Nanomaterials for Environmental Applications and their Fascinating Attributes E-Book
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- Herausgeber: Bentham Science Publishers
- Kategorie: Wissenschaft und neue Technologien
- Serie: Development and Prospective Applications of Nanoscience and Nanotechnology
- Sprache: Englisch
Nanotechnology is a diverse science that has brought about new applications in fields such as colloidal science, device physics and supra molecular chemistry.
Environmental pollution treatment by nanomaterials is an emerging application of nanotechnology
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Seitenzahl: 629
Veröffentlichungsjahr: 2018
Ähnliche
Development and Prospective
Applications of Nanoscience and
Nanotechnology
(Volume 2)
Prof. Sher Bahadar Khan
Prof. Abdullah M. Asiri
Dr. Kalsoom Akhtar
BENTHAM SCIENCE PUBLISHERS LTD.
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Preface
Nano is assuredly of incredible small size but its beauty is its real perfection, potency and wide range of applications. Therefore, nanomaterials and nanotechnology have become a fundamental arena of scientific activities because of their enormous applications especially their roles in environmental monitoring and remediation. The inimitable properties of nanomaterials make them suitable for the removal of pollutants from the environment and ultimately cleaning up the environment. The unique properties of nanomaterials are mainly due to their extremely small size, typically in the range between 1 and 100 nanometres, creating a large surface area in relation to their volume and these properties makes them highly reactive with high capacity and better recyclability. Thus nanomaterials provide high surface area, high capacity, well defined structure, high reactivity, insolubility, good chemical and thermal stability, can be easily recycled, with fast sorption kinetics and readily tailored for application in different environments and these properties make them unique for developing a new generation of efficient, cost effective and environmentally acceptable functional materials for water treatment processes compared to non-nano forms of the same materials.
Environmental pollution treatment by nanomaterials is one of the emerging fields which is becoming important day-by-day because of the current and increasingly establishment of the industries. Majority of the industries uses various toxic organic and inorganic chemicals. These industries discharge their toxic and used chemicals to the nearby water streams which pollutes the aquatic world as well as indirectly influences human’s life. Therefore, scientific awareness and methods are needed to overcome the mentioned challenges. Being a subject of key interest, it was thought to summarized the cutting edge research on nanomaterials utilization for environmental challenges in the form of a book.
The book is composed of eight chapters. The first chapter is related to different treatment techniques of environmental pollutions using nanomaterials. It highlighted how to resolve the old challenges with new solutions, reviewed different methods used for environmental remediation and highlighted the importance of nanomaterials in environmental remediation. The second chapter is related to nanotechnology for safe and sustainable environment. Nanotechnology is one such revolutionary and state-of-the-art for environmental protection, remediation and pollution prevention. This chapter is set to explore the role of nanotechnology in regard to safe and sustainable environment, which can truly be regarded as a “Realm of Wonders”. In the third chapter, basic concepts of photocatalysis are explored. Various parameters which control and influence the photocatalytic process are studied in relation to the mechanistic approach. Nanomaterial such as metal oxides and some new types of materials, like perovskite and metal organic framework, (MOF) are used as efficient photocatalyst. The role and mechanism of these materials have been discussed. All these nanomaterials are used for the environmental remediation, dye sensitized solar cells, air purifications, hydrogen production and self-cleaning process. In the fourth chapter, the role of clay based nanocomposites for environment protection is presented. In particular, the removal of heavy metal ions, toxic organic compounds, hazardous dyes and antibiotics from aqueous environment has been discussed and recent studies are summarized. Purification and remediation of contaminated soil and air with the help of clay based nanocomposites are also discussed. The fifth chapter deals with the introduction of cation exchange materials especially nanocomposite cation-exchange materials, the drivers for green technology. This chapter also describes nanocomposite cation-exchange materials with their technological improvement from old era to the latest age of nano because green chemistry can be applied to real processes. The sixth chapter describes the synthesis of iron oxide and its derivative nanoparticles and their wide scale applications. This chapter summarizes comparative and brief study of the methods for the preparation of iron oxide magnetic nanoparticles with a control over the size, morphology and the magnetic properties. Some future applications of microwave irradiation for magnetic particle synthesis are also addressed. The seventh chapter reviews relative and comprehensive techniques for the preparation of polymeric membrane in cooperated with typical additives and their influence on membrane significant in terms of permeability and selectively. In addition, the recent development in polymeric membranes loaded with nanoparticles for evaluating their properties against biofouling. The eighth chapter offers a brief knowledge about the nanocatalyst for the removal of organic toxins, for instance nitrophenols and dyes, which are at alarming condition. This chapter also deals with the use of metal oxides and layered double hydroxide for the removal of these organic pollutants. Metal oxides and layered double hydroxide worked as a solar catalyst for the removal of contaminant and also how various support work enhance its catalytic performance of these materials. Nanocatalyst on a solid supported materials are also explained in this chapter, which avoids them from aggregation and ease separation after the reaction, which are highly demanded at the industrial level.
We believe that this book will properly convey the savor of the nanotechnology and their approaches toward environmental challenges. We intently anticipate that this book will be beneficial for students, teachers and practitioners.
