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Thursday, April 18, 2019

Nanoparticle

From Wikipedia, the free encyclopedia

TEM (a, b, and c) images of prepared mesoporous silica nanoparticles with mean outer diameter: (a) 20nm, (b) 45nm, and (c) 80nm. SEM (d) image corresponding to (b). The insets are a high magnification of mesoporous silica particle.
 
Nanoparticles are particles between 1 and 100 nanometres (nm) in size with a surrounding interfacial layer. The interfacial layer is an integral part of nanoscale matter, fundamentally affecting all of its properties. The interfacial layer typically consists of ions, inorganic and organic molecules. Organic molecules coating inorganic nanoparticles are known as stabilizers, capping and surface ligands, or passivating agents. In nanotechnology, a particle is defined as a small object that behaves as a whole unit with respect to its transport and properties. Particles are further classified according to diameter.

Definition

IUPAC definition
 
Particle of any shape with dimensions in the 1 × 10−9 and 1 × 10−7 m range.
 Note 1: Modified from definitions of nanoparticle and nanogel.

Note 2: The basis of the 100-nm limit is the fact that novel properties that
differentiate particles from the bulk material typically develop at a critical
length scale of under 100 nm.


Note 3: Because other phenomena (transparency or turbidity, ultrafiltration,
stable dispersion, etc.) that extend the upper limit are occasionally considered,
the use of the prefix nano is accepted for dimensions smaller than 500 nm,
provided reference to the definition is indicated.

 
Note 4: Tubes and fibers with only two dimensions below 100 nm are also
nanoparticles.

The term "nanoparticle" is not usually applied to individual molecules; it usually refers to inorganic materials. 

Ultrafine particles are the same as nanoparticles and between 1 and 100 nm in size, as opposed to fine particles are sized between 100 and 2,500 nm, and coarse particles cover a range between 2,500 and 10,000 nm. The reason for the synonymous definition of nanoparticles and ultrafine particles is that, during the 1970s and 80s, when the first thorough fundamental studies with "nanoparticles" were underway in the USA (by Granqvist and Buhrman) and Japan, (within an ERATO Project) they were called "ultrafine particles" (UFP). However, during the 1990s before the National Nanotechnology Initiative was launched in the USA, the new name, "nanoparticle," had become more common (for example, see the same senior author's paper 20 years later addressing the same issue, lognormal distribution of sizes). Nanoparticles can exhibit size-related properties significantly different from those of either fine particles or bulk materials.

Nanoclusters have at least one dimension between 1 and 10 nanometers and a narrow size distribution. Nanopowders are agglomerates of ultrafine particles, nanoparticles, or nanoclusters. Nanometer-sized single crystals, or single-domain ultrafine particles, are often referred to as nanocrystals

According to ISO Technical Specification 80004, a nanoparticle is defined as a nano-object with all three external dimensions in the nanoscale, whose longest and shortest axes do not differ significantly, with a significant difference typically being a factor of at least 3.

The terms colloid and nanoparticle are not interchangeable. A colloid is a mixture which has solid particles dispersed in a liquid medium. The term applies only if the particles are larger than atomic dimensions but small enough to exhibit Brownian motion, with the critical size range (or particle diameter) typically ranging from nanometers (10−9 m) to micrometers (10−6 m). Colloids can contain particles too large to be nanoparticles, and nanoparticles can exist in non-colloidal form, for examples as a powder or in a solid matrix.

History

Although nanoparticles are associated with modern science, they have a long history. Nanoparticles were used by artisans as far back as Rome in the fourth century in the famous Lycurgus cup made of dichroic glass as well as the ninth century in Mesopotamia for creating a glittering effect on the surface of pots. In modern times, pottery from the Middle Ages and Renaissance often retains a distinct gold- or copper-colored metallic glitter. This luster is caused by a metallic film that was applied to the transparent surface of a glazing. The luster can still be visible if the film has resisted atmospheric oxidation and other weathering.

The luster originates within the film itself, which contains silver and copper nanoparticles dispersed homogeneously in the glassy matrix of the ceramic glaze. These nanoparticles are created by the artisans by adding copper and silver salts and oxides together with vinegar, ochre, and clay on the surface of previously-glazed pottery. The object is then placed into a kiln and heated to about 600 °C in a reducing atmosphere. In heat the glaze softens, causing the copper and silver ions to migrate into the outer layers of the glaze. There the reducing atmosphere reduced the ions back to metals, which then came together forming the nanoparticles that give the color and optical effects. Luster technique showed that ancient craftsmen had a sophisticated empirical knowledge of materials. The technique originated in the Muslim world. As Muslims were not allowed to use gold in artistic representations, they sought a way to create a similar effect without using real gold. The solution they found was using luster.

Michael Faraday provided the first description, in scientific terms, of the optical properties of nanometer-scale metals in his classic 1857 paper. In a subsequent paper, the author (Turner) points out that: "It is well known that when thin leaves of gold or silver are mounted upon glass and heated to a temperature that is well below a red heat (~500 °C), a remarkable change of properties takes place, whereby the continuity of the metallic film is destroyed. The result is that white light is now freely transmitted, reflection is correspondingly diminished, while the electrical resistivity is enormously increased."

Properties

Silicon nanopowder
 
1 kg of particles of 1 mm3 has the same surface area as 1 mg of particles of 1 nm3
 
Nanoparticles are of great scientific interest as they are, in effect, a bridge between bulk materials and atomic or molecular structures. A bulk material should have constant physical properties regardless of its size, but at the nano-scale size-dependent properties are often observed. Thus, the properties of materials change as their size approaches the nanoscale and as the percentage of the surface in relation to the percentage of the volume of a material becomes significant. For bulk materials larger than one micrometer (or micron), the percentage of the surface is insignificant in relation to the volume in the bulk of the material. The interesting and sometimes unexpected properties of nanoparticles are therefore largely due to the large surface area of the material, which dominates the contributions made by the small bulk of the material

Nanoparticles often possess unexpected optical properties as they are small enough to confine their electrons and produce quantum effects. For example, gold nanoparticles appear deep-red to black in solution. Nanoparticles of yellow gold and grey silicon are red in color. Gold nanoparticles melt at much lower temperatures (~300 °C for 2.5 nm size) than the gold slabs (1064 °C);. Absorption of solar radiation is much higher in materials composed of nanoparticles than it is in thin films of continuous sheets of material. In both solar PV and solar thermal applications, controlling the size, shape, and material of the particles, it is possible to control solar absorption. Recently, the core (metal)-shell (dielectric) nanoparticle has demonstrated a zero backward scattering with enhanced forward scattering on Si substrate when surface plasmon is located in front of a solar cell. The core-shell nanoparticles can support simultaneously both electric and magnetic resonances, demonstrating entirely new properties when compared with bare metallic nanoparticles if the resonances are properly engineered. 

