Vietnam is in the process of industrialization, modernization,
many industrial parks and trade villages have sprung up, this has
released a large amount of inorganic and organic pollutants. Heavy
metals are considered to be very dangerous pollutants due to their high
toxicity and high bio-accumulation. Heavy metals like Cadmium,
Lead, Mercury, Silver are highly toxic, when accumulated in the
human body will cause diseases such as blood pressure, nervous
system, brain damage, liver, kidney, circulatory system, severe cases
can lead to death. Despite the state regulations on environmental
protection, there is no guarantee that heavy metals will be collected
and treated thoroughly and safely for the environment. Because of this,
environmental monitoring requires measuring instruments, probes
capable of detecting heavy metals at the trace level, thereby preventing
and treating environmental pollution. To contribute to the protection
of green, clean and beautiful living environment.
Conducting polymers are considered to be the next generation of
sensing materials being studied and used, and the trend is gradually
replacing older sensor materials by conductivity, selectivity and
responsiveness. Conducting polymers have been used to manufacture
converters to detect a wide range of gases such as NOx, CO, CO2,
NH3, solvents, alcohols, organic compounds and heavy metal ions.
The phenyl radical conducting polymers (polyaniline, poly(1.8-
diaminonaphthalene), poly(1.5-diaminonaphthalene)) containing rich
electron groups as -NH, -NH2 easily interact with heavy metal cations.
Thus, in order to use phenyl radical conducting polymers derivatives
as sensors, it is necessary to study the interaction between the
electrochemical activity, the structure of the polymer and the metal
cations. On this basis there are further studies such as improving the
sensitivity and selectivity of polymer films with heavy metal cations.2
From that point of view, the thesis aims to: "Synthesis, studying
properties of phenyl radical polymer film oriented to use as metal ion
sensor" as a research topic.
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1
MINISTRY OF EDUCATION
AND TRAINING
VIETNAM ACADEMY OF
SCIENCE AND TECHNOLOGY
GRADUATE UNIVERSITY SCIENCE AND TECHNOLOGY
...***
VU HOANG DUY
SYNTHESIS, STUDYING THE PROPERTIES
OF PHENYL RADICAL POLYMER FILM ORIONTED TO
USE AS METAL ION SENSOR
Major: Organic Chemistry
Code: 9.44.01.14
SUMMARY OF DOCTORAL THESIS
IN CHEMISTRY
HANOI - 2019
2
The thesis has been completed at: Institute for Tropical
Technology - Graduate university science and technology -
Vietnam Academy of Science and Technology.
Science supervisor: 1. Assoc. Prof. Dr. Nguyen Tuan Dung
2. Prof. Dr. Tran Đai Lam
Reviewer 1: ..
Reviewer 2: .
Reviewer 3:
The thesis was defended at National level Council of Thesis
Assessment held at Graduate University of Science and Technology -
Vietnam Academy of Science and Technology at on
Thesis can be further referred at:
- The Library of Graduate University of Science and Technology
- National Library of Vietnam
1
INTRODUCTION
1. The urgency of the thesis
Vietnam is in the process of industrialization, modernization,
many industrial parks and trade villages have sprung up, this has
released a large amount of inorganic and organic pollutants. Heavy
metals are considered to be very dangerous pollutants due to their high
toxicity and high bio-accumulation. Heavy metals like Cadmium,
Lead, Mercury, Silver are highly toxic, when accumulated in the
human body will cause diseases such as blood pressure, nervous
system, brain damage, liver, kidney, circulatory system, severe cases
can lead to death. Despite the state regulations on environmental
protection, there is no guarantee that heavy metals will be collected
and treated thoroughly and safely for the environment. Because of this,
environmental monitoring requires measuring instruments, probes
capable of detecting heavy metals at the trace level, thereby preventing
and treating environmental pollution. To contribute to the protection
of green, clean and beautiful living environment.
Conducting polymers are considered to be the next generation of
sensing materials being studied and used, and the trend is gradually
replacing older sensor materials by conductivity, selectivity and
responsiveness. Conducting polymers have been used to manufacture
converters to detect a wide range of gases such as NOx, CO, CO2,
NH3, solvents, alcohols, organic compounds and heavy metal ions.
The phenyl radical conducting polymers (polyaniline, poly(1.8-
diaminonaphthalene), poly(1.5-diaminonaphthalene)) containing rich
electron groups as -NH, -NH2 easily interact with heavy metal cations.
