Академический Документы
Профессиональный Документы
Культура Документы
By
Bilal Khalid
CIIT/FA14-MSCHEM-008/LHR
MS Thesis
Master of Science
in
Chemical Engineering
By
Bilal Khalid
CIIT/FA14-MSCHEM-008/LHR
Spring, 2016
ii
Name
Registration Number
Bilal Khalid
CIIT/FA14-MSCHEM-008/LHR
Supervisor
Dr. Mazhar Amjad Gilani
Associate Professor
Department of Chemical Engineering
COMSATS Institute of Information Technology (CIIT)
Lahore
June, 2016
iii
Final Approval
This thesis titled
Supervisor: ________________________________________________
Dr. Mazhar Amjad Gilani (Associate Professor)
Department of Chemical Engineering CIIT Lahore, Pakistan
Co-supervisor: ____________________________________________
Dr. Abdur Rahim (Assistant Professor)
IRCBM, CIIT Lahore, Pakistan
Head of Department: _______________________________________
Prof. Dr. Asad Ullah Khan
Department of Chemical Engineering, CIIT Lahore, Pakistan
iv
Declaration
Date: _________________
Certificate
Date: _____________
________________
Supervisor
Dr. Mazhar Amjad Gilani
Associate Professor
Head of Department:
________________
Prof. Dr. Asad Ullah Khan
Head & Chairman, Department of Chemical Engineering
CIIT, Lahore
vi
DEDICATIONS
vii
ACKNOWLEDGEMENTS
I am very thankful to ALLAHs AlMIGHTY, WHO blessed me with power, potential
and capability to complete my MS Chemical Engineering work. Love for HOLY
PROPHET MUHAMMAD (SAW) who delivered the message of ALLAH and
enlighten us with the light of knowledge and the holy Book Quran.
I am highly indebted to pay my cordial gratitude to my supervisor who has given me
chance to work in his supervision as a Research Assistant under HEC NRPU project.
I am obliged to Higher Education Commission, Pakistan for financial support under
project number 2985. I express my fervent sense of thankfulness to my supervisor
Associate Prof. Dr. Mazhar Gilani, Chemical Engineering department, COMSATS
Institute of Information Technology CIIT, Lahore, and my co-supervisor Asst. Prof.
Dr. Abdur Rahim, IRCBM, CIIT, Lahore, for their generous help, teaching attitude,
guidance and dedicated supervision. This thesis was made possible by their support,
patience and persistence.
A special thanks to Asst. Prof Dr Sobia Tabassum for her support and help in the
absence of my supervisor.
I am highly indebted to pay my cordial gratitude to Dr. Asad ullah Khan (Head of
Department Chemical Engineering), CIIT, Lahore, for providing laboratory facilities
during my research work in COMSATS. I am also pleased to pay my thanks to Asst.
Prof. Dr. Shahid Nazir Department of Chemical Engineering, CIIT, Lahore for
support, help and nice command. I am thankful to Asst. Prof. Dr. Asim Laeeq khan
for providing chemicals and lab ware for research purpose.
Thanks is also extended to Asst. Prof. Dr. Nawshad for their help and all faculty
members and research associates of Department of Chemical Engineering, Lahore as
well as of IRCBM for their help, support and guidance.I want to pay my gratitude and
thanks to all members of my family and specially my father for their support, affection,
Love, prayers and special care. Special thanks to Ghayur Abbas who helped me a lot,
being a good friend and teacher, in material synthesis. A special word of gratitude to
my friends Kamran Ali for his motivation, Hafiz Atif for his worthy advices and all
my colleagues for helping me.
