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Current Analytical Chemistry, 2020, 16, 826-832

REVIEW ARTICLE
ISSN: 1573-4110 Volume 16, Number 6
eISSN: 1875-6727

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Current
Analytical
Chemistry
Review on Polymeric Citrate Precursor and Sono-chemical Methods for
the Synthesis of Nanomaterials

Irfan H. Lone1,*, Jeenat Aslam1, Nagi R.E. Radwan1, Arifa Akhter2, Ali H. Bashal3 and Rayees A. Shiekh4

1
Department of Chemistry, College of Science, Yanbu-30799, Taibah University, Al-Madina, Saudi Arabia; 2Department
of Botany, Faculty of Science, Punjabi University, Patiala-147002, Punjab, India; 3Department of Chemistry, Taibah
University, Al-Madina- 30002, Saudi Arabia; 4Department of Chemistry, Government Degree College Boys Pulwama,
University of Kashmir, Srinagar, 190006, India

Abstract: Background: The properties of materials depend on the way of construction and the ar-
rangement of atoms and molecules. Therefore, it is very important to know synthesis methods for the
preparation of novel materials as per their desired structure. The low-temperature synthesis methods,
such as polymeric citrate precursor and sonochemical methods are efficient enough to control the
preparation of novel nanoparticles with morphological differences that leads to the novel devices
with desired technological performances. These methods are simple, very less expensive and are easy
to handle to operate for the synthesis of nanoparticles as per the expected morphology and dimen-
sions.
Current Analytical Chemistry

ARTICLE HISTORY
Received: August 07, 2019
Revised: November 20, 2019
Accepted: November 25, 2019
DOI:
10.2174/1573411015666191203102837
Methods: Polymeric citrate precursor method, a chelate-based method involves the reaction between
mixed cations with citric acid, and then these cations are cross-linked with the help of ethylene glycol
for the esterification process. Gel composites were heated which burns the organic moieties leaving
behind the nanoparticles, and burning gels becomes essential for the reduction of nanoparticles. The
sonochemical method, on the other hand, uses ultrasonic the irradiation results. The acoustic cavita-
tion and high intensity ultrasound has been exploited for the preparation of different series of nano-
particles.

Results: Commonly known for polymeric citrate method as Pechini gel pyrolysis method gives the
evidence of versatile and elegant method for the synthesis of nanoparticles. The sonochemical meth-
od provides an unusual route of nanoparticle fabrication without bulk and that too with low tempera-
ture and pressure or less reaction time. These two methods have better control for the desired shape
morphology and size and provide many opportunities for the use of these prepared nanoparticles in
various aspects of science and technology.
Conclusion: Polymeric citrate precursor and sonochemical methods are efficient to reduce to pro-
mote desirable reaction conditions and reduce the metal ions for the fabrication of nanoparticles. The
prepared nanoparticles by using such low-cost elegant methods are uniform with a small size distri-
bution, reproducible with good yield as per the demanded applications.

Keywords: A high degree of homogeneity, cavitation bubble, citric acid and ethylene glycol ester bond, less expensive, nano-
particle synthesis, sonochemical method, ultrasound.

1. INTRODUCTION the synthesis of nanomaterials and the fabrication of

The synthesis of only nanoparticles is not only important
but it is also more important to check the size, shape, and
morphology as per the demand of application purpose, and
hence many procedures have been used to achieve this goal.
There are two approaches viz. top down and bottom up for
*Address correspondence to this author at the Department of Chemistry,
College of Science, Yanbu-30799, Taibah University, Al-Madina, Saudi
Arabia; Tel: 552858556; E-mail: irfanchem486@gmail.com
nanostructures [1, 2]. The top down approach refers to the
breaking down of bulk materials to obtain nano-sized parti-
cles and this approach predominantly relies on physical
methods. However, bottom-up approach or self-assembly
approach is the building up from atom to cluster to subse-
quent nanoparticles and is called chemical methods. This
approach has received considerable attention to obtain the
nanoparticles with less defects and highly homogenous
chemical composition. The main advantage of bottom-up
approach is to have enough control on the dimension of

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Review on Polymeric Citrate Precursor and Sono-chemical Methods

