Chapter 2
Chapter 2
Chapter 2
REVIEW OF LITERATURE
[2] This work reports the synthesis of a new adsorbent material (LaP-POT),
synthesised by sol-gel polymerization method from lanthanum phosphate (LaP) and poly o-
toluidine (POT). The sustainability and selectivity of the material as a potential adsorbent is
evaluated for the removal of fluoride from aqueous as well as real water samples using batch
experimental techniques. FESEM and TEM images showed the successful incorporation of rod-
shaped lanthanum phosphate into the poly o-toluidine polymer matrix. The increased degradation
temperature of LaP-POT from TGA curve inferred a definite interaction between two. XPS study
revealed the successful binding of fluoride onto LaP-POT. The selectivity of fluoride ion onto
LaP-POT material was ascertained by the distribution coefficient value. The maximum
adsorption was observed at room temperature with a maximum Langmuir uptake capacity of
10.94 mg. The reusability of the material is tested up to 5 successive cycles for a workable
commercial application purpose. The results showed that LaP-POT provides more active sites,
thus making it a promising adsorbent for the removal of fluoride.
[4] A novel organic, crystalline and conjugated semiconductor copolymer, the poly (4-
nitroaniline-4-toluidine) [DPPNPT] was prepared by oxidative polymerization in acidic medium.
Characterization of the poly (4-nitroaniline-4-toluidine) powder was realized by different
techniques such as FTIR, UV–Vis, XRD, SEM and optical properties. The spin coating
technique was applied to deposit with appropriate adhesion of doped poly (Para-nitro aniline-co-
Para-toluidine) thin film [DPPNPT]TF. The structural properties of resulting doped
[DPPNPT]TF was determined by XRD analysis. The optimization of the molecular structure,
vibration spectra and optical properties have been accomplished depends on the density
functional theory (DFT) utilizing DMol3 and Cambridge Serial Total Energy Package
(CASTEP) program for DPPNPT as the isolated molecule and crystal models. It’s very well-
referred to the molecule’s structure and their contacts. The optical characteristics of UV
spectrum of doped [DPPNPT]TF. Based on the resulting optical doped [DPPNPT]TF was
applied to form optoelectronic devices applications and solar cell.
[6] Networks containing poly (O-toluidine) (POT) and LiCl (5%, 10%, 20%, 30% V/V)
were synthesized in thin films formed using a chemical reaction method. Details analysis of the
surface morphology for the prepared thin films was conducted using scanning electron
microscopy (SEM) along with the Image J software. It is clearly observed that the percentage
rate of LiCl is highly influence on the morphology of the POT surfaces. The Fourier-transform
infrared spectroscopy and X-ray diffraction patterns are utilized to confirm the corresponding
chemical bonds and the crystalline structure of the fabricated networks, respectively. The energy
gap of the POT thin films was calculated based on the UV–Vis measurements and the values
exhibit a directly allowed transition. The room thermal optical coefficients of POT were
evaluated through the thermal lens technique as a function of LiCl concentrations. The
aforementioned findings suggest the high impacts of the fabricated networks in several
applications related to optoelectronics and energy storage areas.
[7] Poly-o-toluidine/stannic(IV) triethanolamine was prepared by incorporating poly-o-
toluidine into stannic(IV) triethanolamine at 300 K and its characterization was done based on
FTIR, XRD, TGA-DTA, SEM coupled with EDX and TEM. The adsorption characteristics of
Pb(II) onto poly-o-toluidine/stannic(IV) triethanolamine (PTSTA) were studied in batch system
at 300, 313 and 323 K. The experimental variables were optimized to achieve the maximum
removal of Pb(II) by central composite design (CCD) under response surface methodology
(RSM). Under the optimum conditions, 98.8% of Pb(II) was removed. The adsorption
equilibrium data were well fitted to Freundlich models and kinetic data obeyed the pseudo
second-order kinetic equation. Thermodynamic parameters (ΔG0, ΔH0 and ΔS0) were computed
which illustrated the spontaneous and endothermic nature of Pb(II) adsorption. The probability
of sticking of Pb(II) ions onto PTSTA was very high. The adsorption system involving a single
batch was designed to remove Pb(II) ions. The regeneration and reusability of PTSTA was also
studied.