Bilal Khalid CIIT/FA14-MSCHEM-008/LHR
viii
Abstract
Synthesis and Characterization of Novel Organic Ionophores:
Application as Selective Electrochemical Sensors
Carbon ceramic sensor was fabricated using Silica-graphite (SiO2/C). Copper oxide
(CuO) was immobilized in situ on (SiO2/C) matrix. SiO2/C/CuO was modified with
benzimidazolium-1-acetate ionic liquid by ultra-sonication. Imidazole group present in
ionic liquid acts as ionophore. Surface area (SBET = 99.87 m2/g) and pore volume
(0.3104 cm/g) of the material was calculated from BET analyzer. Scanning electron
microscopy (SEM) images showed materials compactness having no phase
segregation within the magnification used. These materials were used in the fabrication
of working electrodes i.e. SiO2/C, SiO2/C/CuO, SiO2/C/CuO/IL for the selective
electrochemical determination of catechol (analyte). Secondly CP/Cu/FA, chemically
modified carbon paste electrode was prepared using copper formamidine complex
[Cu/FA] because formamidine also behaves as ionophore in the selective
electrochemical determination of different analytes. Electrochemical impedance
spectroscopy has revealed that the SiO2/C/CuO/IL has the lowest charge transfer
resistance and it assists the charge transfer because of its ionic nature. SiO2/C/CuO/IL
electrode exhibits excellent sensitivity, linear response range and low limit of detection
(LOD) which are 0.678 nA dm3 mmol-1 cm-2, 0.2 mM 10 mM and 6.76 x 10-6 mol dm3
respectively, as compared to other sensor CP/Cu/FA. The sensor also shows very good
ix
Table of Content
Declaration ................................................................................................v
Certificate ................................................................................................ vi
ACKNOWLEDGEMENTS ................................................................. viii
1
Introduction ..........................................................................................2
1.1
Sensors ....................................................................................................... 2
1.2
1.3
1.4
2
2.1
1.2.1
1.2.2
1.2.3
Biosensors ................................................................................................3
1.3.2
1.3.3
1.3.4
1.3.5
2.1.2
Ethanol ...................................................................................................11
2.1.3
2.1.4
Benzimidazole........................................................................................11
2.1.5
2.1.6
2.1.7
Graphite..................................................................................................11
x
2.2
2.3
3
3.1
3.2
2.1.8
2.1.9
2.1.10
2.1.11
2.1.12
2.1.13
2.1.14
L- Cysteine .............................................................................................12
2.1.15
Dopamine ...............................................................................................13
2.2.2
2.2.3
2.2.4
2.2.5
2.2.6
2.2.7
2.2.8
Potentiostat Machine:.............................................................................14
2.3.2
2.3.3
2.3.4
2.3.5
2.3.6
3.1.2
SEM Analysis........................................................................................... 20
xi
3.3
3.2.1
3.2.2
3.2.3
3.3.2
3.4
BET (Brunauer Emmett Teller) surface area and porosity analysis ........ 28
3.5
3.6
3.7
3.8
3.7.1
Cyclic voltammetry:...............................................................................31
3.7.2
Amperometry .........................................................................................34
3.7.3
Calculations............................................................................................37
3.7.4
3.7.5
3.7.6
3.9
3.8.1
3.8.2
3.8.3
Calculations............................................................................................42
Conclusion................................................................................................ 42
References ......................................................................................... 45
xii
List of Figures:
Figure 2-1 Scheme of synthesis of SiO2/C by Sol Gel Method ................................... 15
Figure 2-2 Synthesis of Benzimidazolium-1-acetate ................................................... 16
Figure 2-3 Schematics of carbon ceramic electrode of 6 mm surface area ................. 17
Figure 2-4 Schematic of carbon paste electrode of 3 mm diameter of hole ................ 18
Figure 3-1 SEM image of SiO2/C-graphite with the magnification of 5 kx ................ 21
Figure 3-2 SEM image of SiO2/C-graphite with the magnification of 10 kx .............. 22
Figure 3-3 SEM image of SiO2/C-graphite with the magnification of 25 kx and 50 kx
.............................................................................................................................. 22
Figure 3-4 SEM image of SiO2/C/CuO with the magnification of 5 kx ...................... 23
Figure 3-5 SEM image of SiO2/C/CuO with the magnification of 10 kx .................... 24
Figure 3-6 SEM image of SiO2/C/CuO with the magnification of 25 kx and 50 kx .. 24
Figure 3-7 SEM image of SiO2/C/CuO/IL with the magnification of 5 kx ................. 25
