Metal nanoparticles synthesis: An overview on methods of preparation, advantages and disadvantages, and applications

Accepted Manuscript Metal nanoparticles synthesis: An overview on methods of preparation, advantages and disadvantages, and applications Prasad Govindrao Jamkhande, Namrata W. Ghule, Abdul Haque Bamer, Mohan G. Kalaskar PII:

S1773-2247(18)30818-9

DOI:

https://doi.org/10.1016/j.jddst.2019.101174

Article Number: 101174 Reference:

JDDST 101174

To appear in:

Journal of Drug Delivery Science and Technology

Received Date: 24 July 2018 Revised Date:

29 June 2019

Accepted Date: 21 July 2019

Please cite this article as: P.G. Jamkhande, N.W. Ghule, A.H. Bamer, M.G. Kalaskar, Metal nanoparticles synthesis: An overview on methods of preparation, advantages and disadvantages, and applications, Journal of Drug Delivery Science and Technology (2019), doi: https://doi.org/10.1016/ j.jddst.2019.101174. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Top down methods

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Mechanical milling Laser ablation Sputtering

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Solid state methods Liquid state synthesis methods Gas phase methods Biological methods

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Bottom up methods

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Metal nanoparticles synthesis: an overview on methods of preparation, advantages and disadvantages, and applications

Kalaskar d

Centre for Research in Pharmaceutical Sciences, Sharda Bhavan Education Society's Nanded

Pharmacy College, Nanded 431605, Maharashtra, India. b

Sahyog Sewabhavi Sanstha's Indira College of Pharmacy, Nanded 431606, Maharashtra,

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India. c

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a

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Prasad Govindrao Jamkhande a,*, Namrata W. Ghule b, Abdul Haque Bamer c, Mohan G.

Dnyansadhana College of Pharmacy, Dharmapuri, Parbhani 431401, Maharashtra, India. R.C. Patel Institute of Pharmaceutical Education & Research, Shirpur 425405, Maharashtra,

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India.

Corresponding Author: Prasad G. Jamkhande Complete Postal Address:

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Centre for Research in Pharmaceutical Sciences, Sharda Bhavan Education Society's Nanded Pharmacy College,

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Nanded 431606, Maharashtra, India.

Contact Number: +919860552433 Tel: +91-2462-251118 Fax: +91-2462-254445 E-mail: [email protected] Alternate E-mail: [email protected]

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ABSTRACT Unforeseen changes in surface properties because of particle size have made nanoparticles very

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popular in the field of material science. Decrease in particle size to nano-size demonstrates peculiar and improved properties such as particle size distribution and morphology. This distinctive change in specific surface area is responsible for its high value and affects imperative

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parameters like surface reactivity. Application of nanoparticles in various fields like energy, medicines and nutrition has tremendously increased nowadays. In pharmaceutical and medicinal

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sciences, nanoparticles are playing imperative role. Several approaches are employed for the metallic nanoparticles preparation, which is categorized into two main types on as bottom up methods and top down methods depending on starting material of nanoparticle preparation. Certain metals have distinctive properties like antimicrobial property of gold and silver. Metal particles such as gold are widely used from ancient time for the medicines and Ayurvedic

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preparations in India and China. The use of metal nanoparticles is continuously increasing worldwide in biomedicine and allied disciplines. Nowadays researchers are focusing on metal nanoparticles, nanostructures and nanomaterial synthesis because of their conspicuous

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properties. Present review selectively focuses on different methods of nanoparticle preparations

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and its advantages, disadvantages, and applications. Keywords:

Nanotechnology; Nanoparticles; Metal nanostructures; Surface area; Nanoparticle synthesis

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1. Introduction Nanotechnology, a science that deals preparation of nano-size particles ranging from 1 to 100 nm employing diverse synthesis strategies, and particle structure and size modification. The

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use of nanoparticles in different fields like molecular biology, physics, organic and inorganic chemistry, medicine and material science is unexpectedly augmented nowadays [1,2]. Decrease in particle size to nano-size demonstrates peculiar and improved properties such as particle size

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distribution and morphology, which is not showed by larger particles of bulk material [3]. The term ‘nanoparticle’ was coined from Greek work ‘nano’ that means ‘dwarf or small’ and when

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used as prefix it indicates size 10-9 one billionth of meter is equals to one nanometer [4]. Nanoparticles have both solute and separate particle phase properties. The surface to volume ratio of nanoparticle is 35-45% times higher as compared to large particle or atom. This unique extrinsic property of specific surface area of nanoparticle is a contributory factor for its high

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value and also influences different intrinsic properties such as strong surface reactivity which is size dependent [5]. Overall, these exclusive features of nanoparticles are responsible for its multifunctional properties and developing interest for its application in various fields like energy,

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medicines and nutrition [6].

Metallic nanoparticles or metal nanoparticles, a new terminology has been originated in

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the field of nanoparticles in recent few years. The noble metal like gold, silver, and platinum having beneficial effects on health are utilized for the synthesis of nanoparticles and designated as metallic nanoparticles [7]. Nowadays researchers are focusing on metal nanoparticles, nanostructures and nanomaterial synthesis because of their conspicuous properties that are useful for catalysis [8], composite like polymer preparations [9], disease diagnosis and treatment [10], sensor technology [11,12], and labeling of optoelectronic recorded media [13].