List of Contributors
Nanomaterials and Environmental Remediation: A Fundamental Overview
Kalsoom Akhtar1,Shahid Ali Khan2,3,4,Sher Bahadar Khan2,3,*,Abdullah M. Asiri2,3Abstract
In this chapter, we have made an overview of the whole book and summarized the environmental pollutions and their treatment with new materials and technology. We highlighted how to resolve the old challenges with new solutions. We reviewed different methods used for environmental remediation and highlighted the importance of nanomaterials in environmental remediation. Different processes related to the management of waste water polluted by bacteria, organic, inorganic pollutants, and toxic metal ions, etc. have been discussed. We discussed how nanomaterials are economical solutions for the resolution of the old challenges related to waste water treatment. We also deliberated that the waste water containing harmful metal ions, organic pollutants, bacteria etc. can be treated with nanomaterials and for this purpose, development of novel nanomaterials is paramount because nanomaterials have revolutionized the scenario of emerging catalytic and adsorption technologies with recently certified efficient removal of pollutants along with the low cost and high stability. Therefore, the molecular engineering of nanomaterials to use them to reach stable state-of-the-art efficiency for the removal of pollutants as adsorbent and catalysts is vital and the high efficiency coupled with low cost and easy treatment process of the developed nanomaterials has probability to compete and replace the established technologies.
INTRODUCTION
Water is a fundamental need of all living beings, and its contamination affects them to a great extent. Sea water is mainly polluted containing a lot of waste and metal ions. Some of the water resources are contaminated mainly by the mineral waste products, colored materials, organic byproducts released from the industries and to some extent by microorganisms. The wastes released from the industries particularly textile industries pollute the water to a large extent as it contains colored materials that are carcinogenic and toxic in nature, thereby affecting the living beings and the environment [1-5]. It is very important to protect the environment from pollutants because agriculture and industries wastes cause serious problem and big threat to the environment. Thus, the wastewater from the sea and industries needs to be detoxified and must be treated before use for drinking and agricultural purposes. Therefore, developing new resourceful methods for curing and purification of contaminated water is very much preferred these days [6, 7].
Nanomaterials are considered as effective purification substances regarding elimination of toxic contaminants from waste water. Nanomaterials function as adsorbents and catalysts for the removal heavy metals, SO2, CO, NOx, manganese, iron, arsenic, nitrate, heavy metals, dyes, nitrophenols, aliphatic and aromatic hydrocarbons, viruses, bacteria, parasites, antibiotics etc. Among different materials used for environmental remediation, nanomaterials exhibited excellent performance as compared to micro and macro-materials [8, 9]. The main reason for good performance of nanomaterials is their high capacity, high reactivity, high surface area, well defined structure, easy dispersability, high chemical and thermal stability, and easy regeneration and recyclability. Another advantage of nanomaterials is that they can be easily designed for use in different environment and can be readily modified for a specific new target species. Nanomaterials have generally rigid structure with open pore assembly which usually offers fast sorption kinetics. Due to large surface areas of particles as compared to their volumes, nanomaterials are more suitable for environmental applications. Thus their reactivity in specific surface mediated reactions can be greatly increased in contrast to the similar material having much bigger sizes. The presence of a comparatively larger number of reactive sites is responsible for nanomaterials’ high reactivity along with large surface area to volume ratio; but may also show different reaction rates that surface-area alone cannot rationalize [10, 11]. These properties mark the possibility for increased interaction with contaminants, thus subsequently decreasing contaminant concentrations.
Nanomaterials have been utilized as adsorbent for elimination of metal ions and catalysts for the decontamination of organic pollutants [11]. The adsorption method is extremely valuable toward purifying water. Various adsorbents are developed and applied recently for waste water treatment. However, the nanomaterials are more efficient, cheap, and stable adsorbent and their practical applicability and cost-effectiveness are responsible for their selection toward treatment of waste water [12, 13]. A huge number of metal oxides nanomaterials have been utilized for discarding various environmental contaminants [14, 15]. To increase adsorption ability, the modification of nanomaterials will be carried out.
Nanomaterials, especially nanoparticles [16, 17] and metal oxides have also played important role in the catalysis of organic pollutants [10]. Metal oxides work as photocatalyst for the elimination of different organic impurities and waste water treatment. TiO2, ZnO, Fe2O3, CdO, CeO2, CdS, WO3, SnO2, etc. are widely used as catalysts. TiO2 and ZnO have shown their self as excellent photocatalyst. However, these photocatalyst only encourage photocatalysis during irradiation using UV light as it absorb only in UV region of round about 375 nm with the band gap (~3.2 ev) in UV region. For solar photocatalysis, a photocatalyst must promote photocatalysis through irradiation using visible light. The visible light is almost 46% in solar spectrum which is much more as compared to UV light (5-7%). This least coverage of UV light in the solar spectrum, the high band gap energy (3.2 eV), and fast charge carrier recombination (within nanoseconds) of ZnO confines its extensive application in the solar light [18, 19]. Hence preparation of solar active photocatalyst is vital. For this purpose, several attempt has been made to tune the absorption range of TiO2 and ZnO to visible region of the solar spectrum by doping with various materials. Similarly, LDH have also been largely investigated as solar photocatalyst. We have recently developed different LDHs and have shown high efficiency toward catalytic degradation of organic pollutants under sun light [3, 4]. Dom et al. synthesized MgFe2O4, ZnFe2O4 and CaFe2O4 by low temperature microwave sintering and applied for organic pollutant removal using solar light. They found high photocatalytic activity of these oxides by mineralization of methylene blue under visible light [20]. Raja et al. reported a solar photocatalyst based on cobalt oxide and found as a good solar photocatalyst by degrading azo-dye orange II [21]. Wawrzyniak et al. have synthesized a solar photocatalyst based on TiO2 containing nitrogen and applied for the degradation of azo-dye which completely degraded under solar light [22]. Wang et al. degraded L-acid up to 83% by using S-doped TiO2 under solar light [23, 24]. Mohapatra and Parida have synthesized Zn based layered double hydroxide and applied for the degradation and found that layered double hydroxide will be a prominent solar photocatalyst for the detoxification of toxic chemicals [24]. Zhu et al. have developed several solar photocatalyst based on Sm3+, Nd3+, Ce3+ and Pr3+ doped titania-silica and found as good applicants for industrial applications [25]. Parida and Mohapatra reported Zn/Fe layered double hydroxides as an efficient solar photocatalyst for decolorization of hazardous chemicals [26]. Zhao et al. synthesized TiO2 modified solar photocatalyst and reported as good candidate for the detoxification of plastic contaminants under solar light [27]. Im et al. have synthesized hydrogel/TiO2 photocatalyst for removal of hazardous pollutants under solar light [28]. Pelentridou et al. treated aqueous solutions of the herbicide azimsulfuron with titania nanocrystalline films under solar light and found photodegradation of herbicide in few hours demonstrated titania as best candidate for purification of water containing herbicide [29].
