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Energy & Environmental Science

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A review on nanomaterials for environmental remediation
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Mya Mya Khin,a A. Sreekumaran Nair,*b V. Jagadeesh Babu,b Rajendiran Murugana 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.

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:; seeram@

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, biological oxidation, chemical oxidation and incineration. Supercritical 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 industrialization 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 (photocatalysis) 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.
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pollutants, SCWO is far less costly than incineration or active carbon treatment. In parallel, the rapid growth of nanotechnology 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 Singapore (NUS). She finished her oral defence recently and she is on course to obtain her PhD degree from NUS. She graduated with M. Eng. degree from NUS in Chemical Engineering. She worked as a lecturer and scientist at Ngee Ann Polytechnic and Food & Nutrition in Singapore (2008–2011). Her current research involves environmental remediation using electrospun nanofibres.

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Mya Mya Khin

applications of nanomaterials. The treatment of pollutants in water and air is a great challenge and nanomaterials are important for the environmental remediation. Nanomaterials are excellent adsorbents, catalysts and sensors due to their large specific surface areas and high reactivities. The high surface areato-mass ratio of nanomaterials can greatly improve the adsorption 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 properties 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 A. Sreekumaran Nair worked as a research fellow (2008–2012) at the Healthcare and Energy Materials (HEM) Laboratory of the National University of Singapore. He graduated with a PhD in Chemistry from the Indian Institute 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 clusters 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 graduated with a PhD in Physics from the Indian Institute of Technology (IIT), Madras (2008) and subsequently became a research assistant in the Department of Physics IITMadras from 2008–2009. 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 photocatalysis, photovoltaics, the splitting of water for hydrogen energy and probing electrical charge transport in conducting polymers.
8076 | Energy Environ. Sci., 2012, 5, 8075–8109

Rajendiran Murugan

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 (CLRI–CSIR Lab) from the University of Madras and subsequently became an associate scientific manager at the Synthetic Chemistry Department in Biocon. His research interests include nanocatalysis, the synthesis of small/conjugated molecules and the fabrication of chemosensors.

Prof. Seeram Ramakrishna, FREng, FNAE, FAAAS is a Professor of Materials Engineering and Director of the HEM Labs ( 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 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.
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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 chitosan, silver nanoparticles (nAg), photocatalytic TiO2, and carbon nanotubes (CNT).4–8 Nanotechnology is also used for the 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 fabrication of nanomaterials can be achieved by (1) grinding, milling and mechanical alloying techniques; (2) physical or chemical vapour deposition or vacuum evaporation; (3) sol–gel 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 crystallization 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 nanocomposites 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 nanoparticles (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 foulingresistance 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.

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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 zerovalent 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 biodegradability 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 corresponding 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, 8075–8109 | 8077

lying below the conduction band energy). a faster renovation of catalyst surfaces and accelerated dissolution and mixing..24.19. This is also a common goal in the electrochemical decontamination of organic pollutants in waste waters by anodic oxidation. at least principally. These radicals further react with _OH radicals or O2. which is performed in supercritical water above a critical temperature and pressure due to the properties of supercritical water. During the SCWO of organic acids in waste water containing benzoic acid. The hydroxyl radical is a very strong. The peculiar nature of sonochemical reactions offers alternative pathways. 8078 | Energy Environ. synthesized in situ in the reactor. (i. The adsorption of at least one of the reactants. 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. Fe(H2O)62+ and Fe(H2O)63+. Increased rates upon raising the temperature above the ambient temperature have been reported for the gasphase removal of some pollutants and. very oxidizing _OH might be produced. Under these conditions. Sci.. however. | doi:10.99% or higher. H2O and electron-rich organic compounds. 1 shows a schematic diagram for the different electrochemical treatments. The indirect methods deal with the use of redox mediators as reversibly electrogenerated reagents. O3. Consequently.18 The photocatalytic reaction occurs. yielding _Cl and _CCl3 radicals as primary intermediate products.26–28 Fig. As the adsorption and desorption rates are temperaturedependent.rsc. Fig. above all. by three-electron reduction of O2: O2 + 2H+ + 3eÀ / OH_ + OHÀ HO2 + R–H / H2O2 + R_ Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. In other words. increased organic solubility and decreased inorganic solubility) and the viscosity of the media is decreased to a value similar to gas-like values. for their mineralization rate. both methods are still too costly to be competitive with biological treatment. although many other reactions occur in Fenton systems. Although modern processes have seriously reduced the operation costs for cathodic reduction and anodic oxidation. temperature can have an effect on the photocatalytic reaction rates.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..View Article Online (_OH) and a hydroxide ion (OHÀ).21–23 The term ‘‘Fenton reagent’’ refers to aqueous mixtures of Fe(II) and hydrogen peroxide via the Fenton method.. The reaction in the adsorbed phase. act as an oxidation catalyst to enhance the oxidation rate of organic compounds. 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 O2À overpotential anode. HOCl.1039/C2EE21818F are are the the cobalt manganese oxide nanoparticles.. 2012. Because these reactions known to take place in homogeneous aqueous phases. where the thermolysis of CCl4 molecules takes place at fast rates. and in organic compounds. 8075–8109 . p-tolualdehyde and p-toluic acid. cations in aqueous solution can be directly reduced by conduction band electrons provided that the redox potentials of these cations are adequate (i. The waste water solution was irradiated with light and ultrasound was used for the degradation via sonophotocatalysis. such as cobalt and manganese acetate. Small nanoparticles of metal oxides can be produced by hydrothermal synthesis. This method has indicated the following net reaction as the predominant process: Fe2+ + H2O2 / Fe3+ + HO_ + OHÀ (1) where Fe2+ and Fe3+ represent the hydrated species. A much more direct way of forming the _OH radical is through the oxidation of an adsorbed water molecule or an OHÀ ion by a valence band hole (h+). These effects include an increase in the surface area between the reactants. and 5. whereas the enhancement of heterogeneous reactions can also be related to mechanical effects induced in the fluid system by sonication. Sonochemistry provides a unique. either the reaction temperature can be reduced or the residence time can be shortened.g.1 MPa or 218 atm). Fig. as well as oxidants as irreversibly electrogenerated reagents at the anode (e. 3.e. Cl2 and CO2 as the final degradation products. thus enhancing the mass transfer properties.29–31 This journal is ª The Royal Society of Chemistry 2012 where R–H is an organic species with a labile H atom. At 400–650  C and 3750 psi.g. high-temperature gaseous environment inside the cavitation bubbles. The TOC of the waste water was found to be 37 480 ppm and decreased to 200 ppm after the reaction. respectively. The desorption of the product(s).e. The transfer of the reactants from the fluid phase to the surface. 4. Cl and ClO2) or the cathode (e. 5.25 Sonochemical reactions are related to new chemical species produced during acoustical cavitation. Reaction (1) is often referred to as the Fenton reaction. 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. in principle. Au–TiO2 nanoparticles were prepared by sonicating (20 kHz) an aqueous solution of HAuCl4$3H2O containing polyvinylpyrrolidone. in the adsorbed phase and the overall process can be formally divided into five steps: 1. 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. Halogenated organics are usually toxic and their electroreduction can make them easily biodegradable. H2O2). The removal of the product(s) from the interfacial region. In addition. The chemistry occurring at the surface of a photoexcited semiconductor is based on the radicals formed from O2. The primary utility of the Fenton reagent in the degradation of pollutants is the formation of _OH.. by an electron transfer from these entities to the photoexcited semiconductor). The direct electrolytic processes includes conventional procedures of cathodic reduction and anodic oxidation.e. they believed to occur on the TiO2 surface. nonselective oxidant capable of degrading a wide array of pollutants. yielding stable HCl. 22. 1-propanol and TiO2 (Deguzza P-25) at room temperature under a nitrogen atmosphere. the solubility properties of water are reversed (i. 2. SCWO can be used to achieve complete oxidation of many organic compounds with destruction rate efficiencies of 99. providing a faster or environmentally safer degradation of contaminants. this reaction would also compete with H-atom abstraction from R–H by the _OH radical.

biological processes can often be conducted without the harsh conditions that are necessary during chemical transformations. They also require a supply of macro. 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. toxins. chloroorganic compounds are the ones reduced with the highest rates (eqn (2)).. This result may be sufficient for waste treatment purposes. high temperatures or extremes of pH) are sometimes required to facilitate the chemical transformations. deep blue solutions of solvated electrons are formed when Li. This is certainly true with metals that occur as soluble cations. These media have long been used to reduce organic compounds. predators and high concentrations of the pollutants. Consequently. The number of electrons is referred to as the beam current and is controlled by the cathode size and configuration. In some cases. however. Ca or other group I and group II metals are dissolved in liquid ammonia (eqn (1)). Thus. 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 | doi:10. Of aq particular interest to the application in waste treatment are the reactions with halogenated compounds.rsc. further reaction of the resulting organic radical (R_) may also be desirable to mineralize the compound. Most solvated electron-treated wastes require post treatment. the use of microorganisms provides many rate-limiting factors.37–39 Chemical processes often require the presence of excess quantities of reagents to accomplish transformation to the desired extent. 2012.g. For example. which can be expected to adsorb fairly strongly to iron oxides. 8075–8109 | 8079 This journal is ª The Royal Society of Chemistry 2012 . The lifetime of PRBs using Fe0 as a reactive medium is limited by precipitation at the barrier. Process versatility is provided by the continuous. However.and micro-nutrients for the support of Energy Environ. reactions involving the eÀ often result in the dechloriaq nation of organochlorine compounds. costly and time-consuming methods may be necessary to produce microbial cultures that can degrade the targeted pollutant. the sensitivity of microorganisms to changes in their environment can make these processes difficult to control over the long term. The process is nonselective in the destruction of organic chemicals because strongly reducing reactive species (eÀ /H_) and strongly oxidizing reactive species aq (_OH) are formed at the same time and in approximately the same concentration in solution. The metabolic processes occur as a result of a sequence of reactions conducted inside the cell that are catalyzed by proteins called enzymes. adsorption is the initial step and subsequent transformations help ensure that the process is irreversible. but cannot be reduced to insoluble forms by Fe0: e. many chemical treatment processes are not highly selective in terms of the types of pollutants that are transformed during treatment. Additionally. 5. 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.1039/C2EE21818F Sources of free radicals. which allow for a versatile approach for the ultimate treatment of a variety of pollutants. The eÀ also reacts with many other aq organic compounds and contributes to the removal of these compounds from aqueous solution. However. reduction and co-precipitation. extremes of pH and temperature. rapid treatment potential and a tolerance for feedstocks of varying qualities. Finally. adsorption is the sequestration process of primary importance. principally hydroxyl radicals (_OH).. In addition. K.View Article Online Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. This is accomplished by passing hot water or steam through the jacket of the treatment cell and by condensing the ammonia for reapplication. such as pore diffusion and polymerization. severe conditions. The irradiation of water produces both reducing and oxidizing species.29 (A) represents direct electrolysis by anodic oxidation and (B) represents indirect electrolysis. Sequestration by Fe0 occurs mainly by adsorption. In most cases. In addition. particularly harsh conditions (e. Among the many functional groups reduced by this process. Mn2+ and Zn2+. intermediates and products may irreversibly damage or metabolically inactivate the microbial cells. Na / Na+ + eÀ RCl + eÀ / R_ + ClÀ (1) (2) Fig.g. Sci. modern e-beams have excellent operational reliability.. Mg2+. The first post treatment involves removing and recovering ammonia from the matrix. although other processes may be involved. 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. 1 A schematic diagram for the different electrochemical treatments of organic pollutants.33 In the solvated electron reduction method. such as chemical shock. An excellent source of free radicals for water treatment is ionizing radiation.34–36 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. Furthermore. oxidatively decompose pollutants. Biological processes are designed to take advantage of the biochemical reactions that are carried out in living cells. A generalized reaction is shown below: eÀ + RCl / R_ + ClÀ aq Thus. The eÀ reacts with numerous organic compounds. Na. The energy of the electron determines its depth of penetration in water. Machine-generated electron beams (e-beams) provide reliable and safe radiation sources for the treatment of flowing waste streams on a process-size scale. Such processes use the natural metabolism of cells to accomplish the transformation or production of chemical species.

coprecipitation. A. gasphase reduction. 2012. In this section.55–58 Several materials containing iron.43 thermal decomposition and/or reduction and hydrothermal synthesis techniques are used widely and are easily scalable with high | doi:10. Ag+ ions interact with thiol groups in proteins. the biochemical reactions occur at a rate that is limited by the metabolism of the microorganism and. Niger. accumulating inside the membrane by forming ‘‘pits’’ and causing an increase in the membrane permeability.51 (2) nAg particles could penetrate the bacterial cell. and (v) the treatment of low-volume. and (3) the dissolution of nAg releases antimicrobial Ag+ ions. 8075–8109 categories: (1) physical approaches. (iii) the polishing of a treated waste water or groundwater to meet limitations on specific pollutants or to meet whole effluent toxicity criteria. high-energy ball milling. Nano Ag (nAg) particles have been reported to degrade lipopolysaccharide molecules. titanium oxides. 5. power This journal is ª The Royal Society of Chemistry 2012 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. triangular nAg nanoplates were found to be more toxic than nAg rods. the applications of nanoscale metals and NMOs in environmental remediation are presented. severe plastic deformation.40. Among these synthesis protocols.. etc. coli and P.65 The application of noble metal nanoparticles for the removal of halogenated organics and pesticides from drinking water has also been patented. Sci. ultrasound shot peening. thus. In addition. This catalytic action can be carried out on. there are fewer delays associated with shutdown/startup periods that are normally required to acclimatize biomass to waste streams. The size and shape of NMs and NMOs are both important factors which affect their performance.. were successfully used in the reduction and precipitation of metal ions. conventional biological processes may not be able to improve water quality sufficiently to meet the waste water discharge criteria. aureus and Salmonella entrica. including many of those that may resist biodegradation. Silver nanoparticles are known for their strong antibacterial effects against a wide array of organisms (e. Coli.66. which leads to inactivation of respiratory enzymes and the production of reactive oxygen species (ROS). recent research has focused on developing the environmental applications of enzymes that have been isolated from their parent organisms. such as iron sulfide.50 To date. In an attempt to overcome some of the problems associated with chemical and biological systems.rsc.47 It was also shown that Ag+ ions can prevent DNA replication and affect the structure and permeability of the cell membrane. noble metal nanoparticles were also shown to degrade halocarbons by the same mechanism of reductive dehalogenation.67 Gold nanoparticles also exhibit potential to remove inorganic mercury from drinking water. aeruginosa. 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. pulse electrode position. controlled chemical coprecipitation. chemical vapor condensation. In addition. including inert gas condensation. (iv) the treatment of wastes generated infrequently or in isolated locations. many substances that are toxic to microbes..42. such as polymethoxybenzyl and poly(L-lactic acid)-co-poly(3-caprolactone) nanofibres.49. or in the presence of. pH values and salinity ranges compared to cultures of microorganisms. followed by the alloying of reduced mercury on gold nanoparticle surfaces. liquid-phase reduction. iron bearing oxyhydroxides and aluminosilicate minerals. some enzymes can operate over relatively wide temperatures.53. Out of all the iron-based materials. are often slower than chemical processes. fungi). for which conventional mixed-culture biological treatment might not be feasible. S. The incorporation of nAg into polymer materials. Therefore. bacteria.59 With the advent of nanotechnology.1039/C2EE21818F . Moreover. iron nanoparticles replaced the use of bulk iron-based systems for water purification. Enzymes can be applied to transform targeted contaminants. Importantly. 2. have also shown antimicrobial properties against E. gold. 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. sludge production is reduced because no biomass is generated. (ii) the removal of specific chemicals from dilute mixtures. highconcentration 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. Hg2+ ions were reduced to a zero-valent state. Efficient synthetic methods to obtain shapecontrolled. viruses.41 (B) Environmental remediation by metals/metal oxides For environmental remediation.54 Silver nanoparticles ranging from 1 to 10 nm inhibit certain viruses from binding to host cells by preferentially binding to the virus’ glycoproteins.64. In addition. liquid flame spray. etc. Consequently. including reverse micelle (or microemulsion).63 Sulphur dioxide (SO2) is frequently released to the atmosphere by the combustion of fossil-derived fuels in factories. Furthermore.60 After a few years. Generally. iron oxides. and (2) chemical approaches. the synthesis methods can be classified into two 8080 | Energy Environ.g.44–46 The different mechanisms of antimicrobial activity by nAg+ are shown in Fig. the catalytic action of enzymes enables the development of smaller systems of lower capital cost due to the high reaction rates associated with enzymatic reactions. nAg spheres and even Ag+ ions. resulting in DNA damage.52 Particles of Ag less than 10 nm are more toxic to bacteria such as E. 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. Therefore. silver nanoparticles are widely used for the disinfection of water. the most widely studied nanoscale metals (NMs) and metal oxides (NMOs) include silver. several mechanisms have been postulated for the antimicrobial property of silver nanoparticles: (1) the adhesion of nanoparticles to the surface altering the membrane properties. iron. elemental iron was found to be the most successful for ground water remediation.61–64 In an investigation by Lisha et al. causing an improvement in the UV inactivation of bacteria and viruses.View Article Online microbial growth and often result in the formation of large quantities of biomass that ultimately must be discarded into the environment.48 Silver ions are also photoactive in the presence of UV irradiation. because bacterial growth is not required to accomplish waste transformations. highly stable and monodisperse metal/metal oxide nanomaterials have been widely studied during the last decade. including spill sites and abandoned waste disposal sites.