Other size-dependent property changes include quantum confinement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism in magnetic materials. What would appear ironic is that the changes in physical properties are not always desirable. Ferromagnetic materials smaller than 10 nm can switch their magnetisation direction using room temperature thermal energy, thus making them unsuitable for memory storage.

Suspensions of nanoparticles are possible since the interaction of the particle surface with the solvent is strong enough to overcome density differences, which otherwise usually result in a material either sinking or floating in a liquid. 

The high surface area to volume ratio of nanoparticles provides a tremendous driving force for diffusion, especially at elevated temperatures. Sintering can take place at lower temperatures, over shorter time scales than for larger particles. In theory, this does not affect the density of the final product, though flow difficulties and the tendency of nanoparticles to agglomerate complicates matters. Moreover, nanoparticles have been found to impart some extra properties to various day to day products. For example, the presence of titanium dioxide nanoparticles imparts what we call the self-cleaning effect, and, the size being nano-range, the particles cannot be observed. Zinc oxide particles have been found to have superior UV blocking properties compared to its bulk substitute. This is one of the reasons why it is often used in the preparation of sunscreen lotions, is completely photostable, and toxic [DJS -- ??].

Clay nanoparticles when incorporated into polymer matrices increase reinforcement, leading to stronger plastics, verifiable by a higher glass transition temperature and other mechanical property tests. These nanoparticles are hard, and impart their properties to the polymer (plastic). Nanoparticles have also been attached to textile fibers in order to create smart and functional clothing.

Metal, dielectric, and semiconductor nanoparticles have been formed, as well as hybrid structures (e.g., core–shell nanoparticles). Nanoparticles made of semiconducting material may also be labeled quantum dots if they are small enough (typically sub 10 nm) that quantization of electronic energy levels occurs. Such nanoscale particles are used in biomedical applications as drug carriers or imaging agents with work being done to try to understand the fluid dynamic properties (e.g. drag forces) in nanoscale applications. This has shown the relationship between the fluid forces on nanoparticles and the fluid Reynolds and Knudsen numbers.

Semiconductor nanoparticle (quantum dot) of lead sulfide with complete passivation by oleic acid, oleyl amine and hydroxyl ligands (size ~5nm)
 
Semi-solid and soft nanoparticles have been manufactured. A prototype nanoparticle of semi-solid nature is the liposome. Various types of liposome nanoparticles are currently used clinically as delivery systems for anticancer drugs and vaccines. 

Nanoparticles with one half hydrophilic and the other half hydrophobic are termed Janus particles and are particularly effective for stabilizing emulsions. They can self-assemble at water/oil interfaces and act as solid surfactants.

Hydrogel nanoparticles made of N-isopropylacrylamide hydrogel core shell can be dyed with affinity baits, internally. These affinity baits allow the nanoparticles to isolate and remove undesirable proteins while enhancing the target analytes.

Variation in properties

The chemical processing and synthesis of high-performance technological components for the private, industrial, and military sectors requires the use of high-purity ceramics (oxide ceramics, such as aluminium oxide or copper(II) oxide), polymers, glass-ceramics, and composite materials, as metal carbides (SiC), nitrides (Aluminum nitrides, Silicon nitride), metals (Al, Cu), non-metals (graphite, carbon nanotubes) and layered (Al + Aluminium carbonate, Cu + C). In condensed bodies formed from fine powders, the irregular particle sizes and shapes in a typical powder often lead to non-uniform packing morphologies that result in packing density variations in the powder compact.

Uncontrolled agglomeration of powders due to attractive van der Waals forces can also give rise to microstructural heterogeneity. Differential stresses that develop as a result of non-uniform drying shrinkage are directly related to the rate at which the solvent can be removed, and thus highly dependent upon the distribution of porosity. Such stresses have been associated with a plastic-to-brittle transition in consolidated bodies, and can yield to crack propagation in the unfired body if not relieved.

In addition, any fluctuations in packing density in the compact as it is prepared for the kiln are often amplified during the sintering process, yielding inhomogeneous densification. Some pores and other structural defects associated with density variations have been shown to play a detrimental role in the sintering process by growing and thus limiting end-point densities. Differential stresses arising from inhomogeneous densification have also been shown to result in the propagation of internal cracks, thus becoming the strength-controlling flaws.

Inert gas evaporation and inert gas deposition are free many of these defects due to the distillation (cf. purification) nature of the process and having enough time to form single crystal particles, however even their non-aggreated deposits have lognormal size distribution, which is typical with nanoparticles. The reason why modern gas evaporation techniques can produce a relatively narrow size distribution is that aggregation can be avoided. However, even in this case, random residence times in the growth zone, due to the combination of drift and diffusion, result in a size distribution appearing lognormal.

It would, therefore, appear desirable to process a material in such a way that it is physically uniform with regard to the distribution of components and porosity, rather than using particle size distributions that will maximize the green density. The containment of a uniformly dispersed assembly of strongly interacting particles in suspension requires total control over interparticle forces. Monodisperse nanoparticles and colloids provide this potential.

Monodisperse powders of colloidal silica, for example, may therefore be stabilized sufficiently to ensure a high degree of order in the colloidal crystal or polycrystalline colloidal solid that results from aggregation. The degree of order appears to be limited by the time and space allowed for longer-range correlations to be established. Such defective polycrystalline colloidal structures would appear to be the basic elements of submicrometer colloidal materials science and, therefore, provide the first step in developing a more rigorous understanding of the mechanisms involved in microstructural evolution in high performance materials and components.