Thus, in order to use phenyl radical conducting polymers derivatives
as sensors, it is necessary to study the interaction between the
electrochemical activity, the structure of the polymer and the metal
cations. On this basis there are further studies such as improving the
sensitivity and selectivity of polymer films with heavy metal cations.
2
From that point of view, the thesis aims to: "Synthesis, studying
properties of phenyl radical polymer film oriented to use as metal ion
sensor" as a research topic.
2. The objectives of the thesis
Fabrication of diaphragm sensing material based on phenyl
conductive polymer has stability and high sensitivity with heavy metal
cations, which is used to identify and analyze heavy metal traces in
water.
3. The main contents of the thesis
- Electrochemical polymerization of conductive polymer films
such as polyaniline, poly(1.8-diaminonaphthalene), poly(1.5-
diaminonaphthalene).
- Study characteristics of these polymer films: morphology,
chemical structure, electrochemical activity of conductive polymer
films.
- Study the sensitivity of these polymer films to heavy metal ions
such as Cd(II), Pb(II), Hg(II), Ag(I).
- Research on manufacturing sensing materials based on poly(1.5-
diaminonaphthalene) and carbon nanotubes: synthesis,
characterization and application in simultaneous analysis of Cd(II) and
Pb(II) ions.
CHAPTER 1. OVERVIEW
1.1. Conducting polymer
Conducting polymers are organic polymeric compounds capable
of conducting electricity through the π-conjugate structure. Example
polyaniline (PANi), polypyrrole (PPy), polythiophene (PTh), etc.
Conducting polymers are classified into three main categories:
electron-conducting polymers, oxidation-reducing polymers, and ion-
exchange polymers.
3
There are two methods of polymer synthesis: chemical methods
and electrochemical methods.
The conducting polymer satisfies the conditions of a chemical and
biological sensing material so it is being studied and applied in this
field, particularly the field of ionic sensors.
1.2. Conducting phenyl radical polymer
Conducting phenyl radical polymer are conducting polymers in
the main chain containing phenyl rings. The famous of that is PANi,
the derivatives of polydiaminonaphthalen have also recently begun to
be studied for their special properties due to their -NH2 free-radical
function in the molecule.
1.3. Methods for producing conductive polymer films
At present, there are a number of methods for making polymer
films, such as dip-coating, centrifugation, Langmuir-Blodgett method,
vapor phase condensation, drip method and electrochemical
deposition. Only the electrochemical deposition method, the drip
method, is more suitable for making polymer films. Therefore, in the
thesis, drip coating and electrochemical deposition will be applied to
investigate the formation of conductive polymer films as well as the
conductive polymer composite films - nanotubes as ion sensors.
1.4. Heavy metals, methods for analysis and application of
conductive polymer films for heavy metal analysis
1.4.1. Heavy metals
Heavy metals are natural elements with a density greater than 5
g/cm3. Many heavy metals are used in industry, agriculture, health and
science, resulting in emissions to the environment, increasing the risk
of their potential impact on human health and ecosystems. People with
heavy metals have decreased memory, reduced the ability to
synthesize hemoglobin leading to anemia, lung, stomach and
neurologic causes. Causing harms to fertility, causing miscarriage,
degeneration of the breed.
1.4.2. Methods for analysis of heavy metals
4
For the determination of heavy metal ions, there are currently
several methods that can be identified in trace form. Examples include
atomic emission spectroscopy (AES), atomic absorption spectrometry
(AAS), Inductively Coupled Plasma emission Mass Spectrometry
(ICP-MS), and electrochemical methods.
1.4.3. Conducting polymers for heavy metal ion analysis
Polyaniline, poly(1.8-diaminonaphthalene) (poly(1.8-DAN)) and
poly(1.5-diaminonaphthalene)(poly(1.5-DAN)) are electrochemically
synthesized on glassy carbon electrode (GCE) or platinum electrode.
The above polymer films can be used to analyze the trace of heavy
metal ions such as Cd(II), Pb(II), Hg(II), Ag(I).
In order to improve the sensitivity of the conductive polymer film
to the determination of heavy metal ions, many studies have developed
composite materials between the conductive polymer with carbon
nanotubes (CNTs), graphene (Gr), graphene oxide (GO),
ferromagnetic nano, etc.
