
Fig. 2. Areas encountered with water scarcities on Earth.

The essence of global water scarcity is the geographic and temporal mismatch
between freshwater demand and availability. The increasing world population,
improving living standards, changing consumption patterns, and expansion of irrigated
agriculture are the main driving forces for the rising global demand for water. Climate
change, such as altered weather-patterns (including droughts or floods), deforestation,
increased pollution, green house gases, and wasteful use of water can cause insufficient
supply. At the global level and on an annual basis, enough freshwater is available to meet
such demand, but spatial and temporal variations of water demand and availability are
large, leading to (physical) water scarcity in several parts of the world during specific
times of the year. All causes of water scarcity are related to human interference with
the water cycle. Scarcity varies over time as a result of natural hydrological variability,
but varies even more so as a function of prevailing economic policy, planning and
management approaches. Scarcity can be expected to intensify with most forms
of economic development, but, if correctly identified, many of its causes can be predicted,
avoided or mitigated.
 CONVENTIONAL WATER PURIFICATION METHODS
o Coagulation and flocculation

o Sedimentation
o Filtration
o Disinfection
o Chlorination
o Reverse Osmosis
o Distillation
o UV Treatment
o Biological Treatment
o Chemical Transformation
o Ultrafiltration
o Microfiltration

 Threats to Conventional Water Treatment Technologies
Changing of human lifestyles over the years has consistently added different notorious
anthropogenic pollutants into aquatic matrices. Eradicating these toxic pollutants is either
impossible or difficult using the traditional water purification methods. Here we
summarize the most common threats of current water purification technologies as shown
in Fig. 1. It clearly reflects that a single method is insufficient to remove multiple water
pollutants. Most of the methods typically depend on influent water qualities such as
turbidity, pH, and temperature that could decrease pollutant sensing ability. In addition,
low concentration and small dimensions of some water pollutants are difficult to sense
and mitigate by existing water purification technologies.
Fig. 1 Some major threats of conventional water purification technologies.

Water is treated to meet the objectives of drinking water quality and standards.
Water treatment and water quality are therefore closely connected.
The objectives for water treatment are to prevent acute diseases by exposure to
pathogens, to prevent long-term adverse health effects by exposure to chemicals and
micropollutants, and finally to create a drinking water that is palatable and is conditioned
in such a way that transport from the treatment works to the customer will not lead to
quality deterioration.
Traditional treatment technologies as described are mainly designed to remove

macro parameters such as suspended solids, natural organic matter, dissolved iron and
manganese, etc. The technologies have however only limited performance for removal
of micropollutants. Advancing analytical technologies and increased and changing use
of compounds however show strong evidence of new and emerging threats to drinking
water quality. Therefore, more advanced treatment technologies are required.
Certain bacteria in treated water may release toxins, which may seriously affect
the overall quality of water during the treatment process. For example, cyanobacteria
releases microcystin toxin in water while undergoing the treatment process. Low
concentration and small dimensions of pollutants are difficult to sense and mitigate.
Finally, high operating costs limit their field-level applications. The presence of water
contaminant in water treatment plants also decreases the efficiency of the treatment plants.
In view of these facts, the existing techniques are not sufficiently effective to give 100%
pure and safe water to qualify the waste water discharge criteria. Finally, high operating
costs shrink the availability of effective technologies especially in developing countries.

 WHAT IS NANO-TECHNOLOGY?
Nanotechnology ("nanotech") is manipulation of matter on an atomic, molecular,

and supramolecular scale. The earliest, widespread description of
nanotechnology referred to the particular technological goal of precisely manipulating
atoms and molecules for fabrication of macroscale products, also now referred to
as molecular nanotechnology. A more generalized description of nanotechnology was
subsequently established by the National Nanotechnology Initiative, which defines
nanotechnology as the manipulation of matter with at least one dimension sized from 1 to
100 nanometers. This definition reflects the fact that quantum mechanical effects are
important at this quantum-realm scale, and so the definition shifted from a particular
technological goal to a research category inclusive of all types of research and
technologies that deal with the special properties of matter which occur below the given
size threshold. It is therefore common to see the plural form "nanotechnologies" as well
as "nanoscale technologies" to refer to the broad range of research and applications whose
common trait is size. Because of the variety of potential applications (including industrial
and military), governments have invested billions of dollars in nanotechnology research.
Nanotechnology as defined by size is naturally very broad, including fields of

science as diverse as surface science, organic chemistry, molecular
biology, semiconductor physics, energy storage, microfabrication, molecular
engineering, etc. The associated research and applications are equally diverse, ranging
from extensions of conventional device physics to completely new approaches based
upon molecular self-assembly, from developing new materials with dimensions on the
nanoscale to direct control of matter on the atomic scale.
 HISTORY
The ideas and concepts behind nanoscience and nanotechnology started with a talk
entitled “There’s Plenty of Room at the Bottom” by physicist Richard Feynman at an
American Physical Society meeting at the California Institute of Technology (CalTech)
on December 29, 1959, long before the term nanotechnology was used. In his talk,

Feynman described a process in which scientists would be able to manipulate and control
individual atoms and molecules. Over a decade later, in his explorations of ultraprecision
machining, Professor Norio Taniguchi coined the term nanotechnology. It wasn't until
1981, with the development of the scanning tunneling microscope that could "see"
individual atoms, that modern nanotechnology began.
In the 1980s, two major breakthroughs sparked the growth of nanotechnology in

modern era. First, the invention of the scanning tunneling microscope in 1981 which
provided unprecedented visualization of individual atoms and bonds, and was successfully
used to manipulate individual atoms in 1989.
Second, Fullerenes were discovered in 1985 by Harry Kroto, Richard Smalley,

and Robert Curl, who together won the 1996 Nobel Prize in Chemistry. C60 was not
initially described as nanotechnology; the term was used regarding subsequent work with
related graphene tubes (called carbon nanotubes and sometimes called Bucky tubes)
which suggested potential applications for nanoscale electronics and devices.
Meanwhile, commercialization of products based on advancements in nanoscale

technologies began emerging. These products are limited to bulk applications
of nanomaterials and do not involve atomic control of matter. Some examples include
the Silver Nano platform for using silver nanoparticles as an antibacterial
agent, nanoparticle-based transparent sunscreens, carbon fiber strengthening using silica
nanoparticles, and carbon nanotubes for stain-resistant textiles.
 FUNDAMENTAL CONCEPTS IN NANO-TECHNOLOGY.
It’s hard to imagine just how small nanotechnology is. One nanometer is a billionth of a
meter, or 10-9 of a meter. Here are a few illustrative examples:
 There are 25,400,000 nanometers in an inch
 A sheet of newspaper is about 100,000 nanometers thick
 On a comparative scale, if a marble were a nanometer, then one meter would be the
size of the Earth

 Nanoscience and nanotechnology involve the ability to see and to control

individual atoms and molecules. Everything on Earth is made up of atoms the
food we eat, the clothes we wear, the buildings and houses we live in, and our
own bodies.
 But something as small as an atom is impossible to see with the naked eye. In
fact, it’s impossible to see with the microscopes typically used in a high school
science classes. The microscopes needed to see things at the nanoscale were
invented relatively recently—about 30 years ago.
 Once scientists had the right tools, such as the scanning tunneling microscope
(STM) and the atomic force microscope (AFM), the age of nanotechnology
was born.
 Although modern nanoscience and nanotechnology are quite new, nanoscale

materials were used for centuries. Alternate-sized gold and silver particles
created colors in the stained glass windows of medieval churches hundreds
of years ago. The artists back then just didn’t know that the process they used
to create these beautiful works of art actually led to changes in the
composition of the materials they were working with.
 Today's scientists and engineers are finding a wide variety of ways to

deliberately make materials at the nanoscale to take advantage of their
enhanced properties such as higher strength, lighter weight, increased
control of light spectrum, and greater chemical reactivity than their larger-
scale counterparts.
 Two main approaches are used in nanotechnology. In the "bottom-up" approach,

materials and devices are built from molecular components which assemble
themselves chemically by principles of molecular recognition. In the "top-down"
approach, nano-objects are constructed from larger entities without atomic-level
control.