O O O
H O H
O H
HO C C C O H + M3+
H
H CH
O Cation
H C
O O
Citric acid
O H H
O H H
O H
+ HO C C OH
HO C C C O M
H H
H CH
O
H C
O
Metallic citrate Ethylene glycol
Fig. (1). Proposed reaction mechanism depicting the various steps of polymeric citrate precursor method.
nanoparticles even the size has been achieved on the atomic
and molecular size and this technique is cost effective. There
have been many reported methods for the preparation of na-
noparticles, such as reverse micellar method [3, 4], sol-
vothermal [5], sonochemical [6] and polymeric citrate pre-
cursor methods [7, 8]. In this review article, we have dis-
cussed two chemical methods viz. polymeric citrate precur-
sor and sonochemical methods.
2. POLYMERIC CITRATE PRECURSOR METHOD
This low temperature soft chemistry method,” particular-
ly gel-based Pechini method that gives pure same kind with-
out any secondary phases with microstructure size shape was
controlled in a proper way [9, 10]. This Pechini method was
first developed in 1967 for the fabrication of titanates and
niobates to produce capacitors and then onwards was used
for the chemical synthesis of metal oxide based nanoparti-
cles. This method depends on the bonding between cations
with organic to form polymer gel. Later this matrix of the gel
was burned to form the basic oxide precursor with fine ho-
mogeneity. By using citric acid and ethylene glycol, a poly-
ester complex formed interacted with metal ions with better
distribution and helped the reduction of nanoparticles. Dur-
ing the desired calcination, the pyrolysis and oxidation has
been took place simultaneously, which leads to the formation
of amorphous precursors. On further heating, the crystalline
metal oxide nanoparticles with good homogeneity and dis-
persion are formed. This method becomes so popular that
today the synthesis of dielectric, magnetic fluorescent mate-
rials is easily being prepared, that maybe later further used in
catalysts superconductors’ that will be deposited at specified
coatings. The best thing about this method was its simplicity,
total independence of the process conditions and is less ex-
pensive saving energy and is versatile that allows the simple
and fast preparation of metal oxides ceramic nanoparticles
[11]. The mechanism for the formation of a polymeric cavity
in polymeric citrate precursor method is shown in Fig. (1).
The introduction of a polyol such as ethylene glycol reacts
with citric acid forming an ester bond of polymatrix. Which
later helps the metal ions to deposit in the solution in the
whole polyester matrix. For the preparation of ternary metal
Current Analytical Chemistry, 2020, Vol. 16, No. 7 827
O
HO C C C O M
H CH
H C
O
Metallic citrate
Ester O
O H O
O C C O C C C O M H2O
H H H CH
H C
O
O
Polymer
oxides where two metal ions with 1:1 ratio were added in the
organic matrix and the citric acid and ethylene glycol with
40:10 mass ratio were added. This mixture was further al-
lowed to stir at room temperature for about 2 hours to get a
clear solution. After fully dissolution, a stoichiometric
amount of second metal ions was introduced and again
stirred for further 2 hours. This transparent solution was fur-
ther heated at 70°C for the evaporation of excess water and
leads to accelerate the reaction between citric acid and gly-
col. The solution reaches the level of gel or viscous and was
fully transferred along with a glass beaker into the muffle
furnace setting the temperature at 135°C for long or over-
night. After that, the formed resin needs to be charred at
300°C for about 3 hours inside the muffle furnace. This
whole black precursor in the beaker was scratched and
grounded with a portal pestle into a fine powder with amor-
phous nature. This black amorphous fine powder was cal-
cined in the ceramic boats at the desired temperature in high
temperature furnace. The flow chart describing the polymer-
ic citric synthesis method is shown in Fig. (2). This method
was used as earlier for the synthesis of YMnO3 [12], LaM-
nO3+? [7], Ba1-xSrxZrO3 [13], Ba1-xPbxZrO3 [8] and Multifer-
roic [14] nanoparticles.
3. SONOCHEMICAL METHOD
Ultrasound is a sound wave having a frequency in which
the human ear can respond and generally lies between 20
kHz to 100 MHz and the variable range of sound frequency
is shown in Fig. (3). There were cavitation’s present during
any chemical reactions and if high frequency of ultrasound
above 5 MHz were used, it cannot lead to the formation of
the desired cavitation. Hence, the high frequency range is
normally being used in medical imaging. So, the ultrasound
irradiations during any chemical process may occur due to
the main process, such as acoustic streaming and acoustic
cavitation. Sonochemical and ultrasound-assisted synthesis
methods have been utilized for the preparation of various
novel compounds such as thorium metal organic nanostruc-
tures by two through Microwave Assisted Reverse Micelle
(MARM) and Ultrasound Assisted Reverse Micelle (UARM)
methods [15]. The prepared samples were thermally stable
828 Current Analytical Chemistry, 2020, Vol. 16, No. 7 Lone et al.

