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Environmental Science
Cite this: Energy Environ. Sci., 2012, 5, 8075
www.rsc.org/ees REVIEW
A review on nanomaterials for environmental remediation
Mya Mya Khin,a A. Sreekumaran Nair,*b V. Jagadeesh Babu,b Rajendiran Murugana
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and Seeram Ramakrishna*ab

Received 31st March 2012, Accepted 24th May 2012
DOI: 10.1039/c2ee21818f

This article gives an overview of the application of nanomaterials in environmental remediation. In the
area of environmental remediation, nanomaterials offer the potential for the efficient removal of
pollutants and biological contaminants. Nanomaterials in various shapes/morphologies, such as
nanoparticles, tubes, wires, fibres etc., function as adsorbents and catalysts and their composites with
polymers are used for the detection and removal of gases (SO2, CO, NOx, etc.), contaminated chemicals
(arsenic, iron, manganese, nitrate, heavy metals, etc.), organic pollutants (aliphatic and aromatic
hydrocarbons) and biological substances, such as viruses, bacteria, parasites and antibiotics.
Nanomaterials show a better performance in environmental remediation than other conventional
techniques because of their high surface area (surface-to-volume ratio) and their associated high
reactivity. Recent advances in the fabrication of novel nanoscale materials and processes for the
treatment of drinking water and industrial waste water contaminated by toxic metal ions,
radionuclides, organic and inorganic solutes, bacteria and viruses and the treatment of air are
highlighted. In addition, recent advances in the application of polymer nanocomposite materials for the
treatment of contaminants and the monitoring of pollutants are also discussed. Furthermore, the
research trends and future prospects are briefly discussed.

Introduction
The rapid pace of industrialization and its resulting by-products
have affected the environment by producing hazardous wastes
a
Department of Mechanical Engineering, National University of Singapore,
117574, Singapore
b
NUS Centre for Nanofibres and Nanotechnology (NUSCNN),
Healthcare and Energy Materials Laboratory, National University of
Singapore, 117584, Singapore. E-mail: nniansn@nus.edu.sg; seeram@
nus.edu.sg
and poisonous gas fumes and smokes, which have been released
to the environment. Conventional technologies have been used to
treat all types of organic and toxic waste by adsorption, bio-
logical oxidation, chemical oxidation and incineration. Super-
critical water oxidation (SCWO) has been proposed as a
technology capable of destroying a wide range of organic
hazardous waste. It has been receiving attention due to its ability
to destroy a large variety of high-risk wastes resulting from
munitions demilitarization and complex industrial chemical
processing. In the concentration range of 1% to 20% of organic

Broader context
Environmental pollution is a global menace and the magnitude of it is increasing day-by-day due to urbanization, heavy indus-
trialization and the changing lifestyles of people. In view of this, providing clean air and water and a clean environment for people is
a challenging task. The advent of nanotechnology has given immense scope and opportunities for the fabrication of desired
nanomaterials with large surface-to-volume ratios (and hence excellent chemical reactivities) and unique functionalities to treat
pollutants. The nanomaterials play major roles in environmental remediation and are used for purposes such as the treatment of
natural waters, soils, sediments, industrial and domestic waste water, mine tailings and the polluted atmosphere. The present review
gives an extensive view of the roles of nanomaterials in environmental remediation. Environmental remediation using metal and
metal oxide nanomaterials, dendrimers, carbon nanomaterials and polymer nanocomposites by chemical degradation (photo-
catalysis) and sorption are discussed in detail in addition to water purification by nanofibre media. The review article also features a
section on nanomaterials in the sensing of heavy metals and poisonous gases. We believe that this in-depth review will serve as a
reference guide for scientists in the area and the background information will help in fuelling further innovations on sustainable
solutions for environmental remediation.

This journal is The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 80758109 | 8075

pollutants, SCWO is far less costly than incineration or active
carbon treatment. In parallel, the rapid growth of nanotech-
nology has gained a great deal of interest in the environmental
Mya Mya Khin is currently
working as a research engineer at
the National University of Singa-
pore (NUS). She finished her oral
defence recently and she is on
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course to obtain her PhD degree
from NUS. She graduated with M.
Eng. degree from NUS in Chem-
ical Engineering. She worked as a
lecturer and scientist at Ngee Ann
Polytechnic and Food & Nutrition
in Singapore (20082011). Her
current research involves environ-
Mya Mya Khin
mental remediation using electro-
spun nanofibres.
Dr A. Sreekumaran Nair worked
as a research fellow (20082012)
at the Healthcare and Energy
Materials (HEM) Laboratory of
the National University of Singa-
pore. He graduated with a PhD in
Chemistry from the Indian Insti-
tute of Technology (IIT), Madras
(2006) and subsequently became a
JSPS postdoctoral fellow (2006
2008) in Japan. His research
interests include the fabrication of
materials for energy conversion
A: Sreekumaran Nair and storage, catalysts for solar
hydrogen, nanotechnology-based
environmental remediation and
probing the charge transport mechanism in monolayer-protected clus-
ters and 3-D superlattices.
Dr V. Jagadeesh Babu is currently a
research fellow at the NUS Centre
for Nanofibres & Nanotechnology
(NUSCNN) of the National
University of Singapore. He gradu-
ated with a PhD in Physics from the
Indian Institute of Technology
(IIT), Madras (2008) and subse-
quently became a research assistant
in the Department of Physics IIT-
Madras from 20082009. From the
year 2009 to January 2010, he
worked as a postdoctoral fellow in
V: Jagadeesh Babu the Gwangju Institute of Science and
Technology (GIST), Gwangju,
South Korea. His research interests
include the fabrication of electrospun nanostructured materials for photo-
catalysis, photovoltaics, the splitting of water for hydrogen energy and
probing electrical charge transport in conducting polymers.
8076 | Energy Environ. Sci., 2012, 5, 80758109
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applications of nanomaterials. The treatment of pollutants in
water and air is a great challenge and nanomaterials are impor-
tant for the environmental remediation. Nanomaterials are
excellent adsorbents, catalysts and sensors due to their large
specific surface areas and high reactivities. The high surface area-
to-mass ratio of nanomaterials can greatly improve the adsorp-
tion capacities of sorbent materials. Due to its reduced size, the
surface area of nanomaterials grows exponentially at the same
density as the diameter shrinks. In addition, the mobility of
nanomaterials in solution is high and the whole volume can be
quickly scanned with small amounts of nanomaterials due to
their small size. Because of their reduced size and large radii of
curvature, the nanomaterials have a surface that is especially
reactive (mainly due to the high density of low-coordinated
atoms at the surface, edges and vortices). These unique proper-
ties can be applied to degrade and scavenge pollutants in water
and air.1 The species adsorbed onto the nanomaterials can be
removed by applying mild (and affordable) gravitational
(centrifugal) or magnetic force (in the case of magnetic
Dr Rajendiran Murugan is
currently a research fellow at the
NUSCNN of the National
University of Singapore. He
graduated with a PhD in organic
chemistry (CLRICSIR Lab)
from the University of Madras
and subsequently became an
associate scientific manager at
the Synthetic Chemistry Depart-
ment in Biocon. His research
interests include nanocatalysis,
the synthesis of small/conjugated
Rajendiran Murugan molecules and the fabrication of
chemosensors.
Prof. Seeram Ramakrishna,
FREng, FNAE, FAAAS is a
Professor of Materials Engi-
neering and Director of the HEM
Labs (http://serve.me.nus.edu.sg/
seeram_ramakrishna/) at the
National University of Singapore.
He is an acknowledged global
leader for his pioneering work on
the science and engineering
of nanofibres (http://research
analytics.thomsonreuters.com/m/
pdfs/grr-materialscience.pdf). He
Seeram Ramakrishna has authored five books and five
hundred peer reviewed papers,
which attracted
16 000 citations
and h-index of 65. Various international databases including Thomson
Reuters Web of Science, Elsevier Scopus and Microsoft Academic
place him among the top twenty five authors and most cited materials
scientists in the world. He is an elected International Fellow of Major
Professional Societies in Singapore, ASEAN, India, the UK and the
USA.
This journal is The Royal Society of Chemistry 2012

nanoparticles). Nanomaterials in various shapes/morphologies/
forms have a significant impact on water and air quality in the
natural environment.2 Magnetic nanoadsorbents are particularly
attractive as they can be easily retained and separated from
treated water.3 Nanomaterials also have different distributions of
reactive surface sites and disordered surface regions. In addition,
several natural and engineered nanomaterials have also been
proved to have strong antimicrobial properties, including chi-
tosan, silver nanoparticles (nAg), photocatalytic TiO2, and
carbon nanotubes (CNT).48 Nanotechnology is also used for the
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detection of pesticides and heavy metals (e.g. cadmium, copper,
lead, mercury, arsenic, etc.). Furthermore, nanomaterials have
enhanced redox and photocatalytic properties.9,10 The fabrica-
tion of nanomaterials can be achieved by (1) grinding, milling
and mechanical alloying techniques; (2) physical or chemical
vapour deposition or vacuum evaporation; (3) solgel chemical
synthesis methods; (4) gas-phase synthesis techniques, such as
flame pyrolysis, electroexplosion, laser ablasion and plasma
synthesis, and (5) microwave techniques or combustion methods
or delamination of layered materials (the controlled crystalliza-
tion from amorphous precursors).11 The functionalization
process is applied to nanomaterials by a coating technique or
chemical modification in order to (1) improve the surface and
optical properties, (2) to avoid aggregation and (3) to eliminate
the interaction between the nanomaterials and biological
substances. For example, doping with an appropriate dopant can
improve the photocatalytic activity and cause a red-shift in the
band-gap of TiO2, which leads to its capability to absorb light in
the visible range.12 The small particle size of nanoparticles (NPs)
brings excessive pressure drops when the NPs are applied in a
fixed bed or any other flow-through system, as well as certain
difficulties in their separation and reuse and even a possible risk
to ecosystems and human health caused by the potential release
of nanoparticles into the environment. Therefore, hybrid nano-
composites have been fabricated by impregnating or coating the
fine particles onto solid particles of a larger size to overcome the
limitations of NPs. The resultant polymer-based nanocomposite
(PNC) retains the inherent properties of the nanoparticles;
however, the polymer support materials provide higher stability,
processability and improvements thanks to the nanoparticle
matrix interaction. In addition, the incorporation of nano-
particles (NPs) into polymeric nanocomposites leads to an
enhancement of the mechanical, electrical and optical properties.
NP-based membranes can be fabricated by assembling NPs on
porous membranes13,14 or blending them with polymeric or
inorganic membranes.15 The fabrication of membranes with
metal oxide NPs could increase the permeability and fouling-
resistance as well as the quality of the permeate.13 The
improvements to membranes or membrane surfaces using
nanomaterials provide several changes in the properties, such as
the porosity, the hydrophilicity of the surface properties, its
electropositivity or electronegativity and the surface catalytic
properties. The possible size grading due to the incorporated
nanoporous materials can prevent the passage of a range of
contaminants and microorganisms through the membrane.
Nanofibres can also provide a better filtration with a much
smaller porosity and have the capability to trap much smaller
contaminants. The internal surface areas of nanofibres are much
higher than conventional filter materials. Furthermore,
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nanofibrous materials can have interconnected open pore
structures and can potentially allow high flow rates. This paper
gives an overview of the application of nanomaterials in the
purification of water and air contaminated with toxic metal ions,
greenhouse gases, organic and inorganic solutes, bacteria and
viruses and their performance in environmental remediation,
pollutant sensing and detection, cleaner production and so on.
Environmental remediation technologies
(A) Environmental remediation by chemical degradation
One of the widely used environmental remediation methods is
chemical degradation. Chemical degradation methods include
(1) ozone/UV radiation/H2O2 oxidation, (2) photocatalytic
degradation, (3) supercritical water oxidation, (4) the Fenton
method, (5) sonochemical degradation, (6) the electrochemical
method, (7) the electron beam process, (9) solvated electron
reduction, (9) permeable reactive barriers of iron and other zero-
valent metals and (10) enzymatic treatment methods. Ozone or
UV radiation-based technologies (O3/UV/H2O2) are chemical
oxidation processes applicable to water treatment for the
degradation of individual pollutants or the reduction of the
organic load (chemical oxygen demand, COD) and the biode-
gradability of waste water could be enhanced by using these
techniques. Ozone and UV radiation alone can be used for
disinfection purposes. O3/UV/H2O2 techniques generally involve
two oxidation/photolysis routes to remove foreign matters
present in water. Thus, ozone, hydrogen peroxide and/or UV
radiation can react individually or photolyze the organic matters
directly in water. However, when ozone or hydrogen peroxide
are used in combination with UV radiation, the pollutants can be
degraded by an oxidation process through hydroxyl free radicals
generated in situ. Hydroxyl radicals have the largest standard
redox potential, with the exception of fluorine. Among the most
common water pollutants, phenols and some pesticides are
substances that react rapidly with hydroxyl radicals, whereas
organochlorine compounds are less reactive. Another feature of
this oxidation process is that it is a destructive type of water/air
pollution removal due to the reaction of the pollutants with
hydroxyl radicals.16,17
The term photocatalytic degradation involves photons and a
catalyst. Electrons pertaining to an isolated atom occupy discrete
energy levels. In a crystal, each of these energy levels is split into
many energy levels as there are atoms. Consequently, the
resulting energy levels are very close and can be regarded as
forming a continuous band of energies. For a metal (or
conductor), the highest energy band is half-filled and the corre-
sponding electrons need only a small amount of energy to be
raised into the empty part of the band, which is the origin of the
electrical conductivity at room temperature. In contrast, in
insulators and semiconductors, valence electrons completely fill a
band, which is thus called the valence band, whereas the next
highest energy band (termed the conduction band) is empty, at
least at 0 K. In liquid water, two HO2_ radicals can combine if
their concentrations allow them to react significantly, yielding
H2O2 and O2 (in a disproportionation reaction). In turn, H2O2
can scavenge an electron from the conduction band or from the
superoxide and accordingly can be reduced to a hydroxyl radical
Energy Environ. Sci., 2012, 5, 80758109 | 8077

(_OH) and a hydroxide ion (OH). Because these reactions are
known to take place in homogeneous aqueous phases, they are
believed to occur on the TiO2 surface. In other words, the
very oxidizing _OH might be produced, in principle, by the
three-electron reduction of O2:
O2 + 2H+ + 3e / OH_ + OH
HO2 + RH / H2O2 + R_
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where RH is an organic species with a labile H atom; however,
this reaction would also compete with H-atom abstraction from
RH by the _OH radical. A much more direct way of forming the
_OH radical is through the oxidation of an adsorbed water
molecule or an OH ion by a valence band hole (h+), (i.e., by an
electron transfer from these entities to the photoexcited semi-
conductor). The chemistry occurring at the surface of a photo-
excited semiconductor is based on the radicals formed from O2,
H2O and electron-rich organic compounds. In addition, cations
in aqueous solution can be directly reduced by conduction band
electrons provided that the redox potentials of these cations are
adequate (i.e., lying below the conduction band energy).18 The
photocatalytic reaction occurs, at least principally, in the
adsorbed phase and the overall process can be formally divided
into five steps:
1. The transfer of the reactants from the fluid phase to the
surface;
2. The adsorption of at least one of the reactants;
3. The reaction in the adsorbed phase;
4. The desorption of the product(s); and
5. The removal of the product(s) from the interfacial region.
As the adsorption and desorption rates are temperature-
dependent, temperature can have an effect on the photocatalytic
reaction rates. Increased rates upon raising the temperature
above the ambient temperature have been reported for the gas-
phase removal of some pollutants and, above all, for their
mineralization rate.19,20
The supercritical water oxidation (SCWO) process involves
bringing together an aqueous waste stream and oxygen in a heated
pressurized reactor operating above the critical point of water
(374  C, 22.1 MPa or 218 atm). Under these conditions, the
solubility properties of water are reversed (i.e., increased organic
solubility and decreased inorganic solubility) and the viscosity of
the media is decreased to a value similar to gas-like values, thus
enhancing the mass transfer properties. These unique properties of
hot pressurized water allow oxygen and organics to be contacted
in a single phase in which the oxidation of the organics proceeds
rapidly. At 400650  C and 3750 psi, SCWO can be used to ach-
ieve complete oxidation of many organic compounds with
destruction rate efficiencies of 99.99% or higher. Small nano-
particles of metal oxides can be produced by hydrothermal
synthesis, which is performed in supercritical water above a critical
temperature and pressure due to the properties of supercritical
water. The supercritical hydrothermal synthesis of metal oxide
nanoparticles is green not only because it requires only water as a
solvent but also because the resulting nanomaterials contribute to
a sustainable society. During the SCWO of organic acids in waste
water containing benzoic acid, p-tolualdehyde and p-toluic acid,
and in organic compounds, such as cobalt and manganese acetate,
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cobalt manganese oxide nanoparticles, synthesized in situ in the
reactor, act as an oxidation catalyst to enhance the oxidation rate
of organic compounds. Consequently, either the reaction
temperature can be reduced or the residence time can be short-
ened. The TOC of the waste water was found to be 37 480 ppm
and decreased to 200 ppm after the reaction.2123
The term Fenton reagent refers to aqueous mixtures of Fe(II)
and hydrogen peroxide via the Fenton method. This method has
indicated the following net reaction as the predominant process:
Fe2+ + H2O2 / Fe3+ + HO_ + OH (1)
where Fe2+ and Fe3+ represent the hydrated species, Fe(H2O)62+
and Fe(H2O)63+, respectively. Reaction (1) is often referred to as
the Fenton reaction, although many other reactions occur in
Fenton systems. The primary utility of the Fenton reagent in the
degradation of pollutants is the formation of _OH. The hydroxyl
radical is a very strong, nonselective oxidant capable of
degrading a wide array of pollutants.24,25
Sonochemical reactions are related to new chemical species
produced during acoustical cavitation, whereas the enhancement
of heterogeneous reactions can also be related to mechanical
effects induced in the fluid system by sonication. These effects
include an increase in the surface area between the reactants, a
faster renovation of catalyst surfaces and accelerated dissolution
and mixing. The peculiar nature of sonochemical reactions offers
alternative pathways, providing a faster or environmentally safer
degradation of contaminants. Sonochemistry provides a unique,
high-temperature gaseous environment inside the cavitation
bubbles, where the thermolysis of CCl4 molecules takes place at
fast rates, yielding _Cl and _CCl3 radicals as primary intermediate
products. These radicals further react with _OH radicals or O2,
yielding stable HCl, HOCl, Cl2 and CO2 as the final degradation
products. AuTiO2 nanoparticles were prepared by sonicating
(20 kHz) an aqueous solution of HAuCl4$3H2O containing
polyvinylpyrrolidone, 1-propanol and TiO2 (Deguzza P-25) at
room temperature under a nitrogen atmosphere. The waste water
solution was irradiated with light and ultrasound was used for
the degradation via sonophotocatalysis.2628
Fig. 1 shows a schematic diagram for the different electro-
chemical treatments. Fig. 1(A) represents direct electrolysis by
anodic oxidation in which the pollutant reacts at the electrode
surface with adsorbed _OH produced from water oxidation at a
high O2 overpotential anode. Fig. 1(B) represents indirect
electrolysis where the pollutant reacts in the solution with an
irreversibly electrogenerated reagent (B+) produced from the
oxidation of inactive B at the anode. The direct electrolytic
processes includes conventional procedures of cathodic reduc-
tion and anodic oxidation. The indirect methods deal with the
use of redox mediators as reversibly electrogenerated reagents, as
well as oxidants as irreversibly electrogenerated reagents at the
anode (e.g., O3, ClO, Cl and ClO2) or the cathode (e.g., H2O2).
Halogenated organics are usually toxic and their electro-
reduction can make them easily biodegradable. This is also a
common goal in the electrochemical decontamination of organic
pollutants in waste waters by anodic oxidation. Although
modern processes have seriously reduced the operation costs for
cathodic reduction and anodic oxidation, both methods are still
too costly to be competitive with biological treatment.2931
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Sources of free radicals, principally hydroxyl radicals (_OH),
oxidatively decompose pollutants. An excellent source of free
radicals for water treatment is ionizing radiation. The irradiation
of water produces both reducing and oxidizing species, which
allow for a versatile approach for the ultimate treatment of
a variety of pollutants. Machine-generated electron beams
(e-beams) provide reliable and safe radiation sources for the
treatment of flowing waste streams on a process-size scale.
Process versatility is provided by the continuous, rapid treatment
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potential and a tolerance for feedstocks of varying qualities.
Additionally, modern e-beams have excellent operational reli-
ability. The energy of the electron determines its depth of pene-
tration in water. The number of electrons is referred to as the
beam current and is controlled by the cathode size and config-
uration. The eaq reacts with numerous organic compounds. Of
particular interest to the application in waste treatment are the
reactions with halogenated compounds. A generalized reaction is
shown below:
eaq + RCl / R_ + Cl
Thus, reactions involving the eaq often result in the dechlori-
nation of organochlorine compounds. This result may be
sufficient for waste treatment purposes. However, further reac-
tion of the resulting organic radical (R_) may also be desirable to
mineralize the compound. The eaq also reacts with many other
organic compounds and contributes to the removal of these
compounds from aqueous solution. The process is nonselective
in the destruction of organic chemicals because strongly reducing
reactive species (eaq/H_) and strongly oxidizing reactive species
(_OH) are formed at the same time and in approximately the same
concentration in solution.32,33
In the solvated electron reduction method, deep blue solutions
of solvated electrons are formed when Li, Na, K, Ca or other
group I and group II metals are dissolved in liquid ammonia
(eqn (1)). These media have long been used to reduce organic
compounds. Among the many functional groups reduced by this
process, chloroorganic compounds are the ones reduced with the
highest rates (eqn (2)).
Na / Na+ + e (1)
RCl + e / R_ + Cl (2)
Fig. 1 A schematic diagram for the different electrochemical treatments
of organic pollutants.29 (A) represents direct electrolysis by anodic
oxidation and (B) represents indirect electrolysis.
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Most solvated electron-treated wastes require post treatment.
The first post treatment involves removing and recovering
ammonia from the matrix. This is accomplished by passing hot
water or steam through the jacket of the treatment cell and by
condensing the ammonia for reapplication.3436
The core function of permeable reactive barriers (PRBs) and
many related technologies is to bring the contaminated material
in contact with a reactive material that promotes a process that
results in decontamination. The processes that are responsible
for contaminant removal by zero-valent metals (ZVMs) and
PRBs include both a physical removal from solution to an
immobile phase and a chemical removal by reaction to form less
hazardous products. Sequestration by Fe0 occurs mainly by
adsorption, reduction and co-precipitation, although other
processes may be involved, such as pore diffusion and poly-
merization. In most cases, adsorption is the initial step and
subsequent transformations help ensure that the process is irre-
versible. In some cases, however, adsorption is the sequestration
process of primary importance. This is certainly true with metals
that occur as soluble cations, which can be expected to adsorb
fairly strongly to iron oxides, but cannot be reduced to insoluble
forms by Fe0: e.g., Mg2+, Mn2+ and Zn2+. The lifetime of PRBs
using Fe0 as a reactive medium is limited by precipitation at the
barrier.3739
Chemical processes often require the presence of excess
quantities of reagents to accomplish transformation to the
desired extent. In addition, particularly harsh conditions (e.g.,
high temperatures or extremes of pH) are sometimes required to
facilitate the chemical transformations. This can present a
problem once the desired transformation has taken place because
the resulting stream may be a low-quality mixture that cannot be
released to the environment or reused without subsequent
treatment. Finally, many chemical treatment processes are not
highly selective in terms of the types of pollutants that are
transformed during treatment. Consequently, such processes are
usually more economical for the treatment of dilute waste water
and are often used as a polishing step before waste discharge into
the environment. Biological processes are designed to take
advantage of the biochemical reactions that are carried out in
living cells. Such processes use the natural metabolism of cells to
accomplish the transformation or production of chemical
species. The metabolic processes occur as a result of a sequence
of reactions conducted inside the cell that are catalyzed by
proteins called enzymes. An important advantage of biological
systems is that they can be used to carry out processes in which
no efficient chemical transformations have taken place. In
addition, biological processes can often be conducted without the
harsh conditions that are necessary during chemical trans-
formations. However, the use of microorganisms provides many
rate-limiting factors. For example, costly and time-consuming
methods may be necessary to produce microbial cultures that can
degrade the targeted pollutant. Furthermore, severe conditions,
such as chemical shock, extremes of pH and temperature, toxins,
predators and high concentrations of the pollutants, intermedi-
ates and products may irreversibly damage or metabolically
inactivate the microbial cells. Thus, the sensitivity of microor-
ganisms to changes in their environment can make these
processes difficult to control over the long term. They also
require a supply of macro- and micro-nutrients for the support of
Energy Environ. Sci., 2012, 5, 80758109 | 8079