Synthesis

There are several methods for creating nanoparticles, including gas condensation, attrition, chemical precipitation, ion implantation, pyrolysis and hydrothermal synthesis. In attrition, macro- or micro-scale particles are ground in a ball mill, a planetary ball mill, or other size-reducing mechanism. The resulting particles are air classified to recover nanoparticles. In pyrolysis, a vaporous precursor (liquid or gas) is forced through an orifice at high pressure and burned. The resulting solid (a version of soot) is air classified to recover oxide particles from by-product gases. Traditional pyrolysis often results in aggregates and agglomerates rather than single primary particles. Ultrasonic nozzle spray pyrolysis (USP) on the other hand aids in preventing agglomerates from forming.

A thermal plasma can deliver the energy to vaporize small micrometer-size particles. The thermal plasma temperatures are in the order of 10,000 K, so that solid powder easily evaporates. Nanoparticles are formed upon cooling while exiting the plasma region. The main types of the thermal plasma torches used to produce nanoparticles are dc plasma jet, dc arc plasma, and radio frequency (RF) induction plasmas. In the arc plasma reactors, the energy necessary for evaporation and reaction is provided by an electric arc formed between the anode and the cathode. For example, silica sand can be vaporized with an arc plasma at atmospheric pressure, or thin aluminum wires can be vaporized by exploding wire method. The resulting mixture of plasma gas and silica vapour can be rapidly cooled by quenching with oxygen, thus ensuring the quality of the fumed silica produced.

In RF induction plasma torches, energy coupling to the plasma is accomplished through the electromagnetic field generated by the induction coil. The plasma gas does not come in contact with electrodes, thus eliminating possible sources of contamination and allowing the operation of such plasma torches with a wide range of gases including inert, reducing, oxidizing, and other corrosive atmospheres. The working frequency is typically between 200 kHz and 40 MHz. Laboratory units run at power levels in the order of 30–50 kW, whereas the large-scale industrial units have been tested at power levels up to 1 MW. As the residence time of the injected feed droplets in the plasma is very short, it is important that the droplet sizes are small enough in order to obtain complete evaporation. The RF plasma method has been used to synthesize different nanoparticle materials, for example synthesis of various ceramic nanoparticles such as oxides, carbours/carbides, and nitrides of Ti and Si.

Inert gas condensation

Inert-gas condensation is frequently used to produce metallic nanoparticles. The metal is evaporated in a vacuum chamber containing a reduced atmosphere of an inert gas. Condensation of the supersaturated metal vapor results in creation of nanometer-size particles, which can be entrained in the inert gas stream and deposited on a substrate or studied in situ. Early studies were based on thermal evaporation. Using magnetron sputtering to create the metal vapor allows to achieve higher yields. The method can easily be generalized to alloy nanoparticles by choosing appropriate metallic targets. The use of sequential growth schemes, where the particles travel through a second metallic vapor, results in growth of core-shell (CS) structures.

Radiolysis method

Left) Transmission electron microscopy (TEM) image of Hf nanoparticles grown by magnetron-sputtering inert-gas condensation (inset: size distribution) and right) energy dispersive x-ray (EDX) mapping of Ni and Ni@Cu core@shell nanoparticles.
 
Nanoparticles can also be formed using radiation chemistry. Radiolysis from gamma rays can create strongly active free radicals in solution. This relatively simple technique uses a minimum number of chemicals. These including water, a soluble metallic salt, a radical scavenger (often a secondary alcohol), and a surfactant (organic capping agent). High gamma doses on the order of 104 Gray are required. In this process, reducing radicals will drop metallic ions down to the zero-valence state. A scavenger chemical will preferentially interact with oxidizing radicals to prevent the re-oxidation of the metal. Once in the zero-valence state, metal atoms begin to coalesce into particles. A chemical surfactant surrounds the particle during formation and regulates its growth. In sufficient concentrations, the surfactant molecules stay attached to the particle. This prevents it from dissociating or forming clusters with other particles. Formation of nanoparticles using the radiolysis method allows for tailoring of particle size and shape by adjusting precursor concentrations and gamma dose.

Sol–gel

The sol–gel process is a wet-chemical technique (also known as chemical solution deposition) widely used recently in the fields of materials science and ceramic engineering. Such methods are used primarily for the fabrication of materials (typically a metal oxide) starting from a chemical solution (sol, short for solution), which acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers

Typical precursors are metal alkoxides and metal chlorides, which undergo hydrolysis and polycondensation reactions to form either a network "elastic solid" or a colloidal suspension (or dispersion) – a system composed of discrete (often amorphous) submicrometer particles dispersed to various degrees in a host fluid. Formation of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating metal-oxo or metal-hydroxo polymers in solution. Thus, the sol evolves toward the formation of a gel-like diphasic system containing both a liquid phase and solid phase whose morphologies range from discrete particles to continuous polymer networks.

In the case of the colloid, the volume fraction of particles (or particle density) may be so low that a significant amount of fluid may need to be removed initially for the gel-like properties to be recognized. This can be accomplished in a number of ways. The most simple method is to allow time for sedimentation to occur, and then pour off the remaining liquid. Centrifugation can also be used to accelerate the process of phase separation.

Removal of the remaining liquid (solvent) phase requires a drying process, which typically causes shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the distribution of porosity in the gel. The ultimate microstructure of the final component will clearly be strongly influenced by changes implemented during this phase of processing. Afterward, a thermal treatment, or firing process, is often necessary in order to favor further polycondensation and enhance mechanical properties and structural stability via final sintering, densification, and grain growth. One of the distinct advantages of using this methodology as opposed to the more traditional processing techniques is that densification is often achieved at a much lower temperature.

The precursor sol can be either deposited on a substrate to form a film (e.g., by dip-coating or spin-coating), cast into a suitable container with the desired shape (e.g., to obtain a monolithic ceramics, glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres). The sol–gel approach is a cheap and low-temperature technique that allows for the fine control of the product’s chemical composition. Even small quantities of dopants, such as organic dyes and rare earth metals, can be introduced in the sol and end up uniformly dispersed in the final product. It can be used in ceramics processing and manufacturing as an investment casting material, or as a means of producing very thin films of metal oxides for various purposes. Sol–gel derived materials have diverse applications in optics, electronics, energy, space, (bio)sensors, medicine (e.g., controlled drug release) and separation (e.g., chromatography) technology.

