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Synthesis and Characterization of Novel

Organic Ionophores: Application as Selective


Electrochemical Sensors

By

Bilal Khalid
CIIT/FA14-MSCHEM-008/LHR
MS Thesis

COMSATS Institute of Information Technology


Lahore, Pakistan
Spring, 2016

COMSATS Institute of Information Technology

Synthesis and Characterization of Novel Organic


Ionophores: Application as Selective
Electrochemical Sensors
A Thesis Presented to

COMSATS Institute of Information Technology, Lahore


In partial fulfillment
of the requirement for the degree of

Master of Science
in
Chemical Engineering
By

Bilal Khalid
CIIT/FA14-MSCHEM-008/LHR

Spring, 2016

ii

Synthesis and Characterization of Novel Organic


Ionophores: Application as Selective
Electrochemical Sensors

A Graduate Thesis submitted to the Department of Chemical Engineering as


partial fulfillment of the requirement for the award of Degree of Master of
Science (MS) in Chemical Engineering.

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

Synthesis and Characterization of Novel Organic


Ionophores: Application as Selective
Electrochemical Sensors
Bilal Khalid
CIIT/FA14-MSCHEM-008/LHR
Has been approved
In COMSATS Institute of Information Technology, Lahore
External Examiner: __________________________________________

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

I Bilal Khalid Registration # CIIT/FA14-MSCHEM-008/LHR hereby declare that I


have produced the work presented in this thesis, during the scheduled period of study.
I also declare that I have not taken any material from any source except referred to
wherever due that amount of plagiarism is within acceptable range. If a violation of
HEC rules on research has occurred in this thesis, I shall be liable to punishable action
under the plagiarism rules of the HEC

Date: _________________

Signature of the student: ___________________


Bilal Khalid
CIIT/FA14-MSCHEM-008/LHR

Certificate

It is certified Bilal Khalid (CIIT/FA14-MSCHEM-008/LHR) has carried out all the


work related to this thesis under my supervision at the Department of Chemical
Engineering, COMSATS Institute of Information Technology, Lahore and the work
fulfills the requirement for award of MS degree.

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

I would like to dedicate my thesis


To my respected
Teachers and
parents for
their love,
prayers & endless
support

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

sensitivity for the determination of catechol in environmental samples taken from


Monnoo Yarn Dyeing industry.

ix

Table of Content
Declaration ................................................................................................v
Certificate ................................................................................................ vi
ACKNOWLEDGEMENTS ................................................................. viii
1

Introduction ..........................................................................................2

1.1

Sensors ....................................................................................................... 2

1.2

Types of sensors ......................................................................................... 2

1.3

1.4

2
2.1

1.2.1

Physical sensors .......................................................................................3

1.2.2

Chemical sensors .....................................................................................3

1.2.3

Biosensors ................................................................................................3

Literature review ........................................................................................ 3


1.3.1

Catechol Optical Sensors: ........................................................................4

1.3.2

SiO2/C-graphite based Selective Electrochemical Sensors......................5

1.3.3

CuO based Selective Electrochemical Sensors ........................................7

1.3.4

Ionic Liquid modified selective catechol sensors ....................................7

1.3.5

Formamidine modified selective electrochemical sensor ........................8

Scope and Objectives ................................................................................. 8

Material and Methods ....................................................................... 11


Materials ................................................................................................... 11
2.1.1

TEOS (Tetraethylorthosilicate) ..............................................................11

2.1.2

Ethanol ...................................................................................................11

2.1.3

Acetic Acid ............................................................................................11

2.1.4

Benzimidazole........................................................................................11

2.1.5

Nitric Acid .............................................................................................11

2.1.6

Hydrofluoric Acid ..................................................................................11

2.1.7

Graphite..................................................................................................11
x

2.2

2.3

3
3.1

3.2

2.1.8

Copper Nitrate ........................................................................................12

2.1.9

Ethylene Glycol .....................................................................................12

2.1.10

Sodium Hydroxide .................................................................................12

2.1.11

Uric Acid ................................................................................................12

2.1.12

Ascorbic Acid ........................................................................................12

2.1.13

4 Amino Phenol .....................................................................................12

2.1.14

L- Cysteine .............................................................................................12

2.1.15

Dopamine ...............................................................................................13

Instrumentation and characterization techniques ..................................... 13


2.2.1

Scanning Electron Microscope (SEM) ..................................................13

2.2.2

BET multipoint Technique ....................................................................13

2.2.3

Universal testing machine (UTM) .........................................................13