microbial growth and often result in the formation of large
quantities of biomass that ultimately must be discarded into the
environment. In addition, the biochemical reactions occur at a
rate that is limited by the metabolism of the microorganism and,
thus, are often slower than chemical processes. Moreover,
whereas biological systems are commonly used to remove the
bulk organic load in waste waters, these systems often have
difficulty in removing toxic pollutants to consistently low levels.
Therefore, conventional biological processes may not be able to
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improve water quality sufficiently to meet the waste water
discharge criteria. In an attempt to overcome some of the
problems associated with chemical and biological systems, recent
research has focused on developing the environmental applica-
tions of enzymes that have been isolated from their parent
organisms. Enzymes can be applied to transform targeted
contaminants, including many of those that may resist biodeg-
radation. This catalytic action can be carried out on, or in the
presence of, many substances that are toxic to microbes. In
addition, some enzymes can operate over relatively wide
temperatures, pH values and salinity ranges compared to
cultures of microorganisms. They can also be used to treat
contaminants at high and low concentrations and are not
susceptible to shock loading effects associated with changes in
contaminant concentrations that can often irreversibly damage
or metabolically inactivate microbial cells. Consequently, there
are fewer delays associated with shutdown/startup periods that
are normally required to acclimatize biomass to waste streams.
Importantly, the catalytic action of enzymes enables the devel-
opment of smaller systems of lower capital cost due to the high
reaction rates associated with enzymatic reactions. In addition,
because bacterial growth is not required to accomplish waste
transformations, sludge production is reduced because no
biomass is generated. The following situations are those where
the use of enzymes might be most appropriate: (i) the removal of
specific chemicals from a complex industrial waste mixture
before on-site or off-site biological treatment; (ii) the removal of
specific chemicals from dilute mixtures, for which conventional
mixed-culture biological treatment might not be feasible; (iii) the
polishing of a treated waste water or groundwater to meet limi-
tations on specific pollutants or to meet whole effluent toxicity
criteria; (iv) the treatment of wastes generated infrequently or in
isolated locations, including spill sites and abandoned waste
disposal sites; and (v) the treatment of low-volume, high-
concentration waste water at the point of generation in a
manufacturing facility to allow reapplication of the treated
process waste waters to facilitate recovery of soluble products or
to remove pollutants known to cause problems downstream
when mixed with other wastes from the plant.40,41
(B) Environmental remediation by metals/metal oxides
For environmental remediation, the most widely studied nano-
scale metals (NMs) and metal oxides (NMOs) include silver,
iron, gold, iron oxides, titanium oxides, etc. The size and shape of
NMs and NMOs are both important factors which affect their
performance. Efficient synthetic methods to obtain shape-
controlled, highly stable and monodisperse metal/metal oxide
nanomaterials have been widely studied during the last decade.
Generally, the synthesis methods can be classified into two
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categories: (1) physical approaches, including inert gas conden-
sation, severe plastic deformation, high-energy ball milling,
ultrasound shot peening; and (2) chemical approaches, including
reverse micelle (or microemulsion), controlled chemical co-
precipitation, chemical vapor condensation, pulse electrode
position, liquid flame spray, liquid-phase reduction, gas-
phase reduction, etc. Among these synthesis protocols, co-
precipitation,42,43 thermal decomposition and/or reduction and
hydrothermal synthesis techniques are used widely and are easily
scalable with high yields. In this section, the applications of
nanoscale metals and NMOs in environmental remediation
are presented.
Silver nanoparticles are known for their strong antibacterial
effects against a wide array of organisms (e.g., viruses, bacteria,
fungi). Therefore, silver nanoparticles are widely used for the
disinfection of water.4446 The different mechanisms of antimi-
crobial activity by nAg+ are shown in Fig. 2. Ag+ ions interact
with thiol groups in proteins, which leads to inactivation of
respiratory enzymes and the production of reactive oxygen
species (ROS).47 It was also shown that Ag+ ions can prevent
DNA replication and affect the structure and permeability of the
cell membrane.48 Silver ions are also photoactive in the presence
of UV irradiation, causing an improvement in the UV inactiva-
tion of bacteria and viruses.49,50 To date, several mechanisms
have been postulated for the antimicrobial property of silver
nanoparticles: (1) the adhesion of nanoparticles to the surface
altering the membrane properties. Nano Ag (nAg) particles have
been reported to degrade lipopolysaccharide molecules, accu-
mulating inside the membrane by forming pits and causing an
increase in the membrane permeability;51 (2) nAg particles could
penetrate the bacterial cell, resulting in DNA damage; and (3) the
dissolution of nAg releases antimicrobial Ag+ ions.52 Particles of
Ag less than 10 nm are more toxic to bacteria such as E. coli and
P. aeruginosa.53,54 Silver nanoparticles ranging from 1 to 10 nm
inhibit certain viruses from binding to host cells by preferentially
binding to the virus glycoproteins. Furthermore, triangular nAg
nanoplates were found to be more toxic than nAg rods, nAg
spheres and even Ag+ ions. The incorporation of nAg into
polymer materials, such as polymethoxybenzyl and poly(L-lactic
acid)-co-poly(3-caprolactone) nanofibres, have also shown anti-
microbial properties against E. Coli, A. Niger, S. aureus and
Salmonella entrica.5558 Several materials containing iron, such as
iron sulfide, iron bearing oxyhydroxides and aluminosilicate
minerals, were successfully used in the reduction and precipita-
tion of metal ions. Out of all the iron-based materials, elemental
iron was found to be the most successful for ground water
remediation.59 With the advent of nanotechnology, iron nano-
particles replaced the use of bulk iron-based systems for water
purification.60 After a few years, noble metal nanoparticles were
also shown to degrade halocarbons by the same mechanism of
reductive dehalogenation.6164 In an investigation by Lisha et al.,
Hg2+ ions were reduced to a zero-valent state, followed by the
alloying of reduced mercury on gold nanoparticle surfaces.64,65
The application of noble metal nanoparticles for the removal of
halogenated organics and pesticides from drinking water has also
been patented.66,67 Gold nanoparticles also exhibit potential to
remove inorganic mercury from drinking water.63
Sulphur dioxide (SO2) is frequently released to the atmosphere
by the combustion of fossil-derived fuels in factories, power
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Fig. 2 The different mechanism for the antimicrobial activity of Ag+
ions.47
plants, houses and automobiles. The corrosion of buildings due
to acid rain by SO2 is a serious challenge. TiO2 is the most
commonly used catalyst to convert SO2 to sulfur through the
reaction: SO2 + 2H2S / 2H2O + 3Ssolid. Rodriguez68,69 found
that the combination of a gold (Au) and TiO2 system produced
highly efficient desulfurization. Metallic gold has a very low
chemical and catalytic activity.68,69 However, when gold was
dispersed on some metal oxides (MgO, TiO2, MnOx, Fe2O3,
Al2O3), it gave the positive effects of catalytic activity due to
charge transfer between the oxide and gold and a limited nano-
scale size (usually less than 10 nm).69 Rodriguez69 investigated the
dissociation effects of SO2 using the combined systems of TiO2/
Au and MgO/Au. On both oxide supports, the largest activity for
the full dissociation of SO2 was observed in systems containing
Au coverages that were less than 1 mL when the size of the Au
nanoparticles was below 5 nm. In addition, the combined system
of TiO2/Au provided a more effective dissociation of SO2 than
that of MgO/Au so that TiO2 played a direct active role for the
dissociation of SO2 as well as modified chemical properties of the
supported Au nanoparticles.70 Furthermore, catalytic perfor-
mance tests, such as (1) tests for the reduction of SO2 by H2S
through the reaction: SO2 + 2H2S / 2H2O + 3Ssolid and (2) by
carbon monoxide through the reaction: SO2 + 2CO / 2CO2 +
Ssolid indicated that the combination of Au/TiO2 is 510 times
more active than pure TiO2.
Zero-valence state metals, such as Fe0, Zn0, Sn0 and Al0, are
effective for the remediation of contaminants in contaminated
groundwater.59,71 Bimetallic combination (Fe0/Ni0: the ratio of
Fe to Ni being 3 : 1) has provided better degradation rates.72
Bimetallic particles are composed of two types of zero-valent
iron (ZVI). The structure of bimetals includes cluster-in-cluster
and coreshell structures for nanoscale particles.73 As iron
corrodes, protons from water are reduced to adsorbed H atoms
and to molecular hydrogen at the catalytic Ni surface. Fig. 3
shows a schematic diagram of the reaction of a chlorinated
organic molecule with a bimetallic nanoparticle. Fe or Zn
serves as an electron donor while another species (Pt or Pd)
serves as a catalyst.74,75 TCE is adsorbed onto the surface of
the NiFe particles where the CCl bond is broken and the
chlorine atom is replaced by hydrogen. A similar mechanism
was applied by Cheng et al.76 for the dehalogenation of
4-chlorophenol to phenol on palladized graphite and iron
electrodes.76
This journal is The Royal Society of Chemistry 2012
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Dabro et al. investigated the dehydrochlorination of penta-
chlorophenol to phenol or cyclohexanol on supported palladium
electrodes.77 The rapid and complete dechlorination of all the
chlorinated contaminants was achieved for the water and
groundwater slurries using bimetallic nanoparticle systems
composed of Pd/Fe.78 Contaminants, such as tetrachloroethane
(C2Cl4), could be transformed to ethane by accepting electrons
from the oxidation of iron through the following reaction:
C2Cl4 + 4Fe0 + 4H+ / C2H4 + 4Fe2+ + 4Cl
The removal efficiency was found to be greater than 99% using
iron nanoparticles without a palladium coating after 24 h. In
addition, bimetallic coupling with a second catalytic metal has
also been widely applied for the degradation of contaminants in
contaminated water. The degradation rate by bimetallic combi-
nations was found to be faster than that observed for metal iron
alone.79,80 Bimetallic Pd/Au nanoparticles consist of two catalytic
metals, whereas bimetallic nanoparticles of iron consists of a
catalytic material (Pd or Ni) and an electron donating material
(i.e. Fe). Bimetallic Pd/Au nanoparticles can increase the cata-
lytic activity by a factor of 15 as compared to Pd nanoparticles,
Al-supported Pd nanoparticles and Pd black.81,82
Reducing the size of iron to the nanoscale has been very
efficient for enhancing the rate of reaction and reducing the
formation of by-products.83 However, the material became less
stable with an increase in the reaction activity as zero-valent iron
nanoparticles are easy to oxidize in air and hydrolyze in water.
Therefore, the efficiency of Fe0 particles could be significantly
reduced in large scale environmental remediation. To maintain
the stability of Fe0 nanoparticles, immobilization of Fe0 in the
membrane or bimetallic Fe0 nanomaterials have been used.
Meyer et al. in 2004 found that membrane immobilization for
nanoparticles of Fe0 and bimetallic Ni0/Fe0 offered two advan-
tages in the removal process of toxic organic compounds. Those
advantages were (1) the polymer membrane controlled growth of
zero-valent iron metal nanoparticles and (2) the localization and
higher concentration of organic substances in the membrane
domain led to a significant enhancement of the reaction rates.84
Although bimetallic particles of Ni/Fe showed a relatively high
reactivity towards chlorinated compounds,85,86 there is still an
environmental concern over the toxicity of Ni. Particles of nZVI
have been applied for the efficient removal of different metals,
such as Cr(VI),87 U(IV) and U(VI)88 and Co(II).89 Choe et al. (2001)
reported the reductive denitrification by nanoscale zero-valence
Fig. 3 A nanoscale bimetallic particle for chlorinated solvent removal.75
Energy Environ. Sci., 2012, 5, 80758109 | 8081