[9] This work submit a study of the optical characteristic and EDX of nano ZnO/poly
(o-toluidine) (POT) doping with organic acids dodecylbenzene sulfonate acid (DBSA)
composites were synthesized by chemical oxidative polymerization method of (o-toluidine)
monomer in existence of different ZnO nanoparticles concentration (weight ratio
OT/ZnO:1/0.05, 1/0.1, 1/0.15), the products were washed by the centrifugation method, in order
to avoid a higher loss of ZnO. Those POT-DBSA/ZnO composite films were intended by spin
coating procedure. The optical properties of the prepared films were examined by Fourier
transform infrared (FT-IR), UV–Visible. The structural properties of composite films were tested
by energy-dispersive X-ray spectroscopy (EDX). The results of the FTIR indicate that ZnO were
successfully embedded in the POT via chemical interactions between ZnO and OT monomer.
The results of UV–Visible showed a sharp increase in the band gap from (2.55to2.68) eV with
increasing the percentage ratio of ZnO nanoparticles in POT-DBSA matrix. The EDX spectrum
showed the presence of element Zn in POT-DBSA/ZnO composites, it is absent in POT-DBSA,
which was consistent with the results FTIR.
[14] Wastewater treatment has become a major global issue due of undegradable
pollutants. As toxic water pollutants, namely o-toluidine and p-toluidine are difficult to treat, this
study uses the silicon rubber technology to treat them. A pair of modules having single tabular
nonporous silicon rubber tube and HCl stripping solution were set up to extract o-toluidine and
p-toluidine from high-saline wastewater. Reaction quotient (QC) was calculated after every 12 h
intervals to evaluate the equilibrium reaction. The effect of concentration, pH, temperature, ionic
strength, and flow rate on the permeability (P) and removal efficiency (η) were investigated to
illustrate the process parameters and mechanisms of recovery of both elements from wastewater.
The results showed that the recovery efficiency was more than 96% with concentration of 2–
10g/L. When pH of the extraction solution was 2 or less, the pollutant permeability efficiency
was nearly 95%. Moreover, when the salting strength was over 10%, the recovery efficiency
increased quickly to some extent. Aging of silicon rubber tube was also studied with respect to
salinity, temperature, and acidity. Acidity and temperature was found to have a significant effect
on the tube, permeability increased with an increase in aging, and aging had a minor effect on the
elastic properties of the silicon rubber tube. Absorption and diffusion of water in silicon rubber
tubes decreased when salinity increased more than 10%, which increased separation of p-
toluidine and water. Due to this, there is no need of desalination before membrane extraction in
treatment of p-toluidine wastewater with high saline. Thus, this study demonstrates that
membrane extraction is a highly energy-efficient process for the effective recovery of o-toluidine
and p-toluidine from wastewater with high salinity.
[15] Aerogels are commonly regarded as soft and versatile materials for multiple
applications thanks to their features such as elastic behavior, swelling ability and responsive
characteristics. In the last decades these qualities have ensured them multiple uses in biomedical
field as controlled drug delivery systems and scaffolds for tissue engineering applications.
Recently their employment as sensors has attracted great interest especially thanks to their
tunability and the possibility to be used as soft material instead of conventional and many times
unreliable sensors in multiple sensing applications. We characterized the system through
chemical and mechanical analysis, and we its responsivity as gas sensing device was verified.
Moreover, we investigated the influence of the encapsulation of graphene nanoplatelets on the
responsive ability of the device. The addition of the graphene moieties improves the conductivity
of the system, its compressive mechanical resistance and the applicability of these devices as gas
sensors.
[16] Polyaniline (PANI) with high theoretical specific capacitance demonstrates a broad
application prospect in supercapacitors, but the fact that the disorder and entanglement based on
abundant one-dimensional polyaniline chains lead to low actual specific capacitance and poor
rate capacity. In this work, ionic cross linking can effectively control the randomly oriented
chain growth and the degree of polyaniline aggregation through simply replacing the connector.
The degree of oxidation, conjugation length and π- π stacking of polyaniline chains were
increased, causing more plane accumulation on or between the molecular chains. The polyaniline
structure tends to be ordered, which provides more active sites for the Faraday reaction, and after
heat treatment, the ion transport channel of the prepared material is further expanded, exhibiting
four times the specific capacitance of in situ polymerized polyaniline as well as excellent rate
performance. The symmetrical supercapacitor displays a considerable energy density and fine
integration capability. Such results suggest that ionic cross linking provides the possibility to
prepare high-performance supercapacitor electrode materials.