This chapter aims to summarize nanomaterials based adsorbents and catalysts for polluted water purification. Different novel and innovative nanomaterials were utilized as adsorbents as well as catalysts for the exclusion of pollutants from sea and waste water. We have also discussed which were used as adsorbent for the elimination of metal ion, metal oxides as solar and UV-vis catalysts while zero valent nanoparticles as catalysts for the removal of organic pollutants.
Nanomaterials
Nanometer scale materials are extremely small size and it is estimated that this scale is one ten-thousandth small then the width of human hair. So we can say that this nanoscale constituents includes the sub-microns particle, while the technology which govern, understand and generate substances with dimensions 1-100 nanometers is called nanotechnology. The incredible characteristics of these small scale materials are due to their nano-scale dimensions. Incidental, natural, and engineered materials are the three classes of nanoscale materials. For instance, organic matter, clays, and oxide of Fe inside the soil are comprising in natural nanoscale materials, which playing a key character in biogeochemical practices, while when these small scale substance if come into the environment through waste streams of liquid or solid, atmospheric emissions, fuel combustion, agricultural operations, and weathering process, then it is called incidental nano-scale. After industrial and environmental processing of these materials, if it is applied on industrial or environmental scale, if these are enter environmental through these process it is known as engineered nano-scale materials. There are two methods for nanoscale materials, top down and bottom up methodologies, in the former grinding or milling the macro to nano or by reduction process such as borohydride, creating nano materials by aggregating or combining atoms or molecules [4, 7].
Nanosized materials, nanoparticles, nanomaterials, nanosized particles, nanostructured and nano-objects, are some terms used for nano-scale materials. However, all these materials must have one dimension less than 100 nm. These materials have diverse uses and are highly demanded in the environmental, industrial, biological, chemical, physical and medical fields [14, 24].
The naturally occurring or engineered materials are:
The carbon containing materials carbon nanotubes or fullerenes, existing in the form of ellipsoids, tubes or hollow spheres. They are highly stable, less reactive, with exceptional electrical and thermal conductivity, and are largely used in photovoltaic cells, sensing, super-capacitor and biomedical applications.Metal oxide nanomaterials such as TiO2, ZnO, CeO2, Fe3O4, etc. are to block and absorb ultraviolet light. These nanomaterials are comprise of closely and strictly packed semiconductor crystals, which are composed of hundreds or thousands of atoms. These metal oxide nanomaterials have applications in environmental remediation as photocatalysts and adsorbent for the removal of pollutants.Zero-valent metal nanoparticles such as zero-valent iron, copper, silver, nickle, etc. are the example of engineered nanomaterials. These nanomaterials have high surface area which cause increase in surface reactivity. Zero-valent metal nanoparticles have been utilized in waste water treatment.Excitons are the bounded electron hole pairs, which have three-dimensional arrangement in the so-called quantum dots. Quantum dots are semiconductors having 10 to 50 nanometers. And are largely applied in telecommunications, medical imaging, photovoltaics, and sensing technology.Incorporating various functional groups in dendrimers; exceedingly branched polymers, which are manufactured and designed with different contours like discs, spheres, and cones like structures. It has potential application in chemical sensing, drug delivery, modified electrodes, and DNA transferring agents.Composite is another important materials of this class that are made from two nano or one nano with macro-materials. Such materials can be combined with synthetic and biological molecules, with novel catalytic, electrical, magnetic, thermal, mechanical, and imaging practices. This class of materials is also potentially applied in cancer detection and drugs delivery. It is also used in packaging and auto-parts materials to improve its flame-retardant and mechanical characteristics.Environmental applications of nanomaterials
Nanomaterials efficiently removed various chemical and biological pollutants from waste water. Nanomaterials function as adsorbents and catalysts for the removal heavy metals, SO2, CO, NOx, arsenic, iron, manganese, nitrate, heavy metals, dyes, nitrophenols, aliphatic hydrocarbons, aromatic hydrocarbons, viruses, bacteria, parasites, antibiotics etc. [30-32]. Different materials have been used for environmental remediation. However, the role of nanomaterials is highly appreciated for the water purification as compared to micro and macro-materials. The main reason for better performance of nanomaterials is their high capacity, high reactivity, high surface area, well defined structure, easy dispersability, high chemical and thermal stability, and easy regeneration and recyclability. Another advantage of nanomaterials is that they can be easily designed for use in different environment and can be readily modified for a specific new target species. Nanomaterials, especially mesoporous nanomaterials have generally rigid structure with open pore assembly which usually offers fast sorption kinetics [33].
