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DEPARTMENT OF CHEMISTRY

EXPERIMENTAL TECHNIQUES FOR THE SYNTHESIS AND CHARACTERIZATION

OF NANOMATERIALS
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Introduction.

The synthesis and assembling strategies of nanoparticles will be dependent on precursors noted as

mostly accommodating liquid, solid, and gas phases (Saravanan et al. 2008). The organization of

these nanoparticles provides complementary tools in nanotechnology and the processing of

nanomaterials and particles of bulk shapes from nanopowder. The aspect of retaining the nano size is

not able to be a challenge as long as structural engineering applications are in question. Therefore, the

experimental application of chemical or physical depositions and approaches in characterizing and

synthesizing nanomaterial, and the inclusion of chemical reactivity and physical compaction are used

to integrate and build the nanostructure which becomes the building block within the final

nanomaterial. The various techniques are classified as either top-down or bottom-up approaches will

be used to determine how the assembly of nanomaterial into finer material is affected (Saravanan et

al. 2008). This paper will delve into the known methods used in characterizing and synthesis of

nanoparticles under the top-down approach or bottom-up approach as well as analyze their approach

and use.

Experimental Techniques for the synthesis and characterization of nanomaterials

Applications using nanostructures are rapidly on the rise and this has drawn attention to the

techniques being used to characterize the size, elemental composition as well as crystal structure

including some other physical properties of nanoparticles. According to Pallares, M. et al. (2018),

there exist many varied techniques used to characterize and synthesize nanomaterials depending on

the concept of the techniques being used, the information which they are capable of providing, or the

materials they are supposed to form. There have been extensive advances therefore which have

advantages as well as weaknesses within the available techniques and in the development of science

and technology, studies have shown that nanomaterials are the most promising in this field. Srivastava

(2012) comments on nanomaterials as being metals, ceramics, polymeric materials, or composite

materials and they are notable of small featured sizes in the range of 1-100 nanometers. It is noted that

the nanoworld is between the scale of atomic and quantum phenomena as well as the scale of bulk
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material and therefore at any nanostructure level, material properties do get affected by common laws

of atomic physics.

Synthesis is the formation of complex materials by combining simpler elements, nanostructures

are going to be synthesized to reach a nanoscale. Nanomaterial synthesis is the foremost process

before using them for applications and as the nanomaterial is primarily governed by a wide number of

methods, it can involve physical, chemical methods, and other pathways. The two main approaches

being identified as the top-down approach (physical) and bottom-up approach (chemical and physical)

are characterized to be the comprehensive approaches that might allow the use of a single technique

or a combination in a complementary way. It has been advised however that whichever technique is to

be used in the synthesis, knowing the strengths and limitations of such techniques is crucial to make

sure that they provide reliable information when studying such specific parameters as particle size.

(Pallares, M. et al. 2018)

According to Fernandez J. et al (2014) in their journal on experimental techniques used for the

characterization of soft nanoparticles, they identify that imaging techniques such as the Electron

microscopy (EM) which is characterized by different EM techniques such as transmission electron

microscopy (TEM) and scanning electron microscopy (SEM) are common. They are identified to

offer numerous possibilities allowing for the characterization of the spatial structure of varied samples

including the visualization and elemental analysis of colloidal systems. In 1926 according to

Srivastava (2012), Hans Busch discovered the use of magnetic fields as lenses by converging electron

beams in a focus and six years later it became the basis for the operational use of the electron

microscope(EM) presented by Ernst Ruska & Max Knoll. It has been cited that the first original EM

was a TEM instrument using high-energy electrons to sample imaging. On the other hand, SEM

instruments will collect secondary electrons for obtaining an image.

The use of TEM is noted to be suitable for analyzing particles in a dry state and it gives no

information about swollen states which are achieved at varying temperatures. This has called for the

use of cryogenic techniques. In this, aqueous samples are shock frozen at the liquid temperature of

liquid nitrogen, and the aqueous phase is converted to hyper-quenched glassy water. This maintains

that the particles are embedded in the amorphous water phase where no crystallization effects distort
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their original structure. Notably, there may be the distortion of images during the drying of the thin

aqueous films of negative stain in the TEM instrument. In this, Specimen distortion due to surface

tension forces during evaporative drying or the formation of a saturated salt solution before the final

drying may also occur.

Other microscopy techniques identified are x-rayed diffraction (XRD) techniques which are used

to provide information on the crystal structure and size of nanoparticles including lattice parameters.