75 TCE is adsorbed onto the surface of the Ni–Fe particles where the C–Cl bond is broken and the chlorine atom is replaced by hydrogen. MnOx. Sci. it gave the positive effects of catalytic activity due to charge transfer between the oxide and gold and a limited nanoscale size (usually less than 10 nm). Al-supported Pd nanoparticles and Pd black.rsc. (2001) reported the reductive denitrification by nanoscale zero-valence Fig. could be transformed to ethane by accepting electrons from the oxidation of iron through the following reaction: Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs.59. Fe or Zn serves as an electron donor while another species (Pt or Pd) serves as a catalyst.e. Al2O3). 2012. such as tetrachloroethane (C2Cl4).View Article Online Dabro et al. The degradation rate by bimetallic combinations was found to be faster than that observed for metal iron alone.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. 3 A nanoscale bimetallic particle for chlorinated solvent removal.69 found that the combination of a gold (Au) and TiO2 system produced highly efficient desulfurization.74. whereas bimetallic nanoparticles of iron consists of a catalytic material (Pd or Ni) and an electron donating material (i. In addition. in 2004 found that membrane immobilization for nanoparticles of Fe0 and bimetallic Ni0/Fe0 offered two advantages in the removal process of toxic organic compounds. 5. Therefore. 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. TiO2.84 Although bimetallic particles of Ni/Fe showed a relatively high reactivity towards chlorinated compounds.69 However. Metallic gold has a very low chemical and catalytic activity. Fig. immobilization of Fe0 in the membrane or bimetallic Fe0 nanomaterials have been used. 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.89 Choe et al. Zero-valence state metals.73 As iron corrodes.76 for the dehalogenation of 4-chlorophenol to phenol on palladized graphite and iron electrodes. houses and automobiles. Sn0 and Al0.69 Rodriguez69 investigated the dissociation effects of SO2 using the combined systems of TiO2/ Au and MgO/Au.75 Energy Environ. 8075–8109 | 8081 . when gold was dispersed on some metal oxides (MgO. On both oxide supports.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/ | doi:10.80 Bimetallic Pd/Au nanoparticles consist of two catalytic metals. such as Cr(VI). such as Fe0. 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.85. The structure of bimetals includes cluster-in-cluster and core–shell structures for nanoscale particles. The corrosion of buildings due to acid rain by SO2 is a serious challenge. Fe). 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 5–10 times more active than pure TiO2. 3 shows a schematic diagram of the reaction of a chlorinated organic molecule with a bimetallic nanoparticle. A similar mechanism was applied by Cheng et al.68.70 Furthermore.76 This journal is ª The Royal Society of Chemistry 2012 The removal efficiency was found to be greater than 99% using iron nanoparticles without a palladium coating after 24 h.81.71 Bimetallic combination (Fe0/Ni0: the ratio of Fe to Ni being 3 : 1) has provided better degradation rates. Zn0.83 However. are effective for the remediation of contaminants in contaminated groundwater. protons from water are reduced to adsorbed H atoms and to molecular hydrogen at the catalytic Ni surface.78 Contaminants. catalytic performance tests. Particles of nZVI have been applied for the efficient removal of different metals. Rodriguez68. Bimetallic Pd/Au nanoparticles can increase the catalytic activity by a factor of 15 as compared to Pd nanoparticles.1039/C2EE21818F C2Cl4 + 4Fe0 + 4H+ / C2H4 + 4Fe2+ + 4ClÀ Fig.47 plants. bimetallic coupling with a second catalytic metal has also been widely applied for the degradation of contaminants in contaminated water. TiO2 is the most commonly used catalyst to convert SO2 to sulfur through the reaction: SO2 + 2H2S / 2H2O + 3Ssolid. 2 The different mechanism for the antimicrobial activity of Ag+ ions. Fe2O3. investigated the dehydrochlorination of pentachlorophenol to phenol or cyclohexanol on supported palladium electrodes. To maintain the stability of Fe0 nanoparticles. Meyer et al. In addition.79..86 there is still an environmental concern over the toxicity of Ni.87 U(IV) and U(VI)88 and Co(II).72 Bimetallic particles are composed of two types of zero-valent iron (ZVI). the efficiency of Fe0 particles could be significantly reduced in large scale environmental remediation. 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.

whereby NOx is reduced back to N2 or oxidized to NO2 and HNO3. One dimensional TiO2 nanomaterials and doped TiO2 nanomaterials are widely used for the degradation of halogenated | doi:10.91 reported interesting results on the elimination of antibiotics from water using iron NPs.. which was not degraded by most of the ZVI. S and C. anatase and brookite. such as Cr6+ and Cu2+.72 Complete degradation could be obtained with a high surface reactivity. it is necessary to enhance the performance of TiO2 by using photons from the near visible to visible region.90 Ghauch et al. 2012. therefore.120 the hepatitis B virus. have received much attention for this purpose. Silver has been shown to enable the visible light excitation of TiO2. The corresponding N(2p) states are located above the valence band edge.135 Amezaga-Madrid et al. 5. such as phenolic compounds.121 the Herpes simplex virus122 and MS2 bacteriophage. TiO2 is widely used for NOx control.128 Noble metals. i. A highly selective photoreduction of NO to N2O and N2 is observed on the surface of TiO2.111 Most of this research involved UV photons as the major exciting light sources. Its large bandgap energy (3.91 Bimetallic nanoparticles of ZVI and Al have been utilized for the removal of chlorinated organic solvents. TiO2 has been widely applied in heterogeneous photocatalysis to decompose a host of organic pollutants.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. whereas the same inactivation required 60 min with uncoated containers. especially hydroxyl free radicals and peroxide formed under UV-A irradiation via oxidative and reductive pathways.106 Martin et al.2 eV) requires UV excitation to induce charge separation within the particle. There is 5% of solar irradiation within UV range. In the work of Skubal et al. Table 1 summarizes the application of TiO2 nanomaterials for environmental remediation. including poliovirus 1.101–105 Bimetallic Cu/Al particles have shown a better degradation of CCl4 and CH2Cl2. such as zeolites.92–99 Bimetallic particles of Fe and Al were found to degrade CCl4 by a factor of 6 as compared to micro-sized Fe ZVI. TiO2 is a semiconductor and has three distinct polymorph crystalline structures: rutile. such as N. Both rutile and anatase have been applied in photocatalytic and photoelectrochemical processes due to their easy synthesis by various techniques.108 TiO2 photocatalysts have been a popular choice for much of the published photocatalysis work.rsc.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.129.112–115 The modification TiO2 with noble metal ions could decrease the TiO2 band gap.e. activation by visible light. it was demonstrated that doping TiO2 with silver greatly improved the photocatalytic inactivation of bacteria130 and viruses. The brookite has an orthorhombic structure.125 A strong absorption of UV-A activates TiO2 under solar irradiation and significantly enhances solar-triggered disinfection. F. which concentrate NO on the surface. The oxidation of nitric acid converts it into a raw material with useful applications.107 TiO2 nanoparticles have been extensively used for the oxidative and reductive transformation of organic and inorganic contaminants in air and water. the elimination of toxic intermediates and a durable and stable performance by using bimetallic Pd/Fe nanoparticles. as well as perchlorate ions from waste water.133 Visible light absorption by silver surface plasmons is thought to induce electron transfer to TiO2 resulting in charge separation and. demonstrated that 1 wt% Ag in TiO2 reduced the reaction time required for complete removal of 107 cfu of E.51. sunlight. 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. such as in fertilizers. e. tested the effect of TiO2 thin films deposited on soda lime glass slides by This journal is ª The Royal Society of Chemistry 2012 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. This can be achieved by manipulating the particle size of the photocatalyst or by doping the TiO2 with foreign ions.124 The antibacterial activity of TiO2 is related to the ROS production. Such modified TiO2 materials exhibited larger absorption in the visible region and enhanced the degradation of organic dyes under visible light irradiation. the modified surface properties of noble metal-doped TiO2 photocatalysts could attract more cationic dye. coli per mL from 65 to 16 min under UV-A radiation. The activity of TiO2 is improved by the addition of an adsorbate. thiolactic acid (TLA).64 and 2.132 Silver enhances the photoactivity by facilitating electron–hole separation and/or providing more surface area for adsorption.109 metal ethylene diamine tetra acetate complexes. such as _OH. have reported the use of ferric-oxide NPs to remove and recover phosphate from municipal waste waters.134 Ag/TiO2 or Au/TiO2 therefore shows a great potential as a photocatalytic material due to its photoreactivity and visible light response.116 In addition. the removal of metals and some disinfection processes for drinking water and waste water. Both rutile and anatase have a tetragonal structure. Sci.g.110 airborne microbes and odorous chemicals. which facilitates the formation of oxidative species. containing 6 and 12 atoms per unit cell with an axial ratio of c/a (c ¼ perpendicular axis.129 Recently. which could be adsorbed on the Ag-doped TiO2 surface due to an increased number of electron traps. nitrate and heavy metals. the surfaces of titanium dioxide NPs were modified with a bidentate chelating agent. 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. which benefits the electron transfer from the valence band to the conduction band. a ¼ horizontal axis) 0. respectively. rhodamine B (RB). TiO2 nanoparticles are activated by UV irradiation (radiation at wavelength 320–400 nm) and its photocatalytic properties have been utilized in various environmental applications to remove contaminants from both water and air. thus.117 Recent research has 8082 | Energy Environ. the removal of dyes via photocatalytic oxidation.119 Nano-sized TiO2 was also reported to kill viruses.116.126 An attractive characteristic of TiO2 photocatalytic disinfection is its capability of activation by visible light. respectively.View Article Online iron. Bimetallic nanoparticles of Pd/Fe were found to provide a higher degradation of CCl4 than one dimensional ZVI Fe nanoparticles100 due to the catalytic effects of metals (Pd or Ni) through a direct hydrogen reduction101 and the prevention of oxide formation at the iron surface. 8075–8109 shown that the desired band gap narrowing of TiO2 can be better achieved by using nonmetal elements.. especially silver. In a study by Gelover et al. Metal doping has been shown to improve the visible light absorbance of TiO2127 and increase its photocatalytic activity under UV irradiation. especially under natural solar light irradiation. to remove aqueous cadmium from simulated waste waters.131 Reddy et al.1039/C2EE21818F .

photocatalysis activity under sunlight can be improved. it has also been documented that the presence of transition metals may increase the probability of electron–hole recombination. Recently. all synthesized S single or co-doped catalysts showed larger catalytic activities compared to the commercial TiO2. Titania doping with nonmetal elements (N. In addition. aeruginosa cells was observed. Coli Lead Methylene blue NOx and toluene in air S.7 mg gÀ1. Cu). Co-doping with S and Fe favours the photocatalytic activity of the nanomaterial when it is compared to that of single Fe-doped TiO2. E. reported that bacteria placed on TiO2 coated surfaces were killed in the following order: E.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.138 Inorganic nanoscale ZnO was mostly applied to eliminate H2S as an adsorbant.4% of S in TiO2 nanomaterials. such as transition metal ions (Fe. have been used to enhance the photocatalytic activity of TiO2. aureus > Enterobacter faecium > C. thus facilitating the electron–hole separation and subsequent transfer of the trapped electron to the adsorbed O2.149 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 photocatalytic remediation. silver-doped TiO2 particles were more effective than pure silver nanoparticles of a similar size. ZnO nanoparticles exhibit strong antibacterial activities on a broad spectrum of bacteria.6-Trichlorophenol Type of nanomaterial Ag-doped TiO2 One dimension TiO2/Fe-doped TiO2 Crystalline TiO2 thin film/the composite material of TiO2 and Al2O3 One dimension TiO2 Ag-doped TiO2 nanofibres Ag-doped TiO2 nanofibres Ag-doped TiO2 nanofibres Cu/Fe/Ag-doped TiO2 TiO2 NPs doped with Bi3+ Ag-doped TiO2 Ref. biological toxins (microcystin-LR). P25 and one prepared by a homogeneous precipitation process at low temperature. in order to improve the photocatalytic efficiency of TiO2. which acts as an electron acceptor on the surface of the TiO2. P25. Kuhn et al. while in samples synthesized by sol–gel process either Rb+ or Y3+ dopants greatly improved the photocatalytic activity. However. Due to the surface hydroxy groups. (iv) the dopant prevents the recombination of electron–hole pairs and increases the lifetime of the charge carriers.1039/C2EE21818F Table 1 Photocatalytic processes of environmental remediation by one dimensional or ion doped-TiO2 nanoparticles Category Disinfection Metal removal Dye removal/destruction of biological toxins and inactivation of bacteria Metal removal Dye removal Air treatment Disinfection Nutrient removal Nutrient removal Organic removal Target material Water-borne pathogenic virus in drinking water Arsenic Methylene blue. resulting in a reduction of the semiconductor’s photocatalytic efficiency. such as cerium oxide. the zinc oxide nanopowder showed a higher removal rate of Cu2+ ions from the solution. Metal-doped TiO2 was found to induce the desired red-shift of the adsorption spectrum. Compared with two TiO2 powders. which is probably facilitated Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. have been applied for the removal of Cr(VI) through the adsorption of the metal onto the surface of the NPs.148 ZnO nanosheets prepared via a hydrothermal approach were used to adsorb Pb2+ and then hydrothermally treated in an aqueous solution containing a sulfur source. In this approach. which may result in electron population of the conduction band of the material.2%) in the nanomaterial but it provided a detrimental effect at 0. Co. a 70% reduction of P. emphasis has been given to co-doped TiO2 systems. involving cations and anions.152 Various dopants. nanostructured ZnO could efficiently remove heavy metals. Sci.137 While pure TiO2 had no antibacterial effect in free solution or in agar. It has been suggested that charge separation between electrons and holes is improved by the co-doping of TiO2 with Fe and S. creatinine.153 The photocatalytic activity of the prepared TiO2 catalysts doped with Li+. Under both UV and sunlight irradiation. Two possible parallel mechanisms. albicans. prepared nanometer size zinc oxide (ZnO) powders by a ‘solution–combustion method (SCM)’.154 Increasing amounts of silver in Ag-doped TiO2 significantly increases the rate of degradation of a model dye.View Article Online sol–gel techniques. (iii) the doping ions (Rb+ or Y3+) can act as electron traps. Therefore. 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. Coli in water Nitrate Nitrate 2. 139 140 141 142 143 143 143 144 145 146 This journal is ª The Royal Society of Chemistry 2012 Energy Environ. coli > P. 5. the single S-doped and co-doped S/Fe–TiO2 catalysts showed high selectivity (>90%) toward the partial oxidation of toluene (production of benzaldehyde).136 After 40 min. Rb3 and Y3+ under sunlight irradiation was evaluated using 2-naphthol as a pollutant model. rhodamine. aureus and E. the resultant ZnO nanosheets exhibited a good capacity of Pb2+.147 Lee et | doi:10. The increase in photoactivity may be due to: (i) a decrease of the energy gap. The results showed a great enhancement in the photocatalytic efficiency with the incorporation of Y3+ in samples synthesized by solid grinding. S) has also been considered as an effective approach to extend the spectral response of TiO2 towards visible energy wavelengths. which was found to be 6. which favors a higher photoexcitation efficiency under solar radiation and provides a larger population of excited species (hole–electron pairs). single and co-doped TiO2 catalysts with Fe and S have been reported to exhibit enhanced photocatalytic activity under visible light.4. 2012. Recently.. 8075–8109 | 8083 . Toluene photo-excitation appears to be favoured at a low S concentration (0.rsc. (ii) the small particle size favors the increase in the surfaceto-volume ratio and the scavenging action of the photogenerated electrons by the Y3+ or Rb+ ions results in a prevention of the recombination of electron–hole pairs and increases the lifetime of the charge carriers. C. aeruginosa > S.