Nanomaterials are used for the de-contamination approach of soil, water and environment, as well places contaminated by oil spills dyes, chlorinated solvents and heavy metals. Nanoscale materials got much interest in various scientific sectors due to its large surface/volume ration as compared to their bulk materials. The constituents of the macro, or micro and nano-scale materials are the same, only the difference in the particle size. These materials can be tuned for specific application as compared to their bulk counterparts. Due to their large reactive sites and surface to volume ratio, accelerate the reaction rate with a high rate constant. These characteristics make them their facile contact to chemicals, thus a quick decrease the concentrations of pollutant are achieved. By using a suitable coating around these materials it remains suspended in groundwater due to its small size. These materials achieved a broader dissemination and large traveling than macroscopic particles by using appropriate coatings, which enhanced the reaction rate [32, 33].
Most of these materials are already find its jobs in various sectors, while others are in the process for their full implementations. The ongoing small scale and industrial research are at play as to explore the particles like TiO2, dendrimers, self-assembled monolayers on mesoporous supports, carbon nanotubes, swellable organically modified silica and metalloporphyrinogens. Many un-un-answered questions should be addressed in this field. For instance, much knowledge is needed about the fate and passage of free nanomaterials in the environment, there staying, toxicology, and their broad marketable benefit.
The nanomaterials are highly ambitious and it is important to optimize and characterize adsorbents as well as solar photocatalysts in order to understand their morphology, efficiency and stability relationships in waste water treatment applications. It is also important to develop innovative nanomaterials which are expected to show high record efficiency and lead to a maximum removal of pollutants under full-sun illumination. Further the performance of nanomaterials should be optimized under different conditions. The demanding task of nanomaterials is to address the stability under heat and light soaking conditions. Since, the metal oxides nanomaterials are powder, it is also important to address questions regarding the tolerance limit for recyclability and methods to overcome the problem of recyclability. One possible solution is development and incorporating of metal oxides into the polymer hosts. Given the simple preparation, easy implementation and high efficiency, it is in the interests to develop tailored nanomaterials that show enhanced stability and very high efficiency toward the removal of different pollutants [34].
Nanomaterials Based Processes for Waste Water Treatment
Adsorption Based Environmental Remediation
Adsorption is the most interesting and most used method for water purification [27, 34]. Sorption is a phenomenon where the ions deposited on the solid surface, and this deposition is due to the transfer of the ions from the liquid to solid phase. Fundamentally, mass transfer are occurred in adsorption phenomenon, and attached to the solid surface by chemical or physical processes. Numerous low cost adsorbents, agricultural waste, by-products from industries, biopolymers and its modified form, natural materials and silica have been employed for the heavy metals removal and waste water purification. Beside, the beneficial application of the aforementioned materials as adsorbent, nanoscale materials are preferred as adsorbent materials due to it high surface area, stable nature practical application and low-cost for the treatment of waste water. Usually, the sorbents phenomena occurred in three main process: (i) transportation of the pollutant from the bulk solution to the sorbent surface; (ii) adsorption of the pollutants onto particle surface; and (iii) inward movements inside the sorbent particles [35].
Different Nanomaterials Used as Adsorbent
Metal Oxides
Metal oxides with diverse morphological and textural characteristics has been successfully employed as adsorbent for environmental remediations [35-37]. Fe3+ has been selectively removed through ZnO-CdO nanoblock from iron ions contaminated water [38]. Nickel ions were largely removed by using Cs doped ZnO [32]. SnO2-TiO2 nanocomposite and silver oxide nanoparticles removed La3+ selectively and efficiently [39] while Ag2O3-ZnO nanocones were selective for the adsorption of cobalt ions. Inorganic based nanomaterials and mesoporous structures removed organic contaminants by two different methods (1) static force (containing Lewis adsorption); and (2) weak chemical interaction due to the functional groups located on the surface which facilitate hydrogen bonding. In order to improve the desired adsorption performance, it is utmost to tune the chemical nature of the nanomaterials. For instance, As3+ and As4+ was largely removed by using nanocrystalline TiO2 as compared to TiO2 [40, 41].
The pH of the system in adsorption play a significant role in metal ions removal as it effect the surface charge. For instance, at the zero point charge pH (ZPC), charge on the surface is neutral, where ZPC pH of maghemite nanoparticles is 6.3. In case of metal oxides, the hydroxyl groups usually covers the surface and different pH effect the hydroxyl groups and thus hydroxyl groups on the surface of metal oxide can vary with pH variation [11]. Below the ZPC pH, the surface of adsorbent materials become positive leading to anion adsorption. Above pH 4, the adsorption of MnO42- ions upsurges and became persistent at 4–6 pH [11]. Similarly, the adsorption of MoO42- ions decreases as the pH raise above pH 6 because at pH > pHzpc, the surface becomes negatively charged, thus the electrostatic repulsion increased amongst the negatively charged MoO42- ions and the negatively charged adsorbent, which releases the adsorbed MoO42- ions [11, 42].