Figure 3-8 SEM image of SiO2/C/CuO/IL with the magnification of 10 kx ............... 25
Figure 3-9 SEM image of SiO2/C/CuO/IL with the magnification of 25 kx and 50 kx
.............................................................................................................................. 26
Figure 3-10 EDX spectrum of SiO2/C/Cu ................................................................... 26
Figure 3-11 Weight percentage of elements present in Sensor.................................... 26
Figure 3-12 Color mapping of Cu, Si, O and C as in (a) (b) (c) and (d) respectivlely 27
Figure 3-13 BET nitrogen adsorption-desorption isotherm of SiO2/C-graphite matrix
.............................................................................................................................. 28
Figure 3-14 BET pore size distribution of SiO2/C-graphite material .......................... 29
Figure 3-15 IR spectrum of [BzIm]OAc ...................................................................... 30
Figure 3-16 Cyclic voltammograms f working electrodes in 0.1M NaOH at scan rate
of 20 mV sec-1 against SCE. Inset shows the cyclic voltammogram of SiO2/C... 32
Figure 3-17 Cyclic voltammograms of working electrodes by adding 4mM Catechol
in 0.1 M NaOH at scan rate of 20 mV sec-1 against SCE ..................................... 33
xiii
List of Abbreviations:
AA
Ascorbic Acid
BET
BrunauerEmmettTeller
CC
Catechol
CCC
xiv
CCE
CA
Chronoamperometry
CV
Cyclic Voltammetry
DA
Dopamine
DPV
NN
Sodium Nitrate
HQ
Hydroquinone
L- Cys
L Cysteine
LOD
Limit of detection
Ox
Oxidation
Red
Reduction
Rpm
SEM
TEOS
Tetraethylorthosilicate
UA
Uric Acid
4 APh
4 Amino Phenol
EIS
SiO2/C
Silica Graphite
CMCPE
CP/Cu/FA
SiO2/C/CuO
SiO2/C/Cu/IL
xv
Chapter 1
Introduction
Introduction
1.1 Sensors
A sensor is a device that senses and responds to input from environment. The
specific input in the form of light, impact, heat, motion, humidity, force, etc. The output
is converted into human-readable electrical display [1]. Human five senses also act as
sensors which are smell, taste, sound, vision and touch. Litmus paper is the simplest
sensor which is used for the detection of acids and bases in laboratory [2].
A sensor is a device which provides real information about test samples. It
transforms information about test sample into useful signals or data. A sensor can also
be defined as an instrument that responds or detects any physical stimulus. For example,
thermometer, microphone and seismometer are used to measure temperature, sound and
motion respectively [3].
Sensitivity, selectivity and stability are three important parameters for a good
sensor. Conventional sensors were synthesized from macro-materials. These sensors
had some limitations such as low precision, sensitivity and larger size [4]. To overcome
these problems nanotechnology is the best option. Due to small size and high surface
area to volume ratio, nanotechnology has many advantages over micro and macro
technology such as low response time, selectivity, portability, stability, and very high
sensitivity. Due to these advantages, nanomaterial based sensors have vast applications
in daily life and their development is hot topic of research in the field of sensors [5].
A nanosensors can be defined as, A device constructed by a material in which at least
one component is in nanoscale range and detects any physical or chemical change[6].
1.2
Types of sensors
There are three major types of sensors
1. Physical sensors
2. Chemical sensors
3. Biosensors
1.2.3 Biosensors
These sensors are based on biological or biochemical mechanism. These are used for
the identification of biomolecules [1]. These sensors have applications in both clinical
and non-clinical fields by recognition of DNA, lipids, antigens, cholesterol, urea,
glucose etc [9].
measurements from this device was 1mM while its limit of detection (LOD) was 0.2
mM [14].
Jaafar Abdullah et al. reported that the optical biosensors could be fabricated by using
stacked films of 3-methyl- 2-benzothiazolinone hydrazone (MBTH) immobilized in a
hybrid nafion/sol-gel silicate film and laccase in a chitosan film for the detection of
phenolic compounds. The proposed biosensor exhibited a linear response towards
catechol concentration ranging from 0.5-8.0 mM while the detection limit and response
time calculated were 0.33 mM and 10 min. respectively. The absorption spectrum of
biosensor showed an excellent response at wavelength of 505 nm [15].
hormonal system. The abnormal level of dopamine causes brain diseases like
Schizophrenia and Parkinson. The rapid and precise sensing of dopamine is very
mandatory. Abdur Rahim et al. used SiO2/C/Cu(II)phthalocyanine for the fabrication
of electrochemical sensor for the detection of dopamine. The electrode showed an
excellent response against analyte with sensitivity of 0.63 (0.006) nA dm3 mol1 cm2
while the LOD was 0.6 x 10 -6 mol dm3 [22]. Furthermore, Abdur Rahim et al. reported
a highly sensitive SiO2/C-graphite based sensor for the detection of oxalic acid. Oxalic
acid can be ingested orally as dietary fiber or synthesized as the final product of
metabolic activity performed by amino acids and ascorbic acids present in humans.