therefore.170 Monovalent ions tend to have lower rejections unless they are retained to maintain charge neutrality with multivalent counter ions.157 The availability of clean water has emerged as one of the most serious problems facing the global economy in the 21st century. Van der Bruggen et al. or (2) chemical in nature. A 90% retention was found for multivalent ions. lactose and micro-pollutants. while strontium and barium rarely occur in substantial concentrations. such as hydrogen bonds and complexation or (3) both. membranes must be water permeable and less permeable to solutes or other particles. The adsorption of pollutants onto the membrane can be (1) physical in nature.163 Pore size (nm) Water permeability (L m-2 h-1 bar-1) Operating pressure (bar) Molecular weight cut off (Da) $2 nm 5–50 2–10 >100 This journal is ª The Royal Society of Chemistry 2012 . alternatively.163. calcium and magnesium ions.7–90. or reversible for weak secondary chemical bonds. which holds for the two types Table 2 The typical properties of pressure-driven NF membranes162. the diffusion mechanism becomes less influential than the convection mass transport mechanism and. For NF. natural organic matter. each designed to remove one or more different substances in the source water. such as methylene blue. leading to a large selectivity.165 A better rejection of magnesium ions was also found to be 86.254 nm) and there is a significant fraction of wider pores (1. Membrane technologies are more efficient nowadays due to their reliable contaminant removal without the production of any harmful by-products. such as sulfate. NF is capable of removing hardness. 8075–8109 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs.g.169 Mass transport through a nanofiltration membrane can be achieved by two mechanisms: diffusion and convection. such as sodium and chloride. In addition. In addition.. such as microfiltration (MF). However. glucose. Water treatment systems typically involve a series of coupled processes.. a better retention of Ca2+ ions is found.156.e. When the transmembrane pressure is high.rsc.158–160 Both cellulose acetate and polyamide can be used to form NF membranes. reuse and desalination systems throughout the world.. hardness should be re-added to the drinking water in order to obtain the desired hardness of 1.1039/C2EE21818F results of the manufacturer (in Germany) for a thin film composite of a polyamide membrane with molecular weight cutoff of 300 Da (NF 200B). The role of silver clearly controls the recombination rate and subsequently allows a greater proportion of hydroxyl radicals to form. such as salts.View Article Online by the surface plasmon absorption of the silver-doped materials.9% higher than the expected 8084 | Energy Environ. especially in water and waste water treatment processes. The retention of Ca2+ was found to be very high for NF 70 and a membrane made of polypiperazineamide (UTC20) and remained constant when the pressure was above 10 bar. NF membranes selectively reject substances as well as enable the retention of nutrients in water. the ion size plays a role for membranes with small pores. particles and a number of other organic and inorganic substances via one single treatment.168 In NF membranes. such as polymerization. some metal oxides) can also be used for NF membrane synthesis. Water hardness is caused by calcium and magnesium ions. which is a completely reversible process. the NF membranes contain larger fractions of the smallest pores (0.155 (C) Nanofiltration (C-1) Nanofiltration by membranes. The higher retention of multivalent ions could be obtained over a wide range of concentrations using a membrane with small pore diameters. NF membranes can reject bivalent ions in significantly high amounts. the separation efficiency obtained with NF was larger. observed the order of chloride retention as s c follows: RMgCl2 > RCaCl2 > RNaCl. When groundwater was treated with a NF 70 membrane for the production of drinking water. 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. for photocatalytic studies.168 The pore size distribution of NF membranes have a common feature: the largest fraction of medium-size pores is approximately 0.85 nm. the advantages of NF are comparable to the RO process. which is irreversible for strong chemical bonds.22–0. particles and solutes. RO is very efficient for retaining dissolved inorganic and small organic molecules. 5. The separation performance of NF membranes for cations is 60%. 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. and 60–70% was found for monovalent ions. as a promising membrane | doi:10. the differences in the retention of the examined chlorides are mostly controlled by the size of the cations.g.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. Advances in nanochemistry can provide enhancement of UF and MF processes for recovering dissolved ions from aqueous solutions.. Sci. NF can effectively remove hardness (i. The basic principle of membrane filtration is to apply semi-permeable membranes to remove fluids. Pressure-driven membrane processes. it was suggested that the permeate should be mixed with streams that have been treated by traditional methods or. which is primarily responsible for the sieving effect of the membranes.55 nm) in the skin of the NF membranes. Ca(II)) and natural organic matter. in contaminated water. with the particular treatment process being based on the molecular size and properties of the target contaminants. For the separation of materials from water. ultrafiltration (UF).166 For anions. UF and MF membranes require lower pressures (5–60 psi) but those membranes cannot retain dissolved ions and organic solutes. gases. Nanofiltration (NF). have been applied for water treatment. indeed some commentators have questioned the suitability of dyes.167 Nitrate rejection was 76% for NF70.. Therefore. 2012. Conversely.3% using the same type of membrane due to the stronger hydration of the Mg2+ ion. a limitation of both RO and NF processes is the requirement of high pressures (100–1000 psi) to operate the water treatment.164 The calcium ion rejection was found to be 74. polyvinyl alcohol (PVA) and sulfonated polysulfone) and inorganic materials (e. It is probable that the two mechanisms are happening in parallel.5 mmol LÀ1. However. other polymers (e. which is better than expected anticipated by the manufacturer of NF 70.9–78.161 The typical properties of NF membranes are shown in Table 2.169 Kouti et al. is a method for removing low molecular weight solutes. nanofiltration (NF) and reverse osmosis (RO).

Scaling or the formation of precipitates takes place when the concentration of the ionic salt exceeds its solubility in water. Sci. while reducing the turbidity and DOC.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. 2012.5% via the NF process and removes turbidity by 85. Inorganic foulants in the NF process are found to be carbonate. such as nano-alumina. 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 filtration conditions and the characteristics of the treated water. while a neutral pH favors a high rejection of NOM (90%).180 Organic micro-pollutants present in natural waters used for drinking water production lead to negative effects on human health. 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. the type of membrane.171 The total hardness of the surface water could be reduced by 85. non-electrolytes or solutions of weak acids tend to exhibit strong interactions. found an 80% removal of atrazine and a 40% removal of metazachlor.2%. gel formation and an interaction with multivalent ions.177 The total organic carbon (TOC) content of surface water can be reduced by 93. a large variety of dyes and chemical additives from textile plant are environmental pollutants. which is significantly lower than the expected result.1039/C2EE21818F . monovalent chloride ion.5%. iron oxide. 5. fungicides. insecticides.157 studied the removal of pesticides. 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. the addition of hydrochloric or sulphuric acid can prevent the formation of calcium carbonate during the NF process. even in very low concentrations. cartridge filtration and activated carbon adsorption can be used to prevent membrane fouling by NOM. i. This shows that the charge exclusion influences the retention of ions by the negatively charged NF membranes.179 However. silver. Humic and fulvic acid seem to contribute to the natural color of water. coagulation has been found to provide an efficient hygienic barrier in combination with membranes.e. metal hydroxides. 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. etc.rsc. The fouling mechanisms are adsorption. Montovay et al. Orecki et al. together with pyridine and a chlorinated pyridine compounds.172 The NF process is commonly used for the removal of natural organic matter (NOM) from water. Thus. NOM is a polydisperse mixture of individual particles in natural water originating from degraded and partly re-synthesized plant residues.168 An alternative method to prevent membrane fouling is the addition of antiscalants.169 Such an order was not found for sulfates and this may be due to the ion pairing effect.171 However. in membrane structures has gained a lot of interest. The interaction 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 ª The Royal Society of Chemistry 2012 sorption of organics onto the membrane surface.. Rejection has also been found to be concentration dependent and ionic species may promote conformational changes in the NOM fractions. In addition. 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. which can improve rejection via the NF process.176 When adsorption takes place inside the membrane or on the surface. such as acaricides. the removal of NOM has been significantly affected by the type of coagulant. the limitation in NF is membrane fouling. 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.View Article Online of thin film polyamide NF membranes with slightly lower retention values for the NF-type | doi:10. the effect of coupling the different components. silica.. 8075–8109 | 8085 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. precipitation. observed that the NF process of surface water provided a retention coefficient of 90–99% for sulfate and 82% for carbonate. sulphides and silica. The rejection of both divalent dibasic arsenate.183 Kiso et al. The high rejection of antiscalants by membranes takes place during the NF process due to their high molecular weight and negative charge. pretreatment 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. This is caused by the presence of a fraction of large pores in the surfaces of the membrane.181 The removal efficiencies largely depend on the membranes used and on the pesticides that have to be removed. acidic pH favours a lower rejection of NOM (60–75%).178 Polysulfone membranes have been used in some studies and have caused adsorptive fouling.166 However.172 In addition. Many pesticides and organohalide compounds have been found to be carcinogenic. Flushing of the membrane with permeates from the RO process could prevent membrane plugging and allow a recovery of the initial flux. reliability.1-diphosphonic acid.173 The results observed by researchers include the findings that hydrophobic fractions of NOM appear to be retained best.172 The NF process has many advantages. diethylenetriamine-penta-methyl phosphoric acid and 1-hydroxyethylidene-1.175 Braghetta et al. including ease of operation. such as atrazine and simazine. sulphate and phosphate salts of divalent ions.e.174. herbicides and rodenticides. HAsO42À and sulfate (SO42À) ions was found to be notably higher than the rejection of chloride ions by the charged NF membranes due to the stronger electrostatic repulsion of the former ions than the repulsion of the lesser charged. which is more prevalent in MgSO4 than in Na2SO4 solutions. i. The rejections obtained Energy Environ. surface active materials which can interfere with precipitation during the NF process via threshold inhibition. crystal modification or dispersion. the coagulation conditions. Moreover.172 However. while it rejected 40–55% of the covalent salts. Solutions containing electrolytes. Common surface active agents are sodium hexametaphosphate. The removal of micro-pollutants is traditionally done by activated carbon adsorption. the pore size can become reduced as molecules that have a similar size to the pores block them through permeation. The use of nanoparticles. The interactions that occur in a multi-component solution may improve the rejections of NOM by the membrane due to friction coupling. no requirement of additives and a modular construction that is easy to upscale. which becomes visible if the concentration of the dissolved organic carbon (DOC) is higher than 5 ppm. Four different (unspecified) membranes produced by Nitto–Denko were used.

The results show that DDT was easy to adsorbed on the polyvinylidene fluoride membrane. (3) the degree of membrane desalination. simazine. the mass adsorbed sequence found in both membranes for both mineral and reservoir water was: linuron > diuron > chlortoluron > isoproturon.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. hydrophilic membrane with a smooth surface and a MWCO of 200–300 Da.165.1-bis(4-chlorophenyl)-2. The highest desalting membrane was found to effectively reject almost all pesticides.193 evaluated the removal efficiency of 1.98 and 2. especially for the less hydrophobic compounds (chlortoluron and isoproturon). the reliability of the membrane desalination degree is not an accurate indicator to assess the removal of hydrophobic organic micro-pollutants. which indicates that the main factor responsible for the retention is the MW for the adsorption. the retention efficiency for the cellulose acetate membrane (with a hydrophobic character) followed the sequence: linuron > diuron > chlortoluron > isoproturon. The electrostatic repulsion between negatively charged pesticides and the negative charge of the TFC membrane surface could enhance the overall rejection performance. Membranes with a MWCO varying between 200 and 400 Da are considered to be suitable for the adequate removal of pesticides from water.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.157 Van der Bruggen et al. Sci. However. (2) the membrane porosity. which led to higher concentrations in the permeate. however.183 Van der Bruggen et al. which is negatively charged. and (3) the polarity. Narrower pore sizes counteracted the effect of the presence of NOM.190 Ducom and Cabassud studied the removal of trichloroethylene. 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. 2012. 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 | doi:10. regardless of the membrane salt rejection performance. However. the conductivity rejection was around 65% and the permeate conductivity was between 1.192 Pang et al. 5. and UTC-20.2-trichloroethane (DDT) in contaminated water using a NF unit of a polyvinylidene fluoride (PVDF) membrane. while the cumulated quantity adsorbed reached 506 mg mÀ2. rejection was again found to be a function of the properties of the pesticide.185. The removal efficiency of the former two compounds was satisfactory. which is negatively charged because of its active nanopolymer layer.2.186 This behavior may be due to the higher polarity of CA membranes. This effect was attributed to the selective adsorption of chloroform into the membrane structure. It was found that the retention order for the 8086 | Energy Environ. especially for the most polar compounds because higher retention coefficients as well as higher retentions are obtained for DOC and aromatic compounds. In general.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 hydrophobicity and charge. and (4) the charge of the membrane.156.188. such as (1) the molecular weight and size of the pesticide. The NOM was assumed to enhance the adsorption of pesticides onto the membranes surface and an increased size exclusion and electrostatic repulsion was also observed during the NF process. 8075–8109 thin film membranes (with a hydrophilic character) was isoproturon > linuron > chlortoluron > diuron. but the water flux was lower.189 investigated the application ıtez of NF for the removal of phenyl-urease in natural waters. The color rejection of NF after treatment was almost complete and the permeate color was always lower than 10% Pt–Co. which produced a negatively charged. a Toray membrane) relatively low rejections were found for the removal of diuron and isoproturon. tetrachloroethylene and chloroform by NF.View Article Online with three of these membranes were too low and the rejections with the fourth membrane were very high (over 95%). including pesticides. This may be due to the high polarity of these compounds.182. 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.191 However. the effect of humic acids and calcium ions on the retention coefficients is not significant. which showed that the molecule polarity is the main parameter that influences the retention.1039/C2EE21818F . which is expressed in Dalton. They also observed that the additional presence of humic acids and calcium ions increases membrane fouling. and (2) a cellulose acetate polymer. compared to cellulose acetate membranes (CA).167 This was mainly due to ion adsorption inside the membrane pores. From the results obtained. after the NF process. In addition. 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. Two types of membrane were used in their investigation: (1) a thin film composite (a polypyperazinamide skin layer on a polyester support).. Furthermore. but for two other membranes (NF45. The rejection of pesticides was higher in river water and tap water than in distilled water. which is responsible for the poor rejection of the highly polar pesticides. but the chloroform rejection was significantly lower.2 mg LÀ1.67 mS cmÀ1.189 Ben et al. good removal efficiencies of chloroform were obtained by Waniek et al. On the contrary. 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.169 Important factors that must be considered for the selection of an appropriate membrane are (1) the molecular weight cut-off (MWCO). Moreover.167 also proved that there was no significant effect of concentration on the rejection of pesticides in water. which causes interactions with the charged membrane.184 The rejection of pesticides is reasonably high and correlates positively with the order of their molecular sizes.4 mg LÀ1 to 52. a Dow/Filmtec membrane. diuron and isoproturon. (2) the hydrophobicity. this membrane seemed to be an RO membrane and provided a high NaCl rejection. quite high COD rejections (80–100%) were found with NF. had a lower amount of organic pollutant in the waste effluent compared to the NF operation without the pretreatment.189 Manttari et al. A number of studies confirm that composite polyamide membranes indicate far better rejection performances for several mixtures of micro-pollutants. The DDT concentration decreased significantly from 77.184 obtained good results for the removal of atrazine. Rejections were all over 90% with NF70 (Dow/Filmtec). the rejection of DDT was lower with a This journal is ª The Royal Society of Chemistry 2012 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. Similar to the color.rsc. it can be concluded that the thin film membrane was the most adequate for the removal of phenylureas from natural waters.

