Nanomaterials application in Enviroment

and its protection (air - water)

• Supervisor :
DR / Hamdy sayed el-Wasly .

• Itroduced by :
Mohamed said kandil

Islam gamal ali Hassan

Abdulrahman ashraf Hassan

Abstract

With the increase in the global human population, the

technologies adequate supply of resources has become limited.
The development of pollution-free for environmental
remediation and clean energy supplies for the sustainable
growth of human society is the need of the hour.
Nanotechnology can have a substantial impact on developing
‘cleaner’ and ‘greener’ technologies with significant health and
environmenttal benefits.
The applications of nanotechnology are being explored for their
potential to provide solutions to manage, mitigate, and clean-
up air, water, and land pollution, as well as to improve the
performance of conventional technologies used in
environmental clean-up. Green nanotechnology is the branch
of nanotechnology that envisages sustainability through various
applications.
Introduction

One of the biggest challenges of the present situation is to

provide sustainable development for the coming generations
utilizing the concepts and principles of green chemistry and
green engineering to make nano-products and materials
without noxious end products and to expend lifecycle thinking
in all design and engineering phases.

Nanotechnology has the potential to use novel nanomaterials

for groundwater, surface water, and wastewater remediation
contaminated by heavy metal ions, organic–inorganic solutes,
and a wide range of micro organisms .
At present, several nanomaterials are in the extensive research
and development (R&D) stage for use in environmental clean-
up and site remediation due to their unique activity toward
nondegradable contaminants.
Green manufacturing is the most efficient way to reduce and
eliminate the release of toxic pollutants in soil, water, and air
environments.
The use of nano-adsorbents can effectively remove organic
pollutants, dyes, and dye effluents from contaminated water,
such as clays, zeolites, metals, metal oxides, polymeric
membranes, porous nanofibers, and zero-valent iron.
Semiconductor based photocatalysts are used in the advanced
oxidation processes (AOP) for the degradation and
mineralization under irradiation (natural & artificial) of toxic
organic contaminants into environmentally friendly compounds.
Nanoscience, considered as an emerging field, provides an
informative framework to study the applications and
implications of green chemistry in a broader and safer way. As
compared to the previous remediation technologies.
Green Nanotechnology

As the term green suggests there is something environmentally

friendly here. Green
nanotechnology involves the development and application of
products in an environmentally friendly way, whereas green
chemistry is defined as the “the utilization of the twelve
principles that reduces and eliminates the use or generation of
hazardous substances in the design, production, and
application of chemical products and processes” .
The principles of green chemistry, defined by Anastas and
given in Table 2.1, are applied nowadays for the production of a
wide range of chemicals with the aim of reducing hazards to
health and the environment, minimizing wastes, and
preventing pollution.

The application of the 12 principles of green chemistry has

decreased the consumption of toxic solvents and reagents
manifold, enhanced the design of products for the end-of-life,
and enhanced the material and energy efficiency of chemical
procedures.
The application of these principles of green chemistry to
nanoscience will ease the synthesis and processing of safer and
greener nanomaterials
Green nano involves the application of green chemistry to the
design and development of nanomaterial production methods
(small and large scale) and the application of nanomaterials in
various areas
It also aims to provide knowledge about the properties of
nanomaterials with reference to the toxicity issues and the
design of multifunctional nanomaterials that can be used in
high capacity products, which can pose a threat to human
health and the environment .
Most importantly, it attempts to develop the
synthesis/methods that can eliminate the need for harmful
chemicals while enhancing the efficiency of these existing
synthesis methodologies .
It also provides the outlines for assuring that the as-synthesized
nanoproducts are safer by accessing the ecological risks and
hazards with reference to the design. Further, it seeks the
application of nanotechnology that has a broader societal
benefit by decreasing the adverse impact on health and the
ecosystem. Thus, green nano starts with the development of
materials, their processing, and application, throughout the life
cycle, right from the beginning from the selection of raw
material to the end of life (safer release to the environment)
Figure 2.3 shows the benefits of nanotechnology .
Application of Green Chemistry Principles
to Nanoscience