Cobalt phthalocyanine (CoPc) was in situ immobilized in the mesoporous SiO2/Cgraphite matrix. Detection of oxalic acid is important because, in human body, reactions
of oxalic acid with alkali and alkaline earth metals are responsible for the formation of
stones in Kidney. The limit of detection was LOD=5.8107 molL1 [23].
Mirian P. dos Santos et al. reported a novel SiO2/C-graphite based sensor for the
detection of dopamine (DA, 3,4-dihydroxyphenyl ethylamine). The material was
modified with ensal functional group on which copper was physiosorbed by dissolving
0.01 M copper acetate solution in it. The sensor was highly selective and sensitive for
target analyte with the sensitivity of 21.2 (0.003) nA dm3 mol1 cm2. The presence
of interfering species like ascorbic acid , NADH and uric acid did not affect the
sensitivity of the electrode [24]. Similarly, Abdur Rahim et al. reported SiO2/C-graphite
based sensing material on which cobalt phthalocyanine (CoPc) was in-situ
immobilized. They used SiO2/C/CoPc based electrode for the detection of dissolved
oxygen. The sensor showed a good sensitivity of 2.16 A L mg1 against dissolved
oxygen [25].
Abdur Rahim et al. used a mesoporous SiO2/C/MnPc composite material based
electrochemical sensor for the determination of nitrite in flesh and water. In-situ
immobilization of manganese(II) phthalocyanine on silica-graphite matrix increased
the sensitivity of electrode towards nitrite ions which is 17.31 A dm3 umol-1 [26].
Sergio B.A. Barros et al. presented a SiO2/C/NiPc based sensor for the simultaneous
determination of ascorbic acid (AA) and dopamine (DA, 3,4-dihydroxyphenyl
ethylamine). Nickel (II) phthalocyanine was immobilized in situ on mesoporous
6
The detection of phenolic compounds like catechol is of great interest because of its
toxic nature for humans as well as for environment [38]. A recent report shows that the
phenolic organic compounds are carcinogenic [39]. Environmental transformation
results in conversion of phenol into catechol and chlorophenols into chlorocatechols
[40]. These phenolic compounds are used in many industrial processes, e.g., in the
manufacturing of plastics, paints, dyes, drugs, insecticides, pesticides, and antioxidants
[41]. Skin contact with catechol causes eczematous dermatitis in humans. Large doses
of catechol, taken orally, can cause depression of the central nervous system (CNS) as
well as the rise of blood pressure in humans [42]. Catechol causes eye burn and wounds
produced by it are not easy to heal. Severe exposure to catechol causes fits. It has high
solubility in water i.e. 430 g/L [43]. This high solubility of catechol in water is due to
the polar nature of molecule which is because of hydroxyl groups present on it. Effluent
water from pharmaceutical, dyeing and insecticides industries contains certain amount
of dissolved catechol because they are using catechol for specific purposes or it is
produced as a byproduct. IARC (International Agency for Research on cancers) has
classified catechol (CAS # 120-80-9) as a Group 2B, a possibly carcinogenic chemical
to humans. Catechol produces glandular stomach tumors in rodents [39]. To get away
from cancer, because of its dreadful nature, one should take precautionary measures for
handling those chemicals that are possibly carcinogenic. For this purpose, detection of
phenolic compounds and, specially, catechol is a hot topic of research nowadays. The
maximum acceptable limit (MAL) of phenolic compounds, mainly, catechol in sewage
and industrial effluents is in the range of 1-2 mg/L [15]. A rapid, accurate, cheap and
highly sensitive and selective electrochemical sensor is required for accurate
Chapter 2
Material and Methods
10
2.1 Materials
This section will cover the materials required for the synthesis of working electrodes
2.1.2 Ethanol
It was 99.8% pure and purchased from Merck chemicals. It is available as
colourless solvent having density 0.789 g/mL
2.1.4 Benzimidazole
It is provided by Alfa Aesar 99 % in 25 g bottle having melting point of 157 C
and insoluble in water but easily soluble in methanol.