It was difficult to simultaneously achieve a high permeate flux and high DDT rejection.196 In many of the harsh operational environments.0 mg of TOC per L was found in the permeate.View Article Online higher flux.1039/C2EE21818F . the increased conversion.9% by weight) significantly decreased the number of Escherichia coli that were able to grow on the membrane surface by 99% after filtration with a dilute bacteria suspension. The separation mechanism can be readily expanded to a variety of different hydrophobic and oleophilic liquids. coli suspension to the surface of the immersed membrane by 94%. only inorganic membranes can offer advantages. Then. which have pore sizes below 1 nm. Besides. The amount of TOC was much less than the average amount of TOC (5 mg LÀ1) from MF membrane bioreactors. such as in manufacturing or industry or recharging into groundwater or blending into reservoirs.202 In addition.193 The filtration membrane consisted of a hollow cylinder with radially aligned carbon nanotube (CNT) walls.198. The interaction of ionic silver (which can be released from the silver nanoparticles) with thiol groups and the formation of S–Ag or disulfide bonds can damage bacterial proteins. which results in a reduced flow rate. better selectivity. 5. which reduces the flux and increases the required frequency of cleaning. the selective transfer of chemical species and their relatively low cost. good mechanical strength and a high tolerance of extreme pH conditions and oxidation. Membrane filtration may facilitate an improvement in the disinfection process because it is an extra barrier for viruses and bacteria. most notably the thiol groups (S–H) present in cysteine and other compounds. inorganic membranes are not used extensively because This journal is ª The Royal Society of Chemistry 2012 of the high costs and relatively poor control in pore size distribution.rsc. 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. 2012. The removal of the protozoa giardia and cryptosporidium from surface water sources is a main priority for many governments and drinking water companies.206 used a polyamide NF membrane bioreactor for the reclamation of water from domestic sewage and 0. With the blocking effect of the pores by the ions and the presence of organic matter (humic acid) and inorganic matter (NaCl. but the disadvantages of chlorination were found to be (1) the formation of disinfection by-products (DBPs) and (2) the resistance of cryptosporidium to chlorine and chloramines. The impregnation of nAg (0. biofiltration via MF or UF. Silver nanoparticles (1–70 nm) have been blended into polysulfone membranes by dispersing nanoparticles in a casting solution before dissolving them in the polysulfone resin (PSf).5–2. the elimination of DDT can be enhanced. energy cost was significantly reduced by 2–4 times Energy Environ. such as their easy formation. an increased number of investigations on the use of NF in reducing dissolved organic matters with molecular weights greater than 200 Da have been attempted. inorganic membranes are currently in competition with organic membranes for commercial applications because they have a better resistance to chemical attack. primary sedimentation and secondary treatment by activated sludge were first applied for the clarification of used domestic water. Recently. To produce NEWater.5–10 mm) and protozoan cysts and oocysts (3–15 mm) are larger and their removal can be guaranteed with at least 4 log units by using UF membranes. the effective membrane layer is very thick in comparison to the mean pore size. Pretreatment prior to RO is needed to prevent biofouling. Both super hydrophobicity and superoleophilicity could be obtained due to the dual-scale structure and needle-like nanotube geometry of the mesh with micro-scale pores combined with the low surface energy. Those tubes act as the pores in the membrane. Traditional chlorination is still often applied as a disinfection method.. The successful phase separation of the high viscosity lubricating oil and water emulsions was also carried out. the NF membrane provided a better retention of organic matter than the MF membrane. Thus. Polymeric membranes have many advantages. which may have a high content of organic matter in terms of COD (from 1000 mg LÀ1 to 4000 mg LÀ1) and BOD (up to 1500 mg LÀ1). interrupt the electron transport chain and dimerize deoxyribonucleic acid (DNA).181 Bacteria (0. The smaller viruses may be rejected by NF membranes. The addition of silver nanoparticles did not alter the membrane structure. Srivastava et al. Inorganic membranes composed of metal oxides have higher durability in many water purification applications. Furthermore. The main problem in the reclamation of domestic sewage is biofouling of the RO membranes. application of NF membranes is becoming a potential pretreatment process that reduces the problem of biofouling in the RO process. which led to a reduced TOC in the permeate or feed of the RO process. Filtration processes by a membrane with carbon nanotube walls have been reported. the silver nanoparticles reduced the attachment of an E.199 Singapore began reclamation of domestic sewage in 1998 through the NEWater study.200 An average of 89% rejection for high organic acids from anaerobic effluent was observed using polyamide NF membranes.203 Furthermore. In addition. The salt rejections and organics removal by NF membranes could provide the required water quality for groundwater | doi:10.195 However.194 The nanotube filter could separate diesel and water layers and even surfactant-stabilized emulsions.197 The antibacterial mechanism of silver is related to its interaction with sulfur and phosphorous. the incorporation of inorganic nanoparticles into the polymeric membranes has been considered as a way to make polymeric membranes more attractive for commercialization. reverse osmosis (RO) and UV disinfection processes were applied for applications. 8075–8109 | 8087 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. Choi et al.201 Therefore. Therefore. Membranes that have CNTs as pores could be used in desalination and demineralization. CaCl2 and CaSO4). 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. The removal of viruses and bacteria is extremely important in drinking water purification. however. Indirect portable reuse is practised through the introduction of a suitable amount of NEWater into reservoirs that can be further purified by water treatment techniques before supplying to the public. The permeate flux when using NF membranes at 415– 485 kPa was three times greater than that of RO membrane. DDT can be easily adsorbed by humic acid and can be removed altogether.194 efficiently conducted the removal of Escherichia coli from drinking water using the CNT-aligned membrane. such as brewery waste water. higher rejections of emerging contaminants were observed using polypiperazineamide thin film composite membranes as shown in Table 3. However. Sci.

After 71 days of operations. that are spun from the molten state into the finer fibres differ in terms of the equipment downstream of the spinneret. It was observed that NF can remove almost all turbidity and microorganisms and reduces TDS by 37. both organic and inorganic. although the permeate productivity was found to be lower. they are usually known as nanomembranes. which may have led to an increase in the membrane pore size and a decrease in the surface charge and hydrophobicity of the membrane.163 Rejection rate (%) 96 48 40 40 40 70 80 25 100 90 90 78 90 Constituents TOC Conductivity Sodium Potassium Calcium Magnesium Chloride Pharmaceutically active compounds Salicylic acid Naproxen Gemfibrozil Ketoprofen Carbamazepine 8088 | Energy Environ. particularly for air filtration.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. respectively. the adsorption and/or the pore blocking caused by high COD and salt concentrations. enzymes and aromatic compounds from waste water in the food processing industry. and (5) the removal of organics and multivalent ions from waste water at landfill leachate plants. However. Similarly. 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.204 More than an 80% rejection of divalent ions and an 86. 4 shows thiol-functionalized zonal mercaptopropyl silica nanofibres. which could limit the benefit of an antimicrobial functionality. (C-2) Nanofiltration by nanofibre media. 2012. In addition. Rejection rates for NF membranes for the treatment of tertiary treated effluent201 hardness were achieved using NF prior to the RO process. (4) the reclamation and reuse of water from waste water pulp and the paper industry. The increased presence of DOC in the permeate was due to the hydrolysis of cellulose acetate.1 mm.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 uniform porous channels between the nanofibres facilitated Hg2+ transportation in the adsorption process. NF is widely used for industrial waste water treatments.206.210. (3) the removal of organics and the recovery of proteins. To prevent this pore enlargement problem.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. most of the microorganisms enter the filter with airborne particulate matter and they grow in size due to accumulation and build up on the filter surface. Therefore. after which time only 10% of TOC was removed by the membrane. 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. the salt rejection rates of monovalent and divalent ions were reduced from 40–60% and 70–90%.1039/C2EE21818F the textile industry. the selection of a suitable type of membrane is important. NF membranes are suitable for removing water soluble dyes with molecular weights ranging from 200 to 1000 Da and divalent salts for softening effects. Metallic silver and silver oxides are safe and effective antimicrobial agents at low levels. which enables a wide range of fibre diameters to be produced. Fig. 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.. Sci.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. the retention of TDS. pore enlargement (to 56–95%) 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 10–15 g of Na2SO4 LÀ1 and this was found to due to SO42À pushing through the membrane via transmembrane pressure. Nanofibres are essentially defined by their effective diameters (in the range of 1 to 200 nm) and they can be used for fine filtration.204 The deterioration of the membrane may have been due to | doi:10. the turbidity and the color were found to be greater than 90%. 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. Because these media are capable of removing contaminants to below 0. Furthermore.211 Ionic plasma This journal is ª The Royal Society of Chemistry 2012 Table 3 The typical properties of pressure-driven NF membranes162. 8075–8109 . The synthetic materials. such as (1) color removal and the recovery of salts from waste water in Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. 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. 5. In addition.5% total rejection have been found (Table 3).rsc. which in turn saves the cost of power consumption. to less than 10% after 80 days of operation.172.205 Fersi et al. Thus.204 Furthermore.3%.View Article Online using NF at 415–485 kPa compared to RO membranes operating at 1000–2100 kPa to produce the same permeate flux.200 The concentrations of DOC in the permeate of the cellulose acetate NF membrane bioreactor deteriorated after 130 days operation.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. which showed the deterioration of the membrane. PAN nanofibres were prepared by coating with 3-mercaptopropyl trimethoxysilane via a sol–gel process. Those nanofibres were obtained by the dissolution of electrospun polyacrylonitrile (PAN) nanofibres with dimethylformamide. (2) the recovery of heavy metals and eluents from waste water in metal processing plants. large voids were found on the surface of the cellulose acetate membrane via an AFM image.

the surface modification of the nanofibrous screen filter with a suitable hydrophilic or hydrophobic oligomer is often recommended to reduce the fouling effect.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. a poly(ethylene terephthalate) (PET) non-woven sub-layer was also used. These drawbacks are due to the geometric structure of the pores.221 A coat of TiO2/polyvinyl alcohol (PVA) on the polyester filter effectively modifies the matrix.215 A major trend with regards to filter media is the development of the combination filter. This approach can be scaled-up for the fabrication of ceramic membranes in practical applications. narrows the pore size to 10 mm and reduces the contact angles by 40 because of the hydroxyl groups from PVA and | doi:10. 4 The assembly of a zonal mercaptopropyl silica nanofibre. to prolong the life of these membranes. To increase the mechanical strength of the PES fibre. such as the removal of micro-particles from waste water and in ultrafiltration. e.214 Polymeric nanofibre-based ion exchangers have higher swelling behaviors compared to other media because of their high surface area. 5. Such pre-filters can be used in various applications. The composite membrane (PES–PET) is illustrated in Fig. These improvements are due to the radical changes in the texture of the top-layer. porosity and capillary motion. A novel alumina nanofibre filter. especially when the particles are larger than the largest pore size of the nanofibrous membrane. ventilation and air conditioning (HVAC) air filters. low flux rates and high fouling. A high surface-to-volume ratio of the nanofibrous media increased the degree of fouling. the fabrication of these membranes is relatively simple and economical with low rejection rates. The separation efficiency of the ceramic membranes can be significantly improved by constructing a top separation layer with TiO2 nanofibres. consequently. The turbidity of the permeated suspension was found to decrease significantly with time. 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%).212 It was observed that an electrospun membrane conveniently rejects the microparticles and acts as a screen filter without fouling the membrane.2 wt% titanate nanofibres. synthesized polyacrylonitrile nanofibrous layers supported on nonwoven microfibrous substrates (a melt-blown polyethylene terephthalate mat) and applied a water resistant. conventional porous polymeric membranes have their intrinsic limitations. These combination filters employ a chemically active agent embedded in the filter medium material. Titanate nanofibres have been synthesized via a hydrothermal reaction between a concentrated NaOH solution and TiOSO4.1039/C2EE21818F This journal is ª The Royal Society of Chemistry 2012 .216 For the filtration of liquids. 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. Yoon et al. which was used to apply thin layers on the porous substrate using a spin-coater. Therefore. capable of performing two separation tasks at once. The titanate fibres were dispersed in ethanol to form a suspension containing 0.220. 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. polymer nanofibre ion exchangers are found to have extremely rapid kinetics and higher ion-exchange capacities. The extraction fraction of the nanofibre filter was found to be three orders lower than the HEPA filters. but water permeable. 8075–8109 | 8089 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. Sci.218 It appears that electrospun nanofibrous membranes can overcome some of these limitations and. 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. They are able to retain more than 95% of 60 nm particles at a very high flux rate of about 900 L mÀ2 hÀ1. such as solid–gas separation and the adsorption of a gaseous impurity. The fibrous materials are applied as a support for the ion-exchange functionality due to their ease of preparation. The suspension was sonicated for 10 min to achieve a homogeneous dispersion. Moreover.208 addition.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.View Article Online processing (IPD) is a suitable method for the coating of surface engineered nanosized silver particles on polymeric surfaces for use in heating.215 In Fig.g..rsc. which results in high flux pre-filters with even higher loading capacities. Granular resinous materials have larger pore volumes and low ion-exchange capacities than gel type materials and additionally have a better mechanical strength. coating of chitosan over the nanofibrous layer. or with nanofiltration membranes. 2012. the corresponding pore size distribution217 and the formation of undesirable macro-voids across the whole membrane layer. The PES/PET electrospun nanofibrous membranes (ENMs) indicated that the membranes possess a high initial flux.219 Polysulfone (PSU) nanofibrous membranes possess much higher porosity and have a high surface area. contact efficiency and the physical requirement for strength and dimensional stability. compared to the conventional ceramic membranes. a polyethersulfone (PES) electrospun nanofibre mat has been applied as a membrane for liquid filtration. 5. demonstrating that viruses were effectively retained in the nanofibre filter due to an electrostatic attraction between the electropositive fibre surface and the electronegative aerosol particles. A high flux and low degree of fouling resulted with the use of this nanofibre media. The improved hydrophilicity and anti-fouling properties of the composite membranes enables a highly stabilized (10 m3 mÀ2 hÀ1 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/ Energy Environ.