2.2.4

Fourier Transform Infrared Spectroscopy (FTIR) .................................13

2.2.5

Nuclear Magnetic Resonance ................................................................13

2.2.6

Melting Point Apparatus ........................................................................14

2.2.7

Rotary Evaporator ..................................................................................14

2.2.8

Potentiostat Machine:.............................................................................14

Synthetic procedures for the material preparation ................................... 14


2.3.1

Synthesis of SiO2/C by the solgel method ..........................................14

2.3.2

Synthesis of CuO on SiO2/C matrix.......................................................15

2.3.3

Synthesis of Ionic Liquid .......................................................................16

2.3.4

Synthesis of formamidines .....................................................................16

2.3.5

Fabrication of carbon ceramic electrode ................................................17

2.3.6

Fabrication of carbon paste electrodes ...................................................18

Results and Discussion ..................................................................... 20


Synthesis .................................................................................................. 20
3.1.1

Synthesis of formamidine ......................................................................20

3.1.2

Synthesis of benzimidazolium-1-acetate ...............................................20

SEM Analysis........................................................................................... 20
xi

3.3

3.2.1

SiO2/C-graphite matrix ..........................................................................20

3.2.2

SiO2/C/CuO Material .............................................................................23

3.2.3

SiO2/C/CuO/IL Material ........................................................................24

Energy Dispersive X-rays Spectroscopy (EDX) ...................................... 26


3.3.1

EDX analysis of SiO2/C/CuO ................................................................26

3.3.2

EDX color mapping of material SiO2/C/CuO........................................27

3.4

BET (Brunauer Emmett Teller) surface area and porosity analysis ........ 28

3.5

Fourier transform infrared spectroscopy (FTIR) study of [BzIm]OAc ... 29

3.6

Nuclear Magnetic Resonance (NMR) ...................................................... 30

3.7

Electrochemical analysis of carbon ceramic electrodes: .......................... 31

3.8

3.7.1

Cyclic voltammetry:...............................................................................31

3.7.2

Amperometry .........................................................................................34

3.7.3

Calculations............................................................................................37

3.7.4

Interference study and selectivity: .........................................................38

3.7.5

Real Samples Analysis:..........................................................................38

3.7.6

Electrochemical Impedance Spectroscopy: ...........................................39

Electrochemical Analysis of Chemically modified carbon paste electrodes

(CMCPE- CP/Cu/FA) ............................................................................................ 40

3.9

3.8.1

Cyclic voltammetry of CMCPE- CP/Cu/FA..........................................40

3.8.2

Amperometry of CMCPE- CP/Cu/FA ...................................................41

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

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 ....................................................................................... 34
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
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......................................................... 36
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 ............................................................................. 37
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. .................................................................... 38
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
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
Figure 3-25 CV of CMCPE- CP/Cu/FA with increasing conc. of CC from 0 to 6 mM
.............................................................................................................................. 41
Figure 3-26 Amperogram of CMCPE-CP/Cu/FA with successive addition of 1 mM
catechol (CC) in 0.1 M NaOH solution ................................................................ 41

List of Abbreviations:
AA

Ascorbic Acid

BET

BrunauerEmmettTeller

CC

Catechol

CCC

Carbon Ceramic Composite

xiv

CCE

Carbon Ceramic Electrode

CA

Chronoamperometry

CV

Cyclic Voltammetry

DA

Dopamine

DPV

Differential Pulse Voltammetry

NN

Sodium Nitrate

HQ

Hydroquinone

L- Cys

L Cysteine

LOD

Limit of detection

Ox

Oxidation

Red

Reduction

Rpm

Revolution per minute

SEM

Scanning Electron Microscopy

TEOS

Tetraethylorthosilicate

UA

Uric Acid

4 APh

4 Amino Phenol

EIS

Electrochemical Impedance spectroscopy

SiO2/C

Silica Graphite

CMCPE

Chemically modified carbon paste electrode

CP/Cu/FA

Carbon paste electrode modified with copper formamidine complex

SiO2/C/CuO

CuO synthesized on silica graphite support

SiO2/C/Cu/IL

CuO synthesized on silica graphite support, modified with ionic liquid

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

1.2.1 Physical sensors


Physical sensor is a device that senses and responds to input from the physical
world. The specific input may be light, heat, humidity, impact, moisture, pressure etc.
The output is converted into a signal. The nature of physical phenomena includes
thermal, magnetic, electrical, mechanical, atomic and nuclear, each represent the
specific properties of a body or a system. Effects of these properties are recorded in
useful signals by an instrument. For example: speed of a car recorded by speedometer
and speed of air measured by anemometer are converted into digital signals etc.
Physical sensors have many applications in daily life [7].