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Different physical and chemical methods such as electrochemical changes, chemical reduction, and photochemical reduction are commonly employed for the preparation and stabilization of metallic nanoparticles [14,15]. The selection of preparation method of metallic

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nanoparticle is equally important because during nanoparticle synthesis processes such as kinetics of interaction of metal ions with reducing agent, adsorption process of stabilizing agent with metal nanoparticles and various experimental techniques produces strong influence on its

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morphology (structure and size) stability and physicochemical properties [16].

Many metal particles present in the products such as cosmetic products, detergents, tooth

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paste, soaps, shampoos, medicines and pharmaceutical products are directly coming in contact with human. Gold is widely used in the medicines and Ayurvedic preparations in India and China [7]. Gold nanoparticles are employed for many diagnostic and drug delivery purposes [17]. Apart from this, other metal nanoparticles like silver nanoparticles are also employed for

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various biomedical applications [18] such as separation science [19] and novel drug delivery system [7]. Silver is well known for its antimicrobial and inflammatory potential. This property is selectively used to elevate faster wound healing and commercially adopted in wound dressing,

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different pharmaceutical dosage formulation and medical implant coating. Other metal nanoparticles like platinum nanoparticles also evaluated for their health beneficial effect and

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successfully used in biomedical applications in either pure form or metal alloyed as a single or in combination with other metal nanoparticles. The use of metal nanoparticles is continuously increasing worldwide in biomedicine and allied disciplines [20,21]. In view of this, present review is an assortment of various methods used for the preparation of metallic nanoparticles, their advantages, disadvantages and applications.

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2. Methods of metallic nanoparticle preparation Divers methods are employed for the metallic nanoparticles preparation which are categorized into two main types as bottom up methods and top down methods, and enlisted in

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table 1 [22-26]. The principal difference between both the methods is starting material of nanoparticle preparation. Bulk material is used as starting material in top-down methods and particle size is reduced to nanoparticles by different physical, chemical and mechanical

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processes, whereas atoms or molecules are the starting material in bottom up methods (Figure 1)

Table 1

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[22,23].

Top down methods and bottom up methods of nanoparticle preparation. Top down methods

Bottom up methods

No.

Methods

Examples

1

Mechanical milling

Ball milling

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Sr.

Methods

Examples

Solid state methods

Physical vapor deposition

Mechanochemical method Laser ablation

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4

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2

Sputtering

Chemical vapor deposition Liquid state synthesis

Sol gel methods

methods

Chemical reduction Hydrothermal method Solvothermal method

Gas phase methods

Spray pyrolysis Laser ablation Flame pyrolysis

Biological methods

Bacteria Fungus Yeast Algae Plant extract

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5

Other methods

Electrodeposition process Microwave technique Supercritical fluid precipitation process

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Ultra sound technique

Bulk material

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TOP DOWN METHOD

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Nanoparticles

BOTTOM UP METHOD

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Atoms/ molecules

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Fig. 1. An overview of top down and bottom up method.

2.1. Top down methods

In this method bulk material is converted into small nano-sized particles. Preparation

of nanoparticles is based on size reduction of starting material by different physical and chemical treatments [27]. It includes methods such as mechanical milling, thermal, and laser ablation. Although top down methods are easy to perform, is not suitable method for preparing informal

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shaped and very small size particles. The major problem associated with this method is that change in surface chemistry and physicochemical properties of nanoparticles [28].

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2.1.1. Mechanical milling 2.1.1.1. Ball milling

The working principal of mechanical milling is reduction in the particle size with

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high energy ball milling. In 1970, John Benjamin has developed this method of particle size reduction. This intern is responsible for modification of surface properties. The success of

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mechanical milling is affected by process variable and properties of milling powder [29]. It is categorized into low energy and high energy milling that depend on induced mechanical energy to powder mixture. Nanosized particles are generally produced using high energy ball milling process. This method is widely preferred for intermetallic nanoparticles synthesis [23].

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In this method, bulk powder is added in to a container along with several heavy balls. High mechanical energy is applied on bulk powder material with the help of high speed rotating ball. Particle size reduction can be done using different high energy mills such as attrition ball

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mill, planetary ball mill, vibrating ball mill, low energy tumbling mill and high energy ball mill [23]. In all these method, heavy free moving high-energy balls may roll down on surface of the

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chamber containing bulk powder material in a series of parallel layers or they may fall freely and impact the powder [30]. Advantages

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Useful for large scale production of high purity nanoparticles with superior physical properties such as enhanced solubility of the drug components which are poorly water soluble in a cost effective manner [29,31]. It gives rise to some new and improved properties to the component relaying on their

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grain size and material composition [29].

High energy required.

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Extensive long period of milling time.

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Contamination of powder due to steel balls.

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Very sensitive microstructure can be grinded [32].

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Applications

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Disadvantages

This method is preferred to blend aluminium with magnesium and carbon in order to alter its chemical properties and combustion behavior [33]. Preparation of elemental powder of aluminium (Al) and beta-silicon carbide (β-SiC).

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Recently the ceramic nanoparticles WC-14% magnesium oxide (MgO) has been prepared

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[23]

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It is widely used method for mechanical alloying to produce amorphous alloys such as metal-metal, transition metal-metalloid, and metal-carbon systems for various purposes. [34].