Ion implantation

Ion implantation may be used to treat the surfaces of dielectric materials such as sapphire and silica to make composites with near-surface dispersions of metal or oxide nanoparticles.

Morphology

Nanostars of vanadium(IV) oxide
 
Scientists have taken to naming their particles after the real-world shapes that they might represent. Nanospheres, nanochains, nanoreefs, nanoboxes, and more have appeared in the literature. These morphologies sometimes arise spontaneously as an effect of a templating or directing agent present in the synthesis such as miscellar emulsions or anodized alumina pores, or from the innate crystallographic growth patterns of the materials themselves. Some of these morphologies may serve a purpose, such as long carbon nanotubes used to bridge an electrical junction, or just a scientific curiosity like the stars shown at right. 

Amorphous particles usually adopt a spherical shape (due to their microstructural isotropy), whereas the shape of anisotropic microcrystalline whiskers corresponds to their particular crystal habit. At the small end of the size range, nanoparticles are often referred to as clusters. Spheres, rods, fibers, and cups are just a few of the shapes that have been grown. The study of fine particles is called micromeritics.

Characterization

Nanoparticles have different analytical requirements than conventional chemicals, for which chemical composition and concentration are sufficient metrics. Nanoparticles have other physical properties that must be measured for a complete description, such as size, shape, surface properties, crystallinity, and dispersion state. Additionally, sampling and laboratory procedures can perturb their dispersion state or bias the distribution of other properties. In environmental contexts, an additional challenge is that many methods cannot detect low concentrations of nanoparticles that may still have an adverse effect. For some applications, nanoparticles may be characterized in complex matrices such as water, soil, food, polymers, inks, complex mixtures of organic liquids such as in cosmetics, or blood.

There are several overall categories of methods used to characterize nanoparticles. Microscopy methods generate images of individual nanoparticles to characterize their shape, size, and location. Electron microscopy and scanning probe microscopy are the dominant methods. Because nanoparticles have a size below the diffraction limit of visible light, conventional optical microscopy is not useful. Electron microscopes can be coupled to spectroscopic methods that can perform elemental analysis. Microscopy methods are destructive, and can be prone to undesirable artifacts from sample preparation, or from probe tip geometry in the case of scanning probe microscopy. Additionally, microscopy is based on single-particle measurements, meaning that large numbers of individual particles must be characterized to estimate their bulk properties.

Spectroscopy, which measures the particles' interaction with electromagnetic radiation as a function of wavelength, is useful for some classes of nanoparticles to characterize concentration, size, and shape. X-ray, ultraviolet–visible, infrared, and nuclear magnetic resonance spectroscopy can be used with nanoparticles. Light scattering methods using laser light, X-rays, or neutron scattering are used to determine particle size, with each method suitable for different size ranges and particle compositions. Some miscellaneous methods are electrophoresis for surface charge, the Brunauer–Emmett–Teller method for surface area, and X-ray diffraction for crystal structure, as well as mass spectrometry for particle mass, and particle counters for particle number. Chromatography, centrifugation, and filtration techniques can be used to separate nanoparticles by size or other physical properties before or during characterization.

Functionalization

Functionalization is the introduction of organic molecules or polymers on the surface of the nanoparticle. The surface coating of nanoparticles determines many of their physical and chemical properties, notably stability, solubility, and targeting. A coating that is multivalent or polymeric confers high stability. Functionalized nanomaterial-based catalysts can be used for catalysis of many known organic reactions.

Surface coating for biological applications

For biological applications, the surface coating should be polar to give high aqueous solubility and prevent nanoparticle aggregation. In serum or on the cell surface, highly charged coatings promote non-specific binding, whereas polyethylene glycol linked to terminal hydroxyl or methoxy groups repel non-specific interactions. Nanoparticles can be linked to biological molecules that can act as address tags, to direct the nanoparticles to specific sites within the body, specific organelles within the cell, or to follow specifically the movement of individual protein or RNA molecules in living cells. Common address tags are monoclonal antibodies, aptamers, streptavidin or peptides. These targeting agents should ideally be covalently linked to the nanoparticle and should be present in a controlled number per nanoparticle. Multivalent nanoparticles, bearing multiple targeting groups, can cluster receptors, which can activate cellular signaling pathways, and give stronger anchoring. Monovalent nanoparticles, bearing a single binding site, avoid clustering and so are preferable for tracking the behavior of individual proteins. 

Red blood cell coatings can help nanoparticles evade the immune system.

Health and safety

Nanoparticles present possible dangers, both medically and environmentally. Most of these are due to the high surface to volume ratio, which can make the particles very reactive or catalytic. They are also able to pass through cell membranes in organisms, and their interactions with biological systems are relatively unknown. However, it is unlikely the particles would enter the cell nucleus, Golgi complex, endoplasmic reticulum or other internal cellular components due to the particle size and intercellular agglomeration. A recent study looking at the effects of ZnO nanoparticles on human immune cells has found varying levels of susceptibility to cytotoxicity. There are concerns that pharmaceutical companies, seeking regulatory approval for nano-reformulations of existing medicines, are relying on safety data produced during clinical studies of the earlier, pre-reformulation version of the medicine. This could result in regulatory bodies, such as the FDA, missing new side effects that are specific to the nano-reformulation.

Whether cosmetics and sunscreens containing nanomaterials pose health risks remains largely unknown at this stage. However considerable research has demonstrated that zinc nanoparticles are not absorbed into the bloodstream in vivo.