2.1.7 Graphite
Graphite powder was 99.99% pure with particle size smaller than 125 microns
and mesh size of 120 mesh. It was used as a conducting material in SiO2/C matrix and
was purchased from sigma Aldrich.
11
2.1.14 L- Cysteine
It is purchased from sigma Aldrich and available in white crystalline material. It is used
in interference study of modified electrodes
12
2.1.15 Dopamine
It is available in liquid state and dissolved in (HCl) 40 mg /5 mL which is purchased
from CLINIX, The Medicine store. It was used as an interferent to determine the
selectivity of modified electrode towards target analyte i.e. Catechol
13
13
14
15
The
condensation
reaction
between
4-aminophenazone
and
The reaction mixture was left for stirring at a rate of 220 rpm at a refluxing temperature
of 160 C for 12 hr. The progress of reaction was checked after every 2 hours using
TLC (90 % EtOAC and 10 % methanol). After the completion of reaction as verified
by TLC. To further verify the spots, a solution was made by adding 200 mg ninhydrin
in 5 % v/v acetic acid and 95 % v/v n- butane. Purplish spots appeared by dipping TLC
cards in the above solution. The reaction mixture was cooled down, washed with hexane
to remove any impurity. A yellow crystalline product was obtained after
recrystallization with ethanol. This formamidine was used for the electrochemical
determination of catechol.
16
Apart from this, other formamidines were also prepared following the reported method
[48] by changing the amines like aniline and picolyl amine. The ratio of molar
concentration amines and triethylorthoformate used was in 2:1. A maximum yield was
obtained with 10 mol% cerium ammonium nitrate as catalyst in 20 mL water as solvent.
Solid products were obtained using all these amines which were separated by filtration.
17
18
Chapter 3
19
3.1 Synthesis
3.1.1 Synthesis of formamidine
The formamidine was synthesized by modifying the reported method [37]. 4-Amino
phenazone and triethylorthoformate were refluxed with an addition of few drops of
acetic acid. The progress of the reaction was monitored by thin layer chromatography.
Melting point of the product was measured to be 178 oC.
SiO2/C-graphite matrix
Surface morphology of synthesized material was examined by SEM. Figure 3-1
and Figure 3-2 show the SEM images of SiO2/C-graphite at 10 kV with magnification
of 5kx and 10kx respectively. It showed granular and flakes structures.
SEM images of matrix at higher magnification also illustrated the flakes on the
surface of material as shown in Figure 3-3. It displayed the micrograph at 10 kV with
magnification of 25 and 50 kx. These images showed the high compactness of material
and small gaps between flakes.
20
21
22
23
24
25
Weight%
45.83
37.91
15.27
0.98
100.00
Atomic%
56.58
35.13
8.06
0.23
100.00
26
27
28
0.6
0.5
0.4
0.3
0.2
0.1
0.0
2
10
12
14
16
18
20
22
C=N which are typical for benzimidazolium group as verified from literature [49]. The
characteristic peak of carboxylic group appears at 1697.59 cm-1 while CH
characteristic peak appeared at 2902.38 and 2964.57 cm-1 [50].
29
4000
3500
3000
2500
2000
1500
1000
C NMR (125 MHz, DMSO): 38.444, 112.949, 126.766, 131.002, 131.990, 141.153.