2.1.1.2. Mechanochemical synthesis

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Mechanochemical synthesis method is based on repeated deformation, welding, and fracture of the mixture of reactants. Different chemical modifications are produced at the interface of nano-sized particles during the milling process. Generally, high temperature is

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required to precede chemical reactions for various purposes like to separate reacting phases from the product phase. Nanoparticles can be obtained using a ball mill at low temperatures without any use of external heating [35].

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In mechanochemical method of synthesis, the starting materials (like sodium carbonate and chloride hexahydrate for Fe3O2 nanoparticles synthesis) are mixed stichometrically and

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milled. During milling process, the deformation, fraction and welding of the reactants take place. Several chemical reactions are generated at the surface interface between substrate and reagent, and consequently the reaction that require high temperature will take place at low temperature without any external application of heat. Various displacement reactions occur during the

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process which is given below; SxC + yR= xS + RyC Whereas,

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SxC and yR are reactant, xS is product and RyC is byproduct. The nanoparticles produced are surrounded with the byproduct material, which is

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dispersed in soluble salt matrix. Afterwards the byproduct is removed by washing with suitable solvent and subsequently the particles dried at 105˚C for 12hr [36]. Advantages

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Simple and efficient method of nanoparticle preparation [32].

Disadvantages

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The microstructures (nanostructures/nanoparticles) formed are highly sensitive to grinding condition and may get affected from unwanted contamination from milling media and atmosphere. For the preparation of smaller particles (smaller than 20 nm) long term milling is required

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[32].

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Applications

Synthesis of ferric oxide (Fe2O3) nanoparticles.

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Widely used for nanocrystalline particle synthesis [36].

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Effective method for metal nanoparticles (usually noble metals) preparation with

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improved structural and catalytic properties. Formation of alloying at low temperature.

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Nanomaterial preparation such as silver–aluminum mixed oxide catalyst (Ag/Al2O3) [37].

2.1.2. Laser ablation

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In the laser ablation method, laser irradiation is used to reduce the particle size to nano level. The solid target material is placed under a thin layer and then exposed to pulsed laser

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irradiation. Mainly Nd:YAG (neodymium-doped yttrium aluminium garnet) laser at 106 µm output and its harmonic, Ti:Sapphire (Titanium-doped sapphire) laser and copper vapor lasers are used [38]. The irradiation of material to laser leads to fragmentation of solid material in the form of nanoparticles, which remains in liquid that surrounds the target and produces colloidal solution. The laser pulse duration and energy determines the relative amount of ablated atoms and particles formed [39]. Several parameters such as time duration of laser pulse, wavelength,

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ablation time, laser fluency and effective surrounding liquid medium with or without surfactant influences ablation efficiency and characteristic of metal particle formed [40].

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Relatively simple and effective technique for the formation of large amount of small particles (nano-size) in the form of suspension.

Nanoparticle properties can be changed by selecting the laser parameter and nature of

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liquid accordingly.

Nanoparticles formation is possible without adding surfactant in liquid media [38].

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Disadvantage

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Advantages

Prolong time laser ablation leads to formation of high amount of nanoparticles in the colloidal solution which block the laser path and also laser energy is get absorbed by

ablation rate [41].

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Preparation of Al2O3 nanoparticles coating [42].

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Application

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already formed nanoparticles instead of target surface. This overall leads to reduction in

Preparation of silicon nanoparticles [43].

2.1.2. Ion sputtering

Ion sputtering method includes vaporization of a solid through sputtering with a beam of

inert gas ions. Recently this method was used for the preparation of nanaoparticles from several metals using magnetron sputtering of metal targets. In this method collimated beams of the

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nanoparticles is formed and the mass nanostructured films are deposited on the silicon substrates. The entire process is performed at relatively low pressures (1 mTorr) [44]. Sputter deposition is done in evacuated vacuum chamber where sputtering gas is admitted

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and working pressure (eg. 0.05 and 0.1 mbar) is maintained. A very high voltage is introduced in to the target (cathode) and free electrons are moved in spiral path using magnetic system where they collide with sputtering gas (argon) atoms and leads to ionization of gas. This continuous

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process produces a glow discharge (plasma) to ignite. The positively charged gas ions attracted towards target where they continuously impinge. This event repeated occurs and approaches the

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surface of target with energy above the surface binding energy, an atom can be expelled. The collisions occur between metal atoms and gas molecules continuously in vacuum chamber that leads to scattering of atoms forming a diffuse cloud [45].

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The composition of sputtered material is not altered and remains same as that of the target material [39].

Method of choice for refractory metals and intermetallic compounds than other methods

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Advantages

like evaporation and laser ablation. Economical method as the sputtering equipment is less expensive than electron-beam

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lithography systems [46].

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Less impurities are generated than those created by chemical methods. Alloy nanoparticles can be produced with easier control on composition than other chemical reduction methods [46].

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This method is a versatile technique to synthesize ionic nanoparticles with spacious sizes and compositions that are not obtainable in solution [47].

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Slow deposition of heavier ions or mass-selected ions gives unparalleled control of different parameters such as size, composition and charges of ions deposited onto

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surfaces [47]. Disadvantages

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The nature sputtering gas (He, Ne, Ar, Kr, and Xe) can produce effect on surface

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morphology, composition, texture, and the optical properties of the nanocrystalline metal

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oxide films [6]. Application

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Synthesis of variety of nanomaterials on surface that employed for catalysis process, photovoltaics, magnetism, memory, cluster-surface interactions, hydrophobic coatings,

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and “nanoportals” for hydrogen storage.