 The Significance of the Nanoscale

 The quantum mechanical properties of the particles at the nanoscale influence a
lot on the physical properties of the particles.By nanoscale design of the materials
it is possible to vary micro and macroscopic properties such as charge capacity,
magnetization, melting temperature without changing their chemical composition.
 Creation of new improved products.

 Availability of stronger, tougher and lighter materials for construction and
engineering.
 Nanoscale components have high surface area to volume ratio making them idle
for the use in composite materials, drug delivery and chemical storage.
 Cleaner drinking water due to the creation of filters that can entrap organisms and
toxins.
 Cleaner environment by removal of pollutants from the environment.
 Sophisticated health treatment by using the nano particles in the drug delivery.
 Cheaper and cleaner energy.
 Nanophase ceramics which are very ductile a elevated temperatures as compared
to the normal ones.
 Nanostructured semiconductors are used as window layers in solar cells.
 Nanosized metallic powders have been used for the production of the gas tight
materials and porous coatings.
 Nanostructured metal clusters and colloids are used in the special catalytic
applications.
 Nanostructured metal oxide films are used even as the gas sensors.
 Nanostructured metal oxide finds applications in rechargeable batteries for cars
and consumer goods.
 Nanotechnology is a brand new technology that has just began, it is a revolutionary
science that will change all what we knew before. The future that we were
watching just in science fiction movies will in the near future be real.

 CARBON NANOTUBES
Carbon nanotubes (CNTs)

are allotropes of carbon with
a cylindrical nanostructure. These
cylindrical carbon molecules have
unusual properties, which are
valuable nanotechnology, electron
ics, optics, and other fields
of materials science and
technology. Owing to the material's
exceptional strength and stiffness,
nanotubes have been constructed
with a length-to-diameter ratio of
C-60
up to 132,000,000:1.
Nanotubes are members of the fullerene structural family. Their name is derived
from their long, hollow structure with the walls formed by one-atom-thick sheets of
carbon, called graphene (as well as Buckminster Fuller's name). These sheets are rolled at
specific and discrete ("chiral") angles, and the combination of the rolling angle and radius
decides the nanotube properties, for example, whether the individual nanotube shell is
a metal or semiconductor. Nanotubes are categorized as single-walled
nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). Individual nanotubes
naturally align themselves into "ropes" held together by van der Waals forces, more
specifically, pi-stacking.
Allotropes of carbon

A significant nanoparticle discovery that came to light in 1991 was carbon

nanotubes. Where buckyballs are round, nanotubes are cylinders that haven’t folded
around to create a sphere. Carbon nanotubes are composed of carbon atoms linked in
hexagonal shapes, with each carbon atom covalently bonded to three other carbon atoms.
Carbon nanotubes have diameters as small as 1 nm and lengths up to several centimeters.
Although, like buckyballs, carbon nanotubes are strong, they are not brittle. They can be
bent, and when released, they will spring back to their original shape.
Applied quantum chemistry, specifically orbital hybridization, best describes the
chemical bonding in nanotubes. The chemical bonding of nanotubes involves entirely sp2-
hybrid carbon atoms. These bonds, which are similar to those of graphite and stronger
than those found in alkanes and diamond (which employ sp3-hybrid carbon atoms),
provide nanotubes their unique strength.
 HISTORY OF CARBON NANOTUBES

In 1991, Iijima discovered carbon nanotubes (CNTs). Since then, a new branch of
knowledge in materials science has emerged – Nanoscience. In order to unveil the secrets
of the innovative materials, hundreds of millions of dollars have been invested. Yet, it was
all worth it since these functional nanoscale materials have diverse properties, which are
unique, amazing and new. In fact, a fourth state of matter has been found to be water
trapped inside a carbon nanotube, which does not act as gas, liquid or solid.
It would be in 1993 that Iijima and Donald Bethune found single walled nanotubes
known as buckytubes. This helped the scientific community make more sense out of not
only the potential for nanotube research, but the use and existence of fullerenes.
With this information, the complete discovery of carbon nanotubes was realized
and Iijima and Bethune were ultimately credited with their discovery in their entirety.
Russian nanotechnologists were independently discovering the same visual affirmation.
They were just a little bit later in their announcement and the potential affect of this
discovery.
The continuation of research revealed a great deal about nanotubes and their place
in scientific discovery. The research has indicated that there are three basic types of
nanotubes (zigzag, armchair, and chiral) as well as single walled and multiwalled
nanotubes.

There are buckytubes, which are completely hollow molecules that are crafted
from pure carbon and are bonded together in a pattern of specific hexagon patterns. The
multiwalled nanotubes are likely to suffer from defects. These defects happen in more
than half of all multiwalled nanotubes.
 STRUCTURE OF CARBON NANOTUBES
Carbon can bond in different ways to construct structures with completely different
properties. The sp2 hybridization of carbon builds a layered construction with weak out-
of plane bonding of the van der Waals form and strong inplane bounds. A few to a few
tens of concentric cylinders with the regular periodic interlayer spacing locate around
ordinary central hollow and made MWCNTs. The real space analysis of multiwall
nanotube images has shown a range of interlayer spacing (0.34 to 0.39 nm).
Depending on the number of layers, the inner diameter of MWCNTs diverges from
0.4 nm up to a few nanometers and outer diameter varies characteristically from 2 nm up
Figure - TEM images of SWCNT, MWCNT, and schematic illustration of SWCNT bundle.

to 20 to 30 nm. Both tips of MWCNT usually have closed and the ends are capped by
domeshaped half-fullerene molecules (pentagonal defects), and axial size differs from 1
μm up to a few centimeter. The role of the half-fullerene molecules (pentagonal ring
defect) is to help in closing of the tube at the two ends. On other hand, SWCNT diameters
differ from 0.4 to 2 to 3 nm, and their length is typically of the micrometer range.
SWCNTs usually can come together and form bundles (ropes). In a bundle structure,
SWCNTs are hexagonally organized to form a crystal-like construction.
Graphite consists of layers of carbon atoms. Within the layers the atoms are
arranged at the corners of hexagons which fill the whole plane. The carbon atoms are
strongly (covalently) bound to each other (carbon-carbon distance ∼ 0.14 nm ). The layers
themselves are rather weakly bound to each other (weak longrange Van der Waals type
interaction, interlayer distance of ∼ 0.34 nm). The weak interlayer coupling gives graphite
the property of a seemingly very soft material. The property us to use allows to use
graphite in a pencil.
 TYPES OF CARBON NANOTUBES
o On the Basis of Walls
There is no consensus on some terms describing carbon nanotubes in scientific literature:

both "-wall" and "-walled" are being used in combination with "single", "double", "triple",
or "multi", for example, Single walled carbon Nanotube(SWCNT), multi-walled carbon
nanotube (MWNT).

1. Single-Walled Carbon Nanotube
Single-Walled Carbon Nanotube (SWCNT) is a cylinder formed with only one layer
(wall) of carbon molecules. Commonly, these have fabricated in diameters ranging from
0.4 to 2 mm. The diameters of SWCNTs determined by the range of temperature at which
they synthesized. Increasing temperature results in larger-sized (wider) SWCNTs have
incorporated.
The structure of SWCNTs may vary and may either be zigzag, helical, armchair or chiral
arrangement. The surface area of SWCNTs is also considerably higher, at 1300 m²/g,
which makes it ideal for nano-robotics and future of medicine administering.
2. Multi-Walled Carbon Nanotube
On the other hand, Multi-Walled Carbon Nanotubes (MWCNTs), differ with SWCNTs
by the number of cylindrical walls they have. In MWCNTs, the carbon molecules form
multiple concentric walls of consequentially increasing diameters around one another.
Although there are numerous walls in MWCNTs, each wall is composed of an atom-thick
structure only.