Magnetic Sorbents
Magnetic nanomaterials find its fascinating application in the elimination of organic contaminants, inorganic ions and dissolved carbon. Organic dyes, polycyclic dyes, crystal white and malachite green have been successfully removed from waste water by using various magnetic materials like magnetic chitosan gel particles, magnetic alginates, and immobilization of copper phthalocyanine dye covalently and magnetic charcoal [11]. Similarly, magnetite nanoparticles with surfactant-coated have been used for the removal of 2-hydroxyphenol [43]. Polymer-coated vermiculite iron oxide composites acting as floating magnetic sorbents. These materials lift on water surface, which removed spilled oils from contaminated water [11, 44]. Fe0 nanoparticles removed As3+ and As4+ by rapidly adsorbing than precipitated by weak electrostatic attraction amongst the binding sites of the catalyst and adsorbed materials [11, 45, 46]. Similarly, polyvinyl alcohol-co-vinyl acetate-co-itaconic acid stabilized zero valent iron nanoparticles was used for the uptake of heavy metal ions.
The Zn2+, Cd2+, Cu2+ and Pb2+ are efficiently removed through modified nanoparticles of Fe oxide with 3-aminopropyltriethoxysilane and copolymers of acrylic acid and crotonic acid [11, 47]. Similarly, the heavy metal ions are also removed by reporting the carboxylated chitosan changed magnetic nanoparticles [48]. Qi and Xu altered the chitosan nucleus by ionic gelation with tripolyphosphate used as ionic cross linker for Pb2+ [11, 49]. However, modified chitosan nanoparticles are breakup in the aqueous solution or aggregated in alkaline solution at pH 9, due to weak force attractions between tripolyphosphate molecules and chitosan. Dissolved organic colloids and organic carbon in small size have been identifies as a distinctive non-aqueous organic phase, which adsorbed the pollutants and thus decreases its bioavailability.
Zeolites
Zeolites, have microporous materials consisting of a 3D configuration of [SiO4]4-and [AlO4]5- polyhedra linked with oxygen atoms forming negative lattice providing Lewis and Bronsted acid sites. It has pore size less than 2 nm. Zeolite received significant Bronsted acidic characteristics by cations and protons exchange. Zeolite materials are largely applied in environmental studies due to their vast availability, non-toxic nature, selective adsorbent properties and low cost. It is extensively applied in the deletion of heavy metals, for instance Cu2+, Ni2+, Cr3+, Zn2+, Fe2+, Cd2+ and Pb2+ [11, 50, 51]. Zeolites are stable however below pH 2, it is unstable and collapse. Zeolites are documented to better as compared to activated carbon for the retention of chloroform, methyl-tert-butyl ether, and TCE in water.
Silica and Silica Based Nanomaterials
Another important materials is the mesoporous silica and its derivatives materials having approximately 2–50 nm pore size which successfully adsorbed heavy metals from contaminated water. Mesoporous silica with functionalized monolayers have been valuable for mercury and others heavy metals removal.
Amino-functionalized silica showed better performance for the removal of Cu2+, Ni2+, Zn2+ and Cr2+, whereas, mercuric ions efficiently adsorbed on thio-functionalized silica [11, 52]. Activated alumina, having high porosity, is widely used in filtering apparatuses which are used for the purification of drinking water. Aminated and mesoporous alumina, and alumina-supported MnO are able to take out As3+, As4+, Cu2+ and TCE from the polluted water [11, 53, 54].
Polymer Based Nanomaterials
Various polymers have been assembled in the form of nanoparticles and were applied as adsorbent for the removal of various pollutants. For instance, poly N-isopropylacrylamide nanoparticles eradicate Pb2+ and Cd2+ from contaminated water by Coulombic interaction between the polymer carboxylate group and metal species with positive charge [55]. Nevertheless, the use of poly N-isopropylacrylamide in treatment of polluted water is not extensive because the isopropylacrylamide is not showing promising capability toward metal ions removal. The copolymerization of pyridyl monomer to form polymeric nanoparticles with styrene have been used for metal ions removal. Bipyridine groups on developed nanoparticles surface enhanced the metal removal performance from wastewater due to their high interacting capability with metal ions [56]. Poly(vinylpyridine) nanoparticles specifically removed Cu2+ as compared to other metal ions [11]. Azo-chromophore modified polystyrene nanoparticles showed high adsorption capacity toward Pb+2 Bell et al. [57]. proposed that the polymeric nanoparticles grafted with macrocyclic ligand having core-shell structure are highly active for the selective removal of heavy metals. Without grafting, this unique core–shell morphology removed Hg ion selectively, while with grafting technology it removed Co2+ selectively from other metal ions [58]. Thus, polymeric nanoparticles may be easily structured for the selective removal of heavy metals. Tungittiplakorn et al. suggested that polyurethane-based nanoparticles could be practical in the transportation and desorption of organic contaminants with the hydrophobic core of the nanoparticles [11, 59, 60].