Ethylene Glycol: B3+ ion (0.1M): Citric acid (10:1:40)

2 hrs Stirring

Clear Solution

Addition of A3+ ion (0.1M)

2 hrs Stirring

Dissolution of Metal ions

o
2 hrs Stirring at 70 C
o
Evaporation at 135 C for 20 hrs
o
Charring at 300 C for 2 hrs
Black Mass Precursor
Heated at Desired Temperature

Nanocrystalline ABO3 Compound

Fig. (2). Flow chart of polymeric citrate precursor method and images of black mass precursor at various stages. (A higher resolution / colour
version of this figure is available in the electronic copy of the article).

0 10 102 103 104 105 106 107


 #'

 #(





 $"

 %"




 $"

 $





&
 #"

Fig. (3). Variable range of sound frequencies. (A higher resolution / colour version of this figure is available in the electronic copy of the
article).
and possess high surface area with a large pore size that
could relate with mesoporous structure. In addition, there
have many UARM experiments that result in the synthesis of
various samples by way of fractional factorial design [16].
These two interesting methods, such as reverse micelle (RM)
and Ultrasound Assisted Reverse Micelle (UARM) were
used to prepare thorium based metal organic frameworks
[17] and again it was noticed thermal stability, uniform par-
ticle distribution with average particle size at around 27 nm
and high surface area. There were also involved parameters
that were designed by 2 k-1 factorials and was then subse-
quently analyzed by variance and response surface method-
ology. While in the case of Microwave (Mw) and Ultrasonic
Assisted Microwave (UAMw) methods using environmental
conditions, new Ta Metal Organic Framework (MOF)
nanostructures have been prepared [18]. The prepared prod-
ucts in both the methods have desirable properties and dis-
tinct features such as thermal stability, small particle size and
significant surface area. The introduction, synthesis and the
progress attempts of metal-organic framework MOF in nano-
photocatalysts for the degradation of pollutants were report-
ed [19]. These materials are today's new class of porous sol-
ids to make the inorganic, organic hybrid material with fine
porosity, large surface area with desired shape size and struc-
ture. Uranyl-curcumin Metal-Organic Framework (MOF)
products have thus been prepared with the help of ultra-
sound, reflux, hydrothermal and ultrasound assisted reflux
techniques [20]. In this case, ultrasound samples show excel-
lent properties such as porosity and surface area as compared
with other methods. It was also reported that how 2 k-1 facto-
rial methods to find the effects of several parameters on the
photocatalytic activity of the uranyl-MOF with curcumin
ligands in the degradation of phenol red from aqueous sam-
ples. Ultrasonic method was also developed in combination
with mirco-emulsion to produce CdS/TiO2 core shell nano-
particles with particle size were optimized by certain specific
Review on Polymeric Citrate Precursor and Sono-chemical Methods
parameters and the thickness of the shell controlled by re-
sponse surface methodology [21]. In this reported method,
four different parameters such as temperature, synthesis re-
tention time, TiO2: CdS ratio and strength of ultrasound
waves were optimized to achieve less average particle size at
around the 10 nm.
4. ACOUSTIC STREAMING AND CAVITATION
As the sound wave passes through liquids, it loses its
momentum due to viscous friction [22]. Loss of momentum
is transferred to the liquids that generate motion in the direc-
tion of wave propagation and this kind of driven liquid flow
is generally named as acoustic streaming shown in Fig. (4).
The streaming of liquid flow velocity from few cm to meter
per second and in the presence of smaller particles the fric-
tion between fluid and particles can lead to micro streaming
[23]. Because of these processes, the ultrasound generates
noninvasive mass and heat transfer was enhanced [24]. But
in the actual case, the efficiency of the energy of ultrasound
driven mining is low as compared to conventional mechani-
cal stirring, since a substantial part of the sound energy.
