15.5 Pesticide Removal from Drinking
15.5.1 Noble Metal Nanoparticle Based Mineralization
One of the areas of interest of our research group is the interaction of noble metal nanoparticles with organochlorine and organophosphorus pesticides.
Specifi cally, the nanoparticles used for study are of gold and silver whereas the pesticides are endosulfan, malathion, and chlorpyrifos. This study is a consequence of our fi nding on the possibility of degrading diff erent halocarbons using noble metal nanoparticles [ 19 ].
It was discovered that mineralization of halocarbons happens in two steps:
adsorption of halocarbons on the nanoparticle surface and its consequent mineralization to metal halides and amorphous carbon [ 19 ]. A few of the important revelations from this study are:
Environmentally benign nature of the reaction products and zero production of by-products. One of the key issues to resolve in tackling the pesticide contamination problem in its entirety is the elimination of reaction products.
The products from such a catalytic decomposition are metal halides and amorphous carbon, both of which are environmentally benign. Using advanced mass spectroscopic techniques, it was established that there are no reaction by-products left in the solution and mineralization of pesticides is complete for the molecules investigated.
Demonstration of size selective reactivity for nanoparticles. The experiments were conducted with bulk form of noble metals and it was concluded that this property is demonstrated only in the case of nanoparticles. The absence of such a property being exhibited by the bulk form of noble metals is also explained from thermochemical calculations (explained later).
Capability to target a broad range of organochlorine and organophosphorus pesticides. The reactivity was studied with a broad range of halocarbons (e.g., benzyl chloride, chloroform, and bromoform), organochlorine pesticides
Figure 15.6 Interaction studies of dendrimer with metal ions and their subsequent reduction to prepare encapsulated nanoparticles. Adapted from R.W.J. Scott et al. [18].
Copyright (2003) American Chemical Society.
Addition of metal ions
Addition of reducing agent
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(e.g., endosulfan), and organophosphorus pesticides (e.g., chlorpyrifos, malathion). Using sensitive instrumentation, it was established that all such organics undergo complete mineralization.
Based on the comprehensive study conducted at various reaction conditions, it is postulated that the catalytic decomposition of halocarbons is initiated through the transfer of electrons from metal nanoparticles to the solvent, which in turn causes the mineralization of halocarbons. The scheme of reactions (Equation 15.2) is suggested to be the following (not balanced by stoichiometry as it is diffi cult to predict the number of metal atoms in a nanoparticle) [ 19 ]:
Ag(nano) → Ag+(nano) + e¯
(CH3)2CHOH → (CH3)2CO + 2H+ + 2e¯ (15.2) Ag + CCl4 → AgCl + C
In this specifi c case, presented earlier, (CH 3 ) 2 CHOH was used as a solvent for the bulk mineralization of CCl 4 , studied in a (CH 3 ) 2 CHOH/H 2 O solvent mixture. From a thermodynamic standpoint, the reaction of halocarbons with silver is not favored due to small positive reaction enthalpy (standard enthalpy values for CCl 4 and AgCl are –128.2 and –127.0 kJ mol –1 , respectively). It is suggested that the nano form of the noble metal particles along with the presence of energetic surface atoms helps in overcoming the thermochemical and entropic barriers. It is easy to comprehend that the decrease in particle size leads to drastic changes in the rate kinetics of the reaction owing to an increase in the availability of reaction sites on the metal nanoparticle surface.
The other variable component of the reaction kinetics is the activation energy, which is known to be aff ected by many parameters such as nature of reactants, crystallinity of the reactive surfaces, ease of charge transfer, surface impurities such as dopants, and so on. The reaction outlined earlier can result in the removal of the metal nanoparticle as ions. Hence, it has been used for the creation of nanoshells starting from core-shell nanoparticles [ 20 ]. Such nanoshells have been used for biological applications, namely for the delivery of drug molecules into bacteria [ 21 ]. These mineralization reactions can be used to probe the porosity of the core-shell structures [ 22 ].
The mechanism of nanoparticle reactivity. The dramatic reactivity change at the nanoscale is largely attributed to the perfection achieved in the ordering of atoms (or molecules) [ 23 ] and change in surface energy. The bottom-up approach of material synthesis helps to minimize imperfection and defects present on the surface of the particle. The high degree of atomic order in crystalline nanoparticles helps to control the physical and chemical behavior and consequently creates extremely novel properties [ 24 ]. At the same time, it must be remembered that surface defects play a dominant role in the reactivity of many systems, especially oxide nanoparticles.
Nanoparticle activity based on energy gap. The underlying building blocks of any material, be it nanoparticle or bulk material, are atoms and molecules,
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each of which have discrete energy levels or orbitals. However, owing to the complex nature of interactions between multiple atoms and molecules present in the material, a number of energy bands are formed. In the case of metals, transfer of valence electrons to the conduction band occurs, leading to many novel properties. For metal nanoparticles, delocalized electrons can be excited even by visible light (in some cases, also by near infrared) and it is refl ected in the form of surface plasmon resonance that is characterized through distinct visible color for many nanoparticle solutions ( Fig. 15.7 ). The spacing, δ, between the adjacent energy levels in a band is given by the approximate relationship, δ≈ E F / n , where E F is the Fermi level energy and n is the number of atoms in the particle. As the particle size decreases, at a critical point, the energy band spacing becomes greater than the thermal energy, k T, where the atoms begin to behave as individual species, and the particle may lose its
Figure 15.7 (a) Schematic representation of band transitions and corresponding UV-visible-NIR spectrum for (1) atom, (2) metal, and (3) clusters. (b) Graphical
representation of percentage of atoms found on various facets of a nanoparticle, calculated using a theoretical modeling scheme for cubo-octahedron model (shown in the inset) [28].