(Pallares, M. et al. 2018). One advantage associated with the XRD approach to samples of powder

form is that it results in statistically representative, volume averaged values. Upadhyay et al. as cited

by Pallares, M. et al.( 2018) determined the crystallite average size of magnetite nanoparticles using

X-ray line broadening, and that it was found to be in a range of 9-53nm. Another imaging technique

under microscopy is X-ray absorption spectroscopy (XAS) which includes both the extended X-ray

absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) also referred to

as NEXAFS.

EXAFS conveniently identifies the chemical state of species occurring in very low concentrations.

In this, synchrotrons are needed in acquiring the XAS spectra though it’s not a routine readily

available. According to Pallares, M. et al. (2018), XANES looks into the density of states of empty

partially filled electronic states by taking into consideration the excitation of the inner shell electrons

to those permitted states by dipole selection rules. XAS was used to examine the kinetics and

mechanism of formation of germanium nanoparticles upon the reaction of Mg2Ge and GeCl4. In this,

the EXAF experiments and the TEM results did indicate the formation of GeO2 nanoparticles along

with Ge nanoparticles. Both structural and kinetic parameters in metal catalysts supported for

reactions occurring on a time scale of a few seconds can be determined using energy dispersive

EXAFS. Pallares, M. et al. (2018) identify that this fast operation enables this EXAF technique to be

used at temperatures higher than 200 degrees Celsius and which hinders the use of surface-enhanced

Raman spectroscopy (SERS) which is not fast under the same conditions. Therefore, energy

dispersive EXAFS is used as a quantitatively suitable in situ probe of the dynamics of quick phase

change in supported nanoparticle metal catalysts.

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Since EXAFS possesses a high spatial resolution, providing information on the nearest

environment of an atom in a compound in the absence of long-range order is most convenient

considering that Bugaev and colleagues did determine the parameters of the atomic structure of PtCu

nanoparticles in PtCu/C catalysts. It is therefore a convenient technique for the characterization and

synthesis of nanoparticles with sizes lower than 10nm. EXAFS is therefore important also in the

acquisition of information concerning the coordination number, the nature of the scattering atoms

surrounding the absorbing atom, and the interatomic distance between absorbing and backscattering

atoms.

Further to the above techniques, the organization of nanoparticles in thin-film form is necessary to

render them functional and operational and in this, two techniques which are more chemical methods

can be applied. Saravanan et al. (2008) also identify high-temperature thermal decompositions and

liquid-liquid interface reactions as suitable for preparing films of many varied metals and metal oxide

nanoparticles. High-temperature thermal decomposition is a general schema for preparing mono-

disperse nanoparticles and in this, there is the requirement of a single temporally short nucleation

followed by slower growth on the existing nuclei. (Saravanan et al. 2008).

High-temperature thermal decomposition does provide therefore an approach to preparing

dispersible nanoparticles of most of the transition-metal oxides using metal cupferron complexes used

as single molecular precursors. Nanoparticles obtained in this method are freely soluble in non-polar

organic solvents and it’s possible to precipitate from solutions with polar solvents. On the other hand,

a liquid-liquid interface does offer potential in the synthesis of nanoparticles as well as casting them

into a film. In this, the particles are highly mobile and rapidly they achieve equilibrium assembly.

This method is characterized as a step-by-step process that enables the synthesis of nanoparticle

arrays at the liquid-liquid interface under notable conditions. (Saravanan et al. 2008).

This method is advantageous as it involves a finite growth rate of the ultrathin crystalline film with

controllable parameters such as temperature and concentration. These nanocrystals can be extracted to

aqueous or organic layers by adding suitable capping agents. This obtained film is also transferrable

on a solid support such as mica or a polymer film. With the synthesis of films of Au, Ag, and Cu

nanoparticles, films of CuO nanowhiskers having diameters in the range of 50 nm to 300 nm and
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lengths of several microns are prepared by using reactions at the liquid-liquid interface. It is therefore

important to consider the liquid-liquid technique as very promising in the synthesis of films of

nanocrystals.

Despite the use of chemical methods in the synthesis of nanoparticles, Saravanan et al. (2008)

comment that the utilization of physical methods can be given attention. The identification of the

High-energy ball milling technique is also a common method whereby, it has been widely used for the

synthesis of nanohard/nanocomposite magnetic powders considering its versatility. In this technique,

there is a high energy deformation process that introduces progressively defect structures seen as

dislocations and vacancies, atomic-scale chemical disorder as well as the elastic strain energy to the

initially crystalline starting powders through shearing actions of ball powder collisions. Due to the

complex dependence of nanostructure on milling intensity, temperature, and other factors. Milling is

identified to produce a variety of effects in intermetallic alloys. A common example is the preparation

of nanocomposite magnetic powders of SmCo5 /Fe and their consolidation into bulk magnets by use

of the spark plasma sintering method. (Saravanan et al. 2008).