1.2.2 Chemical sensors


A device that converts the chemical information about composition and concentration
of analytes (particular elements, ions, compounds, or biomolecules) into an output
(current) signal is called chemical sensor. Calibration curve is normally used to check
the linear response of concentration vs current. Sensitivity of the sensor is a measure of
its ability to distinguish among little changes in the concentration of analyte molecules
[1]. The slope of the calibration curve (current vs concentration) determines sensitivity
which also depends on standard deviation of the measurements. High fluctuations
obviously decrease the sensitivity [8]. Chemical sensors are used for the determination
of analytes, to identify chemical substance, determining of selective ions in the solution
and sensing of harmful gases etc [6].

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].

1.3 Literature review


Catechol (1,2-dihydroxybenzene) being major phenolic pollutant, is detected in
environmental samples by means of various electrochemical and optical sensors. This
section will cover the recent literature regarding catechol sensors.
3

S. Chen et al. reported the synthesis of catechol electrochemical sensors by the


immobilization of silver nanoparticles on carboxy-methyl cellulose (CMC)-modified
cellulose nanofibers. The laccase was physiosorbed on AgNPs-CMC/ cellulose by
electrostatic force of attraction and this modified electrode was used as biosensor for
catechol detection. The cyclic voltammogram revealed that Laccase/AgNPsCMC/cellulose/carbon electrode exhibited a detection limit of 1.64l mol dm-3 and linear
range from 4.98 x 10-6 to 3.65 x 10-3 M [10]. Non-enzymatic amperometric sensor of
catechol and hydroquinone using Pt-Au-organo-SiO2 chitosan composites modified
electrode. Pt/Au/OSi /CS showed excellent electrocatalytic response for the oxidation
and reduction of catechol and a good linear range of 0.0690.98 M was observed [10].
L. Wang et al. reported the fabrication of composite electrode made from silver
nanoparticles, graphene and polydopamine which was used for the amperometric
determination of catechol in environmental samples [11]. J. Sun et al. reported the
carbon modified electrodes synthesized from GO (graphene oxide) and manganese
dioxide nanocomposite which were used for the voltammetric detection of
hydroquinone and catechol simultaneously. The limit of detection for catechol was 10
x 10-9 M [12].
Annamalai Senthil Kumar et al. reported the selective electrochemical sensing of
catechol and dopamine using ferrocene bound nafion membrane modified electrode.
Linear response range was 250 mM 2.5 mM for catechol and 250 mM 5 mM for
dopamine, with the corresponding detection limit was 10.8 mM and 22.7 mM
respectively. The sensitivity of membrane sensor was 1.1 A mmol L-1 for both
catechol and dopamine [13].

1.3.1 Catechol Optical Sensors:


An optical MEMS (Microelectromechanical systems) sensor for the detection of
catechol was reported by Peter Dykstraa et al. Catechol, on oxidation, gives products
which when react with chitosan film produces a change in absorbance in UV and near
UV region. Taking the advantage of absorbance property, catechol was detected by
measuring the change in the intensity of light at 472 nm through electrodeposition of
chitosan on conductive and transparent film of indium tin oxide. Interferent like
ascorbic acid did not cause an absorbance change. The lowest concentration
4

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].

1.3.2 SiO2/C-graphite based Selective Electrochemical Sensors


Carbon Ceramic Composites (CCC) is a new class of material having very high stability
and strength. Carbon ceramic electrodes (CCEs) are rigid and porous. They can be
modified with electroactive species and have a renewable surface exhibiting excellent
sensing properties [16]. The surface of electrodes can be regenerated by polishing it
with emery paper [17]. In CCEs, silica is used as reinforcement and provides
mechanically and thermally stable framework and graphite is physiosorbed on silica
backbone which is used for electrical conductance [18]. Literature reveals that
incorporation of different electroactive species on SiO2/C support act as electrocatalysts
and consequently its electrical conductance and sensing properties are increased.
Carbon ceramic material based electrodes have wide range of applications in the field
of catalysis and sensors [19]. Carbon ceramic electrodes have superiority over carbon
paste electrodes and screen printed electrodes because of long durability, regenerative
surfaces, less expensive, easy synthesis and good conductivity [20].
Thiago C. Canevari et al. reported the simultaneous electroanalytical determination of
hydroquinone and catechol on SiO2/C electrode spin-coated with a thin film of Nb2O5.
Differential pulse voltammetry (DPV) was performed to find the oxidation peak of
hydroquinone (HQ) and catechol (CC). Si/C/Nb modified electrode exhibited good
electrochemical response towards catechol [21].
Dopamine (DA, 3,4-dihydroxyphenyl ethylamine) is a catecholamine. It plays an
important role in the functioning of cardiovascular as well as central nervous and
5

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

SiO2/C-graphite. The sensor showed sensitivities of 53.02 A mmol dm3 towards


ascorbic acid and 104.17 A mmol dm3 against dopamine respectively [27].