Fig. (4). Image showing the effect of ultrasound irradiation on
aqueous systems. A large cloud of bubbles is formed directly below
the ultrasound horn. The arrows indicate the direction of acoustic
streaming.
Liquids gas cavities are stabilized against dissolution by
surface adherence dissolution or an impurity [25]. In the
presence of sound wave rarefaction pressure, the cavities that
arise from the vaporization of liquid as well as by gas disso-
lution. The size of these cavities depends on the ultrasound
frequency and the pressure amplitude and pressure differ-
ences cause the radical distribution of cavities. The negative
pressure in the rarefaction phase of sound waves leads to the
expansion of cavity till to maximum radius has been
Current Analytical Chemistry, 2020, Vol. 16, No. 7 829
achieved. While in case of specific conditions, the cavity set
into nonlinear motion and collapses in a very short period of
time as compared to the expansive phase shown in Fig. (5).
So finally, it is the state of these cavities which, when col-
lapses, generate energy for required chemical and mechani-
cal effects and these effects are shown in Fig. (6). When cav-
itation nuclei are exposed to sinusoidal ultrasound waves, the
amplitude of waves is not static but are changing into crests
and trough with sufficient pressure, the cavitation nuclei
naturally expand and contract with the rarefactional (nega-
tive) and compressional (positive) pressure cycles. With each
pressure cycle, the bubbles grow in size and this process is
called rectified diffusion. Finally, bubble reaches a resonant
size and then expands and contracts vigorously reaches the
point where the outcome of the bubble is either collapse vio-
lently or violently or it breaks apart more gently. Collapse
momentum is fast with respect to mass and heat transfer and
the cavity compression with adiabatic temperature increases
the cavity content.
60
50
Acoustic pressure
40
Radius (mm)
30 0
20
10
Hot-Spot
0
0 10 20 30 40 50
Time (ms)
Fig. (5). Acoustic pressure and corresponding radius-time curve for
a single cavitation event, leading to a hot-spot. (A higher resolution
/ colour version of this figure is available in the electronic copy of
the article).
High temperature and pressure with extreme heating and
cooling rates has been observed and under these conditions,
the collapsing cavity is often called a hot spot [26, 27]. Once
the collapse has been formed and is then further followed by
repeating oscillation till the rarefaction phase of the sound
wave set again and the new cycle starts. A large number of
reports have been published to study the various parameters
that affect the sonochemical reactions [28, 29]. These pa-
rameters were further established to physical-chemical and
macroscopic level and such effects are shown in Fig. (7).
The cavitation study and the temperature rise strongly de-
termined the physiochemical properties of liquids and gases
[29]. As the ultrasound frequency increases the number of
collapsing per unit time increases but the intensity of cavita-
tion collapse decreases [30]. Enough number of physical
effects have been studied in a single cavity model dynamic
model [25, 31]. The reactants that were present inside the
cavity are thermally dissociated and nonvolatile reactants
hardly dissociate as shielded by cold liquid shell that
830 Current Analytical Chemistry, 2020, Vol. 16, No. 7 Lone et al.

Fig. (6). Sound propagation in a liquid showing cavitation, bubble formation and collapse. (A higher resolution / colour version of this figure
is available in the electronic copy of the article).

Physical effects
Hydrostatic Pressure
Viscous Force

Temperature
Vapor Pressure
Radius

Gas Pressure

Surface Tension Time

Acoustic Pressure

bulk liquid
Sonochemistry
liquid shell
Horn

cavity
O
Ar H H
H Ar
H O O H O
H H H
H O
H
Chemical effects Macroscopic effects
Fig. (7). Physical, chemical and macroscopic effects in sonochemistry. (A higher resolution / colour version of this figure is available in the
electronic copy of the article).