For preparation of core-satellite Si-Ag and stable Pd-core MgO-shell nanoparticles for the catalytic methanol oxidation reaction [47]. Heavy and complex ions such as peptides, proteins, protein assemblies, organometallic

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complexes, metal clusters, and nanoparticles can be easily placed on the substrates

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without altering their basic properties. This method allows deposition of large molecules like large non-volatile species that are not easy to deposit by traditional atomic and molecular layer deposition techniques [47].

2.2. Bottom up methods Nanoparticle synthesis using bottom up approach is based on formation nanoparticles from smaller molecules like joining of atoms, molecules or small particles. In this method,

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nanostructured building blocks of the nanoparticles first formed and then assembled to produce final nanoparticle [48].

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2.2.1. Solid state methods 2.2.1.1. Physical vapor deposition method

In the physical deposition method, material is deposited on a surface either as a thin film

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or as nanoparticles. Highly controlled vacuum technique such as thermal evaporation and sputtered deposition causes vaporization of material, which is further condensed on a substrate

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[49]. Physical vapor deposition techniques such as pulsed vapor deposition are generally used for the preparation thin film of lanthanum strontium cobalt [50]. For the pulsed laser deposition, laser ablation is employed on solid target that causes formation of plasma of ablated species and further, these ablated species are deposited on a substrate to produce a film (Figure 2) [51]. This

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method is extensively used to deposit metal nanoparticle and thin film on carbon nanotubes [49].

Fig. 2. Pulsed laser deposition of ablated species.

Advantages -

Simple method for the formation of thin metal films.

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Disadvantage Expensive method.

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Generates low volume of material.

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For successful implementation of this method, high throughput at lower cost is necessary at the industrial level [3].

Application

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Preparation of thin film of tungsten selenides.

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Preparation of platinum-ruthenium (Pt-Ru) nanoparticles [52].

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Formation of Yttria-stabilized zirconia [53].

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This method is used for the formation of most efficient thin-film solar cells, Cu (In,Ga)

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Se2 thin film using pulsed laser deposition (PLD). The femtosecond (fs)-pulsed laser

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deposition (Fs-PLD) derived copper indium gallium selenide (CIGS) thin films shows prominent antireflection and excellent crystalline structure [54].

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2.2.1.2. Chemical vapor deposition method

The chemical vapor deposition was first time reported and patented in late 19th century

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and employed for preparation of carbon fiber as filaments and carbon powder for color pigment in electric lamp. In this method of deposition, thin film of target material is deposited on a surface through the chemical reaction of gaseous molecule containing atoms useful for film formation [55]. The target material is released in the form of volatile molecule and works as precursor and then series of chemical reactions take place between the precursor fragment, precursor and substrate surface to produce a thin film. Generally atomic layer deposition (ALD) thin films are produced by the surface chemical reaction in this method [55,56,57].

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The deposition of target material can be achieved by: 1) Thermally active chemical vapor deposition (TACVD) [58] 2) Plasma enhanced chemical vapor deposition (PECVD) [59] and 3) Photo initiated chemical vapor deposition (PICVD) [60]. Thermally activated chemical vapor

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deposition is not suitable for temperatures sensitive substrates like polymers [61,62]. Plasma enhanced chemical vapor deposition technique has scale up issue because of specific operating requirements [63]. The photo-initiated methods as photo initiated chemical vapor deposition

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involve low energy treatment and wide spectrum of possible variation [64]. In addition, photoinitiated operation does not require specialized equipment at pressure condition and ambient

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temperature [65].

In the plasma enhanced chemical vapor deposition method, plasma is generated in the void chamber and deposited as thin film on substrate surface by the chemical reactions of reacting gases. Radio frequency (AC frequency) microwave and inductive coupling (electric

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current) electromagnetic induced electric current also used in this technique. It can be operative relatively at low temperature so it is beneficial for large-scale industrial application and for

Advantages

Particle properties of nanostructures such as surface morphology and crystal structure can

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graphene nanostructure fabrication and nanotubes [66].

be controlled.

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Chemical vapor deposition method of coating exhibits the high film durability [61].

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This method is easy to scale-up [67].

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Produces nanoparticles of controlled surface morphology [61].

Disadvantages

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Chances of chemical hazards because of toxic, corrosive, and explosive precursor gases.

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Multicomponent material deposition is difficult [61].

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Application Preferred method for the preparation of gas sensitive SnO2 nanorod using aerosol assisted chemical vapor deposition [68]. Preparation of zirconia alumina nanopowder [69].

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The chemical vapor deposition of large-area single-layer graphene on metal such as Cu is

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2.2.2. Liquid state synthesis methods 2.2.2.1. Sol gel method

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performed using this technique and has wide industrial applications [70].