Nanomaterials have a high surface to volume ratio and tunable

properties make them efficient for a wide range of applications
from healthcare to environmental remediation .
Nanomaterials are almost everywhere due to their
multifunctionality and properties . The applications of
nanotechnology are growing day by day, promising
environmental benefits, such as nano catalysts for
environmental remediation, thermo-electric materials for
cooling down without the use of refrigerants, efficient
photovoltaic, lightweight nanocomposite materials for vehicles,
mini devices to reduce the consumption of material, and nano
sensors, which eliminate the need of wet chemical analysis.
Nano sensors are fasters and their lower detection limits make
on-site detection possible.
The new nanotechnologies are beneficial yet possess little
harm to human health and the environment; therefore, it is
necessary to design and develop the green nanomaterials and
their synthesis methods .
 First, the nano-manufacturing process has been discussed in
the light of green chemistry, and later the application part has
been discussed.
It is a known fact that nanomaterials have rich structural
diversity, providing a wide opportunity to tune the physical,
chemical, optical, and toxicological properties. During
experimental design and analysis, extreme care should be taken
as the complexity and diversity of nanoparticles can alter the
toxicity related issues .
Significantly, the use of different synthesis methods for the
production of similar products means the difference in the
methodology and reaction routes leads to a difference in
product purity, quantity, intermediate, and end product. Also,
the synthesized nanomaterials should be characterized in detail
by known particle size, shape, size distribution, surface area,
morphology, solubility, crystallinity, physical, chemical, optical,
and electronic properties .
The utilization of these well-characterized nanomaterials allows
accurate biological and ecological impact assessment .
The principles also focused on the impact of nanomaterials that
may be released to the environment after the application. Thus,
the design of material should also focus on the very aspect that
it should reduce harm to the environment by using
environmentally friendly materials .
It also aims to design such materials that are safer and radially
degrade into the environment without generating toxic
intermediates and hazardous end products .

To implement the principles, the fate and life cycle assessment

of the nanomaterial is needed. Various short-term and long-
term effects of the nanomaterials in the water, soil, and air
should also be considered in view of human health as the
prolonged persistence of nanomaterial in the environment
gives rise to nanotoxicity related issues.

Nanotoxicology is intended to describe the toxicological

properties of an engineered nanomaterial to decide whether
and to what extent nanomaterials pose a threat to the
environment and human health (Hoet et al. 2004). In terms of
their fate in the human body and in the environment, the size
of nanoparticles and lack of detection method presents a huge
drawback in the context of identification and remediation .
It is noteworthy that not all the nanoparticles are toxic to the
environment; it depends on their concentration, dosage, and
exposure rate (Martin et al. 2008; Krishnaswamy and Orsat
2017). Over the past decades, the fate, transport, and toxicity
of engineered nanomaterials have been a major focus of
environmental health and safety research throughout the globe.
The basic and fundamental properties concerning the fate of
nanomaterials are not well understood due to the lack of
research studies .
The rapid consumption, usage, and production of
nanomaterials ultimately lead to environmental exposure .
Also, less is known about the eco-toxicological concerns and
chronic effects of nanomaterials to date. Green
nanotechnology focuses on various processes as summarized in
Fig. 2.4:
The major application of Green Nanotechnology involves:
Nanomanufacturing

The application of the principles of green chemistry in the

nanomanufacturing/nano synthesis process is an emerging area
aimed at sustainable development.
It has gained worldwide attention in recent years due to its
potential for designing multifunctional, energy efficient, and
nontoxic synthesis routes .
It is associated with the chemicals, reagents, and solvents used
during the preparation and synthesis methods. This section will
focus on the synthesis routes of nanomaterials and
nanoproducts with special attention to the significant
environmental impacts .
All the nano-products must proceed via the various
development stages to produce the particles, materials, and
devices in the nanoscale dimension. A life-cycle assessment
analysis checks the manufacturing of a nanomaterial and also
its fate after the release in the environment up to its end-of life .
The newly developed materials are expected to (a) possess
high surface functionality, (b) exhibit size-dependent properties,
and (c) incorporate a wide range of material and elemental
compositions (Dahl et al. 2007). The assessment of these
materials, before their acceptance in the commercial front,
presents an opportunity for reducing the negative impact of the
material, which is a must. The production of a highly precise,
low waste generating method for the nanomanufacturing
process will be essential for the commercialization of these
products.
Green chemistry also provides the platform to increase the
public perception of nanotechnology, as the present approach
is comparatively easy to understand and useful to convey the
responsible attitude toward the expansion of green
nanotechnology .
That is the reason green chemistry can play the pivotal role in
the growth of nanotechnology with the aim of providing the
maximum benefit of these products to society .