1.5. Composite materials conducting polymer - carbon nanotubes
Composite of conducting polymer - carbon nanotubes (CNTs)
materials include conductive polymers and carbon nanotubes. CNTs
has a large surface area, good conductivity, promising ability will
increase the sensitivity of the sensor, especially the ion sensor.
CHAPTER 2. EXPERIMENTAL AND METHOD STUDY
2.1. Raw materials, chemicals
Monomers: 1.5-diaminonaphthalene (1.5-DAN), 1.8-diamino-
naphthalene (1.8-DAN) and aniline (ANi) are used to synthesize
polymer films. Other chemicals used in the experiment are pure
chemicals of Merck (Germany). Multi-walled carbon nanotubes
(MWCNT), Nafion® 5% for study of conducting polymer composites
- MWCNT. Glass coal electrodes, integrated platinum electrode are
used for research experiments. The Institute of Tropical Technology's
Autolab/ PGSTAT30 multifunctional electrochemical is used for thin
5
film deposition, study on electrochemical characterization,
determination of metal cations Cd(II), Pb(II), Hg(II), Ag(I).
2.2. Experimental method
2.2.1. Electrosynthersis polymer thin fims and specialty research
Electrosynthersis three polymer fims: PANi, poly(1.5-DAN),
poly(1.8-DAN) by cyclic voltammetry (CV) scanning.
Research on thin-film properties of synthesized films: Study on
electrochemical deposition of polymer films by CV scanning in
electrolyte solution.
Study of polymer structure by infrared spectra. Surface
morphology studies using field emission scanning electron
microscopy (FE-SEM).
2.2.2. Study on cationic sensitivity
Synthetic polymer films were scanned for CV, scanning square
wave voltammetry (ASW) before being stripping in solutions
containing cations (Cd(II), Pb(II), Hg(II), Ag(I)) have a concentration
of 10-2 M to 10-3 M for 30 minutes, at room temperature.
Use ASW technique to dissolve absorbent metal on polymer film
coated on electrode to detect metal ions.
2.2.3. Research on making composed poly(1.5-DAN)/ MWCNT / Pt
sensor film to detected both Cd(II) and Pb(II)
Fabrication of MWCNT film on platinum electrode followed by
poly(1.5-DAN) polymerization on top.
Survey of influencing factors: Study thickness films through the
number of CV synthetic; Study the enrichment potential from -1.4 to
- 0.9 V; Study electrochemical enrichment time from 250 to 600
seconds; Study the effects of other ions.
Analysis determines Cd(II) and Pb(II) at concentrations of 4 to 150
μgL-1, thus making the basis for the determination of sensitivity;
Determination of detection limits;
Application of poly(1.5-DAN)/MWCNT/Pt film determines
Cd(II), Pb(II) in Nhue River.
6
2.3. Research methods
The thesis uses the following basic research methods:
Studies on the polymerization of PANi, poly(1.5-DAN), poly(1.8-
DAN) by electrochemical characterization of polymer films by CV,
SWV.
Studies on cation sensitivity, electrochemical enrichment, metal
dissolution on cathode by SWV method.
Studies on the structure of monomers, polymers by Fourier
transform infrared spectroscopy (FT-IR).
Studies the structure of polymers, MWCNT and composite film
by Raman scattering.
Research on morphology of polymeric structures and thin film
surfaces, composite film by scanning electron microscope.
CHAPTER 3. RESULTS AND DISCUSSION
3.1. Synthetic and characterization of polyanilines
3.1.1. Synthetic polyaniline films
Polyaniline is synthesized on a GC electrode in 0.5 M H2SO4 and
0.1 M aniline, by cyclic voltometry (CV). The results are shown in
figure 3.1. Right from the first round, PANi's CV synthesis lines have
two pairs of redox peaks at +0.18V/+0.02V; +0.48V/+0.42V and
+0.78V/+0.68V as shown in figure 3.1-A.
Figure 3.1. The CV of PANi synthesis in 0.5 M H2SO4 and
0.1 M ANi with (A) two first scans, and (B) 15 scans.
7
As the number of sweeps increases, the redox strength increases
with the sweep cycles (figure 3.1-B), indicating that the development
of the PANi films is conductive on the electrode surface.
3.1.2. Characterization of polyaniline films
3.1.2.1. Characteristics of CV: The CV
spectral characteristics of PANi when
scanning the films in 0.1M H2SO4 obtained
as shown in figure 3.3 is very clearly the
typical redox pulses at +0.24V and -0.05 V.