Single-Walled Carbon Nanotubes (SWCNT) have unique properties. In terms of

mechanics, they are 100 times more tensile than steel at 1/16th weight, but in practice, due
to defects, half of the predicted values are measured. From the aspect of electrical
properties, Single-walled carbon nanotubes has current carrying capacity
of 109amp/cm2 which is higher than those of gold, copper, and semiconductors.
Single-Walled Carbon Nanotubes have wide range of applications which are sensors,
biomedical applications, thin film transistors, transparent electrodes, biomedical
applications, field emissions, conductive composites, interconnects, battery electrodes,
drug delivery, gas storage, super capacitors, fibers, hard coatings, bio-scaffolds, strong
composites, and actuators.
o On the Basis of Symmetry
Carbon Nanotubes are considered to be a curved graphene sheet. Graphene sheets are
seamless cylinders derived from a honeycomb lattice, representing a single atomic layer
of crystalline graphite.
Rolling up the sheet along one of the symmetry axis gives either a zig-zag tube or an
armchair tube. It is also possible to roll up the sheet in a direction that differs from a
symmetry axis to obtain a chiral nanotube. As a well as the chiral angle, the circumference
of the cylinder can also be varied.

o On the Basis of Open-Closed Ends

One type of carbon nanotube has a cylindrical shape with open ends, as shown in the
following figure.
Fig – Open end CNT
Fig – Closed end CNT

 Functions Performed By Carbon Nanotubes In Water

Treatment
Figure illustrates the scaffold functions of CNT in water purifications. According to Fig,
CNT has been widely used as excellent adsorbent media at first for multiple organic,
inorganic, and biological water pollutants. Second, CNTs could be used as hybrid catalysts
where they may participate in photocatalysis, electrocatalysis, and as nanocarrier for
enzyme immobilization or Nanobiohybrid catalysis. These have added new dimension in
catalytic degradation of water pollutants. Herein CNTs have made a suitable platform for
accelerating the catalytic rates. Third, doped CNTs in various membrane engineering
technologies have been used for both the sea and brackish water desalinations. They can
be used as pores in engineered membranes or membranes themselves by aligning them
together. Finally, high electrical conductivities have made CNT suitable for
electrochemical sensor technology to trace and mitigate contaminants,
pathogens and high complexity of wastewater matrices.

o Adsorption
Adsorption is a process where substance (pollutant) concentrations would increase and

adsorb into the layers/sheets of a solid material owing to the operation of surface forces.
Basically, it is a surface phenomenon where the substance that is called adsorbate is
adsorbed and creates a film on the adsorbent (where the adsorbates are adsorbed) surface.
Adsorption present in CNTs has been frequently used for capturing a wide variety of water
pollutants. After absorbing the pollutants for a certain concentration into the adsorbent,
equilibrium is reached and the relationship between the amounts of pollutant adsorbed and
in water, is called an adsorption isotherm. The kinetics of this mechanism have been
evaluated mathematically using different models such as Langmuir, Freundlich, Halsey,
Henderson, Smith, Elovich liquid film diffusion, intraparticle diffusion, and Lagergren
Wang et al. observed the adsorption of Pb(II), Ag(I), Cu(II), and Co(II) ions on
functionalized MWCNT and the adsorption data were fitted well to the Langmuir model.
Adsorption isotherms of acidified MWCNTs to Pb(II), Ag(I),

Cu(II), and Co(II) at
25 °C.
CNTs aggregation due to van der Waals forces, more specifically pi-stacking that
exists along with their length axis differentiates them from other adsorbents such as carbon
fibers, activated carbon (AC) and so on. Adsorption by AC is also the most promising to
eliminate many deleterious pollutants. However, appropriate physicochemical properties

and well known uniformed atomic structure make CNT a magnitude adsorbent media
compared to AC. Pore sizes and energy are the key determinants of AC, whereas well
defined CNT adsorption sites are necessary for adsorbing pollutants on their surface.
Figure below shows some observed evidences of pollutants adsorption onto CNT
surfaces. As we can see, TEM image of MWCNTs after Pb (II) adsorption which is not
uniform and mainly adsorb at the tips and defective sites of the MWCNT (Fig. b). SEM
image of Eschericia coli (E.coli) bacteria exposed to SWCNTs clearly suggests loss of
their morphology (Fig. c). Sponge-like CNT adsorbent floated on oil polluted water and
simultaneously can remove oil with a large adsorption capacity (from 80 to 180 times their
own weight for a wide range of solvents and oils) (Fig. d), and finally salt adsorption by
CNT membranes (Fig. e).
o Hybrid catalysis
One-dimensional CNT is of special interest in the photocatalysis of multiple water

pollutants because of their high electrical conductivity and charge transferring ability.
Good electrical conductivity resulted from the presence of reactive surface groups, sp2
carbons, curvature pattern, topological defects and edge-plane sites. Another potential

hybrid catalyst has been used to degrade water pollutants in a process called catalytic
wet air oxidation (CWAO). This can be defined as the dissolved and suspended water
pollutant's oxidation by using an oxidizing agent such as O2 from air in presence of
catalyst. In addition, recent CNTs have also been used for immobilizing enzymes.
Immobilized enzymes have shown good thermo stability, broad pH ranges and higher
reusability in the fields of water purification, pharmaceuticals, chemical synthesis,
biosensors and so on. The suitability of CNTs for enzyme attachment is because of their
known atomic structure, big surface area, mass transfer and good enzyme loading
capacities, which make nanotubes effective biocatalyst for water purification.
o CNTs in Catalytic Wet Air Oxidation
Wet air oxidation, a process that utilize the oxygen in air to oxidize dissolved and
suspended organic matter in water, has been commercially used as an effective method
for wastewater treatment for around 60 years. However, severe reaction conditions and
high operating costs impede its application for treating the industrial wastewater. Using
catalysts (usually noble metals) in wet air oxidation process helps to promote the oxidation
efficiency and reduce costs. Several studies used CNT as catalyst support in wet air
oxidation for the treatment of organic and toxic wastewaters. CNT supported Pt, Pd and
Ru catalysts have found applications in wet air oxidation of organic pollutants like phenol
and aniline. As compared to activated carbon, the mesoporous nature of CNTs is more
advantageous for the diffusion of pollutants to the surface of catalyst.
CNTs themselves can act as effective catalyst in wet air oxidation processes.
MWCNTs display catalytic activity in the wet air oxidation of phenol, and the mechanisms
are shown in Figure.
Molecular oxygen in water adsorbed on the surface of functionalized CNTs, and

then was dissociated on the graphite layers to produce dissociated oxygen atoms.
Thereafter, the carboxylic groups on CNTs and the oxygen atoms formed HO2 radicals
through hydrogen bonding, leading to the degradation of organic pollutants.

Figure. HO2 radical producing mechanisms in catalytic wet air oxidation of phenol over MWCNTs.
o Desalination
On the basis of current fabrication systems, there are two types of CNT membranes such
as (i) vertically aligned (VA) and (ii) mixed matrix (MM) CNT membranes as shown in
Fig. The VACNT membranes can be synthesized by aligning perpendicular CNTs with
supportive filler contents (epoxy, silicon nitride, etc.) between the tubes (Fig. a). On the
other hand, a MMCNTs membrane consists of several layers of polymers or other
composite materials (Fig.b). These membranes work with low energy consumption
because of CNT’s frictionless water transport capability through nanotubes hydrophobic
hollow cavity. The membrane is highly sensitive toward the multiple water pollutants and
salts. In addition, due to the CNT cytotoxicity, the CNT membrane has antifouling and
self-cleaning abilities with high recrudescence and reusability facilities. Moreover,
functionalities such as positive (–NH3 +), negative (-COO−, sulfonic acids) and
hydrophobic (aromatic) groups could be implanted by using different wet oxidizing agent
treatments of CNT.

Fig. Schematic illustration of two types of CNT membranes.

a) VA and b) MM–CNT
membranes
The groups can reject a selective water pollutant and also attract water molecules through
nanotube hole. Simulated and fabricated CNT membrane (diameter 1.5 nm) with two
zwitterions at tip ends. The group was achieved 100% ion rejection, which was 0.0% in
nonfunctionalized membrane.
o Disinfection
Aggregated mesoporous CNTs [41] have been utilized to remove biological contaminants
such as bacteria and viruses from water. Figure 2.17 shows some possible mechanisms
for disinfecting microbes adsorbed onto CNT sheets. Cytotoxic CNTs have shown higher
pathogens decontamination rate compared with AC [18, 119]. Therefore, pathogen
contaminated effluents could be found in AC treated water.