Ni(II)) are adsorbed on the oxide shell as corrosion proceeds and precipitates on the iron core of the nanoparticle.229 In addition.5 m2 gÀ1) than commonly used microparticles (average area: 0. (2) biotechnology.245 Nanoparticles of nZVI have been prepared by adding freshly made ferric chloride to a reaction vessel containing solid NaBH4.239 Surfactant-coated magnetite nanoparticles have been applied in the extraction of the organic contaminant.249 This journal is ª The Royal Society of Chemistry 2012 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. In general.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. and (6) magnetically assisted processes.247 Since the reactions with organohalides are considered as ‘‘inner-sphere’’ surface-mediated processes.220 ammonium to allow for water reuse in a polyester fibre production plant. derived from agricultural waste.246 Fig. (3) catalytic processes. which allow a recovery rate of greater than 99. crystal white and other organic dyes from waste waters.228. Initially the sites are amorphous Fe(II)/Fe(III) magnetite. 2-hydroxyphenol.226. industrial by-products. The ion exchange resin beads contain a magnetized component within their structure. Iron can reduce water and form hydrogen gas under anaerobic conditions as follows:248.225 Various low cost adsorbents. Resins with a polyacrylic skeleton with macroporous properties are more suitable for the removal of NOM than gel resins.221–224 Sorption is the transfer of ions from the solution phase to the solid phase. 6 shows the reduction of organic pollutants by chemisoprtion on nZVI nanoparticles. such as effective debromination using ozonation. These bacteria have the ability to orient themselves in the direction of the magnetic field. The adsorption technique is the most frequently studied method to purify water. In addition. in the form of polymer-coated vermiculite iron oxide composites. 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.242–244 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. The nature of water was varied with differing types of NOM and passed through the MIEX resin.g. have been formulated. which allows the beads to act as individual magnets. The composites float on the surface of water and can easily remove spilled oil from oil contaminated water.222 (D) Sorbents Water remediation techniques include (1) adsorption.241 In addition. 5. the MIEX resin was used for the removal of some specific inorganic ions. 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. Nanoparticles of nZVIs have higher reactivities due to their larger surface area (average area: | doi:10. the application of iron nanoparticles is becoming a real potential. Sci. Basically. and (iii) transport within the sorbent particle. The magnetic component results in the beads forming agglomerates that can settle rapidly or fluidize at high hydraulic loading rates. Sorption actually describes a group of processes. (4) membrane processes. zero valent iron (nZVI) nanoparticles with a diameter of 1–120 nm are able to remove As(III) and As(V) by rapid adsorption followed by precipitation and result in surface corrosion byproducts. Furthermore. The magnetic part of the resin 8090 | Energy Environ.231. Magnetotactic bacteria have been applied in the removal of organic pollutants from water by enzymatic reactions.9 m2 gÀ1) and they also have reaction rates that are 100 times higher than those of microparticles. the initial reactive sites gradually transform into lepidocrocite and the more crystalline magnetite. (5) ionizing radiation processes. 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.1039/C2EE21818F . Heavy metal ions (e.246 Polyvinyl alcohol-co-vinyl acetate-co-itaconic acid has been found to be an effective surfactant for the stability of nZVI nanoparticles. The very small resin bead size could provide a high surface area to allow the rapid exchange of selective ions. such as As(V) and Cr(VI). 5 The structure of PES/PET composite membranes. The MIEX process has also been applied in a pre-treatment step for catalytic processes. 8075–8109 allows the resin to agglomerate into larger and faster settling particles.233 Magnetic chitosan gel particles. As the treatment progresses.240 Floating magnetic sorbents.232 Coagulation removed 60% of the dissolved organic carbon (DOC) associated with the 1–10 k fraction but had little impact on the DOC concentration of the <1 k fraction. The MIEX process has been applied for the removal of humic acid.9% to be obtained.230 low to moderate organic concentrations over wide range of alkalinities and bromide concentrations. natural materials. which include adsorption and precipitation reactions. 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. It was observed that an increase in the hydrophobicity of the resin reduced the DOC. a magnetite bearing covalently immobilised copper phthalocyanine dye. or modified biopolymers..234–238 Magnetotactic bacteria naturally occur as magnetic sorbent sources in nature. malachite green. Treatment with MIEX removed approximately 80% of the DOC associated with the 1–10 k fraction and almost 60% of the DOC associated with the <1 k fraction. nanomaterials-based processes are becoming promising options for applications in water treatment.View Article Online Fig. 2012. magnetic charcoal and magnetic alginates have all been applied in the removal process of polycyclic dyes.rsc. (ii) adsorption on the particle surface. have been developed recently and applied in the removal of heavy metals from metal-contaminated waste water.

Recently. the degradation rate of TCE by CMC-stabilized nanoparticles was 17 times faster than that of Fe0 nanoparticles.253 In addition. 2012. 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. such as GAC (granular activated carbon)/Fe/ Pd bimetallics.and di-chlorobenzenes (TeCB.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 (2–5 g per 100 mL). In addition.265 Up to 25% of PCB could be removed within 17 h by using fresh nZVI particles. Caalginate is suitable for the entrapment of nZVI to make the nanoparticles relatively stationary in aqueous media (e.. the limitations of using Fe0 nanoparticles are: (1) the high activity leads to the storage of freshly synthesized iron particles becoming a significant problem. can significantly affect the degradation of TCE. The starch-coated Fe0 nanoparticles exhibited markedly greater reactivity during the dechlorination of TCE or PCB in water. the concentration of TCE and the presence of anions. therefore blocking further reaction. The content of Fe0. Thus. To improve the stability of Fe0 nanoparticles against aggregation. In addition. the solution pH. Researchers268. such as nitrate. shows that nZVI entrapment in a This journal is ª The Royal Society of Chemistry 2012 biopolymer matrix (alginate) may increase their overall efficacy in groundwater remediation. The application of bulk zero valent iron metal in environmental remediation has limitations.266 The results showed that the dispersibility of the nanoparticles increased and. Hu et al.251 The degradation rates of trichloroethylene (TCE) has been significantly increased to 3 Â 10À3 L mÀ2 hÀ1 from 6. such as slow reaction rates and the formation of more toxic intermediates resulting from the dechlorination process. while perchloroethylene is dechlorinated. (2) the activity of the iron particles decreases as the reaction proceeds due to the formation of Fe(OH)3. Keum and Li reported the application of Fe0 nanoparticles in the reductive debromination of polybrominated diphenyl ethers (PBDEs). applied Fe0 in the removal of alachlor and pretilachlor.1039/C2EE21818F . iron can remove chlorine by hydrogenolysis as follows: Fe0 + R–Cl + H+ / Fe2+ + R–H + ClÀ where Fe0 is oxidized to Fe2+.263 Kim et al. thus. in the preparation of nZVI nanoparticles could deliver higher adsorption capacities for heavy metals that will lead to better remediation. He and his group members developed palladized iron (Fe–Pd) nanoparticles stabilizing on starch265 or sodium carboxymethylcellulose (CMC). 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. GAC/ZVI. which forms on the surface of the Fe0 nanoparticles and may make the iron core unreactive.250 Iron nanoparticles have been widely applied in the transformation and detoxification of a wide variety of common environmental contaminants. The GAC/ZVI/Pd system showed an efficient dechlorination of 2-chlorobiphenyl (2-ClBP) at 90% after 2 days. which are difficult to destroy. the degree of dechlorination greatly increased. Sci. 5. metal oxides and low molecular weight organic molecules and polymers. TCB and DCB.256 The study by Bezbaruah et al.255 The amount of Ni metal adsorbed by iron-core nanoparticles is higher than by iron oxide nanoparticles (i. About 98% of TCE and 80% of PCB were found to be decomposed after 1 h and 100 h. Ag-modified Fe0 nanoparticles (1% Ag)267 could facilitate the dechlorination of tetra-. GAC/ZVI/Pd.g. The high degradation ability of the GAC/ZVI/Pd system is caused by the synergistic and simultaneous function of adsorption and Energy | doi:10.252 The feasibility of applying nZVI particles in water remediation showed that up to 90% TCE was degraded within 30 min.View Article Online Fig. 8075–8109 | 8091 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. due to their large surface area and surface activity. gFe2O3).. The addition of functional materials. such as chlorinated organic solvents.rsc. such as stable noble metals. non-toxic final products were formed. (3) the freshly fabricated Fe0 can easily form aggregates and this decreases the dispersion ability. Several kinds of assemblies and bimetallics have been investigated. tri.74 Fe0 + 2H2O / Fe2+ + H2 + 2OHÀ In addition.257 The reduction in the nitrate concentration using one dimensional nZVI and trapped nZVI in Ca-alginate beads were 55–73% and 50–73%.254. respectively. however.269 have done lots of work on the dechlorination of PCBs using nanoparticles with activated carbon and bimetallic nanoparticles. groundwater). 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. organochlorine pesticides and PVBs. The debromination of PBDEs by nZVI particles has high potential value for the remediation of PBDEs in the environment. respectively) within 24 h at a metal loading of 25 g LÀ1 and the dechlorination rate was found to positively correlate with the amount of silver loaded on the bimetallic particles. etc. Fe0 nanoparticles in environmental remediation has great potential. 6 A schematic diagram of the reduction of perchloroethylene on the surface of a nZVI particle. Furthermore. over a 2 h remediation period.3 Â 10À5 L mÀ2 hÀ1. respectively. Pd/Mg bimetallics.e. which was obtained when bulk Fe0 particles (>1 micrometer) were used to remove TCE. 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. reported that modified jacobsite (manganese iron oxide) nanoparticles can be applied and regenerated many times without a decrease in their adsorption performance.245 Modified nZVI nanoparticles that have been applied in the removal of metal ions from water are shown in Table 4. research focus have been on solving the above problems.

As(V). chitin and starch and their derivatives. Cd(II).273 The sorbents can also be of mineral.275 Polysaccharide-based materials can be used as sorbents in waste water treatment. non-toxic nature. Pb(II) Mo(VI) Ferrites (MeFe2O4. activated carbons.270 Ge et al.0–6. The perchlorate ion was significantly reduced by 1.274.281–283 The stability of zeolites is high and disintegration was found only at pH values below 2.4-ethylenedioxythiophene) (PEDOT)258 Magnetite nanoparticles modified with dimercaptosuccinic acid259. availability and low cost. 2012. Co(II).281 However. Co. 8075–8109 resins and macroporous hyper-crosslinked polymers).277.280 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]4À and [AlO4]5À polyhedra connected through their oxygen atoms to form large negative lattices with Brønsted and Lewis acid sites. the uptake of Mo(VI) in the form of MoO42À ions decreases at pH values higher than 6 as the adsorption surface becomes negatively charged at pH > pHzpc. Ti(III).260 Maghemite (-Fe2O3)261 Silica-coated magnetite (Fe3O4)262 50–80 Hg2+ dechlorination of PCB. agricultural wastes and biomass) and polymeric materials (e.g.0. The surface charge is neutral at pHzpc (the zero point charge pH.8 and 3. low cost adsorbents (e. Then. Zeolites have been widely applied in the removal of heavy metals.3).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+. Ni2+.3 fold with starch and CMC-modified nZVI. where Me ¼ Mn. 5.279 In recent years. Cu. Zn2+. Pb2+.273 It was observed that the MNPs could efficiently remove the metal ions with a high maximum adsorption capacity at pH 5. If cations are exchanged by protons. Afterwards. when it was compared with nZVI.1039/C2EE21818F Magnetic nanoparticles encapsulated by poly(3. Cu2+ from metal contaminated water. chitosan and cyclodextrin). modified chitosan nanoparticles were used for the removal of metals from waste water. respectively.g.. Hg(II).. Ag(I). which releases the adsorbed MoO4. Some NPs are powerful adsorbents due to their unique structure and electronic properties. zeolites have been applied in the retention This journal is ª The Royal Society of Chemistry 2012 .276 Chitosan has been applied extensively in various research areas of water/waste water treatment. The application of zeolite materials for environmental remediation has gained great attention due to their selective sorption capacities. the limitation of modified chitosan nanoparticles is disintegration in aqueous solution or aggregation in pH 9 alkaline solution due to weak electrostatic interactions between chitosan and TPP molecules. the zeolite acquires considerable Brønsted acidic properties. the adsorbent surface is positively charged and anion adsorption occurs. the carboxylated chitosan was covalently bound to magnetic nanoparticles. Cu2+. applied modified Fe3O4 magnetic nanoparticles (MNPs) (15–20 nm) with 3-aminopropyltriethoxysilane and copolymers of acrylic acid and crotonic acid in the removal of Cd2+. natural polymer adsorbents have been used (e. Then. Zn or Ni)257 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. the uptake of MnO42À ions increases and remains constant in the pH range of 4–6. such as Cr3+. zeolites. this leads to an increasing electrostatic repulsion between the negatively charged species (MoO42À) and the negatively charged adsorbent. clays. Fe2+.g.5 and could be used as a recyclable adsorbents under convenient conditions. silica beads).View Article Online Table 4 Previous studies of the environmental remediation using modified nZVI 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 MoO42À at pH values below 6 and electrostatic repulsion between negatively charged maghemite and MoO42À The dithiocarbamate group after the derivitization of magnetite plays a major role in the removal of Hg2+ Type of nanoparticle Modified jacobsite (MnFe2O4) 255 Particle size (nm) 10 20 11 6 50 Targeted heavy metal ion Cr(VI) Cr(VI) Ag(I).274 The impact of pH on the removal of Mo(VI) from contaminated waste water was studied by Afkhami and Norooz-Asl. Below the pHzpc. Sci. Pb(II) Hg(II). Zn2+.rsc. With an increase in the pH up to pH 4. organic or biological origin (e.g. Dissolved organic carbon and organic colloids in the submicron size range have been recognized as a distinct non-aqueous organic phase to which organic pollutants are adsorbed.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. industrial by-products. The removal efficiency was highly pH dependent and the optimal adsorption was found to be pH 4.278 Chang and Chen modified the chitosan polymer and grafted carboxylic groups.272. Mg. organic polymeric 8092 | Energy | doi:10. Pb2+ and Cd2+ from waste water in the mining industries. where the pHzpc of maghemite nanoparticles is around 6..275 The surfaces of the metal oxides (Fe2O3 suspension) are generally covered with hydroxyl groups that vary in their form at different pHs. In addition. Cu(II).