Concern has also been raised over the health effects of respirable nanoparticles from certain combustion processes. As of 2013 the U.S. Environmental Protection Agency was investigating the safety of the following nanoparticles:
  • Carbon Nanotubes: Carbon materials have a wide range of uses, ranging from composites for use in vehicles and sports equipment to integrated circuits for electronic components. The interactions between nanomaterials such as carbon nanotubes and natural organic matter strongly influence both their aggregation and deposition, which strongly affects their transport, transformation, and exposure in aquatic environments. In past research, carbon nanotubes exhibited some toxicological impacts that will be evaluated in various environmental settings in current EPA chemical safety research. EPA research will provide data, models, test methods, and best practices to discover the acute health effects of carbon nanotubes and identify methods to predict them.
  • Cerium oxide: Nanoscale cerium oxide is used in electronics, biomedical supplies, energy, and fuel additives. Many applications of engineered cerium oxide nanoparticles naturally disperse themselves into the environment, which increases the risk of exposure. There is ongoing exposure to new diesel emissions using fuel additives containing CeO2 nanoparticles, and the environmental and public health impacts of this new technology are unknown. EPA’s chemical safety research is assessing the environmental, ecological, and health implications of nanotechnology-enabled diesel fuel additives.
  • Titanium dioxide: Nano titanium dioxide is currently used in many products. Depending on the type of particle, it may be found in sunscreens, cosmetics, and paints and coatings. It is also being investigated for use in removing contaminants from drinking water.
  • Nano Silver: Nano silver is being incorporated into textiles, clothing, food packaging, and other materials to eliminate bacteria. EPA and the U.S. Consumer Product Safety Commission are studying certain products to see whether they transfer nano-size silver particles in real-world scenarios. EPA is researching this topic to better understand how much nano-silver children come in contact with in their environments.
  • Iron: While nano-scale iron is being investigated for many uses, including “smart fluids” for uses such as optics polishing and as a better-absorbed iron nutrient supplement, one of its more prominent current uses is to remove contamination from groundwater. This use, supported by EPA research, is being piloted at a number of sites across the United States.

Regulation

As of 2016, the U.S. Environmental Protection Agency had conditionally registered, for a period of four years, only two nanomaterial pesticides as ingredients. The EPA differentiates nanoscale ingredients from non-nanoscale forms of the ingredient, but there is little scientific data about potential variation in toxicity. Testing protocols still need to be developed.

Applications

As the most prevalent morphology of nanomaterials used in consumer products, nanoparticles have potential and actual applications in all industries. Table below summarizes the most common nanoparticles used in various product types available on the global markets.

Various nanoparticles which are commonly used in the consumer products by industrial sectors
No. Industrial sectors Nanoparticles
1 agriculture silver, silicon dioxide, potassium, calcium, iron, zinc, phosphorus, boron, zinc oxide and molybdenum
2 automotive tungsten, disulfidesilicon dioxide, clay, titanium dioxide, diamond, copper, cobalt oxide, zinc oxide, boron nitride, zirconium dioxide, tungsten, γ-aluminium oxide, boron, palladium, platinum, cerium(IV) oxide, carnauba, aluminium oxide, silver, calcium carbonate and calcium sulfonate
3 construction titanium, dioxidesilicon dioxide, silver, clay, aluminium oxide, calcium carbonate calcium silicate hydrate, carbon, aluminium phosphate cerium(IV) oxide and calcium hydroxide
4 cosmetics silver, titanium dioxide, gold, carbon, zinc oxide, silicon dioxide, clay, sodium silicate, kojic acid and hydroxy acid
5 electronics silver, aluminum, silicon dioxide and palladium
6 environment silver, titanium dioxide, carbonmanganese oxide, clay, gold and selenium
7 food silver, clay, titanium dioxide, gold, zinc oxide, silicon dioxide, calcium, copper, zinc, platinum, manganese, palladium and carbon
8 home appliance silver, zinc oxide, silicon dioxide, diamond and titanium dioxide
9 medicine silver, gold, hydroxyapatite, clay, titanium dioxide, silicon dioxide, zirconium dioxide, carbon, diamond, aluminium oxide and ytterbium trifluoride
10 petroleum tungsten, disulfidezinc oxide, silicon dioxide, diamond, clay, boron, boron nitride, silver, titanium dioxide, tungsten, γ-aluminium oxide, carbon, molybdenum disulfide and γ-aluminium oxide
11 printing toner, deposited by a printer onto paper or other substrate
12 renewable energies titanium, palladium, tungsten disulfide, silicon dioxide, clay, graphite, zirconium(IV) oxide-yttria stabilized, carbon, gd-doped-cerium(IV) oxide, nickel cobalt oxide, nickel(II) oxide, rhodium, sm-doped-cerium(IV) oxide, barium strontium titanate and silver
13 sports and fitness silver, titanium dioxide, gold, clay and carbon
14 textile silver, carbon, titanium dioxide, copper sulfide, clay, gold, polyethylene terephthalate and silicon dioxide

Scientific research on nanoparticles is intense as they have many potential applications in medicine, physics, optics, and electronics. The U.S. National Nanotechnology Initiative offers government funding focused on nanoparticle research.|The use of nanoparticles in laser dye-doped poly(methyl methacrylate) (PMMA) laser gain media was demonstrated in 2003 and it has been shown to improve conversion efficiencies and to decrease laser beam divergence. Researchers attribute the reduction in beam divergence to improved dn/dT characteristics of the organic-inorganic dye-doped nanocomposite. The optimum composition reported by these researchers is 30% w/w of SiO2 (~ 12 nm) in dye-doped PMMA.|Nanoparticles are being investigated as potential drug delivery system. Drugs, growth factors or other biomolecules can be conjugated to nano particles to aid targeted delivery. This nanoparticle-assisted delivery allows for spatial and temporal controls of the loaded drugs to achieve the most desirable biological outcome.|Nanoparticles are also studied for possible applications as dietary supplements for delivery of biologically active substances, for example mineral elements.

Platinum nanoparticle

From Wikipedia, the free encyclopedia

Platinum nanoparticles are usually in the form of a suspension or colloid of nanoparticles of platinum in a fluid, usually water. A colloid is technically defined as a stable dispersion of particles in a fluid medium (liquid or gas). 

Spherical platinum nanoparticles can be made with sizes between about 2 and 100 nanometres (nm), depending on reaction conditions. Platinum nanoparticles are suspended in the colloidal solution of brownish-red or black color. Nanoparticles come in wide variety of shapes including spheres, rods, cubes, and tetrahedra.

Platinum nanoparticles are the subject of substantial research, with potential applications in a wide variety of areas. These include catalysis, medicine, and the synthesis of novel materials with unique properties.

Synthesis

Platinum nanoparticles are typically synthesized either by the reduction of platinum ion precursors in solution with a stabilizing or capping agent to form colloidal nanoparticles, or by the impregnation and reduction of platinum ion precursors in a micro-porous support such as alumina.