• The advantages of green nanomanufacturing are as

follows:
1. Production of relatively safer and greener nanoproducts
2. Eliminates the necessity of hazardous chemicals and solvents
for the purpose of synthesis
3. Comparatively cheaper and environmentally friendly
4. No toxic end product
5. Requires fewer manufacturing and safety controls for the
production.

Nanomanufacturing processes are widely associated with

human health and environmental impacts .
It is important to evaluate nano-products for their green
approaches, incorporating risk analysis and life-cycle
assessment using the sustainable manufacturing approaches
and employing green chemistry alternatives are the possible
solution (Hutchison 2016, USEPA). Basically, for nanomaterial
manufacturing, the widely used approaches are bottom-up and
topdown techniques .
Wastewater Treatment Using Nanomaterials

The availability of clean and safe drinking water is a global

challenge. Water and wastewater treatment methods are
chemically intensive as well as costly and harmful to the
environment to a certain extent .
The conventional treatment technologies require high capital
input, a large area, and high maintenance costs, and they just
transfer the pollutants from one phase to another, rather than
completely degrading them into an environmentally friendly
end product .
This necessitates an alternative technology for the treatment of
wastewater in a greener and more sustainable way.
At present, many physicochemical methods, such as carbon
adsorption, distillation, ion-exchange, reverse osmosis, and
nanofiltration, are used for the purification of wastewater .
Major drawbacks associated with these methods include
membrane deformation, high cost, handling, sludge formation,
and disposable problems. On the other hand, non-
biodegradable pollutants pose a serious threat as the majority
of these pollutants require a high priority treatment .
 This necessitates an advanced, greener, more cost effective
method for wastewater treatment. Figure 2.9 shows the
conventional and advanced wastewater treatment technologies.

Nanotechnology provides the solution to the existing problem.

Nano-based catalysts, adsorbents, and membranes can create
eco-friendly solutions to wastewater treatment .
Nanomaterials have gained widespread attention in the field of
environmental clean-up and remediation due to their higher
surface-tovolume ratio .
The other specific changes in their physical, chemical, and
biological properties developed owing to their size are also an
added advantage . Research is underway for the development
of novel nanomaterials with increased efficiency, selectivity,
and capacity for the treatment of wastewater.
There are several benefits of using nanomaterials due to their
higher surface reactivity and surface-to-volume ratio .
Nanotechnology for water purification plays an important role
in providing global water purity and security.
 • The application of nanotechnology for the treatment of
wastewater could be summarized under the following
points:

(i) By nanoscale filtration techniques, such as nanofiltration

using membranes,
(ii) By nano-adsorbent materials, such as sorbents, nanoclays,
zeolites,
(iii) Nanophotocatalysis using nano-sized semiconductor
material for environmental remediation,
(iv) Nanocomposites, such as metal–polymer nanocomposites
for various applications,