30
665.3315
665.0503
741.5072
738.02387
0.0
881.3233
860.1098
862.1364
1049.103
1049.103
1004.747
1004.747
956.5347
936.2855
936.2855
1238.095
1238.095
1147.456
1147.456
1489.764
1454.087
1454.087
1697.59761
1700.935
1687.435
1687.435
1651.758
1620.902
1620.902
0.2
2360.481
2973.743
2964.57971
0.4
2902.389
2902.389
Absorbance
0.6
1395.268
1363.448
1363.448
0.8
31
SiO2/C/CuO
SiO2/C/CuO/IL
SiO2/C
1500
500
0
SiO2/C
15
-500
10
Current(uA)
Current (uA)
1000
-1000
-5
-1500
-200
200
400
600
Potential (mV)
-200
200
400
600
800
Potential(mV)
Figure 3-16 Cyclic voltammograms f working electrodes in 0.1M NaOH at scan rate of 20 mV sec -1
against SCE. Inset shows the cyclic voltammogram of SiO2/C
32
800
1800
1500
Current (uA)
1200
900
600
300
0
-300
-600
-900
-1200
-200 -100
100
200
300
400
500
600
700
800
900
Potential (mV)
Figure 3-17 Cyclic voltammograms of working electrodes by adding 4mM Catechol in 0.1 M NaOH at
scan rate of 20 mV sec-1 against SCE
This result was further verified by adding different concentrations of catechol in 0.1 M
NaOH solution. The cyclic voltammograms obtained with SiO2/C/CuO/IL electrode at
different concentrations of catechol were shown in Figure 3-18. It can be seen that with
the increase of catechol concentration oxidation peak current also increases. So it is
proved that the material SiO2/C/CuO/IL was oxidizing catechol electrochemically.
33
SiO2/C/CuO/IL Blank
SiO2/C/CuO/IL + 2mM CC
SiO2/C/CuO/IL + 4mM CC
SiO2/C/CuO/IL + 6mM CC
2700
2400
2100
1800
Currnet (uA)
1500
1200
900
600
300
0
-300
-600
-900
-1200
-1500
-200
-100
100
200
300
400
500
600
700
800
900
Potential (mV)
Figure 3-18 Cyclic voltammograms of working SiO2/C/CuO/IL based electrode obtained at different
catechol concentrations (0, 2, 4, 6 mM) in 0.1 M NaOH at scan rate of 20 mV sec-1
3.7.2 Amperometry
The chronoamperometric technique was used to study the effect of concentration versus
current. Figure 3-19 shows the chronoamperometric curves for successive addition of
0.2 mM of catechol solution at a constant applied potential of 0.6 V after each 50 s.
This curve was obtained in low concentration range of catechol from 0.2 - 2.4 mM,
which shows the response of our electrode in very low concentration of catechol in
solution. Throughout the amperometry, we used modified electrode SiO2/C/CuO/IL
because it was showing good response as verified by cyclic voltammetry.
34
500
y = a + b*x
Equation
Current
Plot
450
No Weighting
Intercept
146.32727
Slope
155.63636
Residual Sum of
350
159.12727
Pearson's r
0.99925
R-Square(COD)
0.99851
Adj. R-Square
0.99834
500
450
300
400
Current (uA)
Current (uA)
400
Weight
250
200
350
300
250
200
150
150
0.0
0.5
1.0
1.5
2.0
Conc (mM)
100
0
100
200
300
400
500
600
700
Time (sec)
Figure 3-19 Amperogram of SiO2/C/CuO/IL electrode at 0.6 V in 0.1M NaOH solution with successive
addition of 0.2 mM Catechol after every 50 sec. Inset shows the calibration curve for the concentration
range of 0.2 2.4 mM
35
2.5
y = a + b*
Equation
2400
Plot
2200
Weight
Intercept
328.9333
Slope
173.1393
Residual S 50992.49
0.98985
Pearson's
1800
1600
1400
R-Square(
0.9798
2000
Adj. R-Squ
0.97727
1800
1600
1200
Current (uA)
Current (uA)
2000
Current
No Weig
1000
800
1400
1200
1000
800
600
600
400
400
200
10
Conc (mM)
0
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
750
800
850
900
950
1000
Time (sec)
Figure 3-20 Amperogram of SiO2/C/CuO/IL electrode at 0.6V in 0.1 M NaOH solution with successive
addition of 1 mM Catechol after 50 sec. Inset figure shows the calibration curve from 1- 10 mM
Electrochemical linear response of electrode for long range of concentration from 0.2
mM to 9.64 mM was further verified chronoamperometrically with successive addition
of 0.2 mM catechol upto 750 sec and after that addition of 0.38 mM catechol upto 1700
sec. Figure 3-21 verifies the response of electrode for large time domain.