The intensity of the reverse decay
oxidation is relatively high and stable,
indicating that the films has a good
electrochemical activity.
3.1.2.2. Infrared spectrum FT-IR.
The infrared spectrum of PANi and aniline is shown in figure 3.4.
In the range of 4000 to 2000 cm-1, the aniline has absorption peaks
at 3426 cm-1 and 3354 cm-1, which characterizes the covalent bonding
of the C-NH2 group. At the same time, PANi spectra exhibit a wide
spectrum at 3257 cm-1 corresponding to the valence range of the N-H
bond, indicating the presence of a second-order amine group. Thus,
the process of the PANi polymerization takes place, via the reaction
of the NH2 group of the aniline with the para position of the benzene
ring.
Figure 3.3. The CV recorded
of PANi film in aqueous
solution of H2SO4 0.1M
Figure 3.4. FT-IR spectrum of (A) Aniline; (B) PANi film
8
The valence range of the C-H bond of the infrared benzene ring
at the ~3000 cm-1, on the infrared spectrum of the aniline, shows the
adsorption peaks at 3214, 3071, 3036 cm-1, and of PANi as peaks weak
at 3036 and 2925 cm-1.
In the range of number wave 2000 to 500 cm-1, the infrared spectra
of the anilines appear infrared absorption peaks at 1620, 1601, 1499,
and 1467 cm-1 waves that characterize the frame oscillations of the
nucleus of benzene core (vibrational covalent bonding C-C). The peak
1276 cm-1, 1207 cm-1 features the oscillation of the C-N bond between
the benzene ring and the nitrogen atom of the amino group. In the case
of PANi, the characteristic absorption peaks at 1594 and 1509 cm-1,
corresponding to the quinoic (Q) and benzoic (B) ring oscillations,
show that the PANi is synthesized at oxidation state (conductance
state). It has also been observed that the peak at 1374 cm-1 is
characterized by Q=N-B boundary oscillation, at 1302 cm-1
corresponding to the perturbation of the C-N-C bond.
The C-H bond in the aniline absorbs infrared at 995, 881, 752 and
692 cm-1 waves, characteristic for off-plane oscillations, while the
peak at 1174, 1153, and 1311 cm-1 for oscillation on the same plane.
PANi variant of the flat surface oscillator exhibits absorption peaks at
825 and 643 cm-1, on the plane at 1161 cm-1. Compared to previously
published literature, PANi's infrared peaks are perfectly matched,
indicating that the PANi films has been successfully synthesized.
3.1.2.3. Characteristic and morphology of PANi film
PANi film was scanned
electronically by Field Emission
- Scanning Electron Microscope
(FE-SEM) and presented in
figure 3.5. The results showed
that PANi synthesized in the
form of fibers, not aligned
closely together.
Figure 3.5. FE-SEM of PANi film with
magnification: a) 10,000 times, b) 100,000
times
9
3.1.3. Study sensitivity heavy metal ions of PANi
Figure 3.6 is a result of square wave voltammetry (SWV) before
and after stripping PANi film electrodes with 5 cycles of CV synthesis
in solution containing Cd(II), Pb(II) Hg(II) and Ag(I) at 10-2, 10-3 M
for 30 minutes, at room temperature. In figure 3.6-a no silver oxidation
peaks appears, indicating no
silver ion absorption on the
PANi film.
In the case of Hg(II) (fig.
3.6-b), the weak peak appears at
a voltage value of 0.18 V, which
is the oxidation peak of the
mercury adsorbed on the PANi
film. Unlike silver and mercury,
Cd(II) and Pb(II) obtain very
sharp and strong oxidation
signals at the voltage values of
0.67 V and -0.51V respectively
(fig. 3.6-c, d). Thus PANi film
have different affinities with the cationic study.
3.2. Synthesis and characterization of poly (1.8-DAN)
3.2.1. Synthetic poly (1.8-DAN)
Poly(1.8-DAN) film were
synthesized on GC electrodes by CV
method as shown in Figure 3.9.
In the first CV cycle, the line starts
to rise from the +0.45V, with two
monomer oxidation peaks at +0.53V and
+0.68 V. From the 3rd CV onwards, the
monomer peak no longer exists but only
the peaks of the polymer at +0,34 and +
Figure 3.6. The SWV lines were recorded on
GC/PANi electrodes before and after 30
minutes in aqueous solutions containing (a)
Ag (I) 10-2 M; (b) Hg (II) 10-2 M; (c) Cd (II)
10-2 M, 10-3 M and (d) Pb (II) 10-2 M, 10-3 M.