Some common examples of platinum precursors include potassium hexachloroplatinate (K2PtCl6) or platinous chloride (PtCl2) Different combinations of precursors, such as ruthenium chloride (RuCl3) and chloroplatinic acid (H2PtCl6), have been used to synthesize mixed-metal nanoparticles Some common examples of reducing agents include hydrogen gas (H2), sodium borohydride (NaBH4) and ethylene glycol (C2H6O2), although other alcohols and plant-derived compounds have also been used.

As the platinum metal precursor is reduced to neutral platinum metal (Pt0), the reaction mixture becomes supersaturated with platinum metal and the Pt0 begins to precipitate in the form of nanoscale particles. A capping agent or stabilizing agent such as sodium polyacrylic acid or sodium citrate is often used to stabilize the nanoparticle surfaces, and prevents the aggregation and coalescence of the nanoparticles. 

The size of nanoparticles synthesized colloidally may be controlled by changing the platinum precursor, the ratio of capping agent to precursor, and/or the reaction temperature. The size of the nanoparticles can also be controlled with small deviation by using a stepwise seed-mediated growth procedure as outlined by Bigall et al. (2008). The size of nanoparticles synthesized onto a substrate such as alumina depends on various parameters such as the pore size of the support.

Platinum nanoparticles can also be synthesized by decomposing Pt2(dba)3 (dba = dibenzylideneacetone) under a CO or H2 atmosphere, in the presence of a capping agent. The size and shape distributions of the resulting nanoparticles depend on the solvent, the reaction atmosphere, the types of capping agents and their relative concentrations, the specific platinum ion precursor, as well at the temperature of the system and reaction time.

Shape and size control

Electron micrographs of Ostwald ripening in Pd nanoparticles dissolved in formaldehyde at 6 (a), 24 (b), 48 (c) and 72 hours (d). The small Pd particles are being consumed as the larger ones grow bigger.
 
Ramirez et al. reported the influence of ligand and solvent effects on the size and shape of platinum nanoparticles. Platinum nanoparticle seeds were prepared by the decomposition of Pt2(dba)3 in tetrahydrofuran (THF) under carbon monoxide (CO). These conditions produced Pt nanoparticles with weakly bound THF and CO ligands and an approximate diameter on 1.2 nm. Hexadecylamine (HDA) was added to the purified reaction mixture and allowed to displace the THF and CO ligands over the course of approximately seven days, producing monodispersed spherical crystalline Pt nanoparticles with an average diameter of 2.1 nm. After the seven-day period, an elongation of the Pt nanoparticles occurred. When the same procedure was followed using a stronger capping agent such as triphenyl phosphine or octanethiol, the nanoparticles remained spherical, suggesting that the HDA ligand affects particle shape. 

Oleylamine, oleic acid and platinum acetylacetonate [Pt(acac)2] are also used in the synthesis of size/shape controlled platinum nanoparticles. Research showed that alkylamine can coordinate with Pt2+ ion and form tetrakis(amine)platinate precursor and replace the original acac ligand in Pt(acac)2, and oleic acid can further exchange with acac and tune the formation kinetics of platinum nanoparticles.

When Pt2(dba)3 was decomposed in THF under hydrogen gas in the presence HDA, the reaction took much longer, and formed nanowires with diameters between 1.5 and 2 nm. Decomposition of Pt2(dba)3 under hydrogen gas in toluene yielded the formation of nanowires with 2–3 nm diameter independent of HDA concentration. The length of these nanowires was found to be inversely proportional to the concentration of HDA present in solution. When these nanowire syntheses were repeated using reduced concentrations of Pt2(dba)3, there was little effect on the size, length or distribution of the nanowires formed. 

Platinum nanoparticles of controlled shape and size have also been accessed through varying the ratio of polymer capping agent concentration to precursor concentration. Reductive colloidal syntheses as such have yielded tetrahedral, cubic, irregular-prismatic, icosahedral, and cubo-octahedral nanoparticles, whose dispersity is also dependent on the concentration ratio of capping agent to precursor, and which may be applicable to catalysis. The precise mechanism of shape-controlled colloidal synthesis is not yet known; however, it is known that the relative growth rate of crystal facets within the growing nanostructure determines its final shape. Polyol syntheses of platinum nanoparticles, in which chloroplatinic acid is reduced to PtCl42− and Pt0 by ethylene glycol, have also been a means to shape-controlled fabrication. Addition of varying amounts of sodium nitrate to these reactions was shown to yield tetrahedra and octahedra at high concentration ratios of sodium nitrate to chloroplatinic acid. Spectroscopic studies suggest that nitrate is reduced to nitrite by PtCl42− early in this reaction, and that the nitrite may then coordinate both Pt(II) and Pt(IV), greatly slowing the polyol reduction and altering the growth rates of distinct crystal facets within the nanoparticles, ultimately yielding morphological differentiation.

Green synthesis

An ecologically-friendly synthesis of platinum nanoparticles from chloroplatinic acid was achieved through the use of a leaf extract of Diospyros kaki as a reducing agent. Nanoparticles synthesized as such were spherical with an average diameter ranging from 212 nm depending on reaction temperature and concentration of leaf extract used. Spectroscopic analysis suggests that this reaction is not enzyme-mediated and proceeds instead through plant-derived reductive small molecules. Another eco-friendly synthesis from chloroplatinic acid was reported using leaf extract from Ocimum sanctum and tulsi as reducing agents. Spectroscopic analysis suggested that ascorbic acid, gallic acid, various terpenes, and certain amino acids were active in the reduction. Particles synthesized as such were shown through scanning electron microscopy to consist in aggregates with irregular shape. It has been shown that tea extracts with high polyphenol content may be used both as reducing agents and capping agents for platinum nanoparticle synthesis.

Properties

The chemical and physical properties of platinum nanoparticles (NP) make them applicable for a wide variety of research applications. Extensive experimentation has been done to create new species of platinum NPs, and study their properties. Platinum NP applications include electronics, optics, catalysts, and enzyme immobilization.

Catalytic properties

Platinum NPs are used as catalysts for proton exchange membrane fuel cell (PEMFC), for industrial synthesis of nitric acid, reduction of exhaust gases from vehicles and as catalytic nucleating agents for synthesis of magnetic NPs. NPs can act as catalysts in homogeneous colloidal solution or as gas-phase catalysts while supported on solid state material. The catalytic reactivity of the NP is dependent on the shape, size and morphology of the particle.