36
Plot
No Weighting
Weight
1600
1400
Intercept
122.92255 19.089
Slope
191.87101 3.7019
1200
110656.96089
Pearson's r
0.99446
R-Square(COD)
0.98896
Adj. R-Square
0.98859
0.38mM
1000
2000
1800
800
1600
1400
600
Current (uA)
Current (uA)
y = a + b*x
Equation
1800
0.2mM
400
1200
1000
800
600
400
200
200
0
0
10
11
Conc. (mM)
0
0
100
200
300
400
500
600
700
800
900
Time (sec)
Figure 3-21 Amperogram of successive addition of 0.2 mM catechol upto750 sec and after that addition
of 0.38 mM catechol upto 1700 sec in 0.1 M NaOH. Inset shows the calibration curves before and after
750 s respectively, for a total range of concentration 0.2- 9.64 mM
3.7.3 Calculations
Sensitivity was calculated from the slope of calibration curve divided by area of
electrode as can be seen in Figure 3-21
Sensitivity = Slope/ Area = 191.87/0.2827 = 0.678 nA dm3 mmol-1cm-2
The limit of detection determines the lowest concentration of analyte molecules that
can be detected for a given type electrochemical sensor.
Limit of Detection (LOD) = 3* (blank solution) /slope = 6.76x10-6 mol dm-3.
General straight line equation Y=mx+c is written in the form.
Y= 191.87 (x conc. in mM of catechol) + 122.92 (I in A) straight line equation of
calibration curve presented above having a correlation coefficient of R2= 0.988
37
2400
CC
2200
2000
Current (uA)
1800
CC 4AP Cys
1600
NaNO2
UA DA AA
1400
1200
1000
800
600
400
200
0
0
100
200
300
400
500
600
Time (sec)
Figure 3-22 Amperometric response of SiO2/C/CuO/IL sensor with successive addition of 3mM ( CC,
4APh, L-Cys, NaNO2, UA, DA, AA ) and again 5mM CC in 0.1M NaOH solution after 50 sec.
0.1 M NaOH. Current vs time response was recorded as shown in Figure 3-23. It is
evident that the current increases with the increase of successive addition of real sample
in equal intervals of time, which shows that the proposed sensor detects catechol in
effluent water from yarn dyeing industry.
1800
1600
1400
Current (uA)
1200
1000
800
600
400
200
0
0
50
100
150
200
250
300
350
400
450
500
550
Time (sec)
Figure 3-23 Catechol determination in effluent water from Monnoo Yarn Dyeing with successive
addition of 0.5 mL effluent water in 50 mL of 0.1 M NaOH
39
The order of conduction of electrons is SiO2/C/CuO/IL > SiO2/C/CuO > SiO2/C which
shows that ionic liquids modified electrode exhibits excellent sensitivity and low limit
of detection achieved for this electrode.
SiO2/C
SiO2/C/CuO
3000
SiO2/C/CuO/IL
2500
80
1500
70
60
-Z imag (ohm)
-Z imag (ohm)
2000
1000
500
50
40
30
20
10
0
50
100
150
200
250
Z real (ohm)
2000
4000
6000
8000
10000
Z real (ohm)
Figure 3-24 Nyquist plots for SiO2/C, SiO2/C/CuO, SiO2/C/CuO/IL electrodes with 4mM catechol in
0.1 M NaOH solution. Inset figure shows the zoom image of SiO2/C/CuO and SiO2/C/CuO/IL.
40
0
2
4
6
200
Current (uA)
150
100
50
-50
-100
0.0
0.2
0.4
0.6
0.8
potential (mV)
Equation
Current
Plot
140
No Weighting
Weight
130
120
49.30303 5.
Slope
7.17133 0.7
Residual Sum of S
110
764.71911
Pearson's r
0.95174
R-Square(COD)
0.90581
Adj. R-Square
0.89639
100
140
90
120
80
100
Current (uA)
Current (uA)
Intercept
70
60
80
60
40
20
50
0
0
40
10
12
Conc. (mM)
30
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
750
Time (s)
41
mM
mM
mM
mM
CC
CC
CC
CC
3.8.3 Calculations
LOD was calculated by 3 / slope was 0.8 mmol dm-3
while the sensitivity was calculated by
Sensitivity = Slope /area = 7.17 / 0.14 = 50 A/ mmol cm -2
The linear range was form 1- 10 mM but R2 was 0.900 which shows very much
deviation from linearity.