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Livage et al (1988) first time review this technique on sol gel chemistry of transition metal oxides. The sol gel method of nanoparticles synthesis involves either; a) Mixing of preformed colloids metal (oxide) with a sol containing the matrix-forming species followed by

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gel formation, b) Direct mixing of metal and metal oxide or nanoparticles within a prehydrolysed silica sol. c) Complexation of metal with silone and reduction of metal before hydrolysis [71]. In

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this method, a network formation is introduced using colloidal suspension (sol) and gelatin to form a network in continuous liquid phase (gel). The ions of metal alkoxides and aloxysilanes are used as a precursor for synthesis of colloids. The tetramethoxysilane (TMS) and tetraethoxysilane are most commonly employed which forms silica gel. Metal alkoxides are organo-metallic precursor for various metals such as silica, aluminium, titanium and many other and are immiscible in water. Alcohol is used as mutual solvent. Initially in this method, homogeneous solution of one or more selected alkoxides is prepared and a catalyst is added to

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initiate a reaction at controlled pH. The sol-gel formation involves four main steps; hydrolysis, condensation, particle growth and agglomeration of particle [23]. In direct precipitation of metal or metal oxide technique, the metal oxide particles are precipitated from silica sol usually by heat

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treatment at low temperature. Thin films are mainly prepared by using this technique [71]. Advantages Simplest method.

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Particle size and morphology is possible to control by systematic monitoring of reaction

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parameters [72]. Applications

It is used for the synthesis of zinc peroxide (ZnO2) nanostructures [72).

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Preparation of Nio2 nanoparticles [73].

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Thin metal films formation [71].

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2.2.2.2. Chemical reduction method

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In chemical reduction method, ionic salt is reduced in an appropriate medium in the

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presence of surfactant using different reducing agents [74]. Reducing agent such as sodium borohydride is used in aqueous solution to prepare metal nanoparticles. Formed metal nanoparticles are capped by using trisodium citrate (TSC) or sodium lauryl sulphate (SLS). Sometimes stabilizing agent is used with reducing agent. The metal nanoparticles stability in the dispersion was monitored by the analysis of absorbance [75]. Reducing agents such as sodium borohydrate (NaBH4), glucose, ethylene glycol, ethanol, citrate of sodium, and hydrazine hydrate etc. are used for silver nanoparticles synthesis [76].

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Advantages -

Simplest method used for preparation of metal nanoparticles [74].

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Disadvantages

Several limitations associated with reducing agents such as toxicity, expensive, poor

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reducing ability, high costs, and impurities [67]. Applications

Preparation of copper nanoparticle using potassium borohydrate as a reducing agent [67].

2.2.2.3. Hydrothermal method

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Hydrothermal method is based on reaction of aqueous solution vapors with solid material

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at high pressure and temperature, and leads to deposition of small particles. In this method cation precipitate in polymeric hydroxide form and further these hydroxides get dehydrated and accelerate formation of metal oxide crystal structure. The second metal cation formed is

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beneficial for controlling particle formation process by preventing the formation of complex hydroxide when base is added to metal salt solution [32].

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Advantages

Desired size and shape nanoparticle can be prepared [32].

Well-crystallized powder can be formed. Produce nanocrystal with high crystallinity [77].

Disadvantage

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Processes are difficult to control.

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Limitation of reliability and reproducibility [32].

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Applications Suitable method for preparation of powders in the form of nanoparticle or even in single crystal [32].

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2.2.2.4. Solvothermal method

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Solvothermal method is used for the preparation of nanophase in presence of water or other organic chemicals like methanol, ethanol and polyol as a solvent. Reaction is produced in pressure vessel that allows solvent (water and alcohol) heating above their boiling point temperature [78]. The kinetics of crystallization (crystal formation) can be increased by the one

solvothermal) [79]. Advantages

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to two orders of magnitude by employing microwave assisted reactions (microwave

Preparation of high quality crystallized monodispersed nanocrystals.

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This method is more preferred for the preparation of narrow size distribution of high degree

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of crystallization of nanocrystallites over conventional oil bath heating [78]. Application -

Synthesis of silver nanoparticles [78]. Rapid synthesis of nanostructures of Pt, Pd, Ag and Au using polyethylene glycol or methanol as reducing agent under the microwave assisted condition [79].

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Wide application for the preparation of high quality crystallized monodispersed nanocrystals of nitrites, metal oxide and new semiconductor material [78].

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2.2.3. Gas phase methods 2.2.3.1. Spray pyrolysis

In the spray pyrolysis method, nanoparticle precursors in vapor form are delivered into

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the hot reactor. For the delivery of precursor, a nebulizer is employed that directly deliver precursor in the minute small droplets form into the hot reactor. Metals such as acetate, nitrate

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and chloride are commonly served as metal precursor [80]. The apparatus (Fig. 3) used for nanoparticle preparation by spray pyrolysis method consist of three main parts 1) A fluid nebulizer for atomization of metal precursor solution 2) A thermostatically (200 ºC to 1200 ºC) controlled vertical tubular reactor 3) A precipitator for collecting nanoparticles [81]. The

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apparatus can be modified by employing atomized techniques such as two fluids nozzle or air assisted (pneumatic) pumps or sprayers, ultrasonic sound, vibrating orifice and spinning disk

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[80].

Fig. 3. Spray pyrolysis apparatus for nanoparticle preparation.

The ultrasonic spray pyrolysis (Fig. 4), is an improved method where ultrasound is used to produce atomized droplet from precursor solution and formed aerosol droplets are further transported from atomizer to reactor furnace by the carrier gas for nanoparticles formation that

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are later collected by collection system. The heavily diluted precursor solution is converted to small aerosol droplet of size 1-10 µm, which depends upon frequency of ultrasound and

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properties of the solution [82]

Fig. 4. Ultrasonic spray pyrolysis technique for nanoparticle preparation. Advantages Relatively simple method.