iron.90 Ghauch et al.91 reported interesting results on the elimi-
nation of antibiotics from water using iron NPs.91 Bimetallic
nanoparticles of ZVI and Al have been utilized for the removal of
chlorinated organic solvents, nitrate and heavy metals, such as
Cr6+ and Cu2+, as well as perchlorate ions from waste water.9299
Bimetallic particles of Fe and Al were found to degrade CCl4 by a
factor of 6 as compared to micro-sized Fe ZVI. Bimetallic
nanoparticles of Pd/Fe were found to provide a higher degra-
dation of CCl4 than one dimensional ZVI Fe nanoparticles100 due
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to the catalytic effects of metals (Pd or Ni) through a direct
hydrogen reduction101 and the prevention of oxide formation at
the iron surface.72 Complete degradation could be obtained with
a high surface reactivity, the elimination of toxic intermediates
and a durable and stable performance by using bimetallic Pd/Fe
nanoparticles.101105 Bimetallic Cu/Al particles have shown a
better degradation of CCl4 and CH2Cl2, which was not degraded
by most of the ZVI.106 Martin et al. have reported the use of
ferric-oxide NPs to remove and recover phosphate from
municipal waste waters.107
TiO2 nanoparticles have been extensively used for the oxida-
tive and reductive transformation of organic and inorganic
contaminants in air and water.108 TiO2 photocatalysts have been
a popular choice for much of the published photocatalysis work.
Its large bandgap energy (3.2 eV) requires UV excitation to
induce charge separation within the particle. TiO2 is a semi-
conductor and has three distinct polymorph crystalline struc-
tures: rutile, anatase and brookite. Both rutile and anatase have a
tetragonal structure, containing 6 and 12 atoms per unit cell with
an axial ratio of c/a (c perpendicular axis, a horizontal axis)
0.64 and 2.51, respectively. The brookite has an orthorhombic
structure. Both rutile and anatase have been applied in photo-
catalytic and photoelectrochemical processes due to their easy
synthesis by various techniques. TiO2 has been widely applied in
heterogeneous photocatalysis to decompose a host of organic
pollutants, such as phenolic compounds,109 metal ethylene
diamine tetra acetate complexes,110 airborne microbes and
odorous chemicals.111 Most of this research involved UV
photons as the major exciting light sources. There is 5% of solar
irradiation within UV range; therefore, it is necessary to enhance
the performance of TiO2 by using photons from the near visible
to visible region. This can be achieved by manipulating the
particle size of the photocatalyst or by doping the TiO2 with
foreign ions.112115
The modification TiO2 with noble metal ions could decrease
the TiO2 band gap, which benefits the electron transfer from
the valence band to the conduction band, which facilitates the
formation of oxidative species, such as _OH.116 In addition, the
modified surface properties of noble metal-doped TiO2 photo-
catalysts could attract more cationic dye, i.e. rhodamine B (RB),
which could be adsorbed on the Ag-doped TiO2 surface due to an
increased number of electron traps. One dimensional TiO2
nanomaterials and doped TiO2 nanomaterials are widely used for
the degradation of halogenated compounds, the removal of dyes
via photocatalytic oxidation, the removal of metals and some
disinfection processes for drinking water and waste water. TiO2
nanoparticles are activated by UV irradiation (radiation at
wavelength 320400 nm) and its photocatalytic properties have
been utilized in various environmental applications to remove
contaminants from both water and air.117 Recent research has
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shown that the desired band gap narrowing of TiO2 can be better
achieved by using nonmetal elements, such as N, F, S and C.
Such modified TiO2 materials exhibited larger absorption in the
visible region and enhanced the degradation of organic dyes
under visible light irradiation, especially under natural solar light
irradiation.118 The relevant mechanisms for the role of nonmetals
in modified TiO2 materials in its visible light photoactivity are
due to the substitution of oxygen for nitrogen in the TiO2 lattice.
The corresponding N(2p) states are located above the valence
band edge. Mixing of the N(2p) states with the O(2p) states
results in a reduction of the band gap in N-doped TiO2 and the
photocatalyst can be active under visible light irradiation.119
Nano-sized TiO2 was also reported to kill viruses, including
poliovirus 1,120 the hepatitis B virus,121 the Herpes simplex
virus122 and MS2 bacteriophage.123 The concentration of TiO2
required to kill bacteria varies between 100 and 1000 ppm
depending on the size of the particles and the intensity and
wavelength of the light used.124 The antibacterial activity of TiO2
is related to the ROS production, especially hydroxyl free radi-
cals and peroxide formed under UV-A irradiation via oxidative
and reductive pathways, respectively.125 A strong absorption of
UV-A activates TiO2 under solar irradiation and significantly
enhances solar-triggered disinfection. In a study by Gelover
et al., the complete inactivation of fecal coliforms was achieved in
15 min at an initial concentration of 3000 cfu per 100 mL by
exposing water in TiO2-coated plastic containers to sunlight,
whereas the same inactivation required 60 min with uncoated
containers.126 An attractive characteristic of TiO2 photocatalytic
disinfection is its capability of activation by visible light, e.g.
sunlight. Metal doping has been shown to improve the visible
light absorbance of TiO2127 and increase its photocatalytic
activity under UV irradiation.128 Noble metals, especially silver,
have received much attention for this purpose. Silver has been
shown to enable the visible light excitation of TiO2.129 Recently,
it was demonstrated that doping TiO2 with silver greatly
improved the photocatalytic inactivation of bacteria130 and
viruses.131 Reddy et al. demonstrated that 1 wt% Ag in TiO2
reduced the reaction time required for complete removal of 107
cfu of E. coli per mL from 65 to 16 min under UV-A radiation.132
Silver enhances the photoactivity by facilitating electronhole
separation and/or providing more surface area for adsorp-
tion.116,133 Visible light absorption by silver surface plasmons is
thought to induce electron transfer to TiO2 resulting in charge
separation and, thus, activation by visible light.129,134 Ag/TiO2 or
Au/TiO2 therefore shows a great potential as a photocatalytic
material due to its photoreactivity and visible light response.
Table 1 summarizes the application of TiO2 nanomaterials for
environmental remediation. TiO2 is widely used for NOx control,
whereby NOx is reduced back to N2 or oxidized to NO2 and
HNO3. The oxidation of nitric acid converts it into a raw
material with useful applications, such as in fertilizers. The
activity of TiO2 is improved by the addition of an adsorbate, such
as zeolites, which concentrate NO on the surface. A highly
selective photoreduction of NO to N2O and N2 is observed on
the surface of TiO2. In the work of Skubal et al. the surfaces of
titanium dioxide NPs were modified with a bidentate chelating
agent, thiolactic acid (TLA), to remove aqueous cadmium from
simulated waste waters.135 Amezaga-Madrid et al. tested the
effect of TiO2 thin films deposited on soda lime glass slides by
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solgel techniques.136 After 40 min, a 70% reduction of P. aeru-
ginosa cells was observed. Kuhn et al. reported that bacteria
placed on TiO2 coated surfaces were killed in the following order:
E. coli > P. aeruginosa > S. aureus > Enterobacter faecium > C.
albicans.137 While pure TiO2 had no antibacterial effect in free
solution or in agar, silver-doped TiO2 particles were more
effective than pure silver nanoparticles of a similar size.138
Inorganic nanoscale ZnO was mostly applied to eliminate H2S
as an adsorbant. Recently, nanostructured ZnO could efficiently
remove heavy metals.147 Lee et al. prepared nanometer size zinc
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oxide (ZnO) powders by a solutioncombustion method
(SCM). Compared with two TiO2 powders, P25 and one
prepared by a homogeneous precipitation process at low
temperature, the zinc oxide nanopowder showed a higher
removal rate of Cu2+ ions from the solution.148 ZnO nanosheets
prepared via a hydrothermal approach were used to adsorb Pb2+
and then hydrothermally treated in an aqueous solution con-
taining a sulfur source. Due to the surface hydroxy groups, the
resultant ZnO nanosheets exhibited a good capacity of Pb2+,
which was found to be 6.7 mg g1.149 The Pb2+-preloaded ZnO
nanosheets were put into a Teflon-lined stainless steel autoclave
containing a sulfur source at 120  C for 12 h and the resulting
ZnO/PbS nanocomposite exhibited a potential use in photo-
catalytic remediation. ZnO nanoparticles exhibit strong anti-
bacterial activities on a broad spectrum of bacteria.150 The
penetration of the cell envelope and the disorganization of the
bacterial membrane upon contact with ZnO nanoparticles were
also indicated to inhibit bacterial growth.151 Other NPs, such as
cerium oxide, have been applied for the removal of Cr(VI)
through the adsorption of the metal onto the surface of
the NPs.152
Various dopants, such as transition metal ions (Fe, Co, Cu),
have been used to enhance the photocatalytic activity of TiO2.
Metal-doped TiO2 was found to induce the desired red-shift of
the adsorption spectrum. However, it has also been documented
that the presence of transition metals may increase the proba-
bility of electronhole recombination, resulting in a reduction of
the semiconductors photocatalytic efficiency. Titania doping
with nonmetal elements (N, C, S) has also been considered as an
effective approach to extend the spectral response of TiO2
towards visible energy wavelengths. In this approach, single and
co-doped TiO2 catalysts with Fe and S have been reported to
exhibit enhanced photocatalytic activity under visible light.
Table 1 Photocatalytic processes of environmental remediation by one dimensional or ion doped-TiO2 nanoparticles
Category Target material
Disinfection Water-borne pathogenic virus in
drinking water
Metal removal Arsenic
Dye removal/destruction of Methylene blue, creatinine,
biological toxins and inactivation of biological toxins (microcystin-LR),
bacteria E. Coli
Metal removal Lead
Dye removal Methylene blue
Air treatment NOx and toluene in air
Disinfection S. aureus and E. Coli in water
Nutrient removal Nitrate
Nutrient removal Nitrate
Organic removal 2,4,6-Trichlorophenol
This journal is The Royal Society of Chemistry 2012
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Recently, emphasis has been given to co-doped TiO2 systems,
involving cations and anions, in order to improve the photo-
catalytic efficiency of TiO2. It has been suggested that charge
separation between electrons and holes is improved by the
co-doping of TiO2 with Fe and S. Under both UV and sunlight
irradiation, all synthesized S single or co-doped catalysts showed
larger catalytic activities compared to the commercial TiO2, P25.
Toluene photo-excitation appears to be favoured at a low S
concentration (0.2%) in the nanomaterial but it provided a
detrimental effect at 0.4% of S in TiO2 nanomaterials. Co-doping
with S and Fe favours the photocatalytic activity of the nano-
material when it is compared to that of single Fe-doped TiO2. In
addition, the single S-doped and co-doped S/FeTiO2 catalysts
showed high selectivity (>90%) toward the partial oxidation of
toluene (production of benzaldehyde).153 The photocatalytic
activity of the prepared TiO2 catalysts doped with Li+, Rb3 and
Y3+ under sunlight irradiation was evaluated using 2-naphthol as
a pollutant model. The results showed a great enhancement in
the photocatalytic efficiency with the incorporation of Y3+ in
samples synthesized by solid grinding, while in samples synthe-
sized by solgel process either Rb+ or Y3+ dopants greatly
improved the photocatalytic activity. The increase in photo-
activity may be due to: (i) a decrease of the energy gap, which
favors a higher photoexcitation efficiency under solar radiation
and provides a larger population of excited species (holeelectron
pairs); (ii) the small particle size favors the increase in the surface-
to-volume ratio and the scavenging action of the photogenerated
electrons by the Y3+ or Rb+ ions results in a prevention of the
recombination of electronhole pairs and increases the lifetime of
the charge carriers; (iii) the doping ions (Rb+ or Y3+) can act as
electron traps, thus facilitating the electronhole separation and
subsequent transfer of the trapped electron to the adsorbed O2,
which acts as an electron acceptor on the surface of the TiO2; (iv)
the dopant prevents the recombination of electronhole pairs
and increases the lifetime of the charge carriers. Therefore,
photocatalysis activity under sunlight can be improved.154
Increasing amounts of silver in Ag-doped TiO2 significantly
increases the rate of degradation of a model dye, rhodamine.
Two possible parallel mechanisms, which may result in electron
population of the conduction band of the material, have been
suggested: (i) rhodamine absorbs visible light and injects an
electron into the conduction band of the TiO2 material or (ii) the
material itself absorbs visible light, which is probably facilitated
Type of nanomaterial Ref.
Ag-doped TiO2 139
One dimension TiO2/Fe-doped TiO2 140
Crystalline TiO2 thin film/the 141
composite material of TiO2 and
Al2O3
One dimension TiO2 142
Ag-doped TiO2 nanofibres 143
Ag-doped TiO2 nanofibres 143
Ag-doped TiO2 nanofibres 143
Cu/Fe/Ag-doped TiO2 144
TiO2 NPs doped with Bi3+ 145
Ag-doped TiO2 146
Energy Environ. Sci., 2012, 5, 80758109 | 8083

by the surface plasmon absorption of the silver-doped materials.
It is probable that the two mechanisms are happening in parallel,
indeed some commentators have questioned the suitability of
dyes, such as methylene blue, for photocatalytic studies. The role
of silver clearly controls the recombination rate and subsequently
allows a greater proportion of hydroxyl radicals to form.155
(C) Nanofiltration
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(C-1) Nanofiltration by membranes. Membrane technologies
are more efficient nowadays due to their reliable contaminant
removal without the production of any harmful by-products,
especially in water and waste water treatment processes. The
basic principle of membrane filtration is to apply semi-permeable
membranes to remove fluids, gases, particles and solutes. For the
separation of materials from water, membranes must be water
permeable and less permeable to solutes or other particles.
Pressure-driven membrane processes, such as microfiltration
(MF), ultrafiltration (UF), nanofiltration (NF) and reverse
osmosis (RO), have been applied for water treatment, reuse and
desalination systems throughout the world. Nanofiltration (NF),
as a promising membrane technology, is a method for removing
low molecular weight solutes, such as salts, glucose, lactose and
micro-pollutants, in contaminated water.156,157 The availability of
clean water has emerged as one of the most serious problems
facing the global economy in the 21st century. Water treatment
systems typically involve a series of coupled processes, each
designed to remove one or more different substances in the
source water, with the particular treatment process being based
on the molecular size and properties of the target contaminants.
RO is very efficient for retaining dissolved inorganic and small
organic molecules. NF can effectively remove hardness (i.e.,
Ca(II)) and natural organic matter. However, a limitation of
both RO and NF processes is the requirement of high pressures
(1001000 psi) to operate the water treatment. Conversely, UF
and MF membranes require lower pressures (560 psi) but those
membranes cannot retain dissolved ions and organic solutes.
Advances in nanochemistry can provide enhancement of UF and
MF processes for recovering dissolved ions from aqueous solu-
tions.158160 Both cellulose acetate and polyamide can be used to
form NF membranes. In addition, other polymers (e.g., poly-
vinyl alcohol (PVA) and sulfonated polysulfone) and inorganic
materials (e.g., some metal oxides) can also be used for NF
membrane synthesis.161 The typical properties of NF membranes
are shown in Table 2. NF membranes selectively reject
substances as well as enable the retention of nutrients in water.
Therefore, the advantages of NF are comparable to the RO
process. The adsorption of pollutants onto the membrane can be
(1) physical in nature, which is a completely reversible process, or
(2) chemical in nature, which is irreversible for strong chemical
bonds, such as polymerization, or reversible for weak secondary
chemical bonds, such as hydrogen bonds and complexation or (3)
both. NF is capable of removing hardness, natural organic
matter, particles and a number of other organic and inorganic
substances via one single treatment. Water hardness is caused by
calcium and magnesium ions, while strontium and barium rarely
occur in substantial concentrations. NF membranes can reject
bivalent ions in significantly high amounts.163,164 The calcium ion
rejection was found to be 74.978.9% higher than the expected
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results of the manufacturer (in Germany) for a thin film
composite of a polyamide membrane with molecular weight cut-
off of 300 Da (NF 200B).165 A better rejection of magnesium ions
was also found to be 86.790.3% using the same type of
membrane due to the stronger hydration of the Mg2+ ion. Van
der Bruggen et al.166 observed that a spiral-wound membrane
made of polyamide materials with a molecular weight cut-off of
250 Da (NF 70) could remove the major fraction of hardness
from groundwater. When groundwater was treated with a NF 70
membrane for the production of drinking water, it was suggested
that the permeate should be mixed with streams that have been
treated by traditional methods or, alternatively, hardness should
be re-added to the drinking water in order to obtain the desired
hardness of 1.5 mmol L1. The separation performance of NF
membranes for cations is 60%.166 For anions, the separation
efficiency obtained with NF was larger. For NF, the ion size
plays a role for membranes with small pores, leading to a large
selectivity.167 Nitrate rejection was 76% for NF70, which is better
than expected anticipated by the manufacturer of NF 70. The
higher retention of multivalent ions could be obtained over a
wide range of concentrations using a membrane with small pore
diameters.168 The pore size distribution of NF membranes have a
common feature: the largest fraction of medium-size pores is
approximately 0.85 nm, which is primarily responsible for the
sieving effect of the membranes. In addition, the NF membranes
contain larger fractions of the smallest pores (0.220.254 nm)
and there is a significant fraction of wider pores (1.55 nm) in
the skin of the NF membranes.169 Mass transport through a
nanofiltration membrane can be achieved by two mechanisms:
diffusion and convection. When the transmembrane pressure is
high, the diffusion mechanism becomes less influential than the
convection mass transport mechanism and, therefore, a better
retention of Ca2+ ions is found. The retention of Ca2+ was found
to be very high for NF 70 and a membrane made of poly-
piperazineamide (UTC20) and remained constant when the
pressure was above 10 bar. A 90% retention was found for
multivalent ions, such as sulfate, calcium and magnesium ions,
and 6070% was found for monovalent ions, such as sodium and
chloride.168 In NF membranes, electrostatic interactions between
the negatively charged membrane and the charged species appear
as an important feature over the size effect and salts containing
divalent sulfate anions are better rejected by the membrane than
salts with a monovalent chloride anion. However, the differences
in the retention of the examined chlorides are mostly controlled
by the size of the cations. The rejection behaviour of the NF
membranes for multivalent ions is due to charge interactions
with the membrane and the size exclusion of hydrated ions.170
Monovalent ions tend to have lower rejections unless they are
retained to maintain charge neutrality with multivalent counter
ions.169 Kosutic et al., observed the order of chloride retention as
follows: RMgCl2 > RCaCl2 > RNaCl, which holds for the two types
Table 2 The typical properties of pressure-driven NF membranes162,163
Pore size (nm)
2 nm
Water permeability (L m-2 h-1 bar-1) 550
Operating pressure (bar) 210
Molecular weight cut off (Da) >100
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of thin film polyamide NF membranes with slightly lower
retention values for the NF-type membranes. This is caused by
the presence of a fraction of large pores in the surfaces of the
membrane.169 Such an order was not found for sulfates and this
may be due to the ion pairing effect, which is more prevalent in
MgSO4 than in Na2SO4 solutions. Orecki et al. observed that the
NF process of surface water provided a retention coefficient
of 9099% for sulfate and 82% for carbonate, while it rejected
4055% of the covalent salts.171 The total hardness of the surface
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water could be reduced by 85.2%. The rejection of both divalent
dibasic arsenate, HAsO42 and sulfate (SO42) ions was found to
be notably higher than the rejection of chloride ions by the
charged NF membranes due to the stronger electrostatic repul-
sion of the former ions than the repulsion of the lesser charged,
monovalent chloride ion. This shows that the charge exclusion
influences the retention of ions by the negatively charged NF
membranes.172
The NF process has many advantages, including ease of
operation, reliability, no requirement of additives and a modular
construction that is easy to upscale.166 However, the limitation in
NF is membrane fouling. Scaling or the formation of precipitates
takes place when the concentration of the ionic salt exceeds its
solubility in water. Inorganic foulants in the NF process are
found to be carbonate, sulphate and phosphate salts of divalent
ions, metal hydroxides, sulphides and silica. Fouling leads to
physical damage to the membrane due to the plugging of pores
and the inability to remove the scales from the membrane
surface.172 However, the addition of hydrochloric or sulphuric
acid can prevent the formation of calcium carbonate during the
NF process.168 An alternative method to prevent membrane
fouling is the addition of antiscalants, i.e. surface active materials
which can interfere with precipitation during the NF process via
threshold inhibition, crystal modification or dispersion.
Common surface active agents are sodium hexametaphosphate,
diethylenetriamine-penta-methyl phosphoric acid and
1-hydroxyethylidene-1,1-diphosphonic acid. The high rejection
of antiscalants by membranes takes place during the NF process
due to their high molecular weight and negative charge.172
The NF process is commonly used for the removal of natural
organic matter (NOM) from water. NOM is a polydisperse
mixture of individual particles in natural water originating from
degraded and partly re-synthesized plant residues. Humic and
fulvic acid seem to contribute to the natural color of water, which
becomes visible if the concentration of the dissolved organic
carbon (DOC) is higher than 5 ppm.172 In addition, a large
variety of dyes and chemical additives from textile plant are
environmental pollutants.173 The results observed by researchers
include the findings that hydrophobic fractions of NOM appear
to be retained best, acidic pH favours a lower rejection of NOM
(6075%), while a neutral pH favors a high rejection of NOM
(90%). Rejection has also been found to be concentration
dependent and ionic species may promote conformational
changes in the NOM fractions, which can improve rejection via
the NF process.174,175 Braghetta et al. observed a decrease in the
rejection of DOC at a low pH and high ionic strength using a
sulfonated polysulfone hollow fibre NF membrane. The inter-
action between the membrane polymer (the hydrophobic
domain) and the organic solute can influence the rejection
behavior as the hydrophobicity of the organic polymer affects the
This journal is The Royal Society of Chemistry 2012
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sorption of organics onto the membrane surface.176 When
adsorption takes place inside the membrane or on the surface, the
pore size can become reduced as molecules that have a similar
size to the pores block them through permeation. The interac-
tions that occur in a multi-component solution may improve the
rejections of NOM by the membrane due to friction coupling; i.e.
the effect of coupling the different components. Solutions con-
taining electrolytes, non-electrolytes or solutions of weak acids
tend to exhibit strong interactions.177 The total organic carbon
(TOC) content of surface water can be reduced by 93.5% via
the NF process and removes turbidity by 85.5%.171 However, the
gradual plugging of the membrane has been observed in the
treatment of surface water with a low initial turbidity and high
TOC conducted by the NF process. Flushing of the membrane
with permeates from the RO process could prevent membrane
plugging and allow a recovery of the initial flux.
The fouling of membranes by NOM and a decline of the flux
are the major problems associated to the NF techniques in the
treatment of drinking water.178 Polysulfone membranes have
been used in some studies and have caused adsorptive fouling.
The fouling mechanisms are adsorption, precipitation, gel
formation and an interaction with multivalent ions. Thus, pre-
treatment with a coagulant has been suggested to prevent these
adverse effects and a combination of a coagulation process and
membrane filtration can significantly reduce the necessary
amount of coagulant required, while reducing the turbidity and
DOC. Moreover, coagulation has been found to provide an
efficient hygienic barrier in combination with membranes.179
However, the removal of NOM has been significantly affected by
the type of coagulant, the coagulation conditions, the type of
membrane, the filtration conditions and the characteristics of the
treated water. In addition, cartridge filtration and activated
carbon adsorption can be used to prevent membrane fouling by
NOM.172 New ways of reducing membrane fouling have been
suggested for the immobilization of TiO2 photocatalysts on the
membrane surface and these have been called composite
membranes. The use of nanoparticles, such as nano-alumina,
silica, silver, iron oxide, etc., in membrane structures has gained a
lot of interest, but their application in water treatment and the
possible release of nanoparticles into the water has remained
open to debate whilst the application of NF has progressed in the
treatment of water.180
Organic micro-pollutants present in natural waters used for
drinking water production lead to negative effects on human
health. Many pesticides and organohalide compounds have been
found to be carcinogenic, even in very low concentrations. The
removal of micro-pollutants is traditionally done by activated
carbon adsorption. This method is very expensive when large
fractions of NOM are present because the adsorption sites are
mainly taken by NOM due to its high concentration.181 The
removal efficiencies largely depend on the membranes used and
on the pesticides that have to be removed. Montovay et al. found
an 80% removal of atrazine and a 40% removal of metazachlor,
which is significantly lower than the expected result.183 Kiso
et al.157 studied the removal of pesticides, such as acaricides,
fungicides, insecticides, herbicides and rodenticides, such as
atrazine and simazine, together with pyridine and a chlorinated
pyridine compounds. Four different (unspecified) membranes
produced by NittoDenko were used. The rejections obtained
Energy Environ. Sci., 2012, 5, 80758109 | 8085