successive layers are added and the sphere can be expanded to the size required by the investigator. isopropylacrylamide. to which carbon and other elements are added by a repeating series of chemical reactions that produce a spherical branching structure. However.295. Polymeric nanoparticles synthesized by the copolymerization of a pyridyl monomer with styrene have been used for the removal of metal ions. Dendritic nanopolymers are highly branched 3D globular nanoparticles with controlled compositions and architectures. 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 adsorption/desorption. 2012. The structure of the polymer is determined by the number of reactive groups of the core. etc. The other pollutant matrix ions had no negative effect on the removal of the cadmium ions. Dendrimers consist of three components: (1) a core. The removal efficiency of As(III) and As(V) was higher for nanocrystalline TiO2 than fumed TiO2.291 Many types of polymers have been assembled into nanoparticles via polymerization techniques. in which divergent or convergent hierarchical assembly strategies are involved. PolyN-isopropylacrylamide nanoparticles remove Pb2+ and Cd2+ from waste water. 5. while the modified nanoparticles could This journal is ª The Royal Society of Chemistry 2012 adsorb Co2+ selectively in the presence of other heavy metal ions. in which metal ions are usually complexed with dendrimer ligands (e.294 Therefore.292 However. They are routinely synthesized from a central polyfunctional core by the repeated addition of monomers. As(III). terminal functional groups) through coordination.296 (E) Dendrimers Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. found that polyurethane-based nanoparticles could be applied in the desorption and transportation of organic pollutants with the hydrophobic core of the nanoparticles. 8075–8109 | 8093 . polymeric nanoparticles can be tailored for the remediation of selective heavy metals. 8.284 Activated alumina. Cu(II) and TCE from the contaminated water.293 modified polystyrene nanoparticles with a specific dye molecule called an azo-chromophore. a porous form of Al2O3.289 Alvaro et al. Mesoporous silica with functionalized monolayers have been useful in the removal of mercury and other heavy metals from waste water. (2) interior branched cells and (3) terminal branched cells. Tungittiplakorn et al. and (2) weak and chemical bonding through hydrogen bonds/p bonds with the surface functional groups. Ni2+ and Cr2+.. Chen et al.. electrostatic interaction. the preparation of functionalized NPs using different methods still remains a great challenge. 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. aminated mesoporous alumina and alumina-supported MnO can remove As(V). Mesoporous silica-based materials (pore size 2–50 nm) have been widely used to remove heavy metals present in waste water.rsc.298 Ammonia is used as the core molecule and it reacts with methylacrylate 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. synthesized mesoporous TiO2 nanoparticles in association with tetraethyl orthosilicate using neutral pluronics as templates.g. The photocatalytic activity for the degradation of phenol was much higher for mesoporous TiO2 nanoparticles compared to standard P-25 TiO2.295 Nano-sized metal particles are expected to exhibit much higher reactivity because of their larger surface area than bulk particles.285–287 Nanoscale diboron trioxide/titanium dioxide composite materials have been used for the separation of trace cadmium ions from polluted water containing cadmium ions. Each complete reaction sequence results in a new dendrimer generation as shown in Fig.297. as shown in Fig. unusual crystal shapes and lattice orders. Dendrimers are relatively monodisperse and highly branched nanoparticles with controlled compositions and design and their sizes are in the range of 1–100 nm. Mesoporous alumina. 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 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.288. such as nitrogen. Dendrimers are built from a starting atom. The original core–shell structure without grafting can adsorb Hg only.View Article Online of methyl-tert-butyl ether. The crucial role played by dendrimers is in the synthesis of dendrimer-stabilized NPs. The dendrimer generation is created by adding monomers to each functional group in turn. interior tertiary amines. whereas Hg2+ was better adsorbed on thio-functionalized silica. 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.290 It was found that the poly(vinylpyridine) nanoparticles could selectively remove Cu2+ despite the presence of other competing ion species. One of the unique approaches used to prepare inorganic NPs is through the use of dendrimers.293 Bell et al.1039/C2EE21818F Metal nanoparticles (NPs) have received great scientific and technological interest in environmental remediation due to their size. As the process repeats. Modification and chemical treatment of the nanomaterials are essential to enhance the target adsorption ability. Zn2+.300 Energy Environ. the utilization of polyN-isopropylacrylamide in waste water treatment is not widespread because the main functional group. the branch lengths and surface group dimensions. chloroform and TCE in water and they were found to be 8–12 times more efficient than activated carbon. has a high porosity so it is widely used in filtering components for drinking water purification. does not show a favorable ability to remove metals. followed by a reduction or other reactions to form inorganic NPs stabilized by dendrimers. The removal of organic pollutants using inorganic nanoparticles and mesoporous structures can be carried out in two ways: (1) static force (including Lewis adsorption). The maximum size is limited by the generation at which the dendrimer becomes tightly | doi:10. leaving the end groups able to react again. Better adsorption capacities were found for amino-functionalized silica in the capture of Cu2+. Sci. 7. The core is characterized by a number of functional groups.

7 The dendritic structure. comparatively lower operating pressures. 5.1039/C2EE21818F 8094 | Energy Environ. Ni(II). 8 A graphical presentation of PAMAM dendrimers (a) PAMAM. carboxylates and hydroxymates. This may enable the development of a new generation of water treatment processes that are flexible.302 Diallo et al. are a new and excellent water-soluble chelating ion exchange material with a distinct selectivity for toxic heavy metal ions.. In those units. first reported the use of PAMAM dendrimers for copper removal in 1999. dendritic nanopolymers have been used to enhance UF and MF processes for the recovery of dissolved ions from aqueous solutions. iron. such as PAMAM dendrimers. Dendritic nanopolymers can encapsulate a broad range of solutes in water. or PAMAM. Investigations on the removal of Co(II). 8075–8109 . copper. carboxylates and hydroxymates. nickel.g. 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. Furthermore. zinc and uranium) by attachment to the functional groups of dendrimers. Diallo et al.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. the recovered concentrated solution of contaminants is collected for disposal or the nanopolymers may be recycled. (c) BoltornÒ and (d) hyperbranched polyglycerol. Pb(II) and Zn(II) have been performed using the PAMAM-supported filtration method. reconfigurable and scalable. which can host inorganic nanoclusters and form stable dendrimer complexes and nanocomposites.306 Investigations have already This journal is ª The Royal Society of Chemistry 2012 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs.View Article Online Fig. Sci. have combined bench scale measurements of metal ion binding to Gx-NH. 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. the reduction of silver cations with NaBH4 and the template role of the dendrimers ensure well dispersed silver nanoparticles with a relatively small size distribution. Cu(II) could form the most stable complexes with the benzoylthiourea-modified PAMAM derivatives and complete retention was achieved at pH>4.0. after surface modification with benzoylthiourea groups. Cu(II).. such as copper (Cu(II)).300 Thus. Ag(I). branched and three-dimensional structure. PAMAM dendrimers with dead-end UF experiments to assess the performance of dendritic polymer filtration to recover Cu(II) from aqueous solutions.298 Poly(amidoamine). including cations (e.299 Dendritic nanopolymers. Finally.0–5. 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. such as primary amines.303 The key novelty of the dendritic polymer filtration process is the combination of dendritic polymers with multiple chemical functionalities with UF and MF. such as primary amines. gold.304 PAMAM dendrimers have great potential as templates for metal composite nanoparticles due to their low toxicity and highly regular. 2012. Polyamidoamine dendrimers (PAMAM).. dendrimers have been developed for applications in the remediation of waste water contaminated with a variety of transition metal | doi:10.305 In general.301 than linear polymers of a similar molar mass because of their much smaller polydispersity and globular shape. PAMAM dendrimers can also be applied in the recovery of perchlorate anions and uranium metals from contaminated groundwater. Dendritic nanopolymers have also much smaller intrinsic viscosities than linear polymers with the same molar mass because of their globular shape. the bound target substance is separated from the nanopolymers by changing the acidity (i. have much less tendency to pass through the pores of ultrafiltration membranes Fig. The results showed that all metal ions could be retained almost quantitatively at pH 9. 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. and could be separated selectively from the other heavy metal ions investigated.303 They also can deactivate bacteria and viruses after binding. (b) poly(glycerol-succinic acid) dendrimer. Poly(amidoamine) dendrimers can remove metal ions (Cu(II). silver. the pH) of the solution. First. thus enabling the recovery of the bound Cu(II) and the recycling of the dendrimer. metal ion (Cu(II)) trapped PAMAM dendrimers can be regenerated by decreasing the solution pH to 4.e.rsc. Therefore.

a narrow size distribution controlled by the composition and a good antimicrobial activity as tested against E. Furthermore. The advantages for processes involved in environmental remediation are due to (1) their great capacity to adsorb a wide range of pollutants. formaldehyde. The unique property of these clusters is their ability to remove bacteria from water by an adsorption method. Adsorption-based separation Thickness of membrane/disc (nm) 300 Æ 76 Targeted contaminants Removal of polycyclic aromatic hydrocarbons (PAH).1039/C2EE21818F indicated that dendrimer-encapsulated silver nanoparticles possess antimicrobial activity. MgSO4. (3) their good surface area. such as a longterm dispersion stability. Cr2O72À from contaminated aqueous solutions Separation of CO2 from a feed gas mixture of CO2 and N2 on porous substrates Separation of CO2 from fossil fuel emission on porous substrates Separation of Cu2+. pure HPAMAM–NH2 also indicated some limited antimicrobial ability with an inhabitation ratio less than 10%. redox processes and magnetic processes.307 Strong bonding is achieved through a mechanism that involves an interaction with noble metals. 2012. making it a green route. aureus. The bacterial inhibition ratio of the HPAMAM– NH2/Ag nanocomposites reached up to 95% at a silver concentration of 2. such as amino or carboxylate groups. trihalogen methane. and (4) their selectivity towards aromatic solutes. 310 300 300 2 mm disc 300 The diameters of the pores in the composite membrane are in the range of nanometers 8 mm pore size for the TiO2 filter and 3 mm pore size for the Al2O3 filter 311 312 313 314 315 316–319 This journal is ª The Royal Society of Chemistry 2012 Energy Environ. (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. the preparation of polymer/metal nanoparticles needed extra reducing agents.View Article Online Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs.. it is imperative that metal ions are trapped in the interior structure of the dendrimer (to offer protection against agglomeration). due to a strong ligand-to-metal interaction. sodium citrate or hydrazine. Table 5 shows some applications of dendrimers for environmental remediation. which facilitate metal–polymer complex formation.7 mg mLÀ1. coli. (ii) the process was conducted at room temperature and under normal pressure and in an aqueous solution. including sodium borohydride (NaHB4). and (iii) the obtained silver nanoparticles have several excellent properties. The activity was enhanced with an increasing silver concentration. NaCl and Na2SO4 Removal of organic pollutants. An amine-terminated hyper-branched poly(amidoamine) (HPAMAM–NH2) has been used to produce antimicrobial silver nanocomposites. Co2+ and Cr3+ from aqueous solutions Separation of CO2 from a feed gas mixture of CO2 and N2 on porous substrates Rejection of salts: MgCl2. Cd2+. Hg2+. such as coconut coir. mobilis. 8075–8109 | 8095 . etc. this hyperbranched polymer was found to serve as a highly effective self-reducing agent. In addition.rsc. All of these polymers possess some strong electron-donating centers. This is usually attempted by selective protonation or hydroxylation of the surface amines Table 5 The applications of dendrimers in environmental remediation Type of composite dendrimer Silica nanoparticles prepared by mixing salicylic acid and hyperbranched 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.. The advantages of this method are: (i) no extra reducing agent was needed. a new technique in adsorption has been reported that applies carbon nanotube clusters. (2) their fast kinetics. their unique structure and electronic properties can make them especially powerful adsorbents. pesticides and methyl-tert-butyl ether Ref. In these studies. and Pb2+. The treatment of water by adsorption methods uses specific ion exchangers or extractants and a combination of adsorption with catalytic treatment methods. Platinum and palladium nanoparticles have also been successfully encapsulated within poly(propyleneimine) dendrimers. To increase the metal adsorption capacity and form metal nanoparticles. Recently. rice husk. such as TiO2.309 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. 5. such as pyrene and phenanthrene.308 More | doi:10. S. Some effort has been made to synthesize dendrimer-protected silver nanodots exhibiting fluorescence. small particle size. Al2O3 and SiC (the surface amine is more basic as it is primary in nature). Adsorption on sorbents has become one of the preferred methods to remove toxic contaminants from contaminated water. is the most popular of the adsorbents.308 The interaction of Cu2+ with PAMAM leads to two changes in the absorption spectrum: a band due to the d–d transition gains prominence and shifts to 605 nm and a new band. appears at 300 nm. B. subtilis and K. such as polycyclic aromatic hydrocarbons. Sci. jute stick.317 Many materials have properties that are dependent on size. such as catalytic palladium nanoparticles in films of linear poly(ethyleneimine) (PEI) and silver.276 Activated carbon from various sources.

When the pH level of the solution increases. which makes the adsorption of dichlorobenzene much easier for the as-grown CNTs. activated carbon). with a particle size of 20–70 nm. For the graphitized CNTs.36 0. But it increases very slowly for the as-grown CNTs and is 3.32 0. At low pH. The surfaces of modified carbon black have negative charges in a wide pH range and Cu2+ or Cd2+ carry a positive charge. carbon beads.rsc.28 0. Sci. such as single-walled carbon nanotubes (SWCNTs). in which the adsorbate has to move from the exterior surface to the inner surface of the pores to achieve the equilibrium. as shown in Fig.323 Li et al. CNTs are graphitic carbon needles and have an outer diameter ranging from 4–30 nm and a length of up to 1 mm. SWCNTs (Fig. 9 (Super) structure representations of (a) a MWCNT and (b) a SWCNT. multi-walled carbon nanotubes (MWCNTs). The adsorption isotherms indicated that different kinds of heavy metals have different affinities for black and activated carbon. the adsorption of dichlorobenzene by Fig.324 Because they have a large specific area. The removal efficiency for KMnO4 oxidized CNTs 8096 | Energy Environ. KMnO4 and HNO3 as shown in Table 6. observed that less time (40 min) was required for CNTs to adsorb dichlorobenzene. 1. This may be because CNTs have no porous structure as traditional adsorbents do (e. Zn(II). 5.325 Due to the large specific area.08 g per 100 mL and was found for KMnO4 oxidized CNTs (19 mg gÀ1)..g. Nanoscale carbon black. found that oxidized CNTs can be good Cd2+ adsorbents and have great potential applications in environmental protection. 9(a).. such as benzene. 2012. it took 20 h for an adsorption equilibrium to be reached for phenol from water).2 g per 100 mL. which is the most commonly used adsorbent to achieve equilibrium conditions (i.4 and 11. The specific area and pore specific volume of CNTs were found to be increased after the oxidation of CNTs with H2O2.e. The adsorption capacities of all adsorbents were observed to be increase with an increase of the CNT dosage.03 to 0. which are both pH dependent.58 Type of sample As grown H2O2 KMnO4 HNO3 This journal is ª The Royal Society of Chemistry 2012 . adsorption has a long residence time for activated carbon.08 g per 100 mL. Peng et al.4 A. CNTs have attracted the interest of researchers as a new type of adsorbent.326 Table 6 The porosity and specific surface area of as-grown CNTs and oxidized CNTs325 Specific surface area (m2 gÀ1) 122 130 128 154 Pore volume Vp (cm3 gÀ1) 0. Adsorption of Cu2+or Cd2+ on the modified carbon black increases with an increasing pH of the solution. The obvious larger adsorption degree takes place at CNT dosages of 0. CNTs can be considered as cylindrical hollow micro-crystals of graphite.1039/C2EE21818F almost arrives at 100% at a CNT dosage of 0.320. Thus. CNMs may exist in several forms. Pd(II) and Cd(II) on nanoscale hydroxyapatite and carbon black.. existing as either Cu2+ and Cd2+. at a CNT dosage of 0.327 The short time needed to achieve equilibrium also suggests that CNTs have very high adsorption efficiencies and the potential to remove dichlorobenzene from water.View Article Online processes are widely applied in the purification of drinking water and natural gas contaminated air. 8075–8109 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs.321 MWCNTs are made of concentric cylinders with  spacings between the adjacent layers322 of about 3.8 mg gÀ1. which suggests that the treatment of CNTs with KMnO4 is an effective method to improve their Cd(II) adsorption capabilities. It was also found that CNTs grown by pyrolysis with a mixture of propylene–hydrogen and a nickel catalyst at 750  C in a ceramic furnace were better at the adsorption of dichlorobenzene when compared to graphitized CNTs. the concentration of competitor H+ ions decreases and Cu2+ or Cd2+ adsorption increases. The increased adsorption of Cu2+ and Cd2+ on the modified carbon black is due to the increased amount of functional groups after oxidation of the carbon black surface. respectively.2-dichlorobenzene325 and ethyl benzene.327 In contrast. whereas the nanosized pores of carbon black are more accessible to humic acid.2 g per 100 mL. 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 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. 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+. CNTs have shown exceptional adsorption capabilities and high adsorption efficiencies for various organic pollutants. 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.319 Carbon nanomaterials (CNMs) have unique properties for sorption processes.5 mg gÀ1 at a CNT dosage of 0. 9(b)) were discovered by Iijima. Zhou and coworkers320 investigated the adsorption of Cu(II). The reason for this was the rough | doi:10. The increasing trend for H2O2 and HNO3 oxidized CNTs is almost identical and the adsorption capacities are 8. 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. carbon fibres and nanoporous carbon. 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.326 Generally.