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Low cost method [80].

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The particle size can be controlled and reproducible [81].

Applications

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Synthesis of nano-metal oxide and mixed metal oxide.

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Synthesis of Zno nanoparticles by using zinc acetate as metal precursor [81]

Preparation of Tio2 nanoparticle [83]

2.2.3.2. Laser pyrolysis Laser pyrolysis technique involves application of laser energy for the preparation of nanoparticles. In this method, the precursor is allowed to absorb laser energy to induce

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homogeneous nucleation reactions. This is responsible for highly localized heating and cooling as compare to heating the gas in a furnace. Most commonly used laser energy for heating is infrared CO2 laser whose energy is get absorbed by sulfur hexafluoride, which is an inert photo-

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sensitizer. Nanoparticle formation in the CO2 pyrolysis begins immediately as sufficient degree of super saturation of condensable product is reached in vapor phase [44].

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Advantages

It is a potentially clean technique, which forms particles of uniform and controllable size

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distribution.

Particle size can be controlled by modifying flow rate of chemicals through the pyrolysis reaction zone.

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It is a simplest method of producing large amount of nanostructures even at pilot plant

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dimensions by balancing CO2 laser exposure and continuous flow of reactor [32]. Applications

Suitable method for development of TiO2, SiO2, and Al2O3 nanoparticles production [84].

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2.2.3.3. Flame pyrolysis

Formation of nanostructures by means of direct spraying of liquid precursor into flame is the working principle of flame pyrolysis method. This method allows delivery of precursors, which do not have sufficiently high vapor pressure in the form of vapor [85]. The gases (vapor-fed aerosol flame synthesis), liquid (flame-assisted spray pyrolysis: FASP and flame spray pyrolysis: FSP) or solid precursor is exposed to the flame and allowed to form nanoparticles [86].

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Advantages -

This is a promising, alternative gas-phase production method for metal oxide

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nanoparticles. -

Most effective method for less volatile raw materials.

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The liquid precursor delivery directly into the flame may be the most effective route as

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several less volatile raw materials can be dissolved in organic solvents or even in water, allowing relatively simple liquid precursor handling and dosing [86].

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Applications -

Preparation of zinc oxide nanoparticles [86]

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Synthesis of silica particles from hexamethyl disiloxane [85].

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2.2.4. Biological method/ biomimetic method/ green synthesis method Preparation of nanoparticles using green synthesis methods is an emerging trend of nanotechnology. These techniques are emerged to overcome problems such as reaction

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complications, high cost and safety issue of conventional methods. The green chemistry approaches incorporated novel techniques to the synthesis processes and numerous applications

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of chemical substances to reduce threat to health and environment. These approaches mainly include; 1) Clean chemistry, 2) Atom economy, 3) Environmentally benign chemistry, and 4) Benign by design chemistry [87]. The biological methods of nanoparticle preparation involve application of different

microorganism and their enzymes, plant products like isolates and extracts. These techniques have number of advantages over other physical and chemical methods as it is a cost effective,

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eco-friendly method, and easily scaled up for large scale production. In addition, green synthesis does not involve use of high pressure, energy, temperature and toxic chemicals [88]. The natural biogenic metallic nanoparticle synthesis is divided into two categories.

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1) Bioreduction: in this method, metal ions are chemically reduced into the biologically stable form using microorganisms and their enzymes. The formed metallic nanostructures are stable and inert in nature that can be safely separated from contaminated sample [89,90].

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2) Biosorption: this is a unique method of nanoparticle synthesis where metal cations in aqueous media is allow to bind with organism cell wall that further leads to formation of stable

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nanoparticles because of cell wall or peptide interaction [89,91]. 2.2.4.1. Nanoparticle synthesis using bacteria

The interest for appropriate implementation of naturally occurring recourses such as

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microorganism for the synthesis of nanoparticles is continuously increasing worldwide. Prokaryotes have gained attention as a mean of metallic nanoparticle synthesis because of their abundance in environment and ability to adopt extreme condition.

Bacteria have certain

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advantages like rapid multiplication, and easy to cultivate and manipulate [89]. The growth can be controlled by controlling conditions like oxygenation, temperature and incubation time. He et

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al (2007) proposed that changing the pH of growth medium during incubation produces nanoparticle of different size and shape [92]. Some of the examples of bacteria used for synthesis of nanoparticles are listed in table 2. Advantages -

Abundantly available and has ability to adapt to extreme conditions [89].

Disadvantage

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-

Safety risk [89].

Table 2

Sr. No. Microorganisms

Nanoparticles

Cellular location of synthesis

Aspergillus terreus

Lead selenide (20-50 nm)

2

Rhodococcus

Au

Intracellular reduction

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species 3

Extracellular

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1

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Examples of bacteria along with cellular locations used for nanoparticle preparation.