with three of these membranes were too low and the rejections
with the fourth membrane were very high (over 95%); however,
this membrane seemed to be an RO membrane and provided a
high NaCl rejection.157 Van der Bruggen et al.184 obtained good
results for the removal of atrazine, simazine, diuron and iso-
proturon. Rejections were all over 90% with NF70 (Dow/Film-
tec), but for two other membranes (NF45, a Dow/Filmtec
membrane, which is a thin film composite on a polyester support
viable for operation at pH from 2 to 10 and temperatures up to
45  C, and UTC-20, a Toray membrane) relatively low rejections
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were found for the removal of diuron and isoproturon. This may
be due to the high polarity of these compounds, which causes
interactions with the charged membrane.183 Van der Bruggen
et al.167 also proved that there was no significant effect of
concentration on the rejection of pesticides in water. The rejec-
tion of pesticides was higher in river water and tap water than in
distilled water, but the water flux was lower.167 This was mainly
due to ion adsorption inside the membrane pores. Narrower pore
sizes counteracted the effect of the presence of NOM. The NOM
was assumed to enhance the adsorption of pesticides onto the
membranes surface and an increased size exclusion and electro-
static repulsion was also observed during the NF process.182,184
The rejection of pesticides is reasonably high and correlates
positively with the order of their molecular sizes.169 Important
factors that must be considered for the selection of an appro-
priate membrane are (1) the molecular weight cut-off (MWCO),
which is expressed in Dalton, (2) the membrane porosity, (3) the
degree of membrane desalination, and (4) the charge of the
membrane. Membranes with a MWCO varying between 200 and
400 Da are considered to be suitable for the adequate removal of
pesticides from water. The rejection of uncharged pesticide
molecules has been positively correlated with the pore size
distribution and the number of pores on the surface of the
membrane. The highest desalting membrane was found to
effectively reject almost all pesticides. However, rejection was
again found to be a function of the properties of the pesticide,
such as hydrophobicity and charge, regardless of the membrane
salt rejection performance. In general, the reliability of the
membrane desalination degree is not an accurate indicator to
assess the removal of hydrophobic organic micro-pollutants. A
number of studies confirm that composite polyamide membranes
indicate far better rejection performances for several mixtures of
micro-pollutants, including pesticides, compared to cellulose
acetate membranes (CA).185,186 This behavior may be due to the
higher polarity of CA membranes, which is responsible for the
poor rejection of the highly polar pesticides. The electrostatic
repulsion between negatively charged pesticides and the negative
charge of the TFC membrane surface could enhance the overall
rejection performance.187 The removal of pesticide is dependent
not only on the properties of the membrane but also on the
properties of the pesticides, such as (1) the molecular weight and
size of the pesticide, (2) the hydrophobicity, and (3) the
polarity.156,165,188,189 Bentez et al.189 investigated the application
of NF for the removal of phenyl-urease in natural waters. Two
types of membrane were used in their investigation: (1) a thin film
composite (a polypyperazinamide skin layer on a polyester
support), which is negatively charged because of its active
nanopolymer layer; and (2) a cellulose acetate polymer, which is
negatively charged. It was found that the retention order for the
8086 | Energy Environ. Sci., 2012, 5, 80758109
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thin film membranes (with a hydrophilic character) was iso-
proturon > linuron > chlortoluron > diuron, which showed that
the molecule polarity is the main parameter that influences the
retention. On the contrary, the retention efficiency for
the cellulose acetate membrane (with a hydrophobic character)
followed the sequence: linuron > diuron > chlortoluron > iso-
proturon, which indicates that the main factor responsible for the
retention is the MW for the adsorption. Moreover, the mass
adsorbed sequence found in both membranes for both mineral
and reservoir water was: linuron > diuron > chlortoluron >
isoproturon. From the results obtained, it can be concluded that
the thin film membrane was the most adequate for the removal of
phenylureas from natural waters, especially for the most polar
compounds because higher retention coefficients as well as higher
retentions are obtained for DOC and aromatic compounds. They
also observed that the additional presence of humic acids and
calcium ions increases membrane fouling, which is a consequence
of the adsorption of various species (NOM and ions on the
membrane) as well as pore blocking and the formation of a cake
layer on the membrane surface. However, the effect of humic
acids and calcium ions on the retention coefficients is not
significant, especially for the less hydrophobic compounds
(chlortoluron and isoproturon).189 Manttari et al.190 investigated
the combined treatment of paper mill effluents with the activated
sludge process and NF using a membrane made of piperazine
and benzene tricarbonyl trichloride, which produced a negatively
charged, hydrophilic membrane with a smooth surface and a
MWCO of 200300 Da. It was reported that a well operated
activated sludge process can be a good pretreatment prior to the
NF operation as a high COD removal can be achieved via
the activated sludge process and the resulting concentrate, after
the NF process, had a lower amount of organic pollutant in the
waste effluent compared to the NF operation without the
pretreatment. The color rejection of NF after treatment was
almost complete and the permeate color was always lower
than 10% PtCo. Similar to the color, quite high COD rejections
(80100%) were found with NF. Furthermore, the conductivity
rejection was around 65% and the permeate conductivity was
between 1.98 and 2.67 mS cm1.190 Ducom and Cabassud studied
the removal of trichloroethylene, tetrachloroethylene and chlo-
roform by NF. The removal efficiency of the former two
compounds was satisfactory, but the chloroform rejection was
significantly lower. This effect was attributed to the selective
adsorption of chloroform into the membrane structure, which
led to higher concentrations in the permeate.191 However, good
removal efficiencies of chloroform were obtained by Waniek
et al.192 Pang et al.193 evaluated the removal efficiency of
1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) in
contaminated water using a NF unit of a polyvinylidene fluoride
(PVDF) membrane. The DDT concentration decreased signifi-
cantly from 77.4 mg L1 to 52.2 mg L1, while the cumulated
quantity adsorbed reached 506 mg m2. The results show that
DDT was easy to adsorbed on the polyvinylidene fluoride
membrane.192 The removal mechanism of DDT by PVDF could
be due to two possible mechanisms: adsorption on the membrane
or repulsion (steric and electrostatic) by the membrane. The
increase of the initial DDT concentration had a negative effect
on the DDT removal and the influence of pH on the rejection is
not obvious. In addition, the rejection of DDT was lower with a
This journal is The Royal Society of Chemistry 2012

higher flux. It was difficult to simultaneously achieve a high
permeate flux and high DDT rejection; however, DDT can be
easily adsorbed by humic acid and can be removed altogether.
With the blocking effect of the pores by the ions and the presence
of organic matter (humic acid) and inorganic matter (NaCl,
CaCl2 and CaSO4), the elimination of DDT can be enhanced.
The removal of viruses and bacteria is extremely important in
drinking water purification. The removal of the protozoa giardia
and cryptosporidium from surface water sources is a main priority
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for many governments and drinking water companies. Tradi-
tional chlorination is still often applied as a disinfection method,
but the disadvantages of chlorination were found to be (1) the
formation of disinfection by-products (DBPs) and (2) the resis-
tance of cryptosporidium to chlorine and chloramines.
Membrane filtration may facilitate an improvement in the
disinfection process because it is an extra barrier for viruses and
bacteria.181 Bacteria (0.510 mm) and protozoan cysts and
oocysts (315 mm) are larger and their removal can be guaran-
teed with at least 4 log units by using UF membranes. The
smaller viruses may be rejected by NF membranes, which have
pore sizes below 1 nm.
Filtration processes by a membrane with carbon nanotube
walls have been reported.193 The filtration membrane consisted of
a hollow cylinder with radially aligned carbon nanotube (CNT)
walls. Srivastava et al.194 efficiently conducted the removal of
Escherichia coli from drinking water using the CNT-aligned
membrane. Membranes that have CNTs as pores could be used
in desalination and demineralization. Those tubes act as the
pores in the membrane. A membrane filter possessing both super
hydrophobicity and superoleophilicity was synthesized from
vertically aligned multi-walled carbon nanotubes on a stainless
steel mesh for the possible separation of oil and water. Both
super hydrophobicity and superoleophilicity could be obtained
due to the dual-scale structure and needle-like nanotube geom-
etry of the mesh with micro-scale pores combined with the low
surface energy.194 The nanotube filter could separate diesel and
water layers and even surfactant-stabilized emulsions. The
successful phase separation of the high viscosity lubricating oil
and water emulsions was also carried out. The separation
mechanism can be readily expanded to a variety of different
hydrophobic and oleophilic liquids, such as brewery waste water,
which may have a high content of organic matter in terms
of COD (from 1000 mg L1 to 4000 mg L1) and BOD (up
to 1500 mg L1).
Polymeric membranes have many advantages, such as their
easy formation, the selective transfer of chemical species and
their relatively low cost.195 However, inorganic membranes are
currently in competition with organic membranes for commer-
cial applications because they have a better resistance to chemical
attack, good mechanical strength and a high tolerance of extreme
pH conditions and oxidation. Inorganic membranes composed
of metal oxides have higher durability in many water purification
applications. In addition, the increased conversion, better selec-
tivity, milder operating conditions and decreased separation load
are some other attractive features which promote inorganic
membranes as chemical reactors in many established and novel
reaction systems.196 In many of the harsh operational environ-
ments, only inorganic membranes can offer advantages.
However, inorganic membranes are not used extensively because
This journal is The Royal Society of Chemistry 2012
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of the high costs and relatively poor control in pore size distri-
bution. Besides, the effective membrane layer is very thick in
comparison to the mean pore size, which results in a reduced flow
rate. Thus, the incorporation of inorganic nanoparticles into the
polymeric membranes has been considered as a way to make
polymeric membranes more attractive for commercialization.
Silver nanoparticles (170 nm) have been blended into poly-
sulfone membranes by dispersing nanoparticles in a casting
solution before dissolving them in the polysulfone resin (PSf).
The addition of silver nanoparticles did not alter the membrane
structure. The impregnation of nAg (0.9% by weight) signifi-
cantly decreased the number of Escherichia coli that were able to
grow on the membrane surface by 99% after filtration with a
dilute bacteria suspension. Furthermore, the silver nanoparticles
reduced the attachment of an E. coli suspension to the surface of
the immersed membrane by 94%.197 The antibacterial mechanism
of silver is related to its interaction with sulfur and phosphorous,
most notably the thiol groups (SH) present in cysteine and other
compounds. The interaction of ionic silver (which can be released
from the silver nanoparticles) with thiol groups and the forma-
tion of SAg or disulfide bonds can damage bacterial proteins,
interrupt the electron transport chain and dimerize deoxy-
ribonucleic acid (DNA).198,199
Singapore began reclamation of domestic sewage in 1998
through the NEWater study. Indirect portable reuse is practised
through the introduction of a suitable amount of NEWater into
reservoirs that can be further purified by water treatment tech-
niques before supplying to the public. To produce NEWater,
primary sedimentation and secondary treatment by activated
sludge were first applied for the clarification of used domestic
water. Then, biofiltration via MF or UF, reverse osmosis (RO)
and UV disinfection processes were applied for applications,
such as in manufacturing or industry or recharging into
groundwater or blending into reservoirs. The main problem in
the reclamation of domestic sewage is biofouling of the RO
membranes, which reduces the flux and increases the required
frequency of cleaning. Pretreatment prior to RO is needed to
prevent biofouling. Recently, an increased number of investiga-
tions on the use of NF in reducing dissolved organic matters with
molecular weights greater than 200 Da have been attempted.
Choi et al.206 used a polyamide NF membrane bioreactor for the
reclamation of water from domestic sewage and 0.52.0 mg of
TOC per L was found in the permeate. The amount of TOC was
much less than the average amount of TOC (5 mg L1) from MF
membrane bioreactors. Therefore, the NF membrane provided a
better retention of organic matter than the MF membrane, which
led to a reduced TOC in the permeate or feed of the RO
process.200 An average of 89% rejection for high organic acids
from anaerobic effluent was observed using polyamide NF
membranes.201 Therefore, application of NF membranes is
becoming a potential pretreatment process that reduces the
problem of biofouling in the RO process. The salt rejections and
organics removal by NF membranes could provide the required
water quality for groundwater recharging.202 In addition, higher
rejections of emerging contaminants were observed using poly-
piperazineamide thin film composite membranes as shown in
Table 3. The permeate flux when using NF membranes at 415
485 kPa was three times greater than that of RO membrane.203
Furthermore, energy cost was significantly reduced by 24 times
Energy Environ. Sci., 2012, 5, 80758109 | 8087

using NF at 415485 kPa compared to RO membranes operating
at 10002100 kPa to produce the same permeate flux. The
advantages of using NF as a pretreatment prior to RO for the
desalination of sea water over sand filters are the use of fewer
chemicals and the more consistent quality of the permeate. In
addition, NF could reduce fouling in RO as other pretreatments
using UF and MF membranes can cause fouling in RO due to
their inability to remove TDS. It was observed that NF can
remove almost all turbidity and microorganisms and reduces
TDS by 37.3%.204 More than an 80% rejection of divalent ions
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and an 86.5% total rejection have been found (Table 3). Rejec-
tion rates for NF membranes for the treatment of tertiary treated
effluent201 hardness were achieved using NF prior to the RO
process.204
Furthermore, NF pretreatment before the RO of sea water
could reduce biofouling and scaling due to the high removal of
microorganisms and hardness and the lower required pressure
for operating the RO process due to the high removal of TDS,
which in turn saves the cost of power consumption.204
The polyamide NF membrane bioreactor was observed to
have a high treatment efficiency and a satisfactory stability for
long term operation compared to NF membrane bioreactors
made from cellulose acetate, although the permeate productivity
was found to be lower.200 The concentrations of DOC in the
permeate of the cellulose acetate NF membrane bioreactor
deteriorated after 130 days operation, after which time only 10%
of TOC was removed by the membrane. Similarly, the salt
rejection rates of monovalent and divalent ions were reduced
from 4060% and 7090%, respectively, to less than 10% after 80
days of operation. The increased presence of DOC in the
permeate was due to the hydrolysis of cellulose acetate, which
may have led to an increase in the membrane pore size and a
decrease in the surface charge and hydrophobicity of the
membrane. After 71 days of operations, large voids were found
on the surface of the cellulose acetate membrane via an AFM
image, which showed the deterioration of the membrane.204 The
deterioration of the membrane may have been due to biodegra-
dation. Therefore, the selection of a suitable type of membrane is
important.
NF is widely used for industrial waste water treatments, such
as (1) color removal and the recovery of salts from waste water in
Table 3 The typical properties of pressure-driven NF membranes162,163
Rejection rate
Constituents (%)
TOC 96
Conductivity 48
Sodium 40
Potassium 40
Calcium 40
Magnesium 70
Chloride 80
Pharmaceutically active 25
compounds
Salicylic acid 100
Naproxen 90
Gemfibrozil 90
Ketoprofen 78
Carbamazepine 90
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the textile industry; (2) the recovery of heavy metals and eluents
from waste water in metal processing plants; (3) the removal of
organics and the recovery of proteins, enzymes and aromatic
compounds from waste water in the food processing industry; (4)
the reclamation and reuse of water from waste water pulp and
the paper industry; and (5) the removal of organics and multi-
valent ions from waste water at landfill leachate plants.172,205
Fersi et al.207 observed that a 90% retention of bivalent cations
and a 60% retention of monovalent cations can be achieved using
a NF membrane (pore size
2 nm) in the treatment of waste
water from the textile industry. In addition, the retention of
TDS, the turbidity and the color were found to be greater than
90%. Thus, NF membranes are suitable for removing water
soluble dyes with molecular weights ranging from 200 to 1000 Da
and divalent salts for softening effects.206,207 The limitation of the
NF membrane to remove color from industrial waste water is the
declination of the flux due to the combined effect of the
concentration polarization, the adsorption and/or the pore
blocking caused by high COD and salt concentrations. However,
pore enlargement (to 5695%) of the NF membrane was found
on the surface of a composite membrane of polyamide and
polysulfone in the presence of a dye solution containing 1015 g
of Na2SO4 L1 and this was found to due to SO42 pushing
through the membrane via transmembrane pressure. To prevent
this pore enlargement problem, an optimum operating pressure
and the proper selection of the membrane must be carried out to
ensure the integrity of the membrane for a long period.
(C-2) Nanofiltration by nanofibre media. Nanofibres are
essentially defined by their effective diameters (in the range of
1 to 200 nm) and they can be used for fine filtration. The synthetic
materials, both organic and inorganic, that are spun from the
molten state into the finer fibres differ in terms of the equipment
downstream of the spinneret, which enables a wide range of fibre
diameters to be produced. Because these media are capable of
removing contaminants to below 0.1 mm, they are usually known
as nanomembranes. Fig. 4 shows thiol-functionalized zonal
mercaptopropyl silica nanofibres. Those nanofibres were
obtained by the dissolution of electrospun polyacrylonitrile
(PAN) nanofibres with dimethylformamide. PAN nanofibres
were prepared by coating with 3-mercaptopropyl trimethoxy-
silane via a solgel process. The uniform porous channels
between the nanofibres facilitated Hg2+ transportation in the
adsorption process.208
Fine spinning techniques have been used for the production of
carbon and ceramic fibres as well as the fibres of other materials
and are obviously used as a filter medium, particularly for air
filtration.209 The introduction of an antimicrobial functionality
agent in the particulate filters has been explored and it has been
found that most microorganisms often become resistant, which
could limit the benefit of an antimicrobial functionality.
Furthermore, most of the microorganisms enter the filter with
airborne particulate matter and they grow in size due to accu-
mulation and build up on the filter surface. Metallic silver and
silver oxides are safe and effective antimicrobial agents at low
levels. Positively charged silver ions attract electronegative
bacterial cells and bind with the sulfhydryl group on the cell
membrane or bacterial DNA and result in the prevention of
proliferation of the microorganisms.210,211 Ionic plasma
This journal is The Royal Society of Chemistry 2012