The results from Bina et al. KMnO4. Ni2+ and Cu2+ by other researchers.328 The amount of cationic dyes. This was the main reason for the enhanced removal of ethylbenzene by HCNTs than MWCNTs. the Fig. 8075–8109 | 8097 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. the sorption/desorption study showed that the Zn2+ ions could be easily removed from the surface site of SWCNTs and MWCNTs by a 0.328 as shown in Fig. This effect was explained in terms of CNTs acting as photosensitizer agents rather than an adsorbents or dispersing agents. the SWCNTs showed the greatest adsorption capacity for ethylbenzene (ethylbenzene: 9. In order to improve the separation of carriers of metal ions from treated | doi:10. Single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) were purified by sodium hypochlorite solutions and were applied as sorbents to study the sorption of Zn2+ from aqueous solutions. Furthermore. indicating a strong interphase interaction between carbon and semiconductor phases.1 mol LÀ1 nitric acid solution and the sorption capacity was maintained after 10 cycles of the sorption/desorption process. Using the same conditions. the degree of aggregation. The precipitates can be easily removed from water by filtration or centrifugation with the subsequent extraction of the metals. In addition.327 Because the ethylbenzene molecules are positively charged. The efficiency of CNT–TiO2 catalysts in the photocatalytic oxidation of mono-substituted organic compounds under visible irradiation was dependent Energy Environ. which have a greater area than MWCNTs for ethylbenzene adsorption. With a C0 of 10 mg LÀ1. During activation.328 The amount of Zn2+ adsorbed on the CNTs increased with an increase in the temperature. metallic impurities and catalyst support materials are dissolved and the surface characteristics are altered due to the introduction of new functional groups. produced the highest synergistic effect for the degradation of phenol under near-UV to visible irradiation. the adsorption of ethylbenzene is thus favored for adsorbents with a negative surface charge. The activation of CNTs plays an important role in enhancing the maximum sorption capacity. while HNO3 oxidation provided a larger specific area. This improvement on the efficiency of the photocatalytic process appeared to be proportional to the shift of the UV–vis spectra of the CNT–TiO2 composites for longer wavelengths. 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 sheet of carbon nanotubes. Original carbon nanotubes. Therefore.e.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 compromises the cell membrane integrity. Sci. This leads to a significant increase in the size of the nanocomposites with the formation of precipitates.1039/C2EE21818F This journal is ª The Royal Society of Chemistry 2012 .331.98 mg gÀ1).View Article Online graphitized CNTs was decreased. 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. However. 10.330 The oxidation of the CNTs with KMnO4 and H2O2 exhibited little enhancement in the specific area. due to the electrostatic interaction between the ethylbenzene molecules and the SWCNT surface. After oxidation with nitric acid. higher ethylbenzene adsorption through the single-walled CNTs than through MWCNT has been observed.326 The activation of CNTs under oxidizing conditions with chemicals such as HNO3. containing moderate amounts of oxygen surface groups. KOH and NaOH has been widely reported. Multi-walled carbon nanotube–TiO2 composite catalysts can be used as catalysts in photocatalytic processes for water treatment.329. thus increasing the surface area of the composite materials. it was suggested that CNTs can be reused several times in water treatment and regeneration. 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.335 The separation of metal ion carriers (i. such as methyl violet and methylene blue.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. The increased capacity of adsorption was found for the removal of Cd2+ (ref. indicated that the equilibrium adsorbed amount for SWCNTs is higher than for hybrid carbon nanotubes (HCNTs) and MWCNTs. the metal ions can be bound to polymeric molecules and/or carbon nanoparticles forming nanocarbon conjugates or polymer nanocomposites in water that are able to precipitate rapidly. NaOCl. Table 7 shows the application of nanocomposites of carbon materials and the advantages of using them for environmental remediation. nanoparticles with metal ions) from water after water treatment is a challenging problem. H2O2. 2012. 5. H2SO4.rsc. indicating that SWCNTs and MWCNTs are effective sorbents. A synergy effect on the photocatalytic degradation of phenol was found mostly for the reaction activated by near-UV to visible light irradiation. They additionally had higher lead adsorption capabilities and are promising adsorbents for use in waste water treatment. 325). The introduction of increasing amounts of CNTs into the TiO2 matrix prevents particles from agglomerating. This results in more electrostatic attraction and thus leads to a higher ethylbenzene adsorption. 10 The equilibrium amount of ethylbenzene adsorbed on CNTs with a C0 of 10 mg LÀ1 (adapted from ref. Activation causes a modification of the surface morphology and surface functional groups and causes removal of amorphous carbon. 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. 328).. the Zn2+ sorption capacity of the CNTs was much greater than that of commercially available powdered activated carbon.332 Carbon nanotubes may therefore be useful for inhibiting microbial attachment and biofouling formation on surfaces.

Zn/Pd).View Article Online Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. chitosan. Cr6+ from waste water 2+ 2+ 2+ 2+ Reference 335 CNT with silver ions and copper nanoparticles CNT with TiO2 nanoparticles and P25 TiO2 Removal of E. and metallic ions from contaminated water Removal of Co2+. For nitrobenzene and benzoic acid a synergy factor near to 1 was obtained. solvation. the use of aqueous suspensions limits their wide applications because of the problems for the separation of the fine particles and the recycling of the catalyst.351 has been available to solve the problems to considerable extent. prevention of particles agglomeration and potential application of convective flow occurring by free-standing particles. In addition.376 cellulose. optical and/ or electronic properties and their chemical functionalities (i.e. Ni2+. Nanocomposite adsorbents were designed by impregnating the inorganic nanoparticles into conventional polymers. cellulose.348 A comparison of the photocatalytic activity of TiO2 and TiO2/CNTs composites for acetone degradation in air shows that the presence of a small amount of CNTs can enhance the photocatalytic activity of TiO2 greatly. and polymeric membranes. which can prevent recombination of the eÀ/h+ pairs.350. the abundant hydroxyl groups adsorbed on the large surface of the composites can lead to the formation of more_OH radicals. organochlorine pesticides. CdS).355–358 These nanoparticles could be loaded onto porous resins.351–354 The generally used NPs include zero valent metals. 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.378 porous resins360 and ion-exchangers.rsc. Porous polymeric adsorbents or Table 7 The applications of nanocomposites of CNTs for environmental remediation Material blends in the nanocomposite Nanocarbon colloids and polyethylenimine Benefits Sorption of metal ions takes place simultaneously with the formation of a nanocomposite and the coagulation and filtration of nanocomposites with metal ions can capture other contaminated materials The improvement was observed for antimicrobial properties due to the increased contact surface area Providing high surface area. alginate. difficult separation and limitation to reuse and possible risk to ecosystems and human health caused by the potential release of nanoparticles into the environment. Cu .364 The common catalytic nanoparticles include nanosized semiconductor materials (such as nano-TiO2. The widely used host materials for nanocomposite fabrication include carbonaceous materials. coli cells was observed to be greater than both acid (–COOH) modified and PAMAM modified MWCNTs.). such as granular activated carbon. bio-compatibility. the PAMAM-grafted MWCNTs contain abundant amine terminated 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.359. wettability. Then. Sr2+ and Ni2+ from the aqueous solution Removal of polar aromatic compounds (p-cresol) from aqueous solutions 336 and 337 338–345 CNT with iron oxide magnetic composites Hybrid diatomite/carbon composites 346 347 8098 | Energy Environ. Moreover. coli and S. chemical stability. ZnO. templating effect. namely. halogenated aliphatics. the retardation of electron–hole recombination and visible light catalysis by modification of the band gap and/or sensitization Improvement in the surface area and adsorption capacity Providing an adequate open porous network comprised of transport pores and micropores and a faster removal rate Target material Removal of Zn . Moreover. such as porous resins. high quality active sites. etc.379 to avoid issues caused by the ultrafine particle size. 5. biopolymers and single-enzyme nanoparticles (SENs). Cu0 and Zn0) and bimetallic nanoparticles (such as Fe/Pd. Fe/Ni. phenol and phenol derivatives. Hg . Sci. 8075–8109 This journal is ª The Royal Society of Chemistry 2012 . zero valence metals (such as Fe0. the disinfection effect on E. and polymeric host materials must possess excellent mechanical strength for long term use. such as phenol and aniline.1039/C2EE21818F from the ring activating/deactivating properties of the aromatic molecules.. alginate.377. sands and polymers.349 In the tricomponent mixture of AgNPs–CNTs–PAMAM prepared by Yuan et al. A higher kinetic synergy effect was observed for compounds presenting electron donor groups. such as PCBs (polychlorinated biphenyls). such as transition loss and excessive pressure drops. 2012. which result in an enhancement of the photocatalytic activity of TiO2. etc. ion exchangers. azo dyes.359–363 The choice of the polymeric support is influenced by their mechanical and thermal behaviour. serving for the reduction of particle loss.345 Electrons excited by TiO2 may easily move to the nanostructure of the CNTs due to the strong interaction between TiO2 and CNTs. metallic oxides. silica. CNTs raise the band gap of TiO2. cellulose or carboxymethyl cellulose. aureus from contaminated water Removal of organic dyes.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.365–375 They are usually applied as catalysts or redox reagents for degradation of a large variety of environmental contaminants. Fe/ | doi:10. It was observed that the strength of the antimicrobial effect on bacteria follows the order: AgNPs– MWCNTs–PAMAM mixture > MWCNTs–PAMAM > MWCNTs–COOH. hydrophobic/hydrophilic balance. humic substances. indicating the inexistence of any synergy effect between the CNTs and TiO2 in the photocatalytic degradation of these pollutants. Immobilization of these nanoparticles onto polymer matrix. halogenated herbicides and nitroaromatics. Cd .

Magnetite (Fe3O4). are very effective in destroying various organic contaminants. the polymer substrates of the nanocomposite catalysts are expected to be antioxidative under UV or visible light illumination. During the adsorption of Cr(VI) onto magnetite Table 8 The application of polymer supported nanomaterials for environmental remediation Type of nanoparticle Fe0/Pd Polymer matrix Polyacrylic acid (PAA)/ polyvinyl alcohol (PVA) Polyaniline Poly (tetrafluoroethylene) Polystyrene–divinylbenzene Poly(3-hexylthiophene) (P3HT) Alginate Carboxymethyl cellulose Poly(vinyl pyrrolidone) Sodium carboxymethyl cellulose Chitosan Cellulose acetate Resin Preparation method Dipping cross-linked electrospun polymer mat in ferric trichloride and palladium chloride solution Polymerization of aniline in the presence of TiO2 nanoparticles Electrophoretic deposition Dipping cross-linked polymer mat in ferric trichloride solution Adding TiO2 nonpartisan to the P3HT solution In situ synthesis of Fe0 in alginate bead from Fe3+ In situ synthesis with FeSO4$7H2O as a precursor Electrospinning In situ synthesis with FeSO4$7H2O and K2PdCl6 as precursors In situ synthesis with Cu(SO4)2$5H2O as a precursor Solvent cast In situ reduction of Sn2+ to Sn0 and then deposition of Pb0 through the reduction of Pb4+ Co-precipitation and hydrosol method Precipitation of iron(III) hydroxides from FeCl3 Precipitation of iron(III) hydroxides from FeCl3 Oxidation of the pre-loaded Mn(II) Mixing Target pollutant Trichloroethylene Ref. such as alginate beads. Cr(VI).384 poly(tetrafluoroethylene).383 polyaniline (PANI).387 such as chlorinated methanes.359. Cd(II). other polychlorinated hydrocarbons. Ameen et al. Sci.View Article Online Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs..rsc. such as poly(dimethylsiloxane) (PDMS). The reported polymeric substrates are usually saturated carbon chain polymers or fluoropolymers. 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.. Mn(II)) and organic dyes402 (methylene blue and methyl orange) from aqueous solutions. Table 8 summarizes some of immobilized nanoparticles in polymer matrix. chlorinated | doi:10. methyl orange 398 399 400 401 402 This journal is ª The Royal Society of Chemistry 2012 Energy Environ.379 The immobilized charged functional groups bound to the polymeric matrix are believed to enhance the permeation of inorganic pollutants of counter charges.1039/C2EE21818F 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. Fe/Ni. 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 counterparts. such as Fe0.385 and Nafion. Ni(II). Pb(II). trihalomethanes.388 The schematic illustration of MB dye degradation over the surface of PNA/TiO2 nanocomposites catalyst is shown in Fig. Due to the high photocatalytic activity of titanium dioxide nanoparticles. Zn(II) Methylene blue. Cu0. Pd/Zn. etc. pesticides and dyes. 8075–8109 | 8099 . Fe/Pd. The high photodegradation efficacy of the MB dye may be attributed to the efficient charge separation of the electrons (eÀ) and hole (h+) pairs at the interfaces of PNA and TiO2. Zn0. Some nanoscale metals and bimetals. brominated methanes. 389 TiO2 TiO2 Fe0 TiO2 Fe0 Fe0 Fe0 Fe0/Pd Cu0 Ni/Fe Pd/Sn Phenol Trichlorobenzene Nitrate Methylene orange Trichloroethylene Cr6+ Bromate para-Nitrochlorobenzene Cr6+ Trichloroethylene Trichloroethylene 384 385 390 391 392 393 355 394 395 396 397 Magnetite Hydrated ferricoxide Hydrated ferric oxide Hydrous Manganese oxide (HMO) Fe3O4 Montmorillonite Polymeric anion exchangers Polymeric cation exchanger Polymeric cation exchanger Alginate Cr6+ As3+ and As5+ Pb(II). 2012. Cd(II) Pb(II). chlorinated ethenes.380 polyvinylpyrrolidone (PVP).386. as suggested by the slightly high red shift in the UV–vis spectra.381 polypropylene (PP). Cu(II). A series of magnetic alginate polymers were prepared and batch experiments were conducted to investigate their ability to remove heavy metal ions403 (Co(II). 11. 5. Magnetic particles in the nanocomposites allowed easy isolation of the beads from the aqueous solutions after the sorption process. Cu(II).382 poly(3-hexylthiophene) (P3HT).355 polyethylene (PE). maghemite (Fe2O3) and jacobsite (MnFe2O4) nanoparticles can be loaded on or in the polymer matrix.