However, the magnetic properties including the degree of exchange coupling being strongly

dependent on the microstructural parameters, such as crystallite size, phase distribution, and volume

fraction of either hard or soft magnetic phases, efforts are been made to synthesize and characterize

the nanostructured magnets through mechanical milling, melt spinning, and thin-film techniques.

(Saravanan et al. 2008). It’s notable to identify that the use of spark plasma sintering (SPS) technique

is being successfully adopted to produce bulk nanocomposite magnets having high coercivity and

excellent properties.

Pallares, M. et al. (2018) also do identify yet another technique in the synthesis and

characterization of nanoparticles referred to as Fourier infrared spectroscopy (FTIR). This technique

they identify as helpful in determining the structure, size, and composition of nanoparticles. It is noted

to be involved and based on the measuring of absorption of electromagnetic radiation where the

wavelengths are between the mid-infrared regions (4000-400 cm-1). It is seen that, when these IR

radiations are absorbed by the molecule, the dipole moment is modified and such molecules become

IR active (Pallares, M. et al. 2018). The information concerning the molecular structures and
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interactions is provided through a recorded spectrum which gives the position of bands, as related to

the strength as well as the nature of the bond and specific functional groups. This technique is noted to

help probe adsorbates electrochemically, therefore, detecting volatile reaction products. Pallares, M.

et al. (2018) concludes therefore that, concerning the experiment by Feliu and coworkers on how Pt

nanostructures performed on ethanol oxidation done in a combined approach with in situ ATR-FTIR

and differential electrochemical mass spectroscopy (DEMS), the results did confirm that the preferred

decomposition products were related to surface structures with CO ads formation on (100) domains and

acetaldehyde/acetic acid formation on (111) domains. In another experiment, carbon-supported

platinum nanoparticles of (3–8 nm size) were used for the oxidation reaction of CO and the catalytic

process was monitored using DRIFTS and quadrupole mass spectrometry (QMS). FTIR measurement

of adsorbed CO did confirm the variations of Coad and Oad in various steps of the experiment.

Another important technique is Nuclear magnetic resonance (NMR) spectroscopy. This is an

analytical quantitative approach concerned with the structural determination of nanoscale materials

(Pallares, M. et al. 2018). It is noted to be based on the NMR phenomenon which is exhibited by

nuclei that possess non-zero spin especially when they are placed in a strong magnetic field. This

tends to cause small energy differences between the “spin up” and “spin down” states. The transition

within these states can therefore be looked into by electromagnetic radiation in the radio wave range

thereby being used to study interactions and or coordination between ligand and surface of

diamagnetic or antiferromagnetic nanoparticles. Pallares identifies that it is not suitable to characterize

ferri- and ferromagnetic materials for such large saturation magnetization can cause variations in local

magnetic fields leading to shifts of signal frequency including the dramatic decrease in relaxation

times. This method is very useful in analyzing the formation and final architecture of noble metal

nanoparticles. NMR is also used to study capping ligands and these measurements get information on

the properties of the nanoparticle core. A good example noted in the report is electronic structure,

atomic composition, or compositional architecture.

Other notable synthesis techniques are precipitation methods which include Modified Emulsion

Precipitation Method, Hydrothermal Synthesis/Solvothermal Synthesis, Sol-Gel Method as well as

Aerosol method (Srivastava, 2012). The Modified Emulsion Precipitation Method involves the
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preparation of thermal stable emulsion systems which are prepared by adding appropriate amounts of

surfactants to a water-oil system. The normal particle growth rate is faster than the equivalent rate of

exchange between droplets implying that nucleation and growth in emulsions will be retarded as

compared to those found in homogenous solutions thereby avoiding the formation of large particles.

Srivastava, (2012) concludes that multisurfactants can be effective when formally thermally stable

emulsions and controlling droplet size.