processing (IPD) is a suitable method for the coating of surface
engineered nanosized silver particles on polymeric surfaces for
use in heating, ventilation and air conditioning (HVAC) air
filters. Porous electrospun nanofibrous scaffolds (porosity larger
than 70%) can be used to replace flux limiting asymmetric porous
ultrafiltration membranes (of porosity in the range of 34%).
Yoon et al. synthesized polyacrylonitrile nanofibrous layers
supported on nonwoven microfibrous substrates (a melt-blown
polyethylene terephthalate mat) and applied a water resistant,
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but water permeable, coating of chitosan over the nanofibrous
layer. A high flux and low degree of fouling resulted with the use
of this nanofibre media.212 It was observed that an electrospun
membrane conveniently rejects the microparticles and acts as a
screen filter without fouling the membrane, especially when the
particles are larger than the largest pore size of the nanofibrous
membrane. A high surface-to-volume ratio of the nanofibrous
media increased the degree of fouling. Therefore, the surface
modification of the nanofibrous screen filter with a suitable
hydrophilic or hydrophobic oligomer is often recommended to
reduce the fouling effect. A novel alumina nanofibre filter, which
consists of a single layer of an alumina nanofibre grafted onto a
microglass fibre backbone has shown potential for the effective
removal and retention of aerosols from polluted air. The
extraction fraction of the nanofibre filter was found to be three
orders lower than the HEPA filters, demonstrating that viruses
were effectively retained in the nanofibre filter due to an elec-
trostatic attraction between the electropositive fibre surface and
the electronegative aerosol particles.212
The addition of polystyrene nanofibres to the coalescence
filters (glass fibres) have shown that the addition of small
amounts of polystyrene nanofibres significantly improve the
coalescence efficiency of the filter but also significantly increase
the pressure drop of the filters.213 Conventional ion exchange
resins are normally either a gel structure or a granular structure
and are typically made of styrene or acrylic as the structural
materials. Granular resinous materials have larger pore volumes
and low ion-exchange capacities than gel type materials and
additionally have a better mechanical strength. The fibrous
materials are applied as a support for the ion-exchange func-
tionality due to their ease of preparation, contact efficiency and
the physical requirement for strength and dimensional
stability.214 Polymeric nanofibre-based ion exchangers have
higher swelling behaviors compared to other media because of
their high surface area, porosity and capillary motion.215 In
Fig. 4 The assembly of a zonal mercaptopropyl silica nanofibre.208
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addition, polymer nanofibre ion exchangers are found to have
extremely rapid kinetics and higher ion-exchange capacities.215
A major trend with regards to filter media is the development
of the combination filter, capable of performing two separation
tasks at once, such as solidgas separation and the adsorption of
a gaseous impurity. These combination filters employ a chemi-
cally active agent embedded in the filter medium material, the
most common of which is activated carbon as an adsorbent.
Recent developments in nanofibre filters offer a range of
adsorptive and chemical treatments and antimicrobial action via
silver zeolite technology. Titanate nanofibres have been synthe-
sized via a hydrothermal reaction between a concentrated NaOH
solution and TiOSO4. The titanate fibres were dispersed in
ethanol to form a suspension containing 0.2 wt% titanate
nanofibres. The suspension was sonicated for 10 min to achieve a
homogeneous dispersion, which was used to apply thin layers on
the porous substrate using a spin-coater. The separation effi-
ciency of the ceramic membranes can be significantly improved
by constructing a top separation layer with TiO2 nanofibres.
These improvements are due to the radical changes in the texture
of the top-layer. It is also found that the top layers of the TiO2
nanofibres on the porous glass and alumina support were similar
in terms of their structure and performance. They are able to
retain more than 95% of 60 nm particles at a very high flux rate of
about 900 L m2 h1. Moreover, the fabrication of these
membranes is relatively simple and economical with low rejection
rates, compared to the conventional ceramic membranes. This
approach can be scaled-up for the fabrication of ceramic
membranes in practical applications.216
For the filtration of liquids, conventional porous polymeric
membranes have their intrinsic limitations; e.g. low flux rates and
high fouling. These drawbacks are due to the geometric structure
of the pores, the corresponding pore size distribution217 and the
formation of undesirable macro-voids across the whole
membrane layer.218 It appears that electrospun nanofibrous
membranes can overcome some of these limitations and, conse-
quently, a polyethersulfone (PES) electrospun nanofibre mat has
been applied as a membrane for liquid filtration. To increase
the mechanical strength of the PES fibre, a poly(ethylene
terephthalate) (PET) non-woven sub-layer was also used. The
composite membrane (PESPET) is illustrated in Fig. 5. The
PES/PET electrospun nanofibrous membranes (ENMs) indi-
cated that the membranes possess a high initial flux. The
turbidity of the permeated suspension was found to decrease
significantly with time.219 Polysulfone (PSU) nanofibrous
membranes possess much higher porosity and have a high
surface area, which results in high flux pre-filters with even higher
loading capacities. Such pre-filters can be used in various appli-
cations, such as the removal of micro-particles from waste water
and in ultrafiltration, or with nanofiltration membranes, to
prolong the life of these membranes.220,221 A coat of TiO2/poly-
vinyl alcohol (PVA) on the polyester filter effectively modifies the
matrix, narrows the pore size to 10 mm and reduces the contact
angles by 40 because of the hydroxyl groups from PVA
and TiO2. The improved hydrophilicity and anti-fouling prop-
erties of the composite membranes enables a highly stabilized
(10 m3 m2 h1 or 10 kPa) pure water flux and a high effluent flux
during long term filtration tests in membrane reactor systems for
the treatment of simulated waste water in the removal of nitrate/
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Fig. 5 The structure of PES/PET composite membranes.220
ammonium to allow for water reuse in a polyester fibre
production plant.222
(D) Sorbents
Water remediation techniques include (1) adsorption, (2)
biotechnology, (3) catalytic processes, (4) membrane processes,
(5) ionizing radiation processes, and (6) magnetically assisted
processes. In addition, nanomaterials-based processes are
becoming promising options for applications in water treatment.
The adsorption technique is the most frequently studied method
to purify water.221224 Sorption is the transfer of ions from the
solution phase to the solid phase. Sorption actually describes a
group of processes, which include adsorption and precipitation
reactions. Basically, adsorption is a mass transfer process by
which a substance is transferred from the liquid phase to the
surface of a solid and becomes bound by physical and/or
chemical interactions.225 Various low cost adsorbents, derived
from agricultural waste, industrial by-products, natural mate-
rials, or modified biopolymers, have been developed recently and
applied in the removal of heavy metals from metal-contaminated
waste water. In general, there are three main steps involved in
pollutant sorption onto solid sorbents: (i) the transport of the
pollutant from the bulk solution to the sorbent surface; (ii)
adsorption on the particle surface; and (iii) transport within the
sorbent particle. Technical applicability and cost-effectiveness
are the key factors that play major roles in the selection of the
most suitable adsorbent to treat waste water.226,227
Magnetic sorbents or magnetic ion exchange (MIEX) resins
have been introduced for the removal of natural organic matter
(NOM) from ambient raw water and was found to be better
than coagulation processes. The ion exchange resin beads
contain a magnetized component within their structure, which
allows the beads to act as individual magnets. The magnetic
component results in the beads forming agglomerates that can
settle rapidly or fluidize at high hydraulic loading rates. The
very small resin bead size could provide a high surface area to
allow the rapid exchange of selective ions. Resins with a poly-
acrylic skeleton with macroporous properties are more suitable
for the removal of NOM than gel resins.228,229 In addition, the
MIEX process involves adsorbing the DOC onto the MIEX
resin in a stirred contactor that disperses the resin beads to
achieve a maximum surface area. The magnetic part of the resin
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allows the resin to agglomerate into larger and faster settling
particles, which allow a recovery rate of greater than 99.9% to
be obtained. The MIEX process has been applied for the
removal of humic acid,230 low to moderate organic concentra-
tions over wide range of alkalinities and bromide concentra-
tions.231,232 Coagulation removed 60% of the dissolved organic
carbon (DOC) associated with the 110 k fraction but had little
impact on the DOC concentration of the <1 k fraction. Treat-
ment with MIEX removed approximately 80% of the DOC
associated with the 110 k fraction and almost 60% of the DOC
associated with the <1 k fraction. The nature of water was
varied with differing types of NOM and passed through the
MIEX resin. It was observed that an increase in the hydro-
phobicity of the resin reduced the DOC. Furthermore, the
MIEX resin was used for the removal of some specific inorganic
ions, such as As(V) and Cr(VI). The MIEX process has also been
applied in a pre-treatment step for catalytic processes, such as
effective debromination using ozonation.233
Magnetic chitosan gel particles, a magnetite bearing covalently
immobilised copper phthalocyanine dye, magnetic charcoal and
magnetic alginates have all been applied in the removal process
of polycyclic dyes, malachite green, crystal white and other
organic dyes from waste waters.234238 Magnetotactic bacteria
naturally occur as magnetic sorbent sources in nature. These
bacteria have the ability to orient themselves in the direction of
the magnetic field. Magnetotactic bacteria have been applied in
the removal of organic pollutants from water by enzymatic
reactions.239 Surfactant-coated magnetite nanoparticles have
been applied in the extraction of the organic contaminant,
2-hydroxyphenol.240 Floating magnetic sorbents, in the form of
polymer-coated vermiculite iron oxide composites, have been
formulated. The composites float on the surface of water and can
easily remove spilled oil from oil contaminated water.241
In addition, zero valent iron (nZVI) nanoparticles with a
diameter of 1120 nm are able to remove As(III) and As(V) by
rapid adsorption followed by precipitation and result in surface
corrosion byproducts.242244 The adsorption of As(III) and As(V)
by iron nanoparticles is due to the weak electrostatic attraction
between the adsorbed species and the binding sites.245 Nano-
particles of nZVI have been prepared by adding freshly made
ferric chloride to a reaction vessel containing solid NaBH4.246
Polyvinyl alcohol-co-vinyl acetate-co-itaconic acid has been
found to be an effective surfactant for the stability of nZVI
nanoparticles. Initially the sites are amorphous Fe(II)/Fe(III)
magnetite. As the treatment progresses, the initial reactive sites
gradually transform into lepidocrocite and the more crystalline
magnetite. Heavy metal ions (e.g. Ni(II)) are adsorbed on the
oxide shell as corrosion proceeds and precipitates on the iron
core of the nanoparticle. Nanoparticles of nZVIs have higher
reactivities due to their larger surface area (average area: 35.5 m2
g1) than commonly used microparticles (average area: 0.9 m2
g1) and they also have reaction rates that are 100 times higher
than those of microparticles.247 Since the reactions with orga-
nohalides are considered as inner-sphere surface-mediated
processes, the application of iron nanoparticles is becoming a
real potential.246 Fig. 6 shows the reduction of organic pollutants
by chemisoprtion on nZVI nanoparticles. Iron can reduce water
and form hydrogen gas under anaerobic conditions as
follows:248,249
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Fig. 6 A schematic diagram of the reduction of perchloroethylene on the
surface of a nZVI particle.74
Fe0 + 2H2O / Fe2+ + H2 + 2OH
In addition, iron can remove chlorine by hydrogenolysis as
follows:
Fe0 + RCl + H+ / Fe2+ + RH + Cl
where Fe0 is oxidized to Fe2+, while perchloroethylene is dech-
lorinated. The application of bulk zero valent iron metal in
environmental remediation has limitations, such as slow reaction
rates and the formation of more toxic intermediates resulting
from the dechlorination process, which are difficult to destroy.250
Iron nanoparticles have been widely applied in the trans-
formation and detoxification of a wide variety of common
environmental contaminants, such as chlorinated organic
solvents, organochlorine pesticides and PVBs, due to their large
surface area and surface activity.251 The degradation rates of
trichloroethylene (TCE) has been significantly increased to 3 
103 L m2 h1 from 6.3  105 L m2 h1, which was obtained
when bulk Fe0 particles (>1 micrometer) were used to remove
TCE.252 The feasibility of applying nZVI particles in water
remediation showed that up to 90% TCE was degraded within 30
min.253 In addition, non-toxic final products were formed. The
capacity of transforming TCE into harmless compounds was
found to be higher than that of micro ZVI particles due to the
higher specific area. The content of Fe0, the solution pH, the
concentration of TCE and the presence of anions, such as nitrate,
can significantly affect the degradation of TCE. Furthermore,
the application of nZVI particles could reduce the presence of
perchlorate ions in contaminated media by 66% within 336 h via
a reduction process on the surface of nZVI and the association of
an oxygen molecule from the perchlorate ions with nZVI.254,255
The amount of Ni metal adsorbed by iron-core nanoparticles
is higher than by iron oxide nanoparticles (i.e. gFe2O3). The
addition of functional materials, such as stable noble metals,
metal oxides and low molecular weight organic molecules and
polymers, in the preparation of nZVI nanoparticles could deliver
higher adsorption capacities for heavy metals that will lead to
better remediation.245 Modified nZVI nanoparticles that have
been applied in the removal of metal ions from water are shown
in Table 4. Hu et al. reported that modified jacobsite (manganese
iron oxide) nanoparticles can be applied and regenerated many
times without a decrease in their adsorption performance.256 The
study by Bezbaruah et al. shows that nZVI entrapment in a
This journal is The Royal Society of Chemistry 2012
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biopolymer matrix (alginate) may increase their overall efficacy
in groundwater remediation. The authors have shown that nZVI
can be effectively trapped in Ca-alginate beads and the reactivity
of the entrapped nZVI toward a model contaminant (nitrate) was
comparable to that of one dimensional ZVI.257 The reduction in
the nitrate concentration using one dimensional nZVI and
trapped nZVI in Ca-alginate beads were 5573% and 5073%,
respectively, over a 2 h remediation period. In addition, Ca-
alginate is suitable for the entrapment of nZVI to make the
nanoparticles relatively stationary in aqueous media (e.g.,
groundwater). Thus, the mobility and settlement problems
associated with one dimensional nZVI can be overcome and
alginate-trapped nZVI can be effectively used in permeable
reactive barriers for groundwater remediation. Keum and Li
reported the application of Fe0 nanoparticles in the reductive
debromination of polybrominated diphenyl ethers (PBDEs). The
debromination of PBDEs by nZVI particles has high potential
value for the remediation of PBDEs in the environment.263 Kim
et al. applied Fe0 in the removal of alachlor and pretilachlor.264
Wang and Zhang reported the utilization of Fe0 nanoparticles in
the dechlorination of several chlorinated aliphatic compounds
and a mixture of PCB at relatively low metal-to-solution ratios
(25 g per 100 mL).265 Up to 25% of PCB could be removed
within 17 h by using fresh nZVI particles. Fe0 nanoparticles in
environmental remediation has great potential; however, the
limitations of using Fe0 nanoparticles are: (1) the high activity
leads to the storage of freshly synthesized iron particles becoming
a significant problem; (2) the activity of the iron particles
decreases as the reaction proceeds due to the formation of
Fe(OH)3, which forms on the surface of the Fe0 nanoparticles
and may make the iron core unreactive, therefore blocking
further reaction; (3) the freshly fabricated Fe0 can easily form
aggregates and this decreases the dispersion ability. Recently,
research focus have been on solving the above problems. To
improve the stability of Fe0 nanoparticles against aggregation,
He and his group members developed palladized iron (FePd)
nanoparticles stabilizing on starch265 or sodium carboxymethyl-
cellulose (CMC).266 The results showed that the dispersibility of
the nanoparticles increased and, thus, the degree of dechlorina-
tion greatly increased. The starch-coated Fe0 nanoparticles
exhibited markedly greater reactivity during the dechlorination
of TCE or PCB in water. About 98% of TCE and 80% of PCB
were found to be decomposed after 1 h and 100 h, respectively. In
addition, the degradation rate of TCE by CMC-stabilized
nanoparticles was 17 times faster than that of Fe0 nanoparticles.
Ag-modified Fe0 nanoparticles (1% Ag)267 could facilitate the
dechlorination of tetra-, tri- and di-chlorobenzenes (TeCB, TCB
and DCB, respectively) within 24 h at a metal loading of 25 g L1
and the dechlorination rate was found to positively correlate with
the amount of silver loaded on the bimetallic particles.
Researchers268,269 have done lots of work on the dechlorination of
PCBs using nanoparticles with activated carbon and bimetallic
nanoparticles. Several kinds of assemblies and bimetallics have
been investigated, such as GAC (granular activated carbon)/Fe/
Pd bimetallics, GAC/ZVI, GAC/ZVI/Pd, Pd/Mg bimetallics, etc.
The GAC/ZVI/Pd system showed an efficient dechlorination of
2-chlorobiphenyl (2-ClBP) at 90% after 2 days. The high degra-
dation ability of the GAC/ZVI/Pd system is caused by the
synergistic and simultaneous function of adsorption and
Energy Environ. Sci., 2012, 5, 80758109 | 8091