(v) Nanomaterials for heavy metal remediation,

(vi) Metal and metal oxides for the removal of deadly microbes
from the water.
Many research studies indicate that nano-based remediation
technologies will be safer, more economical, and more
efficient than the conventional techniques.
Nanomaterials can be used for the sensing and detection of
pollutants, remediation, and prevention of pollution
Additionally, nanomaterials can also be used for the
improvement of membrane separation processes resulting in
higher selectivity and lower cost .
Nanomaterials have several advantages, such as unique size-
dependent properties emerge owing to the quantum
confinement effect. The specific characteristics allow the
development of high-performance nanomaterials for efficient
wastewater remediation .
The most promising applications of nanomaterials for
wastewater remediation are highlighted in Table 2.5.
Nanotechnology offers great potential in the area of water
treatment and purification due to the large surface-to-volume
ratios (SVR) of the nanomaterials.
The preparation of novel photocatalytic membranes by
implanting semiconducting nanomaterials over theconventional
membranes is used for the purification and treatment process
(Krishnan et al. 2008). Various approaches, such as
photocatalysis, nanofiltration, and adsorption, using titanium
dioxide (TiO2), zinc oxide (ZnO), polymer membranes, ceramic
membranes, carbon nanotubes, nanowire membranes, and
magnetic nanoparticles (nZVI), are used to resolve problems
involving treatment of waste water .
Novel metal/metal oxide nanoparticles, nanomembranes, and
other nanomaterials are used for detection and removal of
chemical and biological contaminants, including heavy metals,
pharmaceutical wastes, pesticides and their intermediates,
cyanide, algae, viruses, bacteria, parasites, organics, antibiotics,
etc., from waste water .
Membrane processes, nano-based materials, and the
combination of both offer wide possibilities for water
treatment by filtration and photocatalysis at the same time.
With the sustainability issues, the focus has been shifted
toward the use of greener methods for the treatment of
wastewater for environmental applications. Thus, the
nanomaterials synthesized using green chemistry-based
approaches used for the environmental clean-up will reduce
the risk of hazardous waste generation and eliminate the risk of
toxic end products.
 • Water Filtration Using Nanofiltration

Membrane filtration, frequently referred to as the “technology

of choice”, is a widely accepted and superior technology
treatment of wastewater implemented by providing a barrier
(physical) that effectively removes the unwanted molecules .
For over three decades, membrane technology has been
recognized worldwide for the successful separation of a wide
range of contaminants from water and wastewater .
 A membrane is a thin layer of a semipermeable material that
separates substances when a driving force is applied across the
membrane . Membranes provide the physical barrier that
allows only certain components to pass through on the basis of
their chemical and physical properties. Among all the other
conventional technologies used for the treatment of water,
membrane filtration emerges as the most trusted because it is
very simple, highly effective, does not involve the use of
chemicals and additives, is easy to scale-up, fast, and,
importantly, because of its flexibility to combine with other
advanced treatment technologies . The pressure driven
filtration technology is classified as low pressure (MF & UF) and
high pressure (NF & RO) on the basis of the molecular weight
cut-off values (MWCO) of the particular membrane and trans-
membrane pressure. These four membrane filtration processes
are best understood together in terms of the size of particles
that can be removed from a mixture. Out of these,
nanofiltration emerges as the sustainable alternative for the
remediation of several contaminants.NF is a high pressure
driven technology, used to remove organic contaminants,
bacteria, viruses, dairy, natural organic matter, and salts. It is
also used for softening of hard water by removing multivalent
and divalent ions. The pore size of the NF membrane is around
0.001 microns, typically under the range of 1–100 nm. Up to
99.9% removal of molecules in the range of 1–100 nm was
achieved in the cases of different pesticides using NF
membranes . NF is excellent for the removal of low molecular
weight compounds, as low as 100–200 Da, and therefore
selected for the removal of pesticides . Higher energy is
required for NF than MF and UF. NF is the process between RO
and UF, and is also referred to as loose RO. To date, NF is the
only filtration technology known to remove organic
contaminants and pesticides .

Renewable Energy Generation

The major research area in this field is the design of nano-

enabled solar cells utilizing the principles of green chemistry.
The novel nanomaterials used for solar cells include titanium
dioxide, quantum dots, cadmium telluride, and silver with a
polymer that can absorb a large fraction of solar energy. The
cost of these nano-based solar cells will be much lower
compared to those of commercially available solar cells (Wang
et al. 2008). Intensive research is going on in this field to
increase the efficiency of these solar cells. Other methods, such
as the deposition of nano-crystals, suspended nanoparticles in
quantum dots, nanowires, and the production of the highly
stable laminate layer for the protection of solar cells, are also
considered for sustainable product development .
Nanotechnology research is also happening in the field of
energy storage by developing high-capacity energy storage
devices for application in the area of renewable energy. Nano-
based photovoltaic devices have considerable potential for high
performance and cost reduction .