The hydrothermal synthesis process can be used with a single heterogeneous phase reaction in

aqueous media at high temperatures and pressure to facilitate crystallization by making hydrous

ceramic materials directly from solutions (Srivastava, 2012). He further notes that the synthesis offers

low temperatures, and a direct route to oxide powder having a narrow size distribution thereby

avoiding the calcinations step. This mechanism is characterized by reactions that follow a liquid

nucleation model. In applied ceramics, heating metal salts, oxides, and hydroxides in solution

suspension in a liquid, at controlled temperatures and pressure for approximately around 20 hours.

The product is washed with de-ionized water to get rid of ions in the solvent as well as other

impurities and after drying well in the air, the ceramic nanoparticles are formed depending on the pH

value (Srivastava, 2012). The Sol-Gel synthesis technique is also seen to offer more specific

advantages when preparing multi-component oxide ceramics. The processing starts with metal

alkoxides which are liquids or volatile solids which provide pure oxide precursors if they are purified.

The use of the Aerosol method which is defined as being a gas phase is convenient in large-scale

industries, especially in the production of multi-component materials. The two routes which might be

used in the preparation of ultrafine aerosol particles may involve the generating of supersaturated

vapor from a reactant, which is followed by homogenous nucleation or gas to particle conversion

(Srivastava, 2012). The other is the generation of liquid droplets which then will go through heating to

solid states or liquid to particle conversion. Srivastava identifies within this method the use of spray

drying and pyrolysis as the most common methods for a liquid to solid conversions.

In conclusion, recent innovations and emphasis on nanotechnology techniques identify that it is a

technology on the nanometer scale and deals with the atoms, molecules, or the macromolecules with

the size of approximately 1–100 nm to create and use materials that have novel properties in different
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fields. It has been noted to transform not only the technology and manufacturing industry but also the

food industry. The need for the use of nanoparticles has been on the increase, especially in the fields

of science, and food microbiology (Singh T. et al. 2017). It is hence observed that the materials have

some unique properties different from their macro-scale counterparts arising from the high surface to

volume ratio as well as other special physicochemical properties including color, solubility, strength,

diffusivity, toxicity, magnetic, optical, and thermodynamic properties. Other a wide range of areas

where nanotechnology is being used in the fields of agriculture as well as medicine (Singh T. et al.

2017).

The typical use of the above-mentioned techniques is therefore dependent on the advantages and

limitations of each of the methods and the starting compound as either solid, liquid, or gas. These

starting materials for a top-down approach are solid while for a bottom-up are liquid or gas states.

These properties are specified in governing how these characterizations and synthesis approaches

named; TEM, SERS, EXAFS, DEMS, QMS, FTIR, NMR, and hydrothermal methods including

Aerosol are just some of the discussed known experimental techniques are done. According to

Saravanan (2018), the potential found in these techniques has been to prepare a variety of metal/metal

oxide nanoparticles, films, and two-phase nanocomposites. Other known aspects of chemical

synthesis strategies analyzed such as high-temperature thermal decomposition and liquid-liquid

interface reaction, and physical methods such as high-energy ball milling have been cited as suitable

for either preparing films or assembly or processing them into bulk shapes for different industries.
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References.

Fernandez c. J., Ramos, P. J., Sanz, O., Forcada, J. Vinuesa, O. L.J. Molina, M. Valverde, R. Miguel,

A. & Miranda, T. et. al. (2014). Experimental techniques used for the characterization of soft

nanoparticles. (34). 19-108. Research Gate.

https://www.researchgate.net/publication/

287941107_Experimental_techniques_used_for_the_characterization_of_soft_nanoparticles

Pallares M. R., Mourdikoudis, S. & Thanh, K. T. (2018). Nanoscale: Characterization techniques for

nanoparticles: comparison and complementarity upon studying nanoparticle properties.

https://doi.org/10.1039/C8NR02278J

Saravanan, P. Gopalan, R. Rama Rao, N.V. Manivel Raja, M. & Chandrasekaran, V. (2008).

Synthesis and characterization of nanomaterials. SmCo5/Fe nanocomposite magnetic powders

processed by surfactant and magnetic field assisted ball milling. 58(4). 504-516

https://publications.drdo.gov.in/ojs/index.php/dsj/article/viewFile/1671/774

Singh T. Shruti S. Pradeep. K. Verinder, W. Vivek, K. B. & Rather, I. A. (2017). Frontiers in

Microbiology: Application of Nanotechnology in Food Science: Perception and Overview. vol. 8.

https://doi.org/10.3389/fmicb.2017.01501

Srivastava. R. (2012). International journal of green nanotechnology. Synthesis and characterization

techniques of nanomaterials. 4(1). 17-27. Research Gate.

DOI:10.1080/19430892.2012.654738