Table 4 Previous studies of the environmental remediation using modified nZVI
Particle size
Type of nanoparticle (nm) Targeted heavy metal ion
255
Modified jacobsite (MnFe2O4) 10 Cr(VI)
Ferrites (MeFe2O4, where Me Mn, 20 Cr(VI)
Co, Cu, Mg, Zn or Ni)257
Magnetic nanoparticles encapsulated 11 Ag(I), Hg(II), Pb(II)
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by poly(3,4-ethylenedioxythiophene)
(PEDOT)258
Magnetite nanoparticles modified 6 Hg(II), Co(II), Cu(II), As(V), Ag(I),
with dimercaptosuccinic acid259,260 Cd(II), Ti(III), Pb(II)
Maghemite (-Fe2O3)261 50 Mo(VI)
Silica-coated magnetite (Fe3O4)262 5080 Hg2+
dechlorination of PCB. The perchlorate ion was significantly
reduced by 1.8 and 3.3 fold with starch and CMC-modified
nZVI, respectively, when it was compared with nZVI.270
Ge et al. applied modified Fe3O4 magnetic nanoparticles
(MNPs) (1520 nm) with 3-aminopropyltriethoxysilane and
copolymers of acrylic acid and crotonic acid in the removal of
Cd2+, Zn2+, Pb2+, Cu2+ from metal contaminated water.272,273 It
was observed that the MNPs could efficiently remove the metal
ions with a high maximum adsorption capacity at pH 5.5 and
could be used as a recyclable adsorbents under convenient
conditions.271 Mak and Chen found that methylene blue could be
recovered fast and efficiently from an aqueous solution by
polyacrylic acid-bound iron oxide magnetic nanoparticles (12 nm
average diameter) due to their large specific surface area and the
absence of internal diffusion resistance.274 The impact of pH on
the removal of Mo(VI) from contaminated waste water was
studied by Afkhami and Norooz-Asl.275 The surfaces of the metal
oxides (Fe2O3 suspension) are generally covered with hydroxyl
groups that vary in their form at different pHs. The surface
charge is neutral at pHzpc (the zero point charge pH, where the
pHzpc of maghemite nanoparticles is around 6.3). Below the
pHzpc, the adsorbent surface is positively charged and anion
adsorption occurs. With an increase in the pH up to pH 4, the
uptake of MnO42 ions increases and remains constant in the pH
range of 46. Then, the uptake of Mo(VI) in the form of MoO42
ions decreases at pH values higher than 6 as the adsorption
surface becomes negatively charged at pH > pHzpc; this leads to
an increasing electrostatic repulsion between the negatively
charged species (MoO42) and the negatively charged adsorbent,
which releases the adsorbed MoO4. The removal efficiency was
highly pH dependent and the optimal adsorption was found to be
pH 4.06.0.273
The sorbents can also be of mineral, organic or biological
origin (e.g. activated carbons, zeolites, clays, silica beads), low
cost adsorbents (e.g., industrial by-products, agricultural wastes
and biomass) and polymeric materials (e.g., organic polymeric
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Major binding sites or functional
groups for the removal of the heavy
metal
MnO2 and Fe2O3 are major
adsorptive components
The major adsorption driving force is
the redox reaction between Mn(II)
and incoming Cr(VI)
Major binding sites are the O-donor
atoms and S-donor atoms of PEDOT
Thiol groups from
dimercaptosuccinic acid play a major
role in the binding site
Anionic adsorption between
positively charged maghemite and
MoO42 at pH values below 6 and
electrostatic repulsion between
negatively charged maghemite and
MoO42
The dithiocarbamate group after the
derivitization of magnetite plays a
major role in the removal of Hg2+
resins and macroporous hyper-crosslinked polymers).279 In
recent years, natural polymer adsorbents have been used (e.g.,
chitin and starch and their derivatives, chitosan and cyclodex-
trin).274,275 Polysaccharide-based materials can be used as
sorbents in waste water treatment.276 Chitosan has been applied
extensively in various research areas of water/waste water treat-
ment.277,278 Chang and Chen modified the chitosan polymer and
grafted carboxylic groups. Then, the carboxylated chitosan was
covalently bound to magnetic nanoparticles. Afterwards, modi-
fied chitosan nanoparticles were used for the removal of metals
from waste water.280 Qi and Xu modified the chitosan polymer by
ionic gelation with tripolyphosphate (TPP) as an ionic cross
linker and both the research groups found that modified chitosan
nanoparticles could provide high adsorption capacities of
Pb2+.281 However, the limitation of modified chitosan nano-
particles is disintegration in aqueous solution or aggregation in
pH 9 alkaline solution due to weak electrostatic interactions
between chitosan and TPP molecules. Some NPs are powerful
adsorbents due to their unique structure and electronic proper-
ties. Dissolved organic carbon and organic colloids in the sub-
micron size range have been recognized as a distinct non-aqueous
organic phase to which organic pollutants are adsorbed,280 which
leads to a reduction in their bioavailability.
Zeolites are the microporous materials (pore size < 2 nm) and
consist of a 3-dimensional arrangement of [SiO4]4 and [AlO4]5
polyhedra connected through their oxygen atoms to form large
negative lattices with Brnsted and Lewis acid sites. If cations are
exchanged by protons, the zeolite acquires considerable Brnsted
acidic properties. The application of zeolite materials for envi-
ronmental remediation has gained great attention due to their
selective sorption capacities, non-toxic nature, availability and
low cost. Zeolites have been widely applied in the removal of
heavy metals, such as Cr3+, Ni2+, Zn2+, Cu2+, Fe2+, Pb2+ and Cd2+
from waste water in the mining industries.281283 The stability of
zeolites is high and disintegration was found only at pH values
below 2. In addition, zeolites have been applied in the retention
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of methyl-tert-butyl ether, chloroform and TCE in water and
they were found to be 812 times more efficient than activated
carbon. Mesoporous silica-based materials (pore size 250 nm)
have been widely used to remove heavy metals present in waste
water. Mesoporous silica with functionalized monolayers have
been useful in the removal of mercury and other heavy metals
from waste water. Better adsorption capacities were found for
amino-functionalized silica in the capture of Cu2+, Zn2+, Ni2+ and
Cr2+, whereas Hg2+ was better adsorbed on thio-functionalized
silica.284 Activated alumina, a porous form of Al2O3, has a high
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porosity so it is widely used in filtering components for drinking
water purification. Mesoporous alumina, aminated mesoporous
alumina and alumina-supported MnO can remove As(V), As(III),
Cu(II) and TCE from the contaminated water.285287
Nanoscale diboron trioxide/titanium dioxide composite
materials have been used for the separation of trace cadmium
ions from polluted water containing cadmium ions. The other
pollutant matrix ions had no negative effect on the removal of
the cadmium ions. The removal of organic pollutants using
inorganic nanoparticles and mesoporous structures can be
carried out in two ways: (1) static force (including Lewis
adsorption); and (2) weak and chemical bonding through
hydrogen bonds/p bonds with the surface functional groups.
Modification and chemical treatment of the nanomaterials are
essential to enhance the target adsorption ability. The removal
efficiency of As(III) and As(V) was higher for nanocrystalline
TiO2 than fumed TiO2.288,289 Alvaro et al. synthesized meso-
porous TiO2 nanoparticles in association with tetraethyl ortho-
silicate using neutral pluronics as templates. The photocatalytic
activity for the degradation of phenol was much higher for
mesoporous TiO2 nanoparticles compared to standard P-25
TiO2.291
Many types of polymers have been assembled into nano-
particles via polymerization techniques. PolyN-iso-
propylacrylamide nanoparticles remove Pb2+ and Cd2+ from
waste water. The adsorption of Pb2+ and Cd2+ by the polymer is
due to the Coulombic attraction between the carboxylate group
on the polymer and the positive charged metal species from waste
water.292 However, the utilization of polyN-isopropylacrylamide
in waste water treatment is not widespread because the main
functional group, isopropylacrylamide, does not show a favor-
able ability to remove metals. Polymeric nanoparticles synthe-
sized by the copolymerization of a pyridyl monomer with styrene
have been used for the removal of metal ions. It was observed
that the removal rate of metal ions from the aqueous solution
was fast due to the presence of bipyridine-based metal-chelating
groups on the surface of the nanoparticles.290 It was found that
the poly(vinylpyridine) nanoparticles could selectively remove
Cu2+ despite the presence of other competing ion species. Chen
et al.293 modified polystyrene nanoparticles with a specific dye
molecule called an azo-chromophore. It was observed that the
adsorption efficiency for the removal of Pb2+ increased due to a
modification of the nanoparticle ligand and the nanoparticles
could retain their adsorptive capacity after 3 cycles of adsorp-
tion/desorption.293 Bell et al. demonstrated that the sequestration
selectivity for heavy metals could be altered by grafting a
macrocyclic ligand of the polymeric nanoparticles with a core
shell structure. The original coreshell structure without grafting
can adsorb Hg only, while the modified nanoparticles could
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adsorb Co2+ selectively in the presence of other heavy metal
ions.294 Therefore, polymeric nanoparticles can be tailored for
the remediation of selective heavy metals. Tungittiplakorn et al.
found that polyurethane-based nanoparticles could be applied in
the desorption and transportation of organic pollutants with the
hydrophobic core of the nanoparticles.295,296
(E) Dendrimers
Metal nanoparticles (NPs) have received great scientific and
technological interest in environmental remediation due to their
size, unusual crystal shapes and lattice orders.295 Nano-sized
metal particles are expected to exhibit much higher reactivity
because of their larger surface area than bulk particles. However,
the preparation of functionalized NPs using different methods
still remains a great challenge. One of the unique approaches
used to prepare inorganic NPs is through the use of dendrimers.
Dendritic nanopolymers are highly branched 3D globular
nanoparticles with controlled compositions and architectures.
Dendrimers are relatively monodisperse and highly branched
nanoparticles with controlled compositions and design and their
sizes are in the range of 1100 nm. Dendrimers are built from a
starting atom, such as nitrogen, to which carbon and other
elements are added by a repeating series of chemical reactions
that produce a spherical branching structure, as shown in Fig. 7,
in which divergent or convergent hierarchical assembly strategies
are involved. As the process repeats, successive layers are added
and the sphere can be expanded to the size required by the
investigator. Dendrimers consist of three components: (1) a core,
(2) interior branched cells and (3) terminal branched cells.297,298
Ammonia is used as the core molecule and it reacts with meth-
ylacrylate in the presence of methanol and then ethylenediamine
is added:
NH3 + 3CH2CHCOOCH3N(CH2 CH2COOCH3)3 /
3NH2CH2CH2NH2N(CH2CH2CONHCH2CH2H2)3 + 3CH3OH
At the end of each branch there is a free amino group that can
react with 2 methylacrylate monomers and 2 ethylenediamine
molecules. Each complete reaction sequence results in a new
dendrimer generation as shown in Fig. 8. Dendrimers are a novel
class of polymers with a compact spherical structure and unique
behavior and a narrow size distribution that can be used as
templates or stabilizers to form relatively monodispersed
organic/inorganic hybrid NPs. The crucial role played by den-
drimers is in the synthesis of dendrimer-stabilized NPs, in which
metal ions are usually complexed with dendrimer ligands (e.g.
interior tertiary amines, terminal functional groups) through
coordination, electrostatic interaction, etc., followed by a
reduction or other reactions to form inorganic NPs stabilized by
dendrimers. They are routinely synthesized from a central
polyfunctional core by the repeated addition of monomers. The
core is characterized by a number of functional groups. The
dendrimer generation is created by adding monomers to each
functional group in turn, leaving the end groups able to react
again. The structure of the polymer is determined by the number
of reactive groups of the core, the branch lengths and surface
group dimensions. The maximum size is limited by the genera-
tion at which the dendrimer becomes tightly packed.300
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Fig. 7 The dendritic structure.298
Poly(amidoamine), or PAMAM, dendrimers have been devel-
oped for applications in the remediation of waste water
contaminated with a variety of transition metal ions, such as
copper (Cu(II)). Diallo et al. first reported the use of PAMAM
dendrimers for copper removal in 1999. Dendritic nanopolymers
can encapsulate a broad range of solutes in water, including
cations (e.g., copper, silver, gold, iron, nickel, zinc and uranium)
by attachment to the functional groups of dendrimers, such as
primary amines, carboxylates and hydroxymates.303 They also
can deactivate bacteria and viruses after binding. Poly(amido-
amine) dendrimers can remove metal ions (Cu(II), Ag(I), Fe(III)
and others) by functioning as chelating agents and ultrafiltraters
and the removal capacity can be improved by attaching metal
ions to the functional groups of dendrimers, such as primary
amines, carboxylates and hydroxymates.299 Dendritic nano-
polymers, such as PAMAM dendrimers, have much less
tendency to pass through the pores of ultrafiltration membranes
Fig. 8 A graphical presentation of PAMAM dendrimers (a) PAMAM,
(b) poly(glycerol-succinic acid) dendrimer, (c) Boltorn and (d) hyper-
branched polyglycerol.301
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than linear polymers of a similar molar mass because of their
much smaller polydispersity and globular shape. Therefore,
dendritic nanopolymers have been used to enhance UF and MF
processes for the recovery of dissolved ions from aqueous solu-
tions. First, contaminated water is mixed with a solution of
functionalized dendritic nanopolymers and then the mixtures of
nanopolymers and bound contaminants is transferred to UF or
MF units to recover the clean water. In those units, the bound
target substance is separated from the nanopolymers by
changing the acidity (i.e., the pH) of the solution. Finally, the
recovered concentrated solution of contaminants is collected for
disposal or the nanopolymers may be recycled.302 Diallo et al.
have combined bench scale measurements of metal ion binding
to Gx-NH, PAMAM dendrimers with dead-end UF experiments
to assess the performance of dendritic polymer filtration to
recover Cu(II) from aqueous solutions. The Cu(II) binding
capacities of the PAMAM dendrimers seem to be much larger
and more sensitive to the pH of the solution than those of linear
polymers with amine groups. Furthermore, metal ion (Cu(II))
trapped PAMAM dendrimers can be regenerated by decreasing
the solution pH to 4.05.0, thus enabling the recovery of the
bound Cu(II) and the recycling of the dendrimer. PAMAM
dendrimers can also be applied in the recovery of perchlorate
anions and uranium metals from contaminated groundwater.
Polyamidoamine dendrimers (PAMAM), after surface modifi-
cation with benzoylthiourea groups, are a new and excellent
water-soluble chelating ion exchange material with a distinct
selectivity for toxic heavy metal ions. Investigations on the
removal of Co(II), Cu(II), Ni(II), Pb(II) and Zn(II) have been
performed using the PAMAM-supported filtration method. The
results showed that all metal ions could be retained almost
quantitatively at pH 9. Cu(II) could form the most stable
complexes with the benzoylthiourea-modified PAMAM deriva-
tives and complete retention was achieved at pH>4, and could be
separated selectively from the other heavy metal ions
investigated.303
The key novelty of the dendritic polymer filtration process is
the combination of dendritic polymers with multiple chemical
functionalities with UF and MF. This may enable the develop-
ment of a new generation of water treatment processes that are
flexible, reconfigurable and scalable.300 Dendritic polymer
filtration processes are scalable and could be used to develop
small and mobile water treatment systems as well as large and
fixed treatment systems. Dendritic nanopolymers have also much
smaller intrinsic viscosities than linear polymers with the same
molar mass because of their globular shape.300 Thus, compara-
tively lower operating pressures, energy consumption and the
loss of ligands by shear-force induced during filtration could be
achieved with dendritic polymers in cross-flow UF systems and
this dendritic filtration could be applied in industrial water
treatment.304
PAMAM dendrimers have great potential as templates for
metal composite nanoparticles due to their low toxicity and
highly regular, branched and three-dimensional structure, which
can host inorganic nanoclusters and form stable dendrimer
complexes and nanocomposites.305 In general, the reduction of
silver cations with NaBH4 and the template role of the den-
drimers ensure well dispersed silver nanoparticles with a rela-
tively small size distribution.306 Investigations have already
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indicated that dendrimer-encapsulated silver nanoparticles
possess antimicrobial activity.307 Strong bonding is achieved
through a mechanism that involves an interaction with noble
metals, such as catalytic palladium nanoparticles in films of
linear poly(ethyleneimine) (PEI) and silver. Platinum and palla-
dium nanoparticles have also been successfully encapsulated
within poly(propyleneimine) dendrimers. All of these polymers
possess some strong electron-donating centers, such as amino or
carboxylate groups, which facilitate metalpolymer complex
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(the surface amine is more basic as it is primary in nature).308 The
interaction of Cu2+ with PAMAM leads to two changes in the
absorption spectrum: a band due to the dd transition gains
prominence and shifts to 605 nm and a new band, due to a strong
ligand-to-metal interaction, appears at 300 nm. Some effort has
been made to synthesize dendrimer-protected silver nanodots
exhibiting fluorescence.309 It is quite clear that dendrimers play a
critical role in stabilizing the cluster/nanoparticle surface and
thus dramatically increase the stability of such species. Table 5

formation. In these studies, the preparation of polymer/metal
nanoparticles needed extra reducing agents, including sodium
borohydride (NaHB4), formaldehyde, sodium citrate or hydra-
zine. An amine-terminated hyper-branched poly(amidoamine)
(HPAMAMNH2) has been used to produce antimicrobial silver
nanocomposites.308 More importantly, this hyperbranched
polymer was found to serve as a highly effective self-reducing
agent. The advantages of this method are: (i) no extra reducing
agent was needed; (ii) the process was conducted at room
temperature and under normal pressure and in an aqueous
solution, making it a green route; and (iii) the obtained silver
nanoparticles have several excellent properties, such as a long-
term dispersion stability, small particle size, a narrow size
distribution controlled by the composition and a good antimi-
crobial activity as tested against E. coli, S. aureus, B. subtilis and
K. mobilis. The activity was enhanced with an increasing silver
concentration. The bacterial inhibition ratio of the HPAMAM
NH2/Ag nanocomposites reached up to 95% at a silver concen-
tration of 2.7 mg mL1. Furthermore, pure HPAMAMNH2 also
indicated some limited antimicrobial ability with an inhabitation
ratio less than 10%. To increase the metal adsorption capacity
and form metal nanoparticles, it is imperative that metal ions are
trapped in the interior structure of the dendrimer (to offer
protection against agglomeration). This is usually attempted by
selective protonation or hydroxylation of the surface amines
shows some applications of dendrimers for environmental
remediation.
(F) Carbon nanomaterials
The use of nanoscale activated carbon may have advantages over
conventional materials due to the much larger surface area of the
nanoparticles on a mass basis. In addition, their unique structure
and electronic properties can make them especially powerful
adsorbents.317 Many materials have properties that are depen-
dent on size. The advantages for processes involved in environ-
mental remediation are due to (1) their great capacity to adsorb a
wide range of pollutants, (2) their fast kinetics, (3) their good
surface area, and (4) their selectivity towards aromatic solutes.276
Activated carbon from various sources, such as coconut coir, jute
stick, rice husk, etc., is the most popular of the adsorbents. The
treatment of water by adsorption methods uses specific ion
exchangers or extractants and a combination of adsorption with
catalytic treatment methods, redox processes and magnetic
processes. Recently, a new technique in adsorption has been
reported that applies carbon nanotube clusters. The unique
property of these clusters is their ability to remove bacteria from
water by an adsorption method. Adsorption on sorbents has
become one of the preferred methods to remove toxic contami-
nants from contaminated water. Adsorption-based separation

Table 5 The applications of dendrimers in environmental remediation

Type of composite dendrimer Thickness of membrane/disc (nm) Targeted contaminants Ref.