Reprinted with permission from S. Schimpf, et al. [28]. Copyright (2002) with permission from Elsevier. (c) Changes in the color of the nanoparticle solution on addition of organochlorine molecule. (1) Citrate stabilized gold nanoparticle solution, (2) gold nanoparticle solution incubated with endosulfan, (3) citrate stabilized silver nanoparticle solution, and (4) silver nanoparticle solution incubated with carbon tetrachloride.
Reproduced from A.S. Nair et al. [19,31]. Reproduced by permission of The Royal Society of Chemistry.
(a) (b)
Fermi bands
Plasmon s p
UV Visible IR
Absorbance
(1)
(2)
(3) UV Visible IR
Metallic absorption Inter-band
absorption
Absorbance
UV Visible IR Surface plasmon
absorption
Absorbance
Wavelength (nm)
(2) (3) (4)
(1) (c)
0.8
relative frequency
0.6 (111)
(100) edges corners
Particle diameter dAu [nm]
2
0 4 6 8 10 12 14
0.4 0.2 0.0
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metallic properties. A spacing δ of 2.5 × 10 –2 eV exceeds the thermal energy at room temperature when n is less than 400 (i.e., 2 nm in diameter) [ 25 ].
Mode of decomposition for organic species. For a large variety of organic molecules, the principal mode of decomposition is electron transfer from the metal particles. As the oxidation of metals is generally favored and as these processes are facilitated in aqueous medium, there is availability of electrons at metal particle surfaces. Oxidation of nanoparticles is even more facile, in comparison to bulk. Remember that oxidation is the removal of an electron from the whole nanoparticle and not from an atom. This oxidation can also be tuned by varying the particle dimension, by providing appropriate functionalization, and by attaching the particle on suitable substrates. The oxidized species can be one of the many diff erent oxides or hydroxides that may have reduced solubility in water. The electron removed from the particle surface can be made available for appropriate reduction chemistry. For molecules such as halocarbons, the electron is transferred to the halogen making the C-X bond weak, resulting in the formation of the halide ion. The organic species can participate in various other reactions, depending on the medium or other reagents present. The halide ion formed can also produce the metal halide and it again is dissolved in the medium or precipitated depending on the solubility product.
Discharge of metal ions in water. The presence of metal ions in solution in water is an important concern, especially in the case of toxic chemicals.
However, for Fe, Ag, TiO 2 , ZnO, and CeO 2 derived materials, the solubility of the species concerned is low, and therefore ionic concentration is not beyond allowable limits. This is very important in designing water quality applications.
As water in general is contaminated with several ionic species, the nature of the metal ion can be diff erent from case-to-case. The solubility and stability of ions is strongly dependent on pH. Therefore, the latter is an important parameter in deciding the type of the ion. The important issue of concern is the coverage of the surface with the oxides or hydroxides form inhibiting the electron transfer, thereby reducing the surface activity. Highly dispersed particles of smaller dimensions make it possible to use all the available metals for the chemistry concerned.
Eff ect of atomic arrangement on nanoparticle reactivity. Although the bulk form of gold is expected to be face-centered cubic, the Au 32 cluster is predicted to be an empty icosahedron. Control over synthesis mechanisms has enabled the fi ne-tuning of the properties of the material through changes in the lattice structure. Nanoparticles of diff erent shapes have diff erences in the exposed surfaces. This also leads to diff erences in atomic distribution across the nanoparticle surface, which in turn aff ects the electron transfer rate kinetics between metal nanoparticles and corresponding organic species. Accordingly, the nanoparticles have been reported to have higher catalytic activity when they are present in the tetrahedral structure versus cubic or spherical structure [ 26 ]. This is attributed to enhancement in chemical reactivity at the sharp edges and corners and can easily be correlated with the number of atoms
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found at the respective places ( Fig. 15.7(b) ). The 4.5-nm sized tetrahedral nanoparticle is composed entirely of (111) facets with sharp edges and corners, which comprise approximately 28 percent of the total atoms and approximately 35 percent of the surface atoms. The 7.1-nm sized cubic nanoparticle is composed entirely of (100) facets with a smaller fraction of atoms on their edges and corners, which comprise approximately 0.5 percent of total atoms and approximately 4 percent of surface atoms.
It is well known that high-index planes generally exhibit much higher catalytic activity than the most common stable planes, owing to high density of catalytic sites. On the contrary, due to high surface energy for high-index planes, crystals usually grow perpendicular to high-index planes. The novel nanoparticle synthesis mechanisms have, however, solved this problem. This has contributed signifi cantly to improvement in high-effi ciency catalysis [ 27 ].
As the particle size decreases and it reaches low nanometer dimensions, the atoms at the surface of the particle start to show enhanced vibrational motion normal to the surface, which creates enhanced surface mobility for the atoms.
This is clearly evident through the changes in the physical properties of the material (e.g., the 2-nm gold particles melt at about 300K whereas the bulk melting point is 1337 K).