Dendrimers Based Nanomaterials
Dendrimers based metal nanoparticles (NPs) have got much interest in the scientific research and technology in ecological treatment owing to their unique crystal shapes, size, and lattice morphology [59]. Synthesis of functionalized nanoparticles by different approaches is remain a great deal. One of the exceptional methods used to make inorganic NPs is the dendrimers approach. Dendritic nanopolymers are extremely 3D branched globular nanoparticles with precise shapes and designs. Their sizes are 1–100 nm in range, and are built from a preliminary atoms, for instance, attachment of nitrogen to carbon as well as other elements, which built their self through a series of chemical reactions, that produces a sphere-shaped branching structure by involving hierarchical assembly of divergent or convergent methods. As the development progresses, layers are supplemented succeedingly and the sphere can be extended to the targeted size. It contains three constituents: (1) core, (2) internal branched cells and (3) end branched cells [61, 62]. It is an innovative polymers class with a thick sphere-shaped structure and exceptional performance with narrow size distribution, used as templates or stabilizers to form comparatively monodispersed organic/inorganic hybrid nanoparticles. During the synthesis of dendrimer-stabilized nanoparticles, dendrimer played an extremely important role by coordinating with the metal ions through electrostatic contact, etc., followed by reduction of the nanoparticles to make inorganic nanoparticles. Dendrimer established nanomaterials can sum up a wide range of solutes in water, comprising cations (i.e., iron, silver, gold, zinc, copper, nickel, uranium, cobalt and lead) by connecting to the functional groups of dendrimers, such as carboxylates anions, hydroxymates and primary amines [63]. The removal aptitude and selectivity can be upgraded by varying functional group of dendrimers. Dendrimers-based nanomaterials might be useful in the regaining of uranium metals and perchlorate anions from unclean groundwater.
Carbon Nanomaterials
These materials are largely used for sorption. Carbon nanomaterials are existing in different morphologies, such as activated carbon, carbon fibers, carbon beads, single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), nanoporous carbon, graphene, graphene oxide, carbon nanotubes. These carbon nanomaterials have been largely used to remove different pollutants from waste water because they have many benefits as compared to the old-fashioned materials, because of their high surface/volume ratio. High electronic, mechanical and optical properties make them potent adsorbents [64]. The high degree of successful ecofriendly process is because of high adsorb capacity for diverse pollutants, favorable kinetics, high surface area, and selective removal of aromatic solutes [65].
Carbon Black and Activated Carbon
Activated carbon is a well known adsorbent and has been widely used for the waste water treatment. Usually the carbon black is activated by oxidation in the presence of HNO3 and thus make it functionalize by creating functional groups on the surface of carbon black. This functionalized carbon showed high adsorption of Cu2+ and Cd2+ because of the increased amount of functional groups created by oxidation on the surface of carbon black. The Adsorption behavior of modified carbon black (CB) toward Cu2+or Cd2+ is highly dependent on pH of the solution. Adsorption is directly related to solution pH [11]. The functionalized carbon black uptake most of the metal when pH raise above 5.5 and the reasons might be due to the development of charge on the surface of carbon black (modified) and the concentration distribution of Cd2+ or Cu2+ that are pH dependent. At lower pH, Cd2+ or Cu2+ adsorption on modified CB is lower due H+ and Cd2+ or Cu2+ competition for the adsorption sites. There are negative charges on the modified CB surface for wide pH range and Cd2+ or Cu2+ carrying positive charge, remaining as either Cd2+ or Cu2+. When the pH level of the solution increases, the concentration of competitor H+ ions decreases and Cu2+ or Cd2+ adsorption increases [11]. Nanoscale hydroxyapatite and carbon black have shown strong adsorption of Cu2+, Zn2+, Pd2+ and Cd2+. CB and activated carbon have different adsorption affinities for different metal ions. The adsorption capacity also depend upon the size of carbon particles, smaller the particle size, higher will be the adsorption capacity while carbon with larger particles result in lower adsorption because the micropores at the internal surface of the activated carbon are not accessible to pollutant whereas the nanosized pores of carbon black are more accessible to pollutant [11, 66].
Carbon Nanotubes
CNTs are like cylindrical hollow micro-crystals of graphite. Due to its high specific surface area, CNTs have attracted the interest of researchers as a new type of adsorbent. It is the graphitic carbon needles which have 4–30 nm external diameter and 1 mm a length [67]. MWCNTs are made of concentric cylinders with spacing between the adjacent layers of about 3.4 angstrom [68]. Iijima was first discovered SWCNTs [69]. The modified CNTs which was functionalized by oxidation was found to be a good adsorbent of Cd2+ and it was found that the specific area and pore specific volume of CNTs were increased after oxidation. Due to the large specific area, The modified CNTs have displayed extraordinary adsorption capabilities and adsorption efficiencies toward several organic pollutants [70]. Further it was observed that CNTs require less time to adsorb organic pollutants as compared to activated carbon [44]. The reason behind the fast adsorption is that CNTs are lack of porosity while the activated carbons have porous structure. In order to achieve the equilibrium, adsorbate move from external to internal pores surface [44]. The fastest response of CNTs indicated its high removal potential for dichlorobenzene from water. Even CNTs were found superior adsorbent of dichlorobenzene as compared to graphitized CNTs which is due to the rough surface of CNTs that makes the adsorption of dichlorobenzene much easier for CNTs while the smooth surface of graphitized CNTs reduces the adsorption of dichlorobenzene. It is also adsorbed that SWCNTs exhibit higher adsorption than hybrid carbon nanotubes (HCNTs) and MWCNTs. It is reported that the ethylbenzene adsorption on the surface of CNTs rely on their porosity and chemical nature. HCNT hybride might created more absorbent structure for MWCNTs and exposing larger surface area as compared to MWCNTs for ethylbenzene adsorption and thus predominantly removed ethylebenzene. SWCNT efficiently adsorbed ethylbenzene as compared to MWCNT due to the electrostatic force of interactions between ethylebenzene and SWCNT [44] due to the positively charged ethylbenzene with negatively charged SWCNT, making more electrostatic interactions and thus high adsorption capacity. Zn2+ sorption from the aqueous solutions was studied by SWCNTs and MWCNTs [71], where it was observed that the Zn2+ adsorption on the CNTs was directly related to temperature. Under the same experimental conditions, the sorption capacity of Zn2+ by CNTs was higher compared to commercially powdered activated carbon, indicating that MWCNTs and SWCNTs are effective sorbents. All these results indicated the high reusability of CNTs in wastewater treatment. CNTs activation under oxidizing conditions displaying a key role by increasing the sorption capacity, because it brought changes in surface functional and morphology which helped amorphous carbon removal [72]. The activation alter the surface characteristics of functional with many defects on the surfaces. Additionally they had higher lead adsorption capacity and become a highly adsorbents materials for waste water purifications. The Cu2+, Cd2+ and Ni2+ removal efficiency was documented in the literature. The dyes removal are pH dependent due to the electrostatic force of attraction amongst the negatively charged CNT and positively charged cationic dyes, such as, methylene blue and methyl violet [73, 74].