3.9 Conclusion
Two types of novel sensors for the selective electrochemical detection of catechol were
fabricated. Ionophore used in carbon ceramic sensor and carbon paste sensors were
benzimidazolium-1-acetate and formamidine respectively. Both compounds were novel
organic compounds which were used for the electrochemical determination of catechol.
First carbon ceramic electrode was based on the SiO2/C/CuO/IL material. Silicagraphite matrix was synthesized by sol-gel method. Silica backbone substrate provides
mechanically and thermally stable framework and graphite is used for electrical
conductance. Porosity of the materials plays an important role in the entrapping of
electroactive species. Diffusion of analytes and their interaction with the electroactive
species also occurred through the pores. To enhance the electrical conductance and
sensitivity, the synthesized material was decorated with copper oxide nanoparticles.
SiO2/C/CuO material was further modified with ionic liquid and used to develop
working electrode as sensor for the detection of catechol. Imidazole group present in
ionic liquid worked as an ionophore and facilitated the transfer of charges which has
already been verified by electrochemical response.
The other sensor was fabricated using copper formamidine complex [Cu/FA] which
was CP/Cu/FA. Carbon paste was used for conductance and binding purpose.
Formamidine acted as facilitator for catechol. The response of electrode was checked
but it was very much less sensitive than SiO2/C/CuO/IL. Comparison showed that
SiO2/C/CuO/IL could be used for selective electrochemical determination of catechol
in environmental samples.
42
43
Chapter 4
References
44
References
[1]
[2]
[3]
P. Wang and Q. Liu, Physical Sensors and Measurement, Biomed. Sensors Meas.,
pp. 199275, 2011.
[4]
J. Kong, Nanotube Molecular Wires as Chemical Sensors, Science (80-. )., vol. 287,
no. 5453, pp. 622625, 2000.
[5]
[6]
[7]
B. Jakoby and M. J. Vellekoop, Physical sensors for liquid properties, IEEE Sens. J.,
vol. 11, no. 12, pp. 30763085, 2011.
[8]
[9]
[10]
D. Yuan, S. Chen, F. Hu, C. Wang, and R. Yuan, Sensors and Actuators B: Chemical
Non-enzymatic amperometric sensor of catechol and hydroquinone using Pt-Auorganosilica @ chitosan composites modified electrode, Sensors Actuators B. Chem.,
vol. 168, pp. 193199, 2012.
[11]
[12]
[13]
[14]
45
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
46
Y. Liu, J. Lei, and H. Ju, CuO-Doped Mesoporous Silica Hybrid for Rapid and Sensitive
Amperometric Detection of Phenolic Compounds, pp. 24072412, 2010.
[29]
[30]
Y. Zhao, X. Song, Q. Song, and Z. Yin, CrystEngComm PAPER A facile route to the
synthesis copper oxide / reduced graphene oxide nanocomposites and
electrochemical detection of catechol organic pollutant {, pp. 67106719, 2012.
[31]
X.-Y. Yu, Z.-G. Liu, and X.-J. Huang, Nanostructured metal oxides/hydroxides-based
electrochemical sensor for monitoring environmental micropollutants, Trends
Environ. Anal. Chem., vol. 34, pp. 2835, 2014.
[32]
[33]
[34]
Y. Zhao, X. Song, Q. Song, and Z. Yin, A facile route to the synthesis copper
oxide/reduced graphene oxide nanocomposites and electrochemical detection of
catechol organic pollutant, CrystEngComm, vol. 14, no. 20, p. 6710, 2012.
[35]
[36]
[37]
[38]
Y. Tan, J. Kan, and S. Li, Amperometric biosensor for catechol using electrochemical
template process, Sensors Actuators, B Chem., vol. 152, no. 2, pp. 285291, 2011.
[39]
[40]
J. Michaowicz and W. Duda, Phenols - Sources and toxicity, Polish J. Environ. Stud.,
vol. 16, no. 3, pp. 347362, 2007.
[41]
47
[42]
[43]
[44]
[45]
[46]
[47]
[48]
K. U. Sadek, Cerium (IV) Ammonium Nitrate (CAN) Mediated Reactions IV. A Highly
Efficient Synthesis of N,N-Diarylsubstituted Formamidines in Water at Ambient
Temperature, Green Sustain. Chem., vol. 01, no. 03, pp. 9297, 2011.
[49]
[50]
[51]
[52]
[53]
48