We studied the toxic effects of pristine SWCNTs on both Gram-positive bacteria

such as Staphylococcus aureus (S. aureus), and Bacillus subtilis (B. subtilis) and Gram-
negative bacteria such as E. coli and Pseudomonas aeruginosa (P. aeruginosa). The group
observed that the dispersed individual CNT could puncture cell membrane integrity
rapidly and strongly than aggregated CNTs. Soft and smooth cells such as Gram-positive
bacteria could be more vulnerable to attack by CNTs than Gram-negative bacteria. This
effect can be vice versa depending on the cell membrane compositions. This piercing
effect can be increased using dispersed CNT solution, increasing their concentrations and
shaker speed augmentation during incubation. Although few other possible toxicity
mechanisms have proposed by some groups such as inhibition of electron transports,
leakage, and penetration of cell membrane and generation of reactive oxygen surface
(ROS) (Fig. b); most of these mechanisms are not yet experimentally proofed.
Fig. a) SEM images of bacteria before and after CNT exposures, and b) some possible
mechanisms of CNTs mediated bacterial cell death.
Observed the dominant toxicity resulted from using SWCNTs than MWCNTs.
The group oxidized 4.1 lm of MWCNTs by H2SO4/HNO3 that yielded higher toxicity
than 77 lm of MWCNTs bundles in diameters. It clarifies size-dependent toxicity
mechanisms and can be a key parameter to ascertain antibacterial activity. Scientists
hypothesized higher toxicity induced by short, unzipped, and dispersed MWCNTs toward
bacteria. Other factors such as incubation time, buffer types, concentration, and

functionalities have shown regulatory effects on CNT antibacterial activity. As an initial

foray into the CNT microbial cytotoxicity, we confirmed that the scientists, who have
been active in the field, only focused on bacteria physiological changes upon CNT
treatments using SEM, AFM, and TEM. However, only these characterization methods
cannot accurately explain the effects of CNT toxicity on bacterial cell proliferation. More
biological experiments such as pattern of gene expressions, transcriptomics, proteomics,
and genomics data comparisons along with other system biology approaches of CNTs
treated bacteria could be effective for settling the mechanisms of cellular deaths. In
addition, misinterpretation could be resulted from the use of pristine CNTs contaminated
with amorphous carbons, metal catalysts, nanofibers, etc. scientists hypothesized the CNT
toxicity can be dependent on its geometrical compositions and surface functionalities.
Therefore, more study is necessary to acquire the nature of bacterial cell death when CNT
is an adsorbent media and should be treated with cautions.
o Sensing And Monitoring
Rapid sensing and monitoring of trace water pollutants have remained a critical job by
using conventional sensor technologies. In addition, complex waste water matrices
increased this difficulty on urgent basis. The paradigm called to develop highly sensitive
and fast responsive CNT based devices or sensors. This is because of some CNT
specialties such as fast electro conductivity, high adsorbing power so that water pollutants
can concentrate on their surface before sensing and trapping, hydrophobicity, high
recovery rate and first reaction kinetics as we discussed in preceding sections. Enzymes
immobilized on CNTs oxidize the water pollutants followed by electrons transformation
for high signal detection. In addition, charged or ionic pollutants adsorbed into CNTs give
electrical conductance by measuring the ratio between analyte concentrations and current
fluctuations. López and Merkoçi designed enzyme (Tyrosinase)-integrated-CNTepoxy
composite electrode (CNTECE-Tyr) and compared with tyrosinase biosensor based on a
graphite epoxy-composite (GECE-Tyr) for quantifying phenolic water pollutants such as
catechol. The CNTEC-Tyr electrode was shown higher signals reflecting the good
electrocatalytic properties of CNTs over graphite sheet. It was of 46 mA/mM cm2
forGECE-Tyr and of 294 mA/mM cm2 for CNTEC-Tyr with a current intensity 90%
higher than GECE-Tyr.

 Water transport through CNT hollow tubes
The smooth and hydrophobic inner core of the hollow CNTs can allow the uniterrupted
and spontaneous passage of water molecules with very little absorption (Fig. A). The
specially aligned CNTs are of special interest for the construction of CNT membranes.
The pore diameter has special effects on the water passages through the membranes
consisting of aligned CNTs.
Fig. Structures of some CNT membranes. Shown are (A) cross-sectional scanning electronmicroscope
(SEM) image of a pristine CNT membrane; (B) CNT based water filter with cylindrical
geometry; (C) movement of water molecules through a CNT channel; (D) SEM image of scattered
NaCl nanocrystals on CNT membrane surface; (E) movement of pure water
molecules through CNT-membrane in osmotically imbalanced compartments, and (F) engineered
CNT membranes in industrial set up.

Scientists observed frictionless movement of water molecules with high velocities from
9.5 to 43.0 cm s−1/bar speed through a 7 nm diameter membrane pore.
The flow rates were four to five times faster than those of conventional fluid flow
of between 0.00015 and 0.00057 cm s−1/bar). Molecular simulation dynamics showed
that the water conductance of the (7, 7) and (8, 8) tubes are roughly double and quadruple
that of the (6, 6) tube, respectively. Though a single water chain forms in both the (5, 5)
and (6, 6) tubes, the permeability of the former is a little under half the latter due to the
fact that water chains only form across the narrower pore half of the time. Thus, CNT
types and conformation play significant roles in water passage and permeability. The
equation of motions nicely describes water transport through CNT membranes as a
function of time. Motion reflects dynamics and kinematics of water molecules passing
through the tubular structures. Dynamics employs forces, and energy whereas kinematics
describes displacement, initial velocity, final velocity, acceleration and time.
 Application Of CNTs In Drinking Water Purification
Disinfection and purification of water is of significant importance to ensure clean and

safe drinking water supply for everyone. The present methods used for disinfection are
effective. However, these methods including chlorination are associated with formation
of disinfection by-products (DBPs) that have been shown as harmful as well as some as
carcinogenic in nature by studies done in the last decade that have reported over 600 DBPs
in the literature [7]. Therefore, in order to ensure effective disinfection techniques and to
avoid the formation of harmful DBPs, the existing and conventional water purification
and disinfection methods need to be reconsidered and new techniques should be evaluated.
o Drinking Water Contaminants
The major type of contaminants found in drinking water both in probability of

occurrence as well as quantity in the water treatment plant consist of biological
contaminants that are further classified into three types; cyanobacterial toxins, Natural
Organic Matter (NOM) and microorganisms including fungi, viruses, bacteria and
protozoa. The presence Natural Organic Matter (NOM) is associated with increased

microbial growth as they provide carbon source. Biological toxins that mainly include
cyanobacterial toxins are produced as a result of lyses of cyanobacterial cells present in
the water treatment process. These toxins are not entirely removed from water due to
lower efficiencies of conventional technologies for water treatment. Harmful algal bloom
(HAB) is a toxic species of cyanobacteria that is responsible for producing toxins.
Cyanobacterial cells form a layer of scum on the surface of water due to their buoyancy
and in this way, they are easily transported to treatment plants where they undergo lyses
to form toxins including commonly produced toxin named microcysteine toxins (MC) that
are mainly responsible for causing taste and odor issues. These species commonly present
in non-turbulent rivers and lakes and are found in all around the world with exception of
Antarctica. Microorganisms mainly found in the water treatment plant include taste and
odor causing bacteria, pathogenic bacteria originating from discharge of untreated sewage
into the influent water, nuisance bacteria consisting of sulfur and iron reducing bacteria,
microorganisms that are native to the habitat or environment. Potential contaminants that
consist of biothreat microorganisms that are used for bioterrorism purpose can also occur
among other microorganisms in treatment systems. In addition to biological contaminants,
many studies have shown effectiveness of CNTs in removal of heavy metal ions including
that of nickel, lead, silver and cadmium from drinking water by using multi-walled carbon
nanotubes.
In contrast to conventional technologies for water purification, carbon nanotubes
(CNTs) provide better media for adsorption and removal of a range of biological
contaminants and heavy metals. This is due to the unique functional, physical and
structural properties of CNTs.
o Use of CNTs as Absorbent Media for Removal of Drinking Water