Silica nanoparticles prepared by 300  76 Removal of polycyclic aromatic 310

mixing salicylic acid and hyper-
branched poly(propylene imine)
PAMAM dendrimer composite
membrane with hyaluronic acid in
a chitosan gutter layer
PAMAM dendrimer composite
membrane consisting of chitosan and
a dendrimer
Ni loaded hydrogel PAMAM
PAMAM dendrimer composite
membrane consisting of chitosan and
a dendrimer
Composite membrane PAMAM
dendrimer and trimesoyl chloride on
poly(ether ketone) (TMC)
Impregnation of cross-linked
silylated and cyclodextrin dendritic
poly(propylene imine) and
poly(ethylene imine) on ceramic
membranes, such as TiO2, Al2O3 and
SiC
hydrocarbons (PAH), such as pyrene
and phenanthrene, and Pb2+, Cd2+,
Hg2+, Cr2O72 from contaminated
aqueous solutions
300 Separation of CO2 from a feed gas 311
mixture of CO2 and N2 on porous
substrates
300 Separation of CO2 from fossil fuel 312
emission on porous substrates
2 mm disc Separation of Cu2+, Co2+ and Cr3+ 313
from aqueous solutions
300 Separation of CO2 from a feed gas 314
mixture of CO2 and N2 on porous
substrates
The diameters of the pores in the Rejection of salts: MgCl2, MgSO4, 315
composite membrane are in the range NaCl and Na2SO4
of nanometers
8 mm pore size for the TiO2 filter and Removal of organic pollutants, such 316319
3 mm pore size for the Al2O3 filter as polycyclic aromatic hydrocarbons,
trihalogen methane, pesticides and
methyl-tert-butyl ether

This journal is The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 80758109 | 8095

processes are widely applied in the purification of drinking water
and natural gas contaminated air. Nanoscale carbon black, with
a particle size of 2070 nm, can be modified via oxidized with
65% HNO3 by refluxing 10 g of carbon black with 150 mL HNO3
(65%) in a conical flask at 110  C for 120 min. The modified
carbon black is filtered and washed with deionized water until the
pH of the filtrate is stable and the product is finally dried in a
vacuum oven at 110  C for 24 h. The increased adsorption of
Cu2+ and Cd2+ on the modified carbon black is due to the
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increased amount of functional groups after oxidation of the
carbon black surface. Adsorption of Cu2+or Cd2+ on the modified
carbon black increases with an increasing pH of the solution.
Most of the metals were adsorbed on the modified carbon black
when the pH was above 5.5. This might be caused by the surface
charge development of the modified carbon black and the
concentration distribution of Cu2+or Cd2+, which are both pH
dependent. At low pH, the adsorption of Cu2+ or Cd2+ on
modified carbon black is low because of the competition between
H+ and Cu2+ or Cd2+ for the adsorption sites. The surfaces of
modified carbon black have negative charges in a wide pH range
and Cu2+ or Cd2+ carry a positive charge, existing as either Cu2+
and Cd2+. When the pH level of the solution increases, the
concentration of competitor H+ ions decreases and Cu2+ or Cd2+
adsorption increases. Zhou and coworkers320 investigated the
adsorption of Cu(II), Zn(II), Pd(II) and Cd(II) on nanoscale
hydroxyapatite and carbon black. The adsorption isotherms
indicated that different kinds of heavy metals have different
affinities for black and activated carbon. The smaller nanoscale
carbon particles had a higher adsorption capacity than larger
carbon black and activated carbon because the micropores at the
internal surface of the activated carbon are not accessible to
humic acid, whereas the nanosized pores of carbon black are
more accessible to humic acid.319
Carbon nanomaterials (CNMs) have unique properties for
sorption processes. CNMs may exist in several forms, such as
single-walled carbon nanotubes (SWCNTs), multi-walled carbon
nanotubes (MWCNTs), carbon beads, carbon fibres and nano-
porous carbon. CNTs can be considered as cylindrical hollow
micro-crystals of graphite.320,324 Because they have a large
specific area, CNTs have attracted the interest of researchers as a
new type of adsorbent. CNTs are graphitic carbon needles and
have an outer diameter ranging from 430 nm and a length of up
to 1 mm.321 MWCNTs are made of concentric cylinders with
 as shown
spacings between the adjacent layers322 of about 3.4 A,
in Fig. 9(a). SWCNTs (Fig. 9(b)) were discovered by Iijima.323 Li
et al. found that oxidized CNTs can be good Cd2+ adsorbents and
have great potential applications in environmental protection.
The specific area and pore specific volume of CNTs were found
to be increased after the oxidation of CNTs with H2O2, KMnO4
and HNO3 as shown in Table 6. The adsorption capacities of all
adsorbents were observed to be increase with an increase of the
CNT dosage. But it increases very slowly for the as-grown CNTs
and is 3.5 mg g1 at a CNT dosage of 0.2 g per 100 mL. The
increasing trend for H2O2 and HNO3 oxidized CNTs is almost
identical and the adsorption capacities are 8.4 and 11.8 mg g1,
respectively, at a CNT dosage of 0.2 g per 100 mL. The obvious
larger adsorption degree takes place at CNT dosages of 0.03 to
0.08 g per 100 mL and was found for KMnO4 oxidized CNTs
(19 mg g1). The removal efficiency for KMnO4 oxidized CNTs
8096 | Energy Environ. Sci., 2012, 5, 80758109
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almost arrives at 100% at a CNT dosage of 0.08 g per 100 mL,
which suggests that the treatment of CNTs with KMnO4 is an
effective method to improve their Cd(II) adsorption
capabilities.325
Due to the large specific area, CNTs have shown exceptional
adsorption capabilities and high adsorption efficiencies for
various organic pollutants, such as benzene, 1,2-dichloroben-
zene325 and ethyl benzene.326 Generally, adsorption has a long
residence time for activated carbon, which is the most commonly
used adsorbent to achieve equilibrium conditions (i.e., it took
20 h for an adsorption equilibrium to be reached for phenol from
water).327
In contrast, Peng et al. observed that less time (40 min) was
required for CNTs to adsorb dichlorobenzene. This may be
because CNTs have no porous structure as traditional adsor-
bents do (e.g., activated carbon), in which the adsorbate has to
move from the exterior surface to the inner surface of the pores to
achieve the equilibrium.327 The short time needed to achieve
equilibrium also suggests that CNTs have very high adsorption
efficiencies and the potential to remove dichlorobenzene from
water. It was also found that CNTs grown by pyrolysis with a
mixture of propylenehydrogen and a nickel catalyst at 750  C in
a ceramic furnace were better at the adsorption of dichloroben-
zene when compared to graphitized CNTs. The reason for this
was the rough surface, which makes the adsorption of dichlo-
robenzene much easier for the as-grown CNTs. For the graphi-
tized CNTs, the heat treatment of the CNTs at 2200  C for 2 h in
an inert N2 atmosphere eliminated the defects and the surface of
the graphitized CNTs became smooth after the treatment at this
high temperature. Thus, the adsorption of dichlorobenzene by
Fig. 9 (Super) structure representations of (a) a MWCNT and (b) a
SWCNT.326
Table 6 The porosity and specific surface area of as-grown CNTs and
oxidized CNTs325
Specific surface Pore volume
Type of sample area (m2 g1) Vp (cm3 g1)
As grown 122 0.28
H2O2 130 0.36
KMnO4 128 0.32
HNO3 154 0.58
This journal is The Royal Society of Chemistry 2012

graphitized CNTs was decreased. The results from Bina et al.,328
as shown in Fig. 10, indicated that the equilibrium adsorbed
amount for SWCNTs is higher than for hybrid carbon nanotubes
(HCNTs) and MWCNTs. With a C0 of 10 mg L1, the SWCNTs
showed the greatest adsorption capacity for ethylbenzene (eth-
ylbenzene: 9.98 mg g1). The adsorption of ethylbenzene on
CNTs is dependent on the chemical nature of the surface and its
porosity characteristics. HCNT associated with silica could
result in a more porous structure for MWCNTs and produce a
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sheet of carbon nanotubes, which have a greater area than
MWCNTs for ethylbenzene adsorption. This was the main
reason for the enhanced removal of ethylbenzene by HCNTs
than MWCNTs. Furthermore, due to the electrostatic interac-
tion between the ethylbenzene molecules and the SWCNT
surface, higher ethylbenzene adsorption through the single-wal-
led CNTs than through MWCNT has been observed.327 Because
the ethylbenzene molecules are positively charged, the adsorp-
tion of ethylbenzene is thus favored for adsorbents with a
negative surface charge. This results in more electrostatic
attraction and thus leads to a higher ethylbenzene adsorption.
Single-walled carbon nanotubes (SWCNTs) and multi-walled
carbon nanotubes (MWCNTs) were purified by sodium hypo-
chlorite solutions and were applied as sorbents to study the
sorption of Zn2+ from aqueous solutions.328 The amount of Zn2+
adsorbed on the CNTs increased with an increase in the
temperature. Using the same conditions, the Zn2+ sorption
capacity of the CNTs was much greater than that of commer-
cially available powdered activated carbon, indicating that
SWCNTs and MWCNTs are effective sorbents. In addition, the
sorption/desorption study showed that the Zn2+ ions could be
easily removed from the surface site of SWCNTs and MWCNTs
by a 0.1 mol L1 nitric acid solution and the sorption capacity
was maintained after 10 cycles of the sorption/desorption
process. Therefore, it was suggested that CNTs can be reused
several times in water treatment and regeneration. The activation
of CNTs plays an important role in enhancing the maximum
sorption capacity. Activation causes a modification of the
surface morphology and surface functional groups and causes
removal of amorphous carbon.326
The activation of CNTs under oxidizing conditions with
chemicals such as HNO3, KMnO4, H2O2, NaOCl, H2SO4, KOH
and NaOH has been widely reported. During activation, the
Fig. 10 The equilibrium amount of ethylbenzene adsorbed on CNTs
with a C0 of 10 mg L1 (adapted from ref. 328).
This journal is The Royal Society of Chemistry 2012
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metallic impurities and catalyst support materials are dissolved
and the surface characteristics are altered due to the introduction
of new functional groups. After oxidation with nitric acid,
adsorption isothermal experiments showed that the CNTs had
more defects and they have more functional groups on their
surfaces when they are prepared at 650  C. They additionally had
higher lead adsorption capabilities and are promising adsorbents
for use in waste water treatment. The increased capacity of
adsorption was found for the removal of Cd2+ (ref. 325), Ni2+ and
Cu2+ by other researchers.328 The amount of cationic dyes, such
as methyl violet and methylene blue, adsorbed increased with the
pH due to the electrostatic attraction between the negatively
charged surface of the CNT adsorbents and the positively
charged cationic dyes.329,330 The oxidation of the CNTs with
KMnO4 and H2O2 exhibited little enhancement in the specific
area, while HNO3 oxidation provided a larger specific area.325 A
few studies are available detailing SWNTs with antimicrobial
activity towards Gram-positive and Gram-negative bacteria due
to either a physical interaction or oxidative stress that compro-
mises the cell membrane integrity.331,332 Carbon nanotubes may
therefore be useful for inhibiting microbial attachment and
biofouling formation on surfaces. However, the degree of
aggregation,333 the stabilization effects by NOM334 and the
bioavailability of the nanotubes will have to be considered for
these antimicrobial properties to be fully effective.335
The separation of metal ion carriers (i.e. nanoparticles with
metal ions) from water after water treatment is a challenging
problem. In order to improve the separation of carriers of metal
ions from treated water, the metal ions can be bound to poly-
meric molecules and/or carbon nanoparticles forming nano-
carbon conjugates or polymer nanocomposites in water that are
able to precipitate rapidly. This leads to a significant increase in
the size of the nanocomposites with the formation of precipitates.
The precipitates can be easily removed from water by filtration or
centrifugation with the subsequent extraction of the metals.
Table 7 shows the application of nanocomposites of carbon
materials and the advantages of using them for environmental
remediation. Multi-walled carbon nanotubeTiO2 composite
catalysts can be used as catalysts in photocatalytic processes for
water treatment. The introduction of increasing amounts of
CNTs into the TiO2 matrix prevents particles from agglomer-
ating, thus increasing the surface area of the composite materials.
A synergy effect on the photocatalytic degradation of phenol was
found mostly for the reaction activated by near-UV to visible
light irradiation. This improvement on the efficiency of the
photocatalytic process appeared to be proportional to the shift of
the UVvis spectra of the CNTTiO2 composites for longer
wavelengths, indicating a strong interphase interaction between
carbon and semiconductor phases. This effect was explained in
terms of CNTs acting as photosensitizer agents rather than an
adsorbents or dispersing agents. Surface defects at the surfaces of
carbon nanotubes provide advantages not only for the anchoring
of the TiO2 particles but also for the electron transfer process to
the semiconductor. Original carbon nanotubes, containing
moderate amounts of oxygen surface groups, produced the
highest synergistic effect for the degradation of phenol under
near-UV to visible irradiation. The efficiency of CNTTiO2
catalysts in the photocatalytic oxidation of mono-substituted
organic compounds under visible irradiation was dependent
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from the ring activating/deactivating properties of the aromatic
molecules. A higher kinetic synergy effect was observed for
compounds presenting electron donor groups, such as phenol
and aniline. For nitrobenzene and benzoic acid a synergy factor
near to 1 was obtained, indicating the inexistence of any synergy
effect between the CNTs and TiO2 in the photocatalytic degra-
dation of these pollutants.348 A comparison of the photocatalytic
activity of TiO2 and TiO2/CNTs composites for acetone degra-
dation in air shows that the presence of a small amount of CNTs
can enhance the photocatalytic activity of TiO2 greatly.345 Elec-
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limitation to reuse and possible risk to ecosystems and human
health caused by the potential release of nanoparticles into the
environment. In addition, the use of aqueous suspensions limits
their wide applications because of the problems for the separa-
tion of the fine particles and the recycling of the catalyst.
Immobilization of these nanoparticles onto polymer matrix, such
as porous resins, ion exchangers, and polymeric
membranes,350,351 has been available to solve the problems to
considerable extent, serving for the reduction of particle loss,

prevention of particles agglomeration and potential application

trons excited by TiO2 may easily move to the nanostructure of
the CNTs due to the strong interaction between TiO2 and CNTs.
Then, CNTs raise the band gap of TiO2, which can prevent
recombination of the e/h+ pairs. Moreover, the abundant
hydroxyl groups adsorbed on the large surface of the composites
can lead to the formation of more_OH radicals, which result in an
enhancement of the photocatalytic activity of TiO2.349
In the tricomponent mixture of AgNPsCNTsPAMAM
prepared by Yuan et al. the disinfection effect on E. coli cells was
observed to be greater than both acid (COOH) modified and
PAMAM modified MWCNTs. It was observed that the strength
of the antimicrobial effect on bacteria follows the order: AgNPs
MWCNTsPAMAM mixture > MWCNTsPAMAM >
MWCNTsCOOH. The tricomponent mixture showed the
highest disinfection activity due to favoring of the debundling
(dispersivity) of MWCNTs by PAMAM and increasing the
accessible surface area for bacterial interaction. Moreover, the
PAMAM-grafted MWCNTs contain abundant amine termi-
nated groups which leads to the reduction of Ag+ ions and
regeneration of the AgNPs once Ag+ ions penetrate through the
cell walls of the bacteria.350
(G) Application of polymer supported nanocomposites
The application of the NPs in environmental remediation
provided excessive pressure drops during operating in fixed bed
or any other flow-through systems, difficult separation and
of convective flow occurring by free-standing particles. The
widely used host materials for nanocomposite fabrication include
carbonaceous materials, such as granular activated carbon,
silica, cellulose, sands and polymers, and polymeric host mate-
rials must possess excellent mechanical strength for long term
use.351354 The generally used NPs include zero valent metals,
metallic oxides, biopolymers and single-enzyme nanoparticles
(SENs).355358 These nanoparticles could be loaded onto porous
resins, cellulose or carboxymethyl cellulose, chitosan, alginate,
etc.359363 The choice of the polymeric support is influenced by
their mechanical and thermal behaviour, hydrophobic/hydro-
philic balance, chemical stability, bio-compatibility, optical and/
or electronic properties and their chemical functionalities (i.e.
solvation, wettability, templating effect, etc.).364 The common
catalytic nanoparticles include nanosized semiconductor mate-
rials (such as nano-TiO2, ZnO, CdS), zero valence metals (such as
Fe0, Cu0 and Zn0) and bimetallic nanoparticles (such as Fe/Pd,
Fe/Ni, Fe/Al, Zn/Pd).365375 They are usually applied as catalysts
or redox reagents for degradation of a large variety of environ-
mental contaminants, such as PCBs (polychlorinated biphenyls),
azo dyes, halogenated aliphatics, organochlorine pesticides,
halogenated herbicides and nitroaromatics. Nanocomposite
adsorbents were designed by impregnating the inorganic nano-
particles into conventional polymers, namely, alginate,376 cellu-
lose,377,378 porous resins360 and ion-exchangers,359,379 to avoid
issues caused by the ultrafine particle size, such as transition loss
and excessive pressure drops. Porous polymeric adsorbents or

Table 7 The applications of nanocomposites of CNTs for environmental remediation

Material blends in the

nanocomposite Benefits Target material Reference
2+ 2+ 2+ 2+
Nanocarbon colloids and Sorption of metal ions takes place Removal of Zn , Cd , Cu , Hg , 335
polyethylenimine simultaneously with the formation of Ni2+, Cr6+ from waste water
a nanocomposite and the coagulation
and filtration of nanocomposites
with metal ions can capture other
contaminated materials
CNT with silver ions and copper The improvement was observed for Removal of E. coli and S. aureus 336 and 337
nanoparticles antimicrobial properties due to the from contaminated water
increased contact surface area
CNT with TiO2 nanoparticles and P- Providing high surface area, high Removal of organic dyes, phenol and 338345
25 TiO2 quality active sites, the retardation of phenol derivatives, humic substances,
electronhole recombination and and metallic ions from contaminated
visible light catalysis by modification water
of the band gap and/or sensitization
CNT with iron oxide magnetic Improvement in the surface area and Removal of Co2+, Sr2+ and Ni2+ from 346
composites adsorption capacity the aqueous solution
Hybrid diatomite/carbon composites Providing an adequate open porous Removal of polar aromatic 347
network comprised of transport compounds (p-cresol) from aqueous
pores and micropores and a faster solutions
removal rate

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 View Article Online

ion exchangers have proved to be ideal alternatives to fabricate
similar hybrid adsorbents when considering their excellent
mechanical strength and the adjustable surface chemistry of the
polymeric supports.359,379 The immobilized charged functional
groups bound to the polymeric matrix are believed to enhance
the permeation of inorganic pollutants of counter charges. Table
8 summarizes some of immobilized nanoparticles in polymer
matrix. Due to the high photocatalytic activity of titanium
dioxide nanoparticles, the polymer substrates of the nano-
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and TiO2, as suggested by the slightly high red shift in the UVvis
spectra.388 The schematic illustration of MB dye degradation
over the surface of PNA/TiO2 nanocomposites catalyst is shown
in Fig. 11. Some nanoscale metals and bimetals, such as Fe0, Cu0,
Zn0, Fe/Pd, Fe/Ni, Pd/Zn, etc., are very effective in destroying
various organic contaminants,386,387 such as chlorinated meth-
anes, brominated methanes, trihalomethanes, chlorinated
ethenes, chlorinated benzenes, other polychlorinated hydrocar-
bons, pesticides and dyes. Magnetite (Fe3O4), maghemite

composite catalysts are expected to be antioxidative under UV or
visible light illumination. The reported polymeric substrates are
usually saturated carbon chain polymers or fluoropolymers,
such as poly(dimethylsiloxane) (PDMS),380 polyvinylpyrrolidone
(PVP),355 polyethylene (PE),381 polypropylene (PP),382 poly-
(3-hexylthiophene) (P3HT),383 polyaniline (PANI),384 poly-
(tetrafluoroethylene),385 and Nafion. Ameen et al. prepared
poly-1-naphthylamine (PNA)/TiO2 nanocomposite by in situ
polymerization and observed an enhanced photocatalytic
activity for the degradation of methylene blue (MB) dye under
visible light illumination. The high photodegradation efficacy of
the MB dye may be attributed to the efficient charge separation
of the electrons (e) and hole (h+) pairs at the interfaces of PNA
(Fe2O3) and jacobsite (MnFe2O4) nanoparticles can be loaded on
or in the polymer matrix, such as alginate beads. A series of
magnetic alginate polymers were prepared and batch experi-
ments were conducted to investigate their ability to remove heavy
metal ions403 (Co(II), Cr(VI), Ni(II), Pb(II), Cu(II), Mn(II)) and
organic dyes402 (methylene blue and methyl orange) from
aqueous solutions. Magnetic particles in the nanocomposites
allowed easy isolation of the beads from the aqueous solutions
after the sorption process. The montmorillonite-supported
magnetite nanoparticles synthesized via a hydrosol method
exhibited a better adsorption capacity per unit mass of magnetite
and a better stability for storage than their unsupported coun-
terparts. During the adsorption of Cr(VI) onto magnetite

Table 8 The application of polymer supported nanomaterials for environmental remediation

Type of nanoparticle Polymer matrix Preparation method Target pollutant Ref.