398 Water pollution is certainly one of the major problems faced by the world today. and (2) a loading time was required for loading nanoparticles into the membrane before they reached the peak reaction rate.17 L mÀ2 hÀ1 for removal of tetrachloroethane and the rate of degradation was found to be 0. 5.001 mg LÀ1. Pb.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. namely elemental (Hg0).098 L mÀ2 hÀ1) using bimetallics (the Fe0/Ni0 ratio was 3 : 1). 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 coupling of cellulose acetate membrane and Fe0 has contributed the degradation rate of 0. Several polymer supported nanomaterials have been investigated and further studies of interaction between the host polymers and the encapsulated NPs are still required. in diverse forms constitute some of the major inorganic pollutants and have many harmful effects on humans and environment.409 In a biocatalytic enzyme nanocomposite or single enzyme nanocomposites (SENs). the 1 : 6 silver nanoparticle composite showed better performance than the 1 : 3 Ag nanoparticle composite. The concentration of nitrobenzene quickly decreased by 68. which reduced the reactive sites and led to the oxidation of the Fe0 and Fe2+ during the first several minutes. Metals. the coupling agent (ɣ-amido-propyl-triethoxyl silicane) hydrolyzes to form hydroxyls and then polycondensation occurred to form Si–O–Si bonds. as shown in Fig. such as Hg..View Article Online Fig. Commonly.9% in the first 20 min and was moderately decreased by 15% from 20 to 80 min.12 L mÀ2 hÀ1 for the removal of TCE. Due to the high toxicity effects. ultrasonic cavitation can generate a rigorous environment of local temperature up to 5000 K and local pressure up to 500 atm. Methyl mercury and dimethyl mercury are the most toxic and stable forms of organomercury. 12 A diagram nanocomposites. Preparation and performance evaluation of silver nanoparticles were done using two different ratios of silver to MSA: 1 : 3 and 1 : 6. 2012. Cd and As. protected by mercaptosuccinic acid (MSA) supported on alumina is an effective system to remove mercuric ions from contaminated water at room temperature (28 Æ 1  C). It was found that the iron NPs immobilized in PEG/nylon66 membrane exhibited a high reactivity towards the removal of nitrobenzene.386 nanoparticles. Cr. 12. Lisha et al. which has less toxicity than Cr(VI). 12. Among these two materials. Under ultrasonic conditions.407.405 The reason for the decrease of performance of nanoparticle composite at higher pH was due to forming of stable mercuric hydroxo complexes. Sci. 11 A schematic illustration of the photocatalytic activity of PNA/ TiO2 nanocomposites. At the same time. Cr(VI) can not only be reduced to Cr(III).408 reported that gold NPs supported on alumina were used as adsorbents in order to remove inorganic mercury from drinking water.1039/C2EE21818F Environmental monitoring requires rapid and reliable analytical tools that can perform sample analysis with minimal sample Fig. The solution with a concentration 2 ppm Hg2+ was used to evaluate the degree of removal of Hg2+ ions from the solution. which may not interact with the surface of nanoparticle composite. the World Health Organization (WHO) has set the limit of mercury in drinking water as 0. the main effects of sonication are because of cavitation or the growth and explosive disintegration of microscopic bubbles on a microsecond timescale. This is of high importance for the application of magnetite in the environmental remediation. Under such conditions the modified TiO2 nanoparticles. (H) Nanosensors Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. which was slower than that of TCE (0. 8075–8109 4 : 1) showed that the degradation rate of TCE was found to be 0.rsc. each enzyme molecule is surrounded with a porous composite organic/inorganic network of less than a few nm in thickness. the performance testing of coupling of cellulose acetate and the bimetallic system (the Fe0/Ni0 ratio was 8100 | Energy Environ.404 Mercury exists in three chemical forms. The reduction efficiency of nitrobenzene in groundwater by iron NPs immobilized in a PEG/nylon66 membrane was investigated by Tong et al. The percentage of removal by both the nanoparticle composites is high at pH 5–6 and the performance decreases with an increasing pH of the solution. as shown in Fig. inorganic mercurous and mercuric forms (Hg1+ and Hg2+) and organic alkyl mercury. In addition.410 of the synthesis process for PEI/TiO2 This journal is ª The Royal Society of Chemistry 2012 . The heat stability of the nanocomposite was improved in the presence of TiO2 nanoparticles.407 found that water soluble silver nanoparticle composites of 9 Æ 2 nm and 20 Æ 5 nm core diameter.028 L mÀ2 hÀ1. The fabrication of PEI/TiO2 bionanocomposites has been performed by ultrasonic irradiation techniqus. but it can also be fixed into the iron oxide. Sumesh et al. The decrease in reduction efficiency was due to the reaction between iron NPs immobilized in PEG/nylon66 membrane and nitrobenzene as well as | doi:10. 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.

The V2O5 nanobelts showed greater sensitivity to ethanol of either low (<10 ppm) or high (1000 ppm) concentrations. Compared to traditional detection methods. NH3 and CO.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. etc. With the recent discovery of novel metal oxide nanostructures. A Pd–polyaniline nanocomposite was developed as a selective methanol sensor.417 A highly selective and stable ethanol sensor based on single-crystalline divanadium pentoxide nanobelts was reported by Liu and coworkers. CH4. When detecting NO2 among other common gases. easy processing and scalable productions. NH3. CO) because of large surface area.rsc.421 Yang et al.9 Â 10À14 to 8. Nanoparticle (NP)-based environmental sensors have the potential to detect toxins. methanol. applied a poly(3. adjustable transport properties and chemical specificities. The multiwire sensor showed an even lower detection limit of 5 ppb. A number of studies support the application of ZnO 1D nanostructures as nanosensors. they gained importance in the construction of sensor devices. Tao et al. Gas sensor devices are traditionally comprised of thin films of metal oxides. Chu et al.and Pd-nanoclusters prepared by magnetron sputtering provided higher sensitivity of significantly enhanced gas detection for NO2. Since the chemical and physical properties of polymers may be tailored. 1000 ppm ethanol.such as NOx. Immobilization of nanoparticles by polymer matrix is one of the most efficient approaches to overcome such limitations. Polyaniline nanofibres were developed by interfacial polymerization to sense hydrazine gas and it was found that performance of sensing was better than conventional thin film due to its high surface area. applied a SnO2 nanobelts film for gas sensing and proved its capability to sense gases at 30 ppm CO (350  C). CO2. 200 ppb NO2 (300  C) and 10 ppm ethanol (350  C).4-DNT). is desirable in environmental monitoring.4-DNT) and other explosives by utilizing vibrational signatures. O2 and dioxin behave as charge acceptors. 10 ppm NH3 and 3 ppm NO2 in both dry air and a nitrogen atmosphere at room temperature. as compared to the conventional technique of using permeable polymer coatings. studied a gas sensor based on a non-stoichiometric tungsten oxide nanorod film.4-ethylenedioxythiophene) (PEDOT) nanorods nanosensor for the detection of HCl and NH3 vapor. water and soil and are expected to play an increasingly important role in environmental monitoring. The results revealed that the sensors exhibited higher response and good selectivity to C2H5OH at 370  C.418.7 pg was achieved. heavy metals and organic pollutants in air. with tin oxide.415 Comini et al. This unique property of In2O3 nanowires offers a new way to achieve selectivity. and TiO2. and metal tubes. CO. 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. 8075–8109 | 8101 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. H2S.7 pg was achieved.416 Kim et al. selective response to NO2 was also observed. and other explosives by utilizing vibrational signatures.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 response and recovery times were 30–50 s. This room temperature detection limit is the lowest level so far achieved with all metal oxide film or nanowire sensors. The response time was about 10 s and recovery time was shorter than 20 s. the most common nitroaromatic compound for detecting buried landmines. The PEDOT nanorode sensors gave a measurable response to NH3 and HCl vapor concentration as low as 10 and 5 ppm. The sensor was fabricated on Si wafers as the substrates by using a microelectromechanical system (MEMS) and silicon technology.428 The range of the biosensor was found to be 6. etc. still exists.4-dinitrotoluene This journal is ª The Royal Society of Chemistry 2012 (2. 5. withdrawing charge from the ZnO surface.426 The limitation of nanoparticles in practical applications. such as Pt nanosensor. NO2. using the multiple nanowire devices. sensors comprising nanoarrays or single nanostructures have shown improved performance over the thin films.1039/C2EE21818F . They can both improve detection and sensing of pollutants and can be used to develop new remediation technologies. SnO2. transferring charge from the adsorbate to the surface while NO2.4-dinitrotoluene (2. such as O2. 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 nanostructures. A sensitivity of about 0.423 This improved sensitivity was due to the formation of nanowire/nanowire junctions between the metal electrodes. chemical process controlling and personal safety. such as Co3O4. 2012.411 The measurement of harmful gases .3 Â 10À14 mol LÀ1.432 The synthesized Energy Environ. when exposed to NO2. respectively.6 Â 10À13 mol LÀ1 and the detection limit is 2.424 Functionalization of MWCNTs multiple-films with nominally 5 nm thick Pt. zinc oxide and indium oxide..427 Conductive polymer nanomaterials have attracted particular interests as sensors for air-borne volatiles428–434 (alcohols.419 Comini et al. Jang et al. NP sensors may have higher selectivity. porosity and small diameter.416 Gao and Wang found that the SnO2 nanobelt/CdS nanoparticle core–shell heterostructured sensor had high sensitivity to 100 ppm ethanol vapors in air at 400  C. Fe2O3.435 Polyaniline–SnO2/ TiO2 nanocomposite ultra thin films have also been fabricated for CO gas sensing. A sensitivity of about 0.View Article Online | doi:10. Sci. On the basis of their previous study. such as slow diffusion and aggregation. Such junctions. The studies by researchers indicate that NH3 and CO behave as charge donors. demonstrated the capability of silver nanowire substrates for the detection of 2. observed the high sensitivity of a MoO3 nanorods film sensor to 30 ppm carbon monoxide and 100 ppm ethanol.412–414 Nanotube-based sensors include metal oxide tubes. The sensor responses were observed to be 2% N2 (or air). 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. 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 sol–gel matrix can be used to construct nitrite sensors by immobilizing partially quaternized poly(4-vinylpyridine) complexed with PVP-Os on an electrode. sensitivity and stability and a lower cost. a feature available in the multiple nanowire devices but junctions are not available in the single nanowire devices. also evaluated the gas sensing properties of In2O3 nanowires films. demonstrated the capability of silver nanowire substrates for the detection of 2.418 Kong and Li found a highly sensitive and selective CuO–SnO2 sensor to H2S gas based on SnO2 nanoribbons. compared to the 20 ppb limit of single nanowire sensors. CO and H2.

Nanomembranes have found applications in the production of potable water. have a greater resistance to changes in pH and the concentrations of chemicals present in the contaminated water. When sensor strip made of nylon 6 nano-fibre nets (NFN) was exposed to formaldehyde.442 8102 | Energy Environ. 428 429 430 431 432 433 Downloaded by Centro de Investigaciones Científicas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs. CdTe– CdS core–shell quantum dots (CdTe–CdS). Such pre-filters can be used in various applications. which was done by coating graphene–gold nanocomposites (G-AuNP). 5. CH4 Methanol Zn2+. On-going investigations are under way to develop engineered nanomaterials of various fibre diameters and morphologies to identify their effects on the performance of nanofibres. Moreover. such as glucose and hydrogen peroxide. because of their superior properties. a lower cost. This study remains open as a new challenge and approach to explore the electrochemical features of graphene or its nanocomposites for the potential utilizations.438 | doi:10. 14 shows the fabrication of the biosensor. Nanosensors have also been applied as biosensors.1039/C2EE21818F nanocomposite sensor showed high selectivity and sensitivity to methanol vapors with rapid and reverse response. in-line and real-time detection. CdTe–CdS and AuNPs remarkably improves the electron relay and accelerates the electrochemical reaction and the AuNPs–CS film offers a favorable microenvironment to keep the bioactivity of the HRP. Some applications of polymer-based nanocomposite sensors are shown in Table 9. A high flux could be produced via nanofibrous prefilters with even higher loading capacities. water reclamation. This could be ascribed to the improvement of the conductivity between the graphene nanosheets in the G-AuNP due to introduction of the AuNPs. The electrocatalytic synergy of G-AuNP. 13. This method is effective and promising and can be used in the engineering of water and air improvements. 13 An illustration of the colorimetric detection of formaldehyde based on the nylon 6 NFN membranes. good interconnectivity of the pores and the potential to incorporate active chemistry or functionality at a nanoscale. In addition metal and metal oxide nanomaterials can be used to remove organic pollutants and metals by reduction 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. such as a high specific surface area (depending on the diameter of fibres and intrafibre porosity). greater stability for a longer period of time and cost optimization.438 Fig.. The environmental applications of polymer supported nanocomposites in photocatalytic/chemical catalysis degradation. such as the removal of microparticles from waste water and with ultrafiltration or nanofiltration membranes to prolong the life of these membranes. The application of silica-coated nanosilver as biosensors for the biochemical compounds. Nanofibrous media have a low basis weight. shorter turn-around times. the removal of metals.View Article Online Table 9 Polymer-based nanocomposites for the sensing and detection of pollutants Type of nanoparticle SnO2 SnO2 TiO2 Iron oxide Pd Au Polymer matrix Polystyrene/polyaniline (PSS/PANI) Polyaniline (PANI) Polyaniline (PANI) Polypyrrole Polyaniline Chitosan Preparation method In situ self-assembly Hydrothermal method Chemical polymerization and a sol–gel method Simultaneous gelation and polymerisation Oxidative polymerization of solution with Pd NPs Mixed in solution Target pollutant CO Ethanol.439–441 Formaldehyde is a hazardous air pollutant and prolonged exposure to formaldehyde can cause a nervous system damage as well as asthma. high uniformity and excellent biocompatibility. Cu2+ Ref. acetone Trimethylamine CO2.442 Conclusions and future prospects The application of nanomaterials in the detection and removal of pathogens provides greater sensitivity. This biosensor provided the best sensitivity in all biosensors based on graphene materials for detection of hydrogen peroxide. titanium forms coordination bonds with the amine and carboxyl groups of enzymes and maintains the enzyme’s biocatalytic activity. It was found that sensitivity of the biosensor is more than 11-fold better if G-AuNP. Further improvements must be made in the application of environmental remediation to selectively remove materials. high permeability and small pore size that make them appropriate for a wide range of filtration applications. nanofibre membranes offer unique properties. Sci. such as their nontoxic nature. TiO2 nanomaterials have been frequently proposed as a prospective interface for the immobilization of biomolecules. high surface area. the methyl yellow on the tape reacted with sulfuric acid produced by the reaction of hydroxylamine sulfate with formaldehyde to produce a yellowto-red color change as shown in Fig. 14 The fabrication of AuNPs/Cd-Te-CdS/G-AuNPs/GE. NOM and the removal of pesticides from contaminated water. In addition. 2012.rsc. high adsorptivity.436. gold nanoparticles (AuNPs) and horseradish peroxidase (HRP) in a sequence on the surface of a gold electrode (GE). the This journal is ª The Royal Society of Chemistry 2012 Fig. 8075–8109 . higher throughput and portability in environmental remediation. N2. CdTe–CdS and AuNPs are used. dyes. smaller sample sizes.

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