Limitations of Green Nanotechnology

Green nanotechnology is an emerging area, and it has its own

limitations and challenges to address. According to the report
of the ACS Green Chemistry Institute, the key challenges linked
with green nanotechnologies are:

(i) Handling of toxicity related issues of nanomaterial

(ii) Technical and economic barriers

(iii) Regulatory policies for nanomanufacturing processes

(iv) Deployment of scale-up procedures

(v) Life cycle analysis

The above-mentioned points should be extensively considered
for green and sustainable development. Green nanotechnology
brings products that reduce pollutants and are eco-friendly but
the major limitations are the costs and risks associated with the
production of nano-based products. Though advances have
been made in the development of green nanotechnology, the
level of sustainability for greener applications of
nanotechnology is always a concern. The products synthesized
using green nanotechnologies are efficient, but the main worry
lies with the upstream processing of the products (Clark
1999).Research is under-way for the synthesis and application
of greener nanoproducts, but when talking about the
commercial front, there are very few products commercialized
to date (Constable et al. 2002). It is a general conception that it
will take a few years to fully understand the market potential of
green nanotechnology.
Air pollution
The most important outdoor air pollution problem is global
warming that leads to many changes in the atmosphere, land
and water sources all over the world. Greenhouse gases(GHGs)
are considered the direct contributors to the global warming.
The main greenhouse gases are carbon dioxide ,methane,
nitrous oxide, and fluorinated gases. The problem of GHG
emission is exacerbating by the growing human activitie. The
majority of the green house gases have persistent long-term
effects on climate due to their endency to stay in the
atmosphere for hundreds of years.
Many of control and treatment technologies have been
developed to eliminate and monitor the emission of these
gases and to eliminate their risks on human and the
environment .Nanotechnology is a well-enabled treatment
technology to control and remediate air pollution in several
ways by taking advantage of nanomaterial properties and
applying them a sad sorbents, catalysts, membranes, and
sensors .As can be noticed from Fig. 1, carbon dioxide represent
75 % of GHGs in the environment; thus, several techniques
have been proposed to control its emission either by separation
or capturing, such as filtration, absorption in liquids ,adsorption
on solids, or a combination of these processes.
The adsorption on nanomaterials is proved to be more efficient
and cost-effective process due to the high surface area of
nanomaterials that can significantly enhance the adsorption
capacity, as well as the availability of nanomaterials and their
ability to be regenerated. The solid adsorbents for capturing
carbon dioxide can be divided
into three classes:
(1) the high temperature adsorbents(>400 °C),
(2) the intermediate temperature adsorbents(200–400 °C),
(3) the low temperature adsorbents(<200 °C).
Calcium (Ca)-based nano-adsorbents are used to capture
carbon dioxide at high temperature based on the reversible
carbonation reaction of calcium oxides (CaO). The serious
disadvantage of using the high temperature adsorbents lies in
their ability to aggregate easily leading to a sintering problem
during the carbonation/calcination cycles.