Fe0/Pd Polyacrylic acid (PAA)/ Dipping cross-linked Trichloroethylene 389

polyvinyl alcohol (PVA) electrospun polymer mat in
ferric trichloride and
palladium chloride solution
TiO2 Polyaniline Polymerization of aniline in Phenol 384
the presence of TiO2 nano-
particles
TiO2 Poly (tetrafluoroethylene) Electrophoretic deposition Trichlorobenzene 385
Fe0 Polystyrenedivinylbenzene Dipping cross-linked polymer Nitrate 390
mat in ferric trichloride
solution
TiO2 Poly(3-hexylthiophene) Adding TiO2 nonpartisan to Methylene orange 391
(P3HT) the P3HT solution
Fe0 Alginate In situ synthesis of Fe0 in Trichloroethylene 392
alginate bead from Fe3+
Fe0 Carboxymethyl cellulose In situ synthesis with Cr6+ 393
FeSO4$7H2O as a precursor
Fe0 Poly(vinyl pyrrolidone) Electrospinning Bromate 355
Fe0/Pd Sodium carboxymethyl In situ synthesis with para-Nitrochlorobenzene 394
cellulose FeSO4$7H2O and K2PdCl6 as
precursors
Cu0 Chitosan In situ synthesis with Cr6+ 395
Cu(SO4)2$5H2O as a
precursor
Ni/Fe Cellulose acetate Solvent cast Trichloroethylene 396
Pd/Sn Resin In situ reduction of Sn2+ to Trichloroethylene 397
Sn0 and then deposition of
Pb0 through the reduction of
Pb4+
Magnetite Montmorillonite Co-precipitation and Cr6+ 398
hydrosol method
Hydrated ferricoxide Polymeric anion exchangers Precipitation of iron(III) As3+ and As5+ 399
hydroxides from FeCl3
Hydrated ferric oxide Polymeric cation exchanger Precipitation of iron(III) Pb(II), Cu(II), Cd(II) 400
hydroxides from FeCl3
Hydrous Manganese oxide Polymeric cation exchanger Oxidation of the pre-loaded Pb(II), Cd(II), Zn(II) 401
(HMO) Mn(II)
Fe3O4 Alginate Mixing Methylene blue, methyl 402
orange

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Fig. 11 A schematic illustration of the photocatalytic activity of PNA/
TiO2 nanocomposites.386
nanoparticles, Cr(VI) can not only be reduced to Cr(III), which
has less toxicity than Cr(VI), but it can also be fixed into the iron
oxide. This is of high importance for the application of magnetite
in the environmental remediation.398 Water pollution is certainly
one of the major problems faced by the world today. Metals,
such as Hg, Pb, Cr, Cd and As, in diverse forms constitute some
of the major inorganic pollutants and have many harmful effects
on humans and environment.404 Mercury exists in three chemical
forms, namely elemental (Hg0), inorganic mercurous and
mercuric forms (Hg1+ and Hg2+) and organic alkyl mercury.
Methyl mercury and dimethyl mercury are the most toxic and
stable forms of organomercury. Due to the high toxicity effects,
the World Health Organization (WHO) has set the limit of
mercury in drinking water as 0.001 mg L1. Sumesh et al.407
found that water soluble silver nanoparticle composites of
9  2 nm and 20  5 nm core diameter, protected by mercap-
tosuccinic acid (MSA) supported on alumina is an effective
system to remove mercuric ions from contaminated water at
room temperature (28  1  C). Preparation and performance
evaluation of silver nanoparticles were done using two different
ratios of silver to MSA: 1 : 3 and 1 : 6. The solution with a
concentration 2 ppm Hg2+ was used to evaluate the degree of
removal of Hg2+ ions from the solution.
The percentage of removal by both the nanoparticle composites
is high at pH 56 and the performance decreases with an
increasing pH of the solution.405 The reason for the decrease of
performance of nanoparticle composite at higher pH was due to
forming of stable mercuric hydroxo complexes, which may not
interact with the surface of nanoparticle composite. Among these
two materials, the 1 : 6 silver nanoparticle composite showed
better performance than the 1 : 3 Ag nanoparticle composite.
Lisha et al.408 reported that gold NPs supported on alumina were
used as adsorbents in order to remove inorganic mercury from
drinking water. The coupling of cellulose acetate membrane and
Fe0 has contributed the degradation rate of 0.17 L m2 h1 for
removal of tetrachloroethane and the rate of degradation was
found to be 0.12 L m2 h1 for the removal of TCE. Cellulose
acetate membranes were used for this investigation and were
25 cm  25 cm  100 mm with a metal (Fe0) concentration of 1%
by weight. In addition, the performance testing of coupling of
cellulose acetate and the bimetallic system (the Fe0/Ni0 ratio was
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4 : 1) showed that the degradation rate of TCE was found
to be 0.028 L m2 h1, which was slower than that of TCE
(0.098 L m2 h1) using bimetallics (the Fe0/Ni0 ratio was 3 : 1).406
The limitations of the coupling of a cellulose acetate membrane
with metallic nanoparticles for the removal of chlorinated ethanes
were found to be (1) the incorporated membrane captured Fe0 or
bimetallic (Fe0/Ni0) nanoparticles and prevented them from being
released to the environment, and (2) a loading time was required
for loading nanoparticles into the membrane before they reached
the peak reaction rate. The reduction efficiency of nitrobenzene in
groundwater by iron NPs immobilized in a PEG/nylon66
membrane was investigated by Tong et al. It was found that the
iron NPs immobilized in PEG/nylon66 membrane exhibited a
high reactivity towards the removal of nitrobenzene. The
concentration of nitrobenzene quickly decreased by 68.9% in the
first 20 min and was moderately decreased by 15% from 20 to 80
min. The decrease in reduction efficiency was due to the reaction
between iron NPs immobilized in PEG/nylon66 membrane and
nitrobenzene as well as H2O, which reduced the reactive sites and
led to the oxidation of the Fe0 and Fe2+ during the first several
minutes.407,409 In a biocatalytic enzyme nanocomposite or single
enzyme nanocomposites (SENs), each enzyme molecule is sur-
rounded with a porous composite organic/inorganic network of
less than a few nm in thickness, as shown in Fig. 12. The fabri-
cation of PEI/TiO2 bionanocomposites has been performed by
ultrasonic irradiation techniqus, as shown in Fig. 12. Under
ultrasonic conditions, the coupling agent (-amido-propyl-trie-
thoxyl silicane) hydrolyzes to form hydroxyls and then poly-
condensation occurred to form SiOSi bonds. Commonly, the
main effects of sonication are because of cavitation or the growth
and explosive disintegration of microscopic bubbles on a micro-
second timescale. At the same time, ultrasonic cavitation can
generate a rigorous environment of local temperature up to
5000 K and local pressure up to 500 atm. Under such conditions
the modified TiO2 nanoparticles, which have polar group of
coupling agent and OH group on the surface of TiO2 could be
dispersed completely in polymer matrix via different interactions
with the functional groups of the obtained PEI. The heat stability
of the nanocomposite was improved in the presence of TiO2
nanoparticles. Several polymer supported nanomaterials have
been investigated and further studies of interaction between the
host polymers and the encapsulated NPs are still required.
(H) Nanosensors
Environmental monitoring requires rapid and reliable analytical
tools that can perform sample analysis with minimal sample
Fig. 12 A diagram of the synthesis process for PEI/TiO2
nanocomposites.410
This journal is The Royal Society of Chemistry 2012

handling. Nanoparticle (NP)-based environmental sensors have
the potential to detect toxins, heavy metals and organic pollut-
ants in air, water and soil and are expected to play an increasingly
important role in environmental monitoring. They can both
improve detection and sensing of pollutants and can be used to
develop new remediation technologies. Compared to traditional
detection methods, NP sensors may have higher selectivity,
sensitivity and stability and a lower cost.411 The measurement of
harmful gases ,such as NOx, CO2, CO, methanol, CH4, etc. is
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desirable in environmental monitoring, chemical process
controlling and personal safety. Gas sensor devices are tradi-
tionally comprised of thin films of metal oxides, with tin oxide,
zinc oxide and indium oxide, etc. With the recent discovery of
novel metal oxide nanostructures, sensors comprising nano-
arrays or single nanostructures have shown improved perfor-
mance over the thin films. The improved response of the
nanostructures to different gases has been due to the highly single
crystalline surfaces as well as large surface area of the nano-
structures. A number of studies support the application of ZnO
1D nanostructures as nanosensors. The studies by researchers
indicate that NH3 and CO behave as charge donors, transferring
charge from the adsorbate to the surface while NO2, O2 and
dioxin behave as charge acceptors, withdrawing charge from the
ZnO surface.412414 Nanotube-based sensors include metal oxide
tubes, such as Co3O4, Fe2O3, SnO2, and TiO2, and metal tubes,
such as Pt nanosensor. Jang et al. applied a poly(3,4-ethylene-
dioxythiophene) (PEDOT) nanorods nanosensor for the detec-
tion of HCl and NH3 vapor. The PEDOT nanorode sensors gave
a measurable response to NH3 and HCl vapor concentration as
low as 10 and 5 ppm, respectively.415 Comini et al. observed the
high sensitivity of a MoO3 nanorods film sensor to 30 ppm
carbon monoxide and 100 ppm ethanol.416 Kim et al. studied a
gas sensor based on a non-stoichiometric tungsten oxide nano-
rod film. The sensor was fabricated on Si wafers as the substrates
by using a microelectromechanical system (MEMS) and silicon
technology. The sensor responses were observed to be 2% N2 (or
air), 1000 ppm ethanol, 10 ppm NH3 and 3 ppm NO2 in both dry
air and a nitrogen atmosphere at room temperature.417 A highly
selective and stable ethanol sensor based on single-crystalline
divanadium pentoxide nanobelts was reported by Liu and co-
workers. The V2O5 nanobelts showed greater sensitivity to
ethanol of either low (<10 ppm) or high (1000 ppm) concentra-
tions. The response and recovery times were 3050 s.418 Kong
and Li found a highly sensitive and selective CuOSnO2 sensor to
H2S gas based on SnO2 nanoribbons.418,419 Comini et al. applied
a SnO2 nanobelts film for gas sensing and proved its capability to
sense gases at 30 ppm CO (350  C), 200 ppb NO2 (300  C) and 10
ppm ethanol (350  C).416 Gao and Wang found that the SnO2
nanobelt/CdS nanoparticle coreshell heterostructured sensor
had high sensitivity to 100 ppm ethanol vapors in air at 400  C.420
The authors suggested that the CdS nanoparticles may be served
as additional electron sources that greatly improved the electron
conduction in the SnO2 nanobelts. Tao et al. demonstrated
the capability of silver nanowire substrates for the detection of
2,4-dinitrotoluene (2,4-DNT), the most common nitroaromatic
compound for detecting buried landmines, and other explosives
by utilizing vibrational signatures. A sensitivity of about 0.7 pg
was achieved.421 Yang et al. demonstrated the capability of
silver nanowire substrates for the detection of 2,4-dinitrotoluene
This journal is The Royal Society of Chemistry 2012
View Article Online
(2,4-DNT) and other explosives by utilizing vibrational signa-
tures. A sensitivity of about 0.7 pg was achieved.422
Zhang and co-workers also continuously demonstrated
detection of NO2 down to ppb levels using transistors based on
both single and multiple In2O3 nanowires operating at room
temperature. The multiwire sensor showed an even lower detec-
tion limit of 5 ppb, compared to the 20 ppb limit of single
nanowire sensors. This room temperature detection limit is the
lowest level so far achieved with all metal oxide film or nanowire
sensors.423 This improved sensitivity was due to the formation of
nanowire/nanowire junctions between the metal electrodes, a
feature available in the multiple nanowire devices but junctions
are not available in the single nanowire devices. Such junctions,
when exposed to NO2, should form a depleted layer around the
intersection and thus block the electron flow in a way more
prominent than the surface depletion of the single nanowires
with metal contacts. When detecting NO2 among other common
gases, such as O2, CO and H2, using the multiple nanowire
devices, selective response to NO2 was also observed. On the
basis of their previous study, it was suggested that a large group
of In2O3 nanowires with an appropriate doping level distribution
could have two opposite sensing responses cancelling out each
other and resulting in the immunity to NH3. This unique prop-
erty of In2O3 nanowires offers a new way to achieve selectivity, as
compared to the conventional technique of using permeable
polymer coatings. Chu et al. also evaluated the gas sensing
properties of In2O3 nanowires films. The results revealed that the
sensors exhibited higher response and good selectivity to
C2H5OH at 370  C. The response time was about 10 s and
recovery time was shorter than 20 s.424 Functionalization of
MWCNTs multiple-films with nominally 5 nm thick Pt- and
Pd-nanoclusters prepared by magnetron sputtering provided
higher sensitivity of significantly enhanced gas detection for
NO2, H2S, NH3 and CO, up to a low limit of sub-ppm level.425
Titanate nanotubes (TNT) were proven to be an efficient
supports for the immobilization of methylene blue (MB) for the
detection of dopamine.420 Porous TiO2 solgel matrix can be
used to construct nitrite sensors by immobilizing partially
quaternized poly(4-vinylpyridine) complexed with PVP-Os on an
electrode.426
The limitation of nanoparticles in practical applications, such
as slow diffusion and aggregation, still exists. Immobilization of
nanoparticles by polymer matrix is one of the most efficient
approaches to overcome such limitations. Since the chemical and
physical properties of polymers may be tailored, they gained
importance in the construction of sensor devices.427 Conductive
polymer nanomaterials have attracted particular interests as
sensors for air-borne volatiles428434 (alcohols, NH3, NO2, CO)
because of large surface area, adjustable transport properties and
chemical specificities, easy processing and scalable productions.
Polyaniline nanofibres were developed by interfacial polymeri-
zation to sense hydrazine gas and it was found that performance
of sensing was better than conventional thin film due to its high
surface area, porosity and small diameter.435 PolyanilineSnO2/
TiO2 nanocomposite ultra thin films have also been fabricated
for CO gas sensing.428 The range of the biosensor was found to
be 6.9  1014 to 8.6  1013 mol L1 and the detection limit is
2.3  1014 mol L1. A Pdpolyaniline nanocomposite was
developed as a selective methanol sensor.432 The synthesized
Energy Environ. Sci., 2012, 5, 80758109 | 8101

Table 9 Polymer-based nanocomposites for the sensing and detection of pollutants
Type of nanoparticle Polymer matrix
SnO2 Polystyrene/polyaniline (PSS/PANI)
SnO2 Polyaniline (PANI)
TiO2 Polyaniline (PANI)
Iron oxide Polypyrrole
Pd Polyaniline
Au Chitosan
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nanocomposite sensor showed high selectivity and sensitivity to
methanol vapors with rapid and reverse response. Some appli-
cations of polymer-based nanocomposite sensors are shown in
Table 9. Nanosensors have also been applied as biosensors. The
application of silica-coated nanosilver as biosensors for the
biochemical compounds, such as glucose and hydrogen peroxide,
because of their superior properties, such as their nontoxic
nature, high surface area, high adsorptivity, high uniformity and
excellent biocompatibility. TiO2 nanomaterials have been
frequently proposed as a prospective interface for the immobi-
lization of biomolecules. Moreover, titanium forms coordination
bonds with the amine and carboxyl groups of enzymes and
maintains the enzymes biocatalytic activity.436,437,439441 Form-
aldehyde is a hazardous air pollutant and prolonged exposure to
formaldehyde can cause a nervous system damage as well as
asthma. When sensor strip made of nylon 6 nano-fibre nets
(NFN) was exposed to formaldehyde, the methyl yellow on the
tape reacted with sulfuric acid produced by the reaction of
hydroxylamine sulfate with formaldehyde to produce a yellow-
to-red color change as shown in Fig. 13.438
Fig. 14 shows the fabrication of the biosensor, which was done
by coating graphenegold nanocomposites (G-AuNP), CdTe
CdS coreshell quantum dots (CdTeCdS), gold nanoparticles
(AuNPs) and horseradish peroxidase (HRP) in a sequence on the
surface of a gold electrode (GE). It was found that sensitivity of
the biosensor is more than 11-fold better if G-AuNP, CdTeCdS
and AuNPs are used. This could be ascribed to the improvement
of the conductivity between the graphene nanosheets in the
Fig. 13 An illustration of the colorimetric detection of formaldehyde
based on the nylon 6 NFN membranes.438
Fig. 14 The fabrication of AuNPs/Cd-Te-CdS/G-AuNPs/GE.442
8102 | Energy Environ. Sci., 2012, 5, 80758109
View Article Online
Preparation method Target pollutant Ref.
In situ self-assembly CO 428
Hydrothermal method Ethanol, acetone 429
Chemical polymerization and a solgel method Trimethylamine 430
Simultaneous gelation and polymerisation CO2, N2, CH4 431
Oxidative polymerization of solution with Pd NPs Methanol 432
Mixed in solution Zn2+, Cu2+ 433
G-AuNP due to introduction of the AuNPs. The electrocatalytic
synergy of G-AuNP, CdTeCdS and AuNPs remarkably
improves the electron relay and accelerates the electrochemical
reaction and the AuNPsCS film offers a favorable microenvi-
ronment to keep the bioactivity of the HRP. This biosensor
provided the best sensitivity in all biosensors based on graphene
materials for detection of hydrogen peroxide. This study remains
open as a new challenge and approach to explore the electro-
chemical features of graphene or its nanocomposites for the
potential utilizations.442
Conclusions and future prospects
The application of nanomaterials in the detection and removal
of pathogens provides greater sensitivity, a lower cost, shorter
turn-around times, smaller sample sizes, in-line and real-time
detection, higher throughput and portability in environmental
remediation. In addition metal and metal oxide nanomaterials
can be used to remove organic pollutants and metals by reduc-
tion or oxidation of nanomaterial and degree of removal can be
enhanced through functionalization with chemical groups that
can capture selectively target pollutants in water and air media.
This method is effective and promising and can be used in the
engineering of water and air improvements. Nanomembranes
have found applications in the production of potable water,
water reclamation, the removal of metals, dyes, NOM and the
removal of pesticides from contaminated water. Further
improvements must be made in the application of environmental
remediation to selectively remove materials, have a greater
resistance to changes in pH and the concentrations of chemicals
present in the contaminated water, greater stability for a longer
period of time and cost optimization. Nanofibrous media have a
low basis weight, high permeability and small pore size that make
them appropriate for a wide range of filtration applications. In
addition, nanofibre membranes offer unique properties, such as a
high specific surface area (depending on the diameter of fibres
and intrafibre porosity), good interconnectivity of the pores and
the potential to incorporate active chemistry or functionality at
a nanoscale. A high flux could be produced via nanofibrous pre-
filters with even higher loading capacities. Such pre-filters can be
used in various applications, such as the removal of micropar-
ticles from waste water and with ultrafiltration or nanofiltration
membranes to prolong the life of these membranes. On-going
investigations are under way to develop engineered nano-
materials of various fibre diameters and morphologies to identify
their effects on the performance of nanofibres.
The environmental applications of polymer supported nano-
composites in photocatalytic/chemical catalysis degradation, the
This journal is The Royal Society of Chemistry 2012

adsorption of pollutants and pollutant sensing and detection
result in a greener environment. However, the study of the
interaction between the host polymers and the encapsulated NPs
and its effect on the dispersion in polluted air and water is
necessary. In addition, the large scale production of polymer-
supported nanocomposites and more practical applications
remain open. The extensive application of sorbents in environ-
mental remediation have shown the capability of adsorbing
metals and organic pollutants from contaminated water and air.
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Iron-based nanomaterials, TiO2 nanomaterials and polymeric
adsorbents have shown high adsorption capacities and selectiv-
ities. The surface modification of sorbents are being studied for
process optimization. Enhancing the reusability of sorbents and
the extension of their lifespan must be explored to reduce the cost
in environmental remediation. Sensors have been developed for
sensing gases, chemicals and volatile organic compounds and the
detection and identification of bacteria. Further development is
necessary in the functional properties of nanomaterials to meet
the need for trace detection and the treatment of pollutants in
water and air and important fundamental and mechanistic
studies are required in order to fully explore their real potentials.
One dimensional CNTs with single and multiple layers have
shown superior adsorption capacities in the removal of diverse
range of biological and chemical contaminants due to their
fibrous shape with high aspect ratio and provision of large
external surface area. Small size nanoscale particles composed of
CNTs are difficult to separate from aqueous solution. Ultra
centrifugation separation method is efficient to separate CNTs.
However, high energy is necessary for this method. The
membrane filtration method is an alternative and efficient tech-
nique to separate CNTs from aqueous solutions. However, the
membrane can easily be blocked. The CNTs/metal oxide or
magnetic composites are promising materials in environmental
pollution management at a large scale. More efforts for the
development of practical applications of these CNT composites
are required in the future. Dendritic nanopolymers have been
developed for low pressure filtration processes to remove
perchlorate and uranium from contaminated water and recover
metal ions (e.g., copper, silver, nickel and zinc) from industrial
waste water. The long-term efficiencies of dendritic nanopolymer
composites as an important practical aspect have not been
reported and should be addressed in the future.
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