[17] In this study, the removal of hexavalent chromium from the aqueous solution using
birds' feathers amended by polyaniline is investigated. Firstly, various bird feathers and
polyaniline composites are synthesized and used in batch experiments to separate hexavalent
chromium. Results show optimal performance of polyaniline and bird feathers composite in
chromium removal. Among the bird's feather and polyaniline composites, the polyaniline/ ostrich
feathers/polyethylene glycol composite has the most optimal performance with a removal
percentage of about four times more than that of activated carbon (87.36 %), at pH ¼ 6 and the
contact time of about 30 min. Scanning electron microscope (SEM) images taken from the
surface of the composites show better and more uniform coverage of polyaniline on the ostrich
feather in the polyaniline/ostrich feather/polyethylene glycol composite. The XRD analysis and
FTIR analysis confirm the synthesis of aniline on the resulted composite and it is declared that
the structure of the achieved composite is amorphous.
[18] An attempt has been made to combine interfacial polymerization with a fast mixing
technique without the use of surfactant. Effects of mixing speed, reaction time, temperature,
oxidant-to-monomer molar ratio and nitric-to-monomer molar ratio were tested for electrical
conductivity and polyaniline nanofiber size. The findings demonstrate that the diameter of
polyaniline nanofiber can be reduced by optimising the synthesising parameter, thereby
increasing the electrical conductivity of polyaniline nanofiber. Infrared spectroscopy has shown
increased amplitude of the main absorption peak of polyaniline nanofiber during the conversion
of aniline to conductive polyaniline nanofiber. The crystalline nature of polyaniline nanofiber
has been discovered by the X-ray diffraction spectra. The morphological properties of
polyaniline nanofiber through electron microscopy scanning have confirmed the decreasing size
of polyaniline nanofiber from 50-60 nm to 20e30 nm by increasing the homogenizer speed to
30,000 rpm. These findings demonstrate that higher homogenization speed can split the solution
to smaller molecules during polymerization contributing to the creation of smaller nanofiber
sizes.
[20] This review delivers a summary of the recent advances in polyaniline based
electrocatalyst for direct methanol fuel cell applications. Today’s world is urging for global
energy due to the fossil fuel diminution and ecological contamination which is overthrown by the
direct methanol fuel cell. Amongst the conducting polymers, polyaniline has a significant role in
the direct methanol fuel cell. Due to the high conductivity, unique redox properties, high
flexibility, better solubility, reasonable stability, ease synthesis, and low cost. The
nanocomposite of polyaniline with other electrochemically active materials such as metallic
compounds and carbonaceous materials as well as nitrogen-doped carbon materials derived from
PANI based nanocomposite.
[23] Polyaniline (PANI) and its nanocomposites with graphene have been synthesized
using simple chemistry based method and are utilized to mitigate the problem of electromagnetic
pollutions in high-frequency range (X-band: 8.2–12.4 GHz) of the microwave region. The
PANI/graphene nanocomposites showed total shielding effectiveness as high as 64 dB with 8 wt
% loading of graphene in PANI. The enhancement in shielding effectiveness properties are
occurred due to strong polarization, charge propagation and formation of conducting pathways
due to encapsulation of graphene in PANI. Moreover, the high dielectric losses (ε′′ ≈ 35–175)
and total ac conductivities (σm ≈ 11–102 S/m) contribute in enhanced shielding effectiveness.
The very high values of shielding effectiveness for these samples make them suitable materials
for industrial as well as defense/aerospace applications.
[24] Renewable energy storage devices are being given their share of importance owing
to the depletion of non-renewable fossil fuel reserves. The supercapacitor is such an example of
an energy storage device. The utilization of polyaniline (PANI) for energy storage application,
either as a direct electroactive material or as a conducting agent is being widely explored in the
last few decades. PANI is regarded as an exemplary electrode material due to its tunable pseudo
capacitance owing to its variable oxidation state, superior theoretical capacitance, unchallenging
fabrication, durable chemical stability, and reasonable cost. However, due to its considerable
changes of dimensions during the release/doping of ions, low conductivity, and low surface area,
pure PANI electrodes have low power density and poor mechanical properties. In this review, the
recent advances on design, fabrication processes, mechanism, and application of PANI based
supercapacitors with other electrochemically active carbon materials along with some metals is
discussed.