Nanocomposites
Nanocomposites play an important role in water purification. Nanocomposites are either carbon nanocomposites or polymer nanocomposites which shows applications in environmental remediation.
Carbon based nanocomposites have shown excellent performance for adsorption as compared to pure carbon based materials, such carbon black, carbon nanotube, graphene and graphene oxides. Carbon based nanomaterials are used widely in the field of removal heavy metals in recent decades, due to its nontoxicity and high sorption capacities. Activated carbon is used firstly as sorbents, but it is difficult to remove heavy metals at ppb levels. Then, with the development of nanotechnology, carbon nanotubes, fullerene, and graphene are synthesized and used as nanosorbents. These carbon nanomaterials have shown significantly higher sorption efficiency comparing with activated carbons. Therefore CNT/MO nanocomposites sorption capacity are highly demanded for environmental remediation. It was reported that for the physical adsorption of contaminants, nanocomposites being the highly demanded materials due to its inert and specific surface areas, with comparatively uniform assemblies, leading to high adsorption sites. For instance, the hybride nanocomposite (MWCNT/alumina) has been described an effective sorbent for lead ions removal 3-7 pH [75]. For instance, magnetic composites adsorbent (CNT-iron oxides) has been effectively practiced for different metals removal from wastewater. The europium adsorption was achieved by incorporating iron oxide magnetite with CNTs. This composite is potentially a promising to facilitate the separation and recovery of CNTs from solution with magnetic separation technique. CNTs become not the part of pollutants and can be easily be recovers [76]. For instance, different nanostructure materials was water purification including magnetic MMWCNT nanocomposite for removal of cationic dyes removal [77] and manganese oxide-coated carbon nanotubes for Pb(II) removal, the Pb(II) is enhanced with manganese oxide loading, as manganese oxide provide high adsorption sites [78]. Graphene and reduced graphene oxide (rGO) are kinds of novel and interesting carbon materials and have attracted tremendous attentions as adsorbents for the removal of different pollutants. Because of very high specific surface area, graphene and reduced graphene oxide are good candidates as an adsorbent [79]. Graphene-based manganese oxide composites were applied as adsorbent materials for water purification [79]. Graphene-based iron oxide nanocomposites have been used as adsorbents for the removal of tetracycline, dyes, As(III), As(V), chromium, lead, cobalt, and so on [79]. More recently, a ternary composite of highly reduced graphene oxide/Fe3O4/TiO2 has been reported, which exhibited high selectivity and capacity for the removal of phosphopeptides. In another study, graphene/zinc hydroxide nanocomposites were shown high removal efficiency toward hydrogen sulfide. Recently, graphene-based composites have been applied for the extraction of polycyclic aromatic hydrocarbons and parathyroid pesticides with excellent removal efficiency. The preparations of graphene-based magnetic nanocomposites have reported for the removal of arsenic. Similarly, the magnetic reduced graphene oxide nanocomposite have been reported for the removal of dyes and heavy metals such as arsenate, nickel, and lead [80].