Figure 3.9. Spectrophotometer
of poly(1.8-DAN) in HClO4 1M
and 1.8-DAN 5mM solutions.
10
0,19V, indicating that the poly (1,8-
DAN) has been formed on the electrode
surface.
3.2.2. Study characteristic of poly (1.8-
DAN)
3.2.2.1. Electrolytic activity of poly(1.8-
DAN) film:
It can be observed that the
characteristic redox peaks of poly (1.8-
DAN) films synthesized 8 potential scans at +0.41 V/+ 0.19 V (Figure
3.11), however, it is not clear, indicating that the membrane has a very
limited electrochemical activity.
3.2.2.2. Infrared spectrum FT-IR
The infrared spectrum of poly(1.8-DAN) and 1.8-DAN are shown
in figure 3.12.
In the range of 4000 to 2000 cm-1, the infrared spectra of 1.8-DAN
monomers have absorption peaks at 3413, 3320 and 3223 cm-1, which
characterize the chemo-oscillation of the -NH2 group. The infrared
spectrum of poly(1.8-DAN) appeared a wide absorption peak at 3420
cm-1 which characterized the valence range of the N-H bond,
demonstrating the polymerization of the polymer. Unlike the PANi
case, the absorption peak at 3239 cm-1 was observed on the infrared
spectrum of poly(1.8-DAN), which is related to the valence range of
the -NH2 group. Oscillation deformation of the functional group -NH2
Figure 3.11. The CV line of poly(1.8-
DAN) film in HClO4 0.1M solution.
Figure 3.12. Infrared absorption of 1.8-DAN (A) and of poly (1.8-DAN) (B)
11
is shown with the absorption peak at the 1616 cm-1 wave on the
monomer spectrum and at 1626 cm-1 on the polymer spectrum. This
proves that in the 1.8-DAN molecule there is one -NH2 group involved
in the polymerization, one group in the free state. In addition, it is
observed that the adsorption peaks at 3033 cm-1 of the spectrum of the
monomer, and at the 2977 cm-1 wavelength of the polymer spectrum
are the covalent vibrations of the C-H bond.
In the range of 2000 to 500 cm-1, the peaks are absorbed at wave
number 1585, 1519, 1425 cm-1 on the infrared spectrum of 1.8-DAN,
and the absorption peaks at wave number 1584, 1416 cm-1 on the
infrared spectrum of poly(1.8-DAN) are characterizes the oscillation
of the C=C bond within the aromatic naphthalene. Out-of-plane
chemotaxis of the C-H bond is characterized by absorption peaks at
wave number 925, 868, 768 cm-1 on the spectrum of the monomer, and
at 927, 816, 756 cm-1 on the spectrum of the polymer. In this area, 1.8
-DAN polymerization can be observed through the appearance of
infrared absorption peaks at 1277 cm-1, which characterizes the
valence range of the bond. The oscillate of covalent of the chemistry
of the C-N bond in the first-order amine group is shown in the infrared
spectrum of the monomer at 1361, 1298 cm-1, on the polymer spectrum
at 1391 cm-1. Thus, in the macromolecular circuit (1.8-DAN), there is
still a free -NH2 functional group. Another sign that the polymerization
has been successful is the appearance of a wide absorption peak at
1081 cm-1, which is characterized by the presence of a ClO4- is anion-
doped in the membrane.
Compared to previously published documents, the peaks
adsorption of poly(1.8-DAN) are perfectly matched. This proves
successful synthesis of poly(1.8-DAN). Thus poly(1.8-DAN)
polymerization may occur according to the steps shown in figure 3.14.
12
3.2.2.3. Morphological analysis of structure:
Figure 3.15 presents the FE-
SEM image of the face poly(1.8-
DAN) film after 1 and 8 CV cycles.
The results showed that the
poly(1.8-DAN) formed had a
particle size of 50-100 nm in the
first 1 cycles, then poly(1.8-DAN)
covered the electrode surface, non-
flat film surface, not fiber as PANi.
3.2.3.Study the sensities metal ionic
poly(1.8-DAN)
In Figures 3.16-a and 3.16-b the
cadmium and lead oxidation peaks
very weakly on the poly(1.8-DAN)
film at -0.713V and -0.33V.
Meanwhile Ag(I) and Hg(II