[25] Though multiple number of strategies have investigated for toxic Cr(VI) removal,
still researchers are chasing after innovative and environmental friendly substrate for efficient
removal of pollutant. Herein, we report a polyaniline coated date seed derived biochar
(PANIDSC) prepared via polymerization which acts as a proficient adsorbent for Cr(VI)
remediation. A thorough investigation using FESEM, Raman, TGA, FTIR, XRD, zeta potential,
and BET analytical techniques confirmed the structural stability and suitable morphology of the
as-made PANIDSC. Spongy like carbonaceous structure with uniformly distributed pore is
evidenced from FESEM and broad XRD peak. Thermal stability up to 650◦C of material is
demonstrated even after polyaniline grafting. Conducting batch experiments, the influence of
adsorbent dose, pH, time, initial concentration, temperature, and stirring rate on removal of
Cr(VI) is investigated. In agreement with the isoelectric point at 5.8, maximum Cr(VI)
adsorption on PANIDSC perceived at pH range of 4–5. The thermodynamic parameters
indicated that the process of adsorption is spontaneous and endothermic in nature (ΔH = 25.084
kJ mol/1). Furthermore, the efficient regeneration up to 5 successive cycles makes the low-cost
bio adsorbent a promising one for field applications study.
[26] Polyaniline, as the pseudo capacitive electrode material, has been extensively
studied for supercapacitors. However, their cycling stability is limited by the structural instability
arising from large volumetric swelling/shrinking, which has been the main obstacle to their
practical applications. Herein, this work reports metal organic frameworks(MOFs)-derived
porous carbon frameworks as the substrate and further deposit polyaniline by chemical
polymerization. The assembled semi-solid symmetrical supercapacitors delivers good
electrochemical performance (energy density of 9.72 μWh cm/2 ) and excellent cyclic stability
(94.4% at 10,000 cycles), which can also power a commercial LED.
[27] Cellulose nanocrystals (CNC) have a wide range of applications due to the high
aspect ratio, crystallinity and mechanical properties in addition to being renewable and
biodegradable. Polyaniline (PANI) is a conductive polymer that has attracted extensive attention
due to low density and high electrical conductivity. However, polyaniline in the bulk form has
some limitations in terms of use because of its chemical nature as a consequence of secondary
hydrogen bonds that reduces conformability and mechanical strength. Aiming at the applicability
of polyaniline as films or gels, this work combines two types of materials: cellulose nanocrystals
(CNC) and polyaniline through an in situ polymerization of PANI in CNC suspensions to create
a nanostructured material. Thermal stability (TGA), particle size (Zeta-sizer), physical and
chemical characteristics (FTIR, UV-vis), the process of polymerization (Voc) as well as
conductivity was evaluated according to the different PANI/CNC ratios (R ¼ 0.05, 0.1, 0.2, 0.3
and 0.4). Results show that particle size, thermal stability and time of polymerization increase
with CNC concentration, indicating that cellulose nanostructure works as a backbone to PANI
deposition. FTIR and UV via show the evolution of the main characteristics absorption bands
around 381~391 nm, respectively while the PANI/CNC ratios increase.
[30] In this study, novel anticorrosion coatings including doped polyaniline, reduced
graphene oxide (RGO) and modified clay sodium montmorillonite (Na-MMT) were synthesized.
The nanocomposite particles were coated on carbon steel after optimal mixing and dispersion in
epoxy resin. In order to increase the dispersibility and increase the functional groups between the
graphene plates, the initial graphene oxide nanoparticles were re-oxidized and finally reduced to
have a better dispersibility in the composite environment. Sodium dodecyl benzene sulfonic acid
(SDBS) was used as a secondary dopant and surfactant. Synthesized nanocomposites were
characterized using Fourier-transform infrared spectroscopy (FTIR), X-Ray Diffraction (XRD),
Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM).
Furthermore, Open Circuit Potential (OCP), Electrochemical Impedance Spectroscopy (EIS),
Fourier-transform infrared spectroscopy (FFT), and salt spray test were used to investigate the
electrochemical and anticorrosion behavior of the synthesized composite. The results showed
that the initiative of adding certain ratios of RGO and Na-MMT to the polyaniline polymer
significantly increased the anticorrosion properties of the coating. It was also found that at the
same part ratios, the anticorrosion property of RGO is higher than the anticorrosion property of
Na-MMT. Also, after 720 h of Salt spray test (In 3.5% wt NaCl), a very high and desirable
durability of this sample (Sample a) has been observed.
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