The difficult separation process limit the reuse of metallic oxides nanoparticles and other nanoscale materials and possible risk to ecosystems and human health caused by the potential release of nanoparticles into the environment. In addition, the use of aqueous suspensions limits their wide applications because of the problems for the separation of the fine particles and the recycling of the catalyst. Immobilization of these nanoparticles in polymer matrix has been available to solve the problems to considerable extent, serving for the reduction of particle loss, prevention of particles agglomeration and potential application of convective flow occurring by free-standing particles [81-85]. The widely used host materials for nanocomposite fabrication are polymers and polymeric host materials must possess excellent mechanical strength for long term use. The choice of the polymeric support is influenced by their mechanical and thermal behavior, hydrophobic/hydrophilic balance, chemical stability, bio-compatibility, optical and/ or electronic properties and their chemical functionalities (i.e. solvation, wettability, templating effect, etc.) [86]. Nanocomposites based on magnetite (Fe3O4), maghemite (Fe2O3) and jacobsite (MnFe2O4) nanoparticles loaded alginate beads have shown high ability to remove heavy metal ions (Co(II), Cr(VI), Ni(II), Pb(II), Cu(II), Mn(II)) and organic dyes (methylene blue and methyl orange) from aqueous solutions [87]. Magnetic particles in the nanocomposites allowed easy isolation of the beads from the aqueous solutions after the sorption process. Cellulose/Mn3O4 have shown high uptake capacity for the removal of chromium. It has been studied for the removal of Cu2+, Cd2+, Co2+, Cr3+, Fe3+, Ni2+, Zn2+ and Zr4+. The nanocomposite has followed the uptake capacity order Cr3+ ˃ Zn2+ ˃ Fe3+ ˃ Cd2+ ˃ Zr4+ ˃ Ni2+ ˃ Co2+ ˃ Cu2+ [36]. Similarly, ZrO2 embedded cellulose adsorb Ni2+ selectively [34]. Cellulose acetate/ZnO nanocomposite has been utilized for the removal of heavy metals [8]. Polymer based nanocomposites were used as adsorbent for the uptake of cadmium and yttrium [33] while poly(propylene carbonate)/exfoliated graphite nanocomposites extracted Au+3 selectively [88]. Polybenzimidazole hybrid membranes were found to be selective for the adsorption of mercury [13]. Cellulose-lanthanum hydroxide nanocomposite selectively removed copper ions [30]. Various chitosan based nanocomposites have showed excellent adsorption capability for different dyes [36].
Chemical Degradation Based Environmental Remediation
There are different methods for water treatment. Among them, chemical degradation is the most widely used methods [11]. Chemical degradation methods include the following:
Ozone/UV Radiation/H2O2 Oxidation
Supercritical Water Oxidation
Fenton Method
Sonochemical Degradation
Electrochemical Method
Electron Beam Process
Solvated Electron Reduction
Enzymatic Treatment Methods
Photocatalytic Degradation
The word “photocatalytic degradation” means the degradation in the presence of photon and catalyst while the word “photocatalyst” is a combination of photons and catalyst. Thus photocatalyst is a chemical substance which can accelerate the rate of chemical reaction under illumination of light while the photocatalysis is photon induced redox processes at the surface of a photocatalyst in suspension [89]. Photocatalysis is a type of heterogeneous catalysis for which the basic requirements are as follow.
Photocatlyst: Metal oxides, Metal sulfides, Metal selenides, LDH, Nanocomposite
Redox/Donor or acceptor medium: Water or any other polar solvent (e- donar)
Adsorbed or dissolved O2 (e- acceptor)
Photon source: Halogen lamps, Mercury vapor lamps and sunlight
A photocatalyst must have the following properties.
It must be active under illumination of light and have band gap energy (Eg)It should be inert both biologically and chemically.It should be stable toward photocorrosion.It should be economical and non-toxic.It must have suitable valance and conduction band potentials to establish a redox reaction.The valance and conduction band potential means that a photocatalyst must have band gap. Electrons of an atom occupy discrete energy levels. In a crystal, each of these energy levels is split into many energy levels. 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. Thus it means that metal has no band gap. Only reduction or oxidation takes place which depends on the band. In contrast, in semiconductors and insulators, 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. Thus both semiconductors and insulators has bandgap. Semiconductors have low bandgap (bandgap ˂ 5) while insulators have high bandgap (bandgap ˃ 5). Thus semiconductors are much more important because semiconductors can easily excite valance band electrons to generate e--h+ pair [3, 4, 90]. Generally, a potential difference is established across valance band and conduction band of semiconductor when it in contact with solvent. When semiconductor is illuminated by light and get energy equal or more then bandgap energy, it excite valence band electron and generate e--h+ pair. This e--h+ pair cause redox reaction when a donor and acceptor get adsorbed on the surface of the semiconductor. The photo-generated holes at the surface of the irradiated semiconductor can oxidize a variety of hazardous species or produce ̇OH radicals [91-94]. However, the main problem is the recombination of this generated e--h+ pair before proceeding the redox reaction. Therefore, it is vital to avoid this recombination. The recombination of e--h+ pair in semiconductors can be avoided by the following methods.
Surface modification by metal ion impregnationComposite formationMetal ions (Mn+) doping or nonmetal (S and N) dopingUse of organic molecules such as methanol for hole captureIn aqueous media, the semiconductor follow the following mechanism in the presence of light. They produces OH and O2- radicals which are highly reactive and can easily degrade the organic pollutants.
The rate of a photocatalytic reaction depends on various factors such as temperature, pH, amount of catalyst, amount of pollutants etc.
Photocatalyst can be divided on the basis of light absorption into UV photocatalyst and solar photocatalyst. Those photocatalysts which absorb UV light and only encourage photocatalysis upon irradiation by UV light because it absorb only in the UV region of round about 375 nm with the band gap (~3.2 ev) in UV region. TiO2, ZnO, Fe2O3, CdO, CeO2, CdS, WO3, SnO2, etc. are UV catalysts which absorb only UV light below the visible range of light spectrum [95].
Solar photocatalyst are those which absorb light in visible range and promote photocatalysis by irradiation with light. For solar photocatalysis, a photocatalyst must promote photocatalysis by irradiation with visible light because solar spectrum consists of 46% of visible light while the UV light is only 5-7% in the solar spectrum. This least coverage of UV light in the solar spectrum, the high band gap energy (3.2 eV), and fast charge carrier recombination (within nanoseconds) of ZnO confines its extensive application in the solar light [77