One type of platinum NPs that have been researched on are colloidal platinum NPs. Monometallic and bimetallic colloids have been used as catalysts in a wide range of organic chemistry, including, oxidation of carbon monoxide in aqueous solutions, hydrogenation of alkenes in organic or biphasic solutions and hydrosilylation of olefins in organic solutions. Collodial platinum NPs protected by Poly(N-isopropylacrylamide) were synthesised and their catalytic properties measured. It was determined that they were more active in solution and inactive when phase separated due to its solubility being inversely proportional to temperature.

Optical properties

Platinum NPs exhibit fascinating optical properties. Being a free electron metal NP like silver and gold, its linear optical response is mainly controlled by the surface plasmon resonance. Surface plasmon resonance occurs when the electrons in the metal surface are subject to an electromagnetic field that exerts a force on the electrons and cause them to displace from their original positions. The nuclei then exert a restoring force that results in oscillation of the electrons, which increase in strength when frequency of oscillations is in resonance with the incident electromagnetic wave.

The SPR of platinum nanoparticles is found in the ultraviolet range (215 nm), unlike the other noble metal nanoparticles which display SPR in the visible range Experiments were done and the spectra obtained are similar for most platinum particles regardless of size. However, there is an exception. Platinum NPs synthesized via citrate reduction do not have a surface plasmon resonance peak around 215 nm. Through experimentation, the resonance peak only showed slight variations with the change of size and synthetic method (while maintaining the same shape), with the exception of those nanoparticles synthesized by citrate reduction, which did not exhibit and SPR peak in this region..

Through the control of percent composition of 2–5 nm platinum nanoparticles on SiO2, Zhang et al. modeled distinct absorption peaks attributed to platinum in the visible range, distinct from the conventional SPR absorption. This research attributed these absorption features to the generation and transfer of hot electrons from the platinum nanoparticles to the semiconductive material. The addition of small platinum nanoparticles on semiconductors such as TiO2 increases the photocatalytic oxidation activity under visible light irradiation. These concepts suggest the possible role of platinum nanoparticles in the development of solar energy conversion using metal nanoparticles. By changing the size, shape and environment of metal nanoparticles, their optical properties can be used for electrontic, catalytic, sensing, and photovoltaic applications.

Applications

Fuel cells application

Hydrogen fuel cells

Among the precious metals, platinum is the most active toward the hydrogen oxidation reaction that occurs at the anode in hydrogen fuel cells. In order to meet cost reductions of this magnitude, the Pt catalyst loading must be decreased. Two strategies have been investigated for reducing the Pt loading: the binary and ternary Pt-based alloyed nanomaterials and the dispersion of Pt-based nanomaterials onto high surface area substrates.

Methanol fuel cells

The methanol oxidation reaction occurs at the anode in direct methanol fuel cells (DMFCs). Platinum is the most promising candidate among pure metals for application in DMFCs. Platinum has the highest activity toward the dissociative adsorption of methanol. However, pure Pt surfaces are poisoned by carbon monoxide, a byproduct of methanol oxidation. Researchers have focused on dispersing nanostructured catalysts on high surface area supporting materials and the development of Pt-based nanomaterials with high electrocatalytic activity toward MOR to overcome the poisoning effect of CO.

Electrochemical oxidation of formic acid

Formic acid is another attractive fuel for use in PEM-based fuel cells. The dehydration pathway produces adsorbed carbon monoxide. A number of binary Pt-based nanomaterial electrocatalysts have been investigated for enhanced electrocatalytic activity toward formic acid oxidation.

Modifying conductivity of zinc oxide materials

Platinum NPs can be used to dope zinc oxide (ZnO) materials to improve their conductivity. ZnO has several characteristics that allow it to be used in several novel devices such as development of light-emitting assemblies and solar cells. However, because ZnO is of slightly lower conductivity than metal and indium tin oxide (ITO), it can be doped and hybridized with metal NPs like platinum to improve its conductivity. A method to do so would be to synthesize ZnO NPs using methanol reduction and incorporate at 0.25 at.% platinum NPs. This boosts the electrical properties of ZnO films while preserving its transmittance for application in transparent conducting oxides.

Glucose detection applications

Enzymatic glucose sensors have drawbacks that originate from the nature of the enzyme. Nonenzymatic glucose sensors with Pt-based electrocatalysts offer several advantages, including high stability and ease of fabrication. Many novel Pt and binary Pt-based nanomaterials have been developed to overcome the challenges of glucose oxidation on Pt surfaces, such as low selectivity, poor sensitivity, and poisoning from interfering species.

Other applications

Platinum catalysts are alternatives of automotive catalytic converters, carbon monoxide gas sensors, petroleum refining, hydrogen production, and anticancer drugs. These applications utilize platinum nanomaterials due to their catalytic ability to oxidize CO and NOx, dehydrogenate hydrocarbons, and electrolyze water and their ability to inhibit the division of living cells.

Biological interactions

The increased reactivity of nanoparticles is one of their most useful properties and is leveraged in fields such as catalysis, consumer products, and energy storage. However, this high reactivity also means that a nanoparticle in a biological environment may have unintended impacts. For example, many nanoparticles such as silver, copper, and ceria interact with cells to produce reactive oxygen species or ROS which can cause premature cell death through apoptosis. Determining the toxicity of a specific nanoparticle requires knowledge of the particle’s chemical composition, shape, size and is a field that is growing alongside advances in nanoparticle research.

Determining the impact of a nanoparticle on a living system is not straightforward. A multitude of in vivo and in vitro studies must be done to fully characterize reactivity. In vivo studies often use whole organisms such as mice or zebrafish to infer the interaction of the nanoparticle on a healthy human body. In vitro studies look at how nanoparticles interact with specific cell colonies, typically of human origin. Both types of experiments are needed for a complete understanding of nanoparticle toxicity, especially human toxicity, since no one model has complete human relevance.