As a result, surface coating of the Ca-based nano-adsorbents is

used to prevent the aggregation of these adsorbents and
consequently avoid the sintering problem .reported that
titanium dioxide (TiO2)-coated nano calcium carbonate can
prevent the sintering of nano calcium carbonate and effectively
capture carbon dioxide using the adsorption phase technique.
Moreover, the treated nanoparticles with alkali metals (Li,Na, K,
Cs, Fr) showed the ability to capture carbon dioxide at high
temperature, for instance nano-sized citric acid pretreatment
rice husk ash (CRHA) lithium ortho-silicate based (CRHA-Li4SiO4)
adsorbents exhibited a sintering-resistant character and
captured carbon dioxide (CO2) at 700 °C .
Furthermore, the alkali nanotubes (e.g., potassium titanate (K-
Ti-NT) and sodium titanate (Na-TiNT)) have been used to
capture carbon dioxide at low temperature (below 200 °C) .
Another example of CO2 low temperature adsorbents is
carbon-based materials (CNMs). They are used widely due to
their high surface and high amenability to pore structure
modification and surface functionalization.
Functionalized carbon nanotubes (CNTs) have been successfully
used to capture CO2 and enhance the adsorption performance
in the presence of moisture, which decline the adsorption
capacity due to water molecules competing with CO2 for the
active adsorption sites . pointed out that functionalization of
carbon nanotubes by 3-aminopropyl-triethoxysilane (CNTs-
APTS) grafted the surface of CNTs with abundant amine groups
that provide numerous chemical sites for CO2 adsorption which
makes CNTs adsorb more CO2 gases at low temperature range
(20–100 °C). In addition, it was suggested that there are two
possible reasons for the increase of (CNTs-APTS) adsorption
capacity in the presence of moisture and they ar (1) CO2 gas
may dissolve into the adsorbed water on the surface of (CNTs-
APTS) and (2) the reaction between CO2 and surface amino
groups forms carbonate ions which may undergo further
reaction with CO2 and water to form bicarbonate (HCO3) (or
the amino groups itself can also directly react with CO2 and
H2O to form HCO3) .
As another illustration of nanotechnology role in GHG
treatment, many catalytic processes have been devoted for
conversion or decomposition of methane (CH4) and nitrous
oxides (NOx). For instance, metallic nickel nanoparticles were
employed as catalysts for thermal decomposition of methane
to produce hydrogen (Wang and Lua 2012), and TiO2 coated
with stainless steel web net was efficiently used for
photocatalytic degradation of (CH4) .
On the other hand, titanate nanotubes (TNTs) and their
derivatives have been widely reported for the photocatalytic
oxidation of NOx. Many studies attempted to obtain the
optimum parameters that effect the decay rate and the
removal efficiency of NOx. have proved that the surface area,
the amount of crystalline, and the remnant sodium content of
TNTs increased by washing at pH 3–5 and accordingly increased
the removal efficiency of both NO and NO2. Moreover,
modified TiO2 with different loads of silver was used for the
photocatalytic decomposition of (N2O) to nitrogen and oxygen .
The silver deposited on the surface of TiO2 provokes a decrease
in the electronhole recombination rate .
In addition to GHGs, sulfur dioxide is one of the industrial
emissions that is linked to different environmental problems
and serious human health risks. Nanomaterials have been used
to eliminate SO2 release to environment either by
desulfurization of fossil fuel (Saleh et al. 2015) or by its removal
directly from the emission source by various technologies, such
as adsorption processes and catalytic oxidations. Removal of
SO2 occasionally leads to some changes in the morphology or
characteristics of the used materials. For instance, during the
application of activated carbon with deposited iron
nanoparticles as adsorbent, formation of weakly acidic groups
on the adsorbent surface was involved with the SO2 adsorption
process which increases the surface acidity (Arcibar-Orozco et
al. 2013). Moreover, it was proved that SO2 adsorption process
can lead to clear changes in magnetism when using magnetic
nanoparticles (MNPs). For example, SO2 adsorption on the
surface of COFe2O4 MNPs leads to a decrease in their
saturation and remnant magnetization by approximately 20 %
and a decrease in their coercivity by approximately 9 %
(Gloveret al. 2012). Table 1 shows more examples of
nanomaterials used to treat different types of air pollutants.
Conclusions

Nanotechnology offers the opportunity to find the solution to

global problems that significantly affect society. As the name
implies, green nanotechnology has a certain green purpose.
After reviewing the advances and applications of the field, the
focus has been shifted to nano-based applications, as
nanotechnology provides the framework to consider the
application of green chemistry.
Through research, it has been revealed that even after various
advantages it has certain limitations and challenges to address.
Green nanotechnology has the significant potential to make a
contribution to addressing the green challenge along with
sustainable development. The sustainable development of
nanotechnology will require the incorporation of life cycle
thinking to analyze the environmental impacts of the
nanoproducts.
Also, certain points such as possible life cycle assessment of the
newly synthesized nanoproducts through nanomanufacturing
before release to the commercial front must be taken seriously
in accessing the contribution to the green growth. Application
of the principles of green chemistry to nanotechnology helps to
identify better products and processes but there is always hope
for improvement .
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