Contaminants
CNTs have shown improved and higher efficiencies for adsorption of bacteria and
other microorganisms than other adsorbents such as granulated activated carbon (GAC)
and powdered activated carbon (PAC) commonly used in the water treatment processes
that have large surface areas but the surface area of the micropores is not accessible by
them that in turn contributes to lower adsorption capacities. In addition to this, studies
have shown that the fibrous structure of CNT filters result in simultaneous capture and

deactivation and removal of pathogenic microorganisms as compared to carbon based

filters that only capture but do not deactivate the pathogens.
o Adsorption of microorganisms on CNTs
CNTs offer higher efficiency adsorption of various microorganism as compared to other

adsorbents. Many studies have shown that single-walled nanotubes (SWNTs) show higher
adsorption capacities for many bacteria than other available adsorbents mainly due to the
fibrous structure and external surface accessibility. A study showed that adsorption of a
bacterial strain, Bacillus subtilis in SWNT is up to 37 times greater than in other
adsorbents such as Nanocream and activated carbon. Another distinguishing feature of
CNTs is that these adsorbents offer selective adsorption of bacterial species. Studies have
shown selective adsorption and concentration of one bacterial species over another. In
addition to this, CNTs show instantaneous adsorption kinetics of bacteria which can
extend their use as sensors of pathogens for rapid concentration of desired pathogenic
strain. A study showed that SWNT adsorbed approximately 95% of the bacteria present
in a solution within half an hour. In this way, CNTs can be used in point of use (POU)
water treatment systems for adsorption of a variety of microorganism.
o Adsorption of natural organic matter (NOM)
Carbon adsorbents provide efficient removal of a variety of NOM from raw water. At
present, powdered activated carbon, granulated activated carbon and biological activated
carbon are commonly used carbon-based adsorbents for adsorption of NOM in water
treatment processes. Factors such as chemical composition and size of NOM found in
water, physical characteristics of carbon surface, use of mesopores or microporeses in the
carbon surface, type of functional group present on the surface affect the sorption
efficiency of NOM. In most cases the size of the mesopores is 1 nm whereas the NOM
have size in the range of 0.5-5nm which leads to lowered efficiencies of sorption on carbon
based surfaces. In addition to this, different sections of NOM interact differently with the
surface of adsorbents which also effects the sorption capacity for NOM. Adsorption of
NOM on CNTs is superior to adsorption of NOM on microporous adsorbents due to
factors such as comparable less surface charge of CNT adsorbents and large mesoporous

volumes of aggregated pores. CNTs not only offer high sorption capacity of NOM but
also offers effective removal of microorganisms due to the colloidal stability of CNTs
which is enhanced by the presence of NOM in water. Studies have also shown faster and
higher desorption of NOM than in granulated activated carbon mainly because dissolved
organic carbon (DOC) is caught in the aggregated pores whereas in case of GAC, DOC is
trapped in the interior region which results in slower and less efficient desorption. In
addition to this, CNTs in contrast to microporous adsorbents, offer efficient and
unaffected removal of NOM in the presence of other competitive adsorbates including
micropollutants due to the large surface area that can remove a variety of contaminants
adsorbents.
o Adsorption of cyanobacterial toxins
Conventional processes of water purification such as coagulation and flocculation offer

inefficient removal of cyanobacterial toxins including MC’s that commonly occur in raw
waters. Due to the sensitivity towards the changes of temperature and pH conditions, the
use of strong oxidizers (ozone, chlorine, hydrogen peroxide and potassium permanganate)
also proved to be ineffective for the deactivation of MC toxins. Activated carbon is shown
as effective adsorbent media for the removal of cyanobacterial toxins as compared to clay
adsorbents. Granular based activated carbon shows the highest adsorption efficiency as
compared to coconut based powdered and wood based activated carbon adsorbents.
However, CNTs prove to be even better adsorbents as compared to activated carbon and
shows four times higher adsorption efficiency than clay minerals. A study was conducted
to test the adsorption efficiency of CNTs for the deactivation and removal of two types of
cyanobacterial toxins including MC-RR and MC-LR. Many studies have found various
factors that are associated with higher adsorption capacities of CNTs for the removal of
MC’s. These include symmetrical structure and external diameter of CNTs, large volume
of mesopores, increased surface area of adsorbent, surface defects on CNTs. On the other
hand, the studies done in the past show that the cytotoxic property of CNTs prevents
bioremediation cyanobacterial toxins. However recent studies show that bio-compatible
CNTs allow bacterial growth on these CNTs that leads to efficient bioremediation of
MC’s. A study showed that growth of a plant based bacteria named Ralstonia
solanacearum on bio-compatible which was also non-toxic resulted in considererable

removal of MC’s from water. The efficiency of this simultaneous existence of selected
pathogen and CNTs higher than the removal efficiencies achieved by the CNTs and this
plant based pathogen separately
o Adsorption of heavy metals.
Many studies have shown that pH level plays an important role in removing heavy metals
through CNTs. A study indicated that efficiency of removal of lead from water can be
increased by optimizing the pH level. It was also seen that maintaining the pH higher than
4 can result in efficient removal of chromium. This study concluded that CNTs can serve
as effective adsorbents for removal of heavy metals increases by increasing the pH that
results in decrease in the protonation of the surface that in turn increases the adsorption
capacity of CNTs.
 Application of CNTs for Waste Water Treatment

Wastewater produced from two major sources one is residential source other is non-
residential source. The water that is mostly diluted and produced from public dwellings is
termed as sewage. Residential waste water is also known as sewage. Sewage comprises
of 99.8% of water and 0.11% of suspended solids, inorganic solids, metals, decomposable
organic compounds, and pathogenic micro-organisms. Nutrients like nitrogen &
phosphorous also present in sewage which are contaminants and should be removed in
order to avoid toxicity.
The water that is produced from agriculture fields, industries and commercial actions
is termed as Non-residential wastewater. Rain water obtained from streets is comprises of
both organic & inorganic contaminants is also a form of non-residential waste water.
Present technologies of waste water requires large areas for installing plant, high operating
cost, high maintenance cost & high energy demand. Nanotechnology suggest low cost
substituted technology for waste water treatment. Carbon-based nanotechnology involves
carbon-based nanomaterials like carbon nanotubes for the treatment of wastewater
contaminants. Other various nanomaterials like metal oxides, metal nanoparticles, and
zeolite are also used in these techniques

o CNT based membranes and membrane processes.

Nano-filtration (NF) is defined as a membrane separation technique that require low
energy consumption. As nanofiltration technique involves unique filtration process and
due to the presence of different kinds of membranes, so this technique is more appropriate
to filter out all organic & inorganic pollutants from waste water. Type of membrane
material decide the working of nanofiltration membrane systems. Efficient membrane
permeability, mechanical & thermal strength, fouling resistance, and pollutant
decomposition can be obtained by incorporating nanmaterials into membranes. Because
of easy preparation, high powered strength and best rejection ability carbon base
nanomaterials are mostly used for membrane production. CNT membrane comprises of
open end single empty structure which is settled upright with resistant filter media. These
CNT membranes are considered as a model water distillation tool.
One of the CNT based membrane advantage is these membranes are tough like
ceramic membrane & elastic or soft like polymeric membranes. The second major
advantage is CNT membrane allow fast infiltration of water. Graphenes membrane
produced more accurate results then CNTs membranes. Graphenes membrane shows same
chemical & thermal strength with best elasticity. These membrane show high rejection of
organic dye in water. As compared to other membranes CNTs membrane show high
innovativeperformances and in coming future has the ability to be feasible commercially.
The marketable accessibility of the CNT membranes must follow definite criterions such
as desalination ability, toughness, water penetrability, solute discrimination, antifouling,
energy funds, material costs, and compatibility with industrialized sites. By adding
nanomaterials in to active layer of TFN composite membrane through doping in casting
solution better performance of membrane is achieved. TFN membrane show better anti-
bacterial characteristics. TFN membrane kills 61% bacteria in almost one hour interaction
time. These membrane minimize membrane bio-fouling. Unaligned CNTs because of
their anti-microbial activities covalently bonded single walled nanotubes to a TFC
membrane surface for reducing microbes.