Drug delivery

A topic of research within the field of nanoparticles is how to use these small particles for drug delivery. Depending on particle properties, nanoparticle may move throughout the human body are promising as site-specific vehicles for the transport of medicine. Current research using platinum nanoparticles in drug delivery uses platinum-based carries to move antitumor medicine. In one study, platinum nanoparticles of diameter 58.3 nm were used to transport an anticancer drug to human colon carcinoma cells, HT-29. Uptake of the nanoparticles by the cell involves compartmentalization of the nanoparticles within lysosomes. The high acidity environment enables leaching of platinum ions from the nanoparticle, which the researchers identified as causing the increased effectiveness of the drug. In another study, a Pt nanoparticle of diameter 140 nm was encapsulated within a PEG nanoparticle to move an antitumor drug, Cisplatin, within a prostate cancer cell (LNCaP/PC3) population. Use of platinum in drug delivery hinges on its ability to not interact in a harmful manner in healthy portions of the body while also being able to release its contents when in the correct environment.

Toxicology

Toxicity stemming from platinum nanoparticles can take multiple forms. One possible interaction is cytotoxicity or the ability of the nanoparticle to cause cell death. A nanoparticle can also interact with the cell’s DNA or genome to cause genotoxicity. These effects are seen in different levels of gene expression measured through protein levels. Last is the developmental toxicity that can occur as an organism grows. Developmental toxicity looks at the impact the nanoparticle has on the growth of an organism from an embryonic stage to a later set point. Most nanotoxicology research is done on cyto- and genotoxicity as both can easily be done in a cell culture lab.

Platinum nanoparticles have the potential to be toxic to living cells. In one case, 2 nm platinum nanoparticles were exposed to two different types of algae in order to understand how these nanoparticles interact with a living system. In both species of algae tested, the platinum nanoparticles inhibited growth, induced small amounts of membrane damage, and created a large amount of oxidative stress. In another study, researcher tested the effects of differently sized platinum nanoparticles on primary human keratinocytes. The authors tested 5.8 and 57.0 nm Pt nanoparticles. The 57 nm nanoparticles had some hazardous effects including decreased cell metabolism, but the effect of the smaller nanoparticles was much more damaging. The 5.8 nm nanoparticles exhibited a more deleterious effect on the DNA stability of the primary keratincoytes than did the larger nanoparticles. The damage to the DNA was measured for individual cells using single-gel electrophoresis via the comet assay

Researchers have also compared the toxicity of Pt nanoparticles to other commonly used metallic nanoparticles. In one study, the authors compared the impact of different nanoparticle compositions on the red blood cells found in the human bloodstream. The study showed that 5–10 nm platinum nanoparticles and 20–35 nm gold nanoparticles have very little effect on the red blood cells. In the same study it was found that 5–30 nm silver nanoparticles caused membrane damage, detrimental morphological variation, and haemagglutination to the red blood cells.

In a recent paper published in Nanotoxicology, the authors found that between silver (Ag-NP, d = 5–35 nm), gold (Au-NP, d = 15–35 nm), and Pt (Pt-NP, d = 3–10 nm) nanoparticles, the Pt nanoparticles were the second most toxic in developing zebrafish embryos, behind only the Ag-NPs. However, this work did not examine the size dependence of the nanoparticles on their toxicity or biocompatibility. Size-dependent toxicity was determined by researchers at the National Sun Yat – Sen University in Kaohsiung, Taiwan. This group’s work showed that the toxicity of platinum nanoparticles in bacterial cells is strongly dependent on nanoparticle size and shape/morphology. Their conclusions were based on two major observations. First, the authors found that platinum nanoparticles with spherical morphologies and sizes less than 3 nm showed biologically toxic properties; measured in terms of mortality, hatching delay, phenotypic defects and metal accumulation. While those nanoparticles with alternative shapes—such as cuboidal, oval, or floral—and sizes of 5–18 nm showed biocompatibility and no biologically toxic properties. Secondly, out of the three varieties of platinum nanoparticles which exhibited biocompatibility, two showed an increase in bacterial cell growth.

The paper introduces many hypotheses for why these observations were made, but based on other works and basic knowledge of bacterial cell membranes, the reasoning behind the size dependent toxicity observation seems to be twofold. One: The smaller, spherically shaped nanoparticles are able to pass through cell membranes simply due to their reduced size, as well as their shape-compatibility with the typically spherical pores of most cell membranes. Although this hypothesis needs to be further supported by future work, the authors did cite another paper which tracked the respiratory intake of platinum nanoparticles. This group found that 10 µm platinum nanoparticles are absorbed by the mucus of the bronchi and trachea, and can travel no further through the respiratory tract. However, 2.5 µm particles showed an ability to pass through this mucus layer, and reach much deeper into the respiratory tract. Also the larger, uniquely shaped nanoparticles are too large to pass through the pores of the cell membrane, and/or have shapes which are incompatible with the more spherically shaped pores of the cellular membrane. In regards to the observation that the two largest platinum nanoparticles (6–8 nm oval, and 16–18 nm floral) actually increase bacterial cell growth, the explanation could originate in the findings of other works which have shown that platinum nanoparticles have demonstrated significant antioxidative capacity. However, it must be noted that in order for these antioxidative properties to be exploited, the platinum nanoparticles must first enter the cells, so perhaps there is another explanation for this observation of increased bacterial cell growth. 

Most studies so far have been size based using an in vivo mouse model. In one study, researchers compared the effects of sun 1 nm and 15 nm platinum nanoparticles on mice. The 15 mg/kg dose of sub 1 nm platinum nanoparticles were found to cause liver damage while the larger particles had no effect. A similar study using a singular injection as an exposure source of platinum nanoparticles into the mouse model found necrosis of tubular epithelial cells for particles under 1 nm, but no effect with those particles of 8 nm. These in vivo studies show a trend that the toxicity of the platinum nanoparticles is size dependent, most likely due to the ability of the nanoparticle to get into a high impactful region within the body. A complete study analyzing the effect of varying sized platinum nanoparticles used both in vivo and in vitro models is used to gain a better understanding what impact these nanoparticles could have. Using mice as a model, they found retention of the platinum nanoparticles by the respiratory tract of the mouse. This was accompanied by a minor to mild inflammation of the surrounding lung tissue. However, their in vitro tests using human and lung epithelial cells found no cytotoxic or oxidative stress effects caused by the platinum nanoparticles despite clear evidence of cellular uptake.

Introduction to entropy

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