E. coli

Cd telluride

References

93

94

Extracellular

95

Cd telluride

Extracellular

96

Pd, Pt, Ag

Extracellular reduction

90, 97

Extracellular biosorption

98

(2-3 nm) 4

Saccharomyces

5

E. coli

6

Loctobacillus species

7

Klebsiella

8

Enterobacter

9

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coacae

Ag

Ag

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pneumonias

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cerevisiae

Bacillus species

Ag

Ag

and reduction Bioreduction (Using nitro 98 reductase enzyme) Bioreduction (Using

98

nitroreductase enzyme) Intracellular reduction

99

2.2.4.2. Nanoparticle synthesis using fungi Enzyme and protein secreted by fungi functions as reducing agent that can be used for metal nanoparticle synthesis from metal salt. Metal such as Ag has ability to bind with cytoplasmic membrane due to electrostatic interaction and get reduced which further forms silver

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nuclei and eventually leads to accumulation of silver nuclei and nanoparticles [48,100]. Commonly used fungi for nanoparticle preparation such as Fusarium oxysporum, Aspergillus fumigates, Trichoderma reesei and Fusarium oxysporum secrets certain reducing agents that

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reduces these metal ions. Practically microorganism based nanoparticle syntheses is not feasible as they require maintenance of high aseptic condition [89].

-

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Advantages

Nanoparticle synthesis is easy to scale up and downstream processing, economical

-

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flexibility and large surface area because of mycelia.

Productivity is more than bacteria as fungi secret more amounts of proteins [89].

Disadvantage Safety risk.

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Nanoparticles produced are of variable size [89].

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2.2.4.3. Nanoparticle synthesis using plant and plant products

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Recently plant mediated nanoparticle synthesis gaining wide attention worldwide [101].

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Numerous plant products such as extracts are used for the preparation of variety of metallic nanoparticle like gold, silver, copper and zinc. The crude extracts are rich in plant secondary metabolites like phenolic acid, flavonoids, terpenoid and alkaloid that selectively reduces metallic ion and leads to formation of bulk metallic nanoparticle. The primary and secondary metabolites of plant are consistently involved in redox reactions of plant metabolic pathways. These properties are employed as reducing agent and capping agent and leads to synthesis of eco-friendly nanoparticle [102,103]. Plants such as Brassica juncea, Ilex crenata, Sesbania

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drummondii, Clethra barbinervis, and Acanthopanax scidophylloides have ability to produce photoremediation of heavy metal [103]. Nanoparticle synthesis includes purification of bioreducing agent form biological extract and mixing it with aqueous solution of relevant metal

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precursor solution in controlled manner. Several spontaneous reactions occur at room temperature that produces nanosized particles. Sometimes addition of Cd with stirring and heating are needed to hasten synthesis process. Plant extracts are generally preferred because of

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its easy availability, suitable for bulk production and byproducts or waste products formed are

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ecofriendly [89]. Advantages

No pathogenicity as that of fungi and bacteria.

-

Fairly homogenous nanoparticles are produced [89].

Disadvantages -

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Heating conditions such as temperature is required which increases production cost of

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nanoparticles [89].

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2.2.4. Other methods of nanoparticle synthesis 2.2.4.1. Electrochemical deposition Methods such as electrodeposition synthesis or template synthesis are used for the

production of nanomaterials [104]. Ion etching technique is used for the production of porous alumina membranes [105]. In addition, for the manufacturing of porous semiconductor structures, an electrochemical deposition method such as electrochemical anode dissolving processes is preferred [104].

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The metal nanoparticles are prepared by electrochemical deposition (ED) using baths containing metal salts. The baths are either acidic or basic and use a three terminal potentiostat. In this technique an electrode, cathode is needed where the metal nanoparticles are deposited

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whereas another anode electrode and Ag\AgCl or calomel is a reference electrode. Slight voltage is applied for suitable time in an electrolytic bath containing metal salt. This technique is widely employed for different purposes such as cyclic voltammetry, double pulse and potential step

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deposition [106].

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Advantages Simple, fast and inexpensive method.

-

Unique method that produces nanoparticles of controlled size and morphology.

-

Major advantage is that the nanoparticles get directly attached to the substrate [107].

Applications

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Synthesis of nanoparticles, nanowire, and nanorods.

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Nanomaterial production such as nanowires of Au, Co, Ni, and Pt [107]

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2.2.4.2. Microwave assisted nanoparticles preparation Nowadays microwave techniques are more proffered over thermal heating for the

preparation nanoparticles. Microwave frequency of range 300 MHz to 300 GHz is applied that leads to orientation of polar molecule such as H2O with the electric field. The re-orientation of dipolar molecules with an alternating electric field causes molecular friction and loss of energy in the form of heat. Recently this technique was successfully implemented for the preparation of

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silver nanoparticles where silver nitrate solution is irradiated with carboxymethyl chitosan, which acts as reducing agent and a stabilizer [108].

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Advantages Highly effective technology for nanoparticle preparation.

-

Simple, rapid volumetric heating and the consequent dramatic increase in reaction rate.

-

Homogenous heating throughout the process can speed up the reaction rate by the orders

Disadvantages -

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of magnitude compared with conventional heating.

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Shorter crystallization time and homogeneous nucleation because of uniform heat of microwave oven [109].

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Applications

Useful technique in various fields of chemistry and materials science.

-

Widely used for several plant-based extracts to prepare various metal nanoparticles [110].

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-

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2.2.4.3. Supercritical fluid technology Supercritical fluids (SCFs) are widely used in the several areas of material and chemical

science. The SCFs have distinguishing feature that their physicochemical properties can be modified between gaseous and liquid states by simply altering the pressure or temperature, which provides opportunity to change reaction environment like density, viscosity, diffusivity or surface tension [111,112]. The ability of SCFs to get rapid expansion is a main feature, which is selectively employed for the synthesis of fine powders such as nanoparticles [112]. Many of the

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physical properties of SCFs vary with density. The most commonly used SCFs are carbon dioxide (scCO2), nitrous oxide, water, methanol, ethanol, ethane, propane, n-hexane and ammonia [113].