o CNTs for Disinfection
Now a days, for water industry, development of harmful (DBPs) & their current
disinfection shows a great challenge. DBPs are formed by conservative disinfectants
which includes ozone & chlorine disinfectants. Nano-materials have low ability to form
DBPs and without strong oxidation show anti-microbial properties. Such nano-materials
includes nano-ZnO, nano-Ag, nano-TiO2 and CNTs. By disrupting particular microbial
process, and by causing physical discomposure of cell membrane, CNTs remove bacteria.
Graphene which is another carbon based membrane also show anti-microbial properties
with same process. Physiochemical properties determine cytotoxicity of CNTs. CNTs
consisting of small diameter are more harmful. Membrane bio-fouling can also be reduced
by antimicrobial nanomaterials (nanoAg and CNTs). Through direct contact CNTs
deactivate bacteria. By using polyvinyl-N-carbazole-SWNT, almost 91% bacterial
inactivation has been attained. No replacement is required as CNTs are not absorbed as
well as are not soluble in water. Long time filtration experiments are required to define
the effect of fouling on the antimicrobial activity of CNTs, as direct contact is required
for inactivation.
o CNT Filters as Anti-microbial Materials
Millions of people die each year from water related diseases. The removal of bacteria and
other organisms from drinking water is an extremely important process. CNTs, especially
SWCNTs, exhibit strong antimicrobial activity. Direct contact with SWCNTs causes
severe membrane damage and subsequently cell death. SWCNT filter showed high
bacterial retention, and MWCNT filter exhibited high viral removal at low pressure, both
14 Recent Progress in Carbon Nanotube Research / Book 2 through size exclusion effect.
To combine their advantages, SWCNT-MWCNT hybrid filter achieved efficient bacterial
inactivation and viral retention at low pressure. By applying external electric field, viral
removal by CNT filter was markedly enhanced as a result of increased viral particle
transport. In combination with silver nanoparticles or silver nanowires, enhanced
antibacterial ability were achieved.

Figure. Removal of E. coli bacteria using CNT filter. (a) E. coli-ridden solution, (b) colonies of E.
coli bacteria (marked by arrows) grown by the culture of the polluted water,
(c) cylindrical CNT filter, (d) filtrate, (e) no bacterial colonies grown by the culture of the filtrate.
The above-mentioned CNT filters were prepared by simple filtration of CNT

suspensions through a porous substrate. Scientists fabricated a monolithic uniform
macroscopic hollow cylinder having radially aligned CNT walls by using a continuous
spray pyrolysis method. The CNT aligns had a uniform nanoporous structure which was
favorable for filtration with low blockage. The cylinder also had high mechanical strength
and thermal stability. Figure shows the application of CNT filter in the removal of E. coli
bacteria from water. The CNT filter had a major advantage over conventional membrane
filters: it can be cleaned repeatedly by simple ultrasonication and antoclaving. After
regeneration, the filter regained its full filtering efficiency.
o CNTs for sensing and monitoring of wastewater
Due to the tremendously low quantity of some pollutants present in water, the high
difficulty of the wastewater mediums and the deficiency of pathogen detection water
quality is an important challenge for water industry now a days. Advanced sensors that
consist of high discrimination & sensitivity, with fast reaction are required for sensing
contaminants detection in waste water.

 CNTs for detection of pathogens in wastewater

In waste water presence of pathogen detection is of great importance as these
pathogens are directly related to public health and environment. Regular indicator like
Coliform bacteria are regular indicators and are fail to sense the presence of pathogens in
water. For pathogen detection mostly used nanomaterials are Quantum dots (QDs),
magnetic nanoparticles, noble metals, and CNTs. For sample concentration &
purification, magnetic nanoparticles and CNTs are used on large scale. CNTs considered
as best electrode material due to its high conductivity. Subsequently, by enhancing
electron transfer & electrode analysis contact, CNTs can enable electrochemical detection.
Detection sensitivity can also be enhanced through the adsorption ability of CNTs.
Heterogeneity of CNTs is a great challenge for CNT based sensors. For environmental
analysis of trace metal, CNTs have huge capability as CNTs have best recovery rate, great
adsorption ability and rapid kinetics.
o CNTs as Additives for Anti-fouling Membranes
Fouling of polymer membranes depends on the interaction between membrane surface

and foulants, which is related to the membrane morphology and chemistry as well as the
properties of foulant. Tuning the membrane surface chemistry is an effective method to
control membrane fouling. It is generally accepted that increasing the surface
hydrophilicity offers a better fouling resistance because many organic foulants are
hydrophobic. CNTs, although hydrophobic in nature, can be changed to hydrophilic via
acid treatment. It has been demonstrated that CNT blended polysulfone membrane and
polyethersulfone membrane are more hydrophilic and have an enhanced fouling resistance
due to the hydrophilic carboxylic groups of functionalized CNTs. Other functional groups
can also be introduced onto CNT surface, such as hydrophilic isophthaloyl chloride groups
and amphilic-polymer groups with protein-resistant ability
.
Biofouling, the growth of a biofilm on membrane surfaces, can also be alleviated
by the incorporation of CNTs. As mentioned before, CNTs have anti-bacterial properties,
so the introduction of CNTs to polymer membranes could impart biocidal properties to
the membrane, resulting in a better biofouling resistance. CNT can also be used to

Figure. Schematic diagram of Ag/MWCNT coated polyacrylonitrile hollow

fiber membrane with antibacterial activity.
improve the dispersion of other antimicrobial agents, like Ag nanoparticles (Figure). The
Ag nanoparticles loaded on MWCNTs achieved an excellent dispersion with size around
2- 5 nm, leading to more direct contact with bacteria and more effective antibacterial
activity.
 Synthesis of CNTs
There are several techniques that have been developed for fabricating CNT structures
which mainly involve gas phase processes. Commonly, three procedures are being used
for producing CNTs: (1) the chemical vapor deposition (CVD) technique, (2) the laser-
ablation technique, and (3) the carbon arc-discharge technique (Table 3). High
temperature preparation techniques for example laser ablation or arc discharge were first
used to synthesize CNTs, but currently, these techniques have been substituted by low
temperature chemical vapor deposition (CVD) methods (<800°C), since the nanotube
length, diameter, alignment, purity, density, and orientation of CNTs can be accurately
controlled in the low temperature chemical vapor deposition (CVD) methods.

o Electric arc discharge
Arc-discharge technique uses higher temperatures (above 1,700°C) for CNT synthesis
which typically causes the expansion of CNTs with fewer structural defects in comparison
with other methods. The most utilized methods use arc discharge between high-purity
graphite (6 to 10-mm optical density (OD)) electrodes usually water-cooled electrodes
with diameters between 6 and 12 mm and separated by 1 to 2 mm in a chamber filled with
helium (500 torr) at subatmospheric pressure (helium can be replaced by hydrogen or
methane atmosphere).
The chamber contains a graphite cathode and anode as well as evaporated carbon
molecules and some amount of metal catalyst particles (such as cobalt, nickel, and/or
iron). Direct current is passed through the camber (arcing process), and the chamber is
pressurized and heated to approximately 4,000 K. In the course of this procedure and
arcing, about half of the evaporated carbon solidifies on the cathode (negative electrode)
tip, and a deposit forms at a rate of 1 mm/min which is called ‘cylindrical hard deposit or
cigar-like structure’, whereas the anode (positive electrode) is consumed. The remaining
carbon (a hard gray shell) deposited on the periphery and condenses into ‘chamber soot’

nearby the walls of the chamber and ‘cathode soot’ on the cathode. The inner core, cathode
soot and chamber soot, which are dark and soft, yield either single-walled or multiwalled
carbon nanotubes and nested polyhedral graphene particles. By using scanning electron
microscopy (SEM), two different textures and morphologies can be observed in studying
of the cathode deposit; the dark and soft inner core deposits consist of bundle-like
structures, which contain randomly arranged nanotubes and the gray outer shell, which is
composed of curved and solid grapheme layers.
o Laser ablation method
By using of high-power laser vaporization (YAG type), a quartz tube containing a block
of pure graphite is heated inside a furnace at 1,200 ± C, in an Ar atmosphere [12]. The
aim of using laser is vaporizing the graphite within the quartz. As described about the
synthesis of SWNT by using arc-discharge method, for generating of SWNTs, using the
laser technique adding of metal particles as catalysts to the graphite targets is necessary.
Studies have shown the diameter of the nanotubes depends upon the laser power. When
the laser pulse power is increased, the diameter of the tubes became thinner. Other studies
have indicated ultrafast (subpicosecond) laser pulses are potential and able to create large
amounts of SWNTs. The authors revealed that it is now promising to create up to 1.5 g/h
of nanotube material using the laser technique.
Figure: Schematic diagram for laser ablation