surrounds the cavity. This will generate different types of
radicals and have been influenced by the chemical effect
from the irradiation of ultrasound. It has been discussed be-
fore that the chemical and physical effects are related to the
level of the single cavity that was formed. However, macro-
scopic phenomena were developed that play a great role to
influence the sonochemical reaction. There was a large dif-
ference in the acoustic impedance between the gas and liq-
uids and hence the bubbles scatter and could absorb the
sound waves. It was observed that the surrounding bubbles
modification the shape distortions and would reduce the cav-
itation collapsing efficiency. This effect was encouraged
under the influence of acoustic force between the cavities to
self-organization and clustering the cavities. Most of the
sonochemical reactions occur in a sonochemical water bath
or with the help of a probe. Therefore, two types of equip-
ment are normally used for sonochemical reactions.
In order to study the effect of parameters on the cavita-
tion, various parameters were chosen and different types of a
liquid medium with different physicochemical properties
were considered as cavitation medium [32]. These parame-
ters have a direct link between the cavitation bubble dynam-
Review on Polymeric Citrate Precursor and Sono-chemical Methods Current Analytical Chemistry, 2020, Vol. 16, No. 7 831

ics and for the production of oxidizing species such as OH.

and H2O2 species and are considered to play a great role in Reaction Mixture Water+Detergent
the sonochemical process. By adjusting the ultrasonic fre-
quency and saturating gas during sonolysis causes to opti-
mize the ultrasonic irradiation and during the sonolysis, the
production of hydrogen peroxide H2O2 and hydroxyl radical
OH. was studied at different frequencies [33]. In the presence Heater
of four different saturating gases at a given frequency, the
hydrogen peroxide was measured by KI dosimeter and the
formation of OH was monitored by trapping with terephthal-
Stainless
ic acid. It has also been reported that high-intensity ultra- Steel Tank
sound scanning may induce scattered cavitation in the myo-
cardium with value for tissue reduction therapy and anesthe- Transducers
Bonded to Base
tized rats were heated in heater bath with 1.5 MHz focused
ultrasound pulses, guided by an 8 MHz imaging transducer Fig. (8). The ultrasonic cleaning bath used for sonochemical reac-
[34]. Rapid efficient and novel ultrasound assisted reverse tions.
method have been used for the synthesis of Ta-MOF@Fe3O4
core/shell nanostructures in optimal conditions [35]. These tions and reduce the metal ions for the fabrication of nano-
ideal physicochemical properties products were observed particles. The prepared nanoparticles by these two low-cost
best compounds for enzyme immobilization and due to the elegant methods are uniform with a small size distribution,
high surface area, unsaturated metal centers these products reproducible with good yield as per the demanded applica-
act as solid supports for lipase immobilization. There were tions. These two methods have better control for the desired
also reported for the use of ultrasound irradiation to prepare shape morphology and size and provide an ample opportuni-
new Tantalum Ta metal organic framework with various ty for the use of these prepared nanoparticles in various as-
morphologies, size distributions, thermal behaviors, and sur- pects of science and technology.
face areas [36]. Ultrasonic parameters affect the properties of
prepared products and experimental data were inconsistent AUTHORS CONTRIBUTION
with theory model results obtaining by selecting appropriate
parameters during ultrasonic irradiations. Irfan H. Lone drafted the manuscript and provided over-
all supervision. Jeenat Aslam and Nagi R.E. Radwan collect-
5. CLEANING ULTRASONIC BATH AND ULTRA- ed the literature and contributed to the scientific discussions.
SONIC PROBE Ali H. Bashal and Rayees A. Shiekh contribute to the further
refinement of the manuscript. Arifa Akhter contributed to the
The simple ultrasonic cleaning bath has mostly used the biological part.
equipment for the ultrasonic irradiation of the chemical reac-
tions. Simply using the only bath is impossible as the walls CONSENT FOR PUBLICATION
are prone to corrosion and impurities come out from the
evolved vapors and gases. Hence in the general use, the Not applicable.
standard glass vessels need to be improved into the bath that
helps uniform distribution of energy inside the reaction that FUNDING
is shown in Fig. (8) By this process, the reaction vessel does None.
not require any further modification that causes simply
placed into the bath with inert atmosphere maintained during CONFLICT OF INTEREST
the sonochemical reaction. The minimum amount of energy
around between 1 to 5 W cm-1 reaches the react inside the The authors declare no conflict of interest, financial or
vessel walls. Commercial cleaning bath has a disadvantage otherwise.
that its temperature control is generally poor and therefore, it
requires further thermostat control. This helps to allow ACKNOWLEDGEMENTS
acoustic energy directly into the system instead of transfer IHL thanks to the Taibah University.
through the water tank and reaction vessel walls. Although
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