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In this method, the nonaggregated nanoparticles are formed by coating nanoparticles in a protective layer that binds to their surfaces, quenches particle growth and provides a steric barrier to aggregation [114]. The nanostructure synthesis happens in a reactor containing high-

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pressure pumps and pressurized with a backpressure regulator valve. The precursor dissolved in different solvents is injected into the reactor. The formed product (nanomaterial) can be

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recovered whether as a powder material using a particle filter positioned before the backpressure regulator valve or in the form of suspension at the outlet of the process. Advantages Low cost and easy method [115].

-

No organic solvents is required using this method for iron nanoparticle synthesis and

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particle size can be efficiently controlled [109]. The films formed using SCFs do not exhibit quantum confinement effects [114].

-

Fast synthesis of nanomaterial (tens of second) than conventional methods [116].

-

Carbon dioxide or water can be used as a supercritical fluid, which is substitute for an

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-

organic solvent [115].

Disadvantages -

It requires high temperature and critical pressure for nanoparticle preparation [109].

Applications

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For the synthesis of mesoporous single crystals and elongated irregular nanotubes [109].

-

Synthesis of metal and semiconductor nanoscale materials [111,114]

-

Synthesis of metal oxide nanoparticles [116].

-

It is a versatile technology for the synthesis of divers range of metal nanoparticles (Cu,

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-

Ag, Pt, Pd), oxides (ZrO2, CeO2,Fe2O3,Cu2O, Cr2O3,Al2O3, ZnO,), nitrides (Ni3N, Cu3N,

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Co2N, Cr2N, Fe4N) and very complex structures such as core shell particles [116]. 2.2.4.4. Ultra sound technique

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The use of ultra sound for material synthesis has been extensively increased in recent few years. Ultrasound assisted synthesis techniques include two main methods, sonochemistry and ultrasonic spray pyrolysis [117]. The ultrasonic spray pyrolysis method has been already discussed in gas phase methods of nanostructure synthesis.

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In sonochemistry method of ultra sound, no direct interaction occurs between ultrasound and the chemical species or target molecule. The acoustic cavitation is characteristic feature of this method, which means bubble formation, growth and implosive collapse of these bubbles in

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liquids due to high intensity ultrasound. Exposure of liquids to ultrasound produces alternating expansive and compressive acoustic waves that forms bubbles and oscillate them. The oscillating

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bubbles holds ultrasound energy. At certain condition the bubble overgrow, collapse and release concentrated energy immediately, and leads to light emission or sonoluminescence. The main working principle is that every cavitation bubble serves as a plasma chemical microreactor and offers a highly energetic environment at almost room temperature of the bulk solution. The commercially available apparatus such as ultrasonic cleaning baths, direct-immersion ultrasonic horns, and flow reactors are the examples of sonochemical apparatus that works on sonochemistry principle [118,119].

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Advantages It is an ecofriendly, green, fast and easy method of nanostructures synthesis [120].

-

Successfully employed for less volatile organic liquids.

-

By modifying reaction conditions several forms of nanostructures of metals, oxides, sulfides and carbides can be prepared [119].

For reduction of noble metal salts during nanostructure formation reducing agent is not

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-

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-

required, reaction rate is generally fast and very tiny metal particles are produced [119].

-

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Disadvantage

The rate of sonochemical reduction completely depends on ultrasonic frequency [119].

Applications

It is used to produce unusual nanostructured inorganic materials such as carbonyl

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compounds (Fe(CO)5, Co(CO)3NO, Mo(CO)6, and W(CO)6) [119,121]. Nanostructure material preparation from volatile organometallic compounds [118,122].

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3. Summary and future prospective

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The application of metal nanoparticles is immensely increasing worldwide in different fields like material science, physics, chemistry and biomedicine. The synthesis of nanostructures is very dynamic and complex process. Several approach such as physical vapor deposition, chemical vapor deposition, sol gel methods, chemical reduction, hydrothermal method, solvothermal method, spray pyrolysis, laser ablation, flame pyrolysis, green synthesis method, electrodeposition process, microwave technique, supercritical fluid precipitation process, and ultra sound technique have been made to synthesize nanoparticles of correct morphology. Each

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method has its own particular advantages and limitations. Green synthesis of nanoparticle synthesis is sustainable, eco-friendly, inexpensive and generally free of chemical contaminants. Although many methods are successfully emerged for nanoparticle synthesis, more precise

at commercial level. Conflict of interest statement

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The authors declare no conflict of interest.

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techniques are required to overcome limitations of existing methods and proper implementation

Acknowledgement

The authors gratefully acknowledge facilities from School of Pharmacy, Swami Ramanand Teerth Marathwada University Nanded, Maharashtra, India.

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Conflicts of interest To

The Journal of Drug Delivery Science and Technology

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The Editor

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All the authors have contributed to complete present research work and have never submitted the manuscript previously elsewhere. The present manuscript ‘Metal nanoparticles synthesis: an

includes any conflicts of interest. Yours Sincerely Mr. Prasad G. Jamkhande

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Email ID: [email protected]

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overview on methods of preparation, advantages and disadvantages, and applications” do not