Many parameters can affect the properties of CNTs synthesized by the laser ablation
method such as the structural and chemical composition of the target material, the laser
properties (peak power, cw versus pulse, energy fluence, oscillation wavelength, and
repetition rate), flow and pressure of the buffer gas, the chamber pressure and the chemical
composition, the distance between the target and the substrates, and ambient temperature.
This method has a potential for production of SWNTs with high purity and high quality.
The principles and mechanisms of laser ablation method are similar to the arc-discharge
technique, but in this method, the needed energy is provided by a laser which hit a pure
graphite pellet holding catalyst materials (frequently cobalt or nickel).
The main advantages of this technique consist of a relatively high yield and
relatively low metallic impurities, since the metallic atoms involved have a tendency to
evaporate from
the end of the tube once it is closed. On other hand, the main disadvantage is that the
obtained nanotubes from this technique are not necessarily uniformly
straight but instead do contain some branching.
Unfortunately, the laser ablation method is not economically advantageous because the
procedure encompasses high-purity graphite rods, the laser powers required are great (in
some cases two laser beams are required), and the quantity of nanotubes that can be
synthesized per day is not as high as arc-discharge technique.
o Chemical Vapor Deposition
One of standard methods for production of carbon nanotubes is chemical vapor deposition
or CVD. There are many different types of CVD such as catalytic chemical vapor
deposition (CCVD)—either thermal or plasma enhanced (PE) oxygen assisted CVD,
water assisted CVD , microwave plasma (MPECVD), radiofrequency CVD (RF-CVD),
or hot-filament (HFCVD). But catalytic chemical vapor deposition (CCVD) is currently
the standard technique for the synthesis of carbon nanotubes. This technique allows CNTs
to expand on different of materials and involves the chemical breakdown of a hydrocarbon
on a substrate. The main process of growing carbon nanotubes in this method as same as
arc discharge method also is exciting carbon atoms that are in contact with metallic

catalyst particles. For all intents and purposes, tubes are drilled into silicon and also
implanted with iron nanoparticles at the bottom. After that, a hydrocarbon such as
acetylene is heated and decomposed onto the substrate. Since the carbon is able to make
contact with the metal particles implanted in the holes, it initiates to create nanotubes
which are a ‘template’ from the shape of the tunnel. With using of these properties, the
carbon nanotubes can grow very well aligned and very long, in the angle of the tunnel.
Figure: Schematic diagram for CVD
In CVD processing, a layer of metal catalyst particles prepare and process a

substrate at approximately 700°C. Most commonly, metal catalyst particles are nickel,
cobalt [28], iron, or a combination [29]. The aim of using the metal nanoparticles in
combination with a catalyst support such as MgO or Al2O3 is to develop the surface area
for higher by-product of the catalytic reaction of the pure carbon with the metal particles.
In the first step of nanotube expansion, two types of gases fueled the reactor (the most
widely used reactor is fluidized bed reactor [30,31]): a carboncontaining gas (such as
ethylene, acetylene, methane, or ethanol) and a process gas (such as nitrogen, hydrogen,
or ammonia). At the surface of the catalyst particle, the carbon-containing gas is broken
apart and so the carbon became visible at the edges of the nanoparticle where the
nanotubes can produce. This mechanism is still under discussion [32]. Studies have shown
the conventionally accepted models are base growth and tip growth [33]. Depending on
the adhesion and attachment between the substrate and the catalyst particle, the catalyst

particles can remain at the nanotube base or nanotube during growth and expansion [34].
As compared with laser ablation, CCVD is an economically practical method for large-
scale and quite pure CNT production and so the important advantage of CVD are high
purity obtained material and easy control of the reaction course.
 Nanotube purification
Depending on technique of carbon nanotube synthesis, there are many different methods
and procedure for purification. All purification procedures have the following main steps:
deletion of large graphite particles and aggregations with filtration, dissolution in
appropriate solvents to eliminate catalyst particles (concentrated acids as solvent) and
fullerenes (use of organic solvents), and microfiltrations and chromatography to size
separation and remove the amorphous carbon clusters. Purification of MWNTs produced
by arc-discharge techniques can be done by using oxidation techniques which
can take apart MWNTs from polyhedral graphite-like particles.
The main disadvantages of this method are low purity, high destroying rate of starting
materials (95%), as well as high reactivity of the remaining nanotubes at end of process
due to existence of dangling bonds (an unsatisfied valence) and for elimination of such
dangling bonds is necessary to use high-temperature annealing (2,800 ± C).
The nondestructive methods for separating CNTs couple well-dispersed colloidal

suspensions of tubes/particles with materials which prevent aggregation such as
surfactants, polymers, or other colloidal particles. The other method as aim of size
exclusion nanotubes uses size exclusion chromatography and porous filters as well as
ultrasonically assisted microfiltration which purifies SWNTs from amorphous carbon and
catalytic particles.
Studies have shown the boiling of SWNTs in nitric acid or hydrofluoric acid aqueous
solutions for purification of SWNTs and removing amorphous carbon and metal particles
as an efficient and simple technique. For the purification of carbon tubules, scientist
prefers to use sonication of nanotube in different media and afterward thermal oxidation
of SWNT material (at 470°C) as well as hydrochloric acid treatments. Another way for

oxidizing unsatisfied carbonaceous particles is use of gold clusters (OD 20 nm) together
with the thermal oxidation of SWNTs at 350°C.
Scientists introduce a new way for separation of semiconducting and metallic SWNTs by
using of size exclusion chromatography (SEC) of DNA-dispersed carbon nanotubes
(DNA-SWNT), which have the highest resolution length sorting. The density-gradient
ultracentrifugation has been used for separation of SWNT based on diameter.
Combination of ion-exchange chromatography (IEC) and DNA-SWNT (IEC-DNA-
SWNT) has also been used for purification of individual chiralities. In this process,
specific short DNA oligomers can be used to separate individual SWNT chiralities.
Scientists have used fluorination and bromination processes as well as acid treatments of
MWNT and SWNT material with the aims of purifying, cutting, and suspending the
materials uniformly in certain organic solvents.
As discussed above, depending on nanotube synthesis way, there are many different
methods for purification of carbon nanotubes, and therefore, existence of methods which
are single-step processes and unaffected on properties of carbon nanotube products is
essential for producing clean nanotubes and should be targeted in the future.
 Properties of CNTs
Size, shape, surface or molecular space are the most cited properties of carbonaceous
materials for environmental applications. Unique properties of individual as well as bulk
carbonaceous nanomaterial configurations including electrical conductivity and
adsorption offer potential for expansion of their environmental applications. Detailed
characterization of properties, methods of synthesis and methods for purification of
carbon nanotubes (CNTs) can help in technical and environmental advancements. Solvent
chemistry and bundling state of CNTs greatly influence physical properties of
carbonaceous nanomaterials that include shape, surface area and size. In addition to this,
mechanical strength, physicochemical, thermal and electrical properties as well as
bundling behavior of CNTs are greatly influenced by the nature of impurities such as
heavy metals and biomolecules of vapors. Although most of the studies have addressed

physical properties of CNTs, less literature is available on the characterization of

inconsistent physicochemical properties of CNTs that are associated with the secondary
structure of bundles or aggregates of carbonaceous nanomaterials.
This review paper covers modern developments and the application of carbon based nano
technology in water and wastewater treatment. This paper also underlining the possible
usage of CNTs or CNTs based membrane to report numerous encounters confronted by
the present water/wastewater treatment technologies.
 Other Potential Applications of CNTs
o Biomedical applications
o Artificial implants
o Tissue engineering
o Cancer cell identification
o Drug and gene delivery by CNTs
o Interconnects
o Transistors
o Electronic Design And Design Automation
o Electro Acoustic
o Electromagnetic
 Current hurdles and future challenges
Following are the five present hurdles which are as follows:

 First complication is the difficult process which involves the breakdown of CNTs
with even pore size and distribution. Present CVD process failed to breakdown
such controlled-pores with even distribution. Bottom up approach which is
expensive & time consuming could be used for breakdown of these controlled-
pores.
 Second hurdle involves minimization of diameter of CNT membrane & pore size.
Good desalination properties can be obtained only with single walled carbon nano
tubes (SWCNTs). Large pore diameter nano tubes have minimum ion rejection

efficiencies as compared to small pore diameter nano tubes which have high ion
rejection efficiencies.
 Third complication may be growth of CNT with appropriate alignment. Toxic
effects on water path & salt rejection was seen due to the abnormalities in
membrane shape.
 Fourth complication involves at CNT tips addition of suitable useful groups. In
order to allow efficient water flow closed tip ends of CNTs must be opened by
suitable wet chemical treatments. Adding new functions or properties which is
termed as functionalization is considered as a limiting step. This should be handle
properly to adjust CNT membrane penetrability to solutes & water molecules.
 Fifth complication is cost that is a major limiting factor as single walled carbon
nano tubes (SWCNTs) are not cost effective. With sub-nanometer pore diameter,
MWCNTs cannot be used to breakdown CNT membranes. As compared to
SWCNTs and MWCNTs Few walled carbon nano tubes for 1 nm pore diameter
membrane are proved very cost effective.
 Conclusions
Global challenges particularly industrialization, urbanization, and anthropogenic

activities have been continuously polluted water, raising the issues of various diseases,
food safety and biodiversity of terrestrial, aquatic, and aerial, flora and fauna. In order to
overcome the fresh water availability, CNT-based water purifications sowed the seeds of
novel and innovative wastewater purification technologies because of its large surface
area, high aspect ratio, greater chemical reactivity, lower cost, and energy, less chemical
mass, and impact on the environment.
Here we reviewed CNT-mediated effective decontamination processes such as adsorption,

hybrid catalysis, desalination, disinfection, sensing and monitoring of three major classes
such as organic, inorganic, and biological water pollutants. Nanobiohybrid catalysis has
recently been grown as a novel technology with high selectivity, sensitivity, stability, and
reusability. But a few studies have been adopted and/or published on Nanobiohybrid
decontaminations, and most of them have dealt only to determine permissive and non-

permissive levels of water pollutant concentrations. It appeals more study to mature the
field from various angles not only to sense the novel toxic water pollutants, but to mitigate
them from complex wastewater matrices.
As a corollary, we emphasized the importance of Nanobiohybrid-mediated water

purification technology. We believe that upgrading the Nanobiohybrid technology by
controlling its steering speeds and improving its performances would be a robust solution
to face current threats, and challenges of water purifications through both incremental and
revolutionary ways.
Finally,Carbon Nanotube in Water Treatment forayed into the deeper thoughts and
compiled promises, facts and challenges of the important water purification technologies.
Since water purification is a complex process, hydrologists, membrane technologists,
environmentalists and industrialists can design “ONE POT” combination where effective
water purification technologies would instate to tackle both the conventional and newly
emerging toxic pollutants effectively.
With the hope of this, let us think a best future of improved and efficacious
decontamination platform, and thereby ensure plethora of fresh water for all.

 References
 Chapter 2 Carbon Nanotube in Water Treatment Thousands have lived without

love, not one without water.—Source: W.H. Auden: Collected Poems: Auden
by W.H. Auden, 1991.
 Carbon nanotube membranes for water purification: A bright future in water
desalination Rasel Das a, Md. Eaqub Ali a,⁎, Sharifah Bee Abd Hamida, Seeram
Ramakrishna b,c, Zaira Zaman Chowdhury a
 Multifunctional carbon nanotubes in water treatment: The present, past and future
Rasel Das a, Sharifah Bee Abd Hamid a,⁎, Md. Eaqub Ali a, Ahmad Fauzi Ismail
b, M.S.M. Annuar c, Seeram Ramakrishna d,e
 Applications of carbon nanotubes (CNTs) for the treatment of drinking and waste
water-a brief review Alizae Salaam Ahmad, Mariya Irfan Ali Qureshi, Savita
Anum, Dr. Ghazala Yaqub Department of Environmental sciences, Kinnaird
College for Women, Lahore, Pakistan
 Potential of Carbon Nanotubes in Water Treatment Xitong Liu, Shujuan Zhang

and Bingcai Pan.
 Carbon nanotubes: properties, synthesis, purification, and medical applications

Ali Eatemadi1, Hadis Daraee1, Hamzeh Karimkhanloo1, Mohammad Kouhi4*,
Nosratollah Zarghami1, Abolfazl Akbarzadeh2,5*, Mozhgan Abasi1, Younes
Hanifehpour3 and Sang Woo Joo3*
 Carbon nanotube: A review on its mechanica properties and application in

aerospace industry To cite this article: A Raunika et al 2017 IOP Conf. Ser.:
Mater. Sci. Eng. 270 012027
 http://phycomp.technion.ac.il/~talimu/structure.html
 https://en.wikipedia.org/wiki/Nanotechnology_for_water_purification#Health_an
d_safety
 http://www.understandingnano.com/what-are-carbon-nanotubes.html

 https://en.wikipedia.org/wiki/Carbon_nanotube
 https://nanografi.com/blog/singlewalled-carbon-nanotubes-descriptions-usage-
and-applications/

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To address this problem, various water purification technologies have been

UDCT Amravati Page 1

Since water purification is a complex process; hydrologists, membrane technologists,

Water is important in many geological processes. Groundwater is present in

UDCT Amravati Page 2

UDCT Amravati Page 3

 WATER SCARCITY AND ITS CONSEQUENCES

UDCT Amravati Page 4

Fig. 1 Schematic representation of population growth (outer plot) and their

UDCT Amravati Page 5

World population is increasing at a rate of 80 million/year, putting an additional

Fig. 2. Areas encountered with water scarcities on Earth.

 CONVENTIONAL WATER PURIFICATION METHODS

o Coagulation and flocculation

UDCT Amravati Page 7

 Threats to Conventional Water Treatment Technologies

Fig. 1 Some major threats of conventional water purification technologies.

UDCT Amravati Page 8

Traditional treatment technologies as described are mainly designed to remove

UDCT Amravati Page 9

Nanotechnology ("nanotech") is manipulation of matter on an atomic, molecular,

Nanotechnology as defined by size is naturally very broad, including fields of

UDCT Amravati Page 10

In the 1980s, two major breakthroughs sparked the growth of nanotechnology in

Second, Fullerenes were discovered in 1985 by Harry Kroto, Richard Smalley,

Meanwhile, commercialization of products based on advancements in nanoscale

 FUNDAMENTAL CONCEPTS IN NANO-TECHNOLOGY.

 A sheet of newspaper is about 100,000 nanometers thick

UDCT Amravati Page 11

 Nanoscience and nanotechnology involve the ability to see and to control

 Although modern nanoscience and nanotechnology are quite new, nanoscale

 Today's scientists and engineers are finding a wide variety of ways to

 Two main approaches are used in nanotechnology. In the "bottom-up" approach,

UDCT Amravati Page 12

 The Significance of the Nanoscale

 Creation of new improved products.

UDCT Amravati Page 13

Carbon nanotubes (CNTs)

UDCT Amravati Page 14

A significant nanoparticle discovery that came to light in 1991 was carbon

 HISTORY OF CARBON NANOTUBES

UDCT Amravati Page 15

 STRUCTURE OF CARBON NANOTUBES

UDCT Amravati Page 16

 TYPES OF CARBON NANOTUBES

o On the Basis of Walls

There is no consensus on some terms describing carbon nanotubes in scientific literature:

UDCT Amravati Page 17

1. Single-Walled Carbon Nanotube

2. Multi-Walled Carbon Nanotube

UDCT Amravati Page 18

Single-Walled Carbon Nanotubes (SWCNT) have unique properties. In terms of

o On the Basis of Symmetry

UDCT Amravati Page 19

o On the Basis of Open-Closed Ends

Fig – Open end CNT

Fig – Closed end CNT

UDCT Amravati Page 20

 Functions Performed By Carbon Nanotubes In Water

UDCT Amravati Page 21

Adsorption is a process where substance (pollutant) concentrations would increase and

Adsorption isotherms of acidified MWCNTs to Pb(II), Ag(I),