1.3.3 CuO based Selective Electrochemical Sensors


J. Lei et al. reported that CuO doped with mesoporous silica hybrid for amperometric
detection of phenolic compounds like catechol. CuO incorporated on mesoporous silica
showed a good linear response from 1.2 x 10-9 to 3.0 x 10-5 M for the determination of
catechol [28]. Y. W. Hsu et al. used CuO/graphene as a non-enzymatic glucose sensor.
A sensitivity of 1.065 nA dm3 mmol1 cm2 was calculated [29]. X. Song et al. reported
that cupric oxide adsorbed on reduced graphene oxide CuO/rGO composite showed
remarkable electrocatalytic activity of sensor towards catechol oxidation and used that
sensor for highly sensitive determination of catechol [30].
Metal oxides based sensors are inexpensive, rapid and highly sensitive. Nanostructure
transition metals such as Ag, Au, Ni, Cu, Zn, Ti and Pt oxides and composites have vast
applications in sensors [31]. Among these metal oxides, copper oxide has many
advantages such as natural abundance, low production cost, good catalytic and
electrochemical properties [32]. Among the numerous metal oxides available, copper
oxide (CuO), a semi-conducting material with electric as well as photocatalytic
properties, is being used as an electrocatalyst in electrochemical reaction at the surface
of electrodes [33]. Due to attractive features of copper oxide, it is being thought the best
material for sensing purposes. According to the literature, catechol sensors based on
copper oxide nanostructure have excellent stability, selectivity and sensitivity [34].

1.3.4 Ionic Liquid modified selective catechol sensors


Y. Wang et al. reported that poly (crystal violet) functionalized graphene modified
carbon ionic liquid electrode showed good electrochemical response towards the
detection of hydroquinone and catechol simultaneously. The electrode exhibited good
sensitivity with increased conductivity and decreased resistances [35]. A. Ivaska et al.
reported that ionic liquids which were composed of two asymmetrical ions i.e. bulky
cyclic and acyclic cations and smaller organic and inorganic anions showed high
conductivity, non-volatility, less toxicity, large electrochemical linear response and

good electrochemical stability when used for the selective electrochemical


determination of different analytes [36].

1.3.5 Formamidine modified selective electrochemical sensor


N,N- bis (benzophenone imine)formamidine (b-BPEF) was synthesized and used as an
ionophore for the determination of silver ion. (b-BPEF) [37]. Linear response range
was 2.2 107 to 2.2 102 mol L1 with a detection limit of 5.0 108 mol L1 and a
slope of 59.54 0.2 mV decade1 over a wide pH range (2.09.0) [37].
1.4

Scope and Objectives

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

determination of catechol in environmental samples [30]. According to literature,


different types of materials have been reported for the fabrication of catechol sensors
including metals, metal oxides, biomolecules and it has already been reported in a
patent that imidazole group, present in ionic liquid, acts as an ionophore for the
selective electrochemical sensing of analytes. Different types of electrodes and
ionophores were used for the selective electrochemical determination of catechol.
Our aim is to synthesize two types of electrochemical sensors: (1) carbon ceramic novel
selective electrochemical sensor based on SiO2/C (support), copper oxide (electroactive
specie) and ionic liquid (ionophore), for the detection of catechol in industrial effluent
water samples. (2) Chemically modified carbon paste electrode based on carbon paste
and formamidine Cu complex [Cu/FA] for the selective electrochemical detection of
catechol in environmental samples. Response of each sensor will be measured in term
of selectivity, sensitivity and linear limit of detection.

Chapter 2
Material and Methods

10

Material and Methods


This section will cover the experimental details, synthetic procedure and

characterization techniques for the materials preparation.

2.1 Materials
This section will cover the materials required for the synthesis of working electrodes

2.1.1 TEOS (Tetraethylorthosilicate)


Analytical grade TEOS purity of 99% was used for the synthesis of SiO 2 /C as a
precursor to silica. It is a colorless liquid of density 0.933 g/mL by Merck.

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

2.1.3 Acetic Acid


It has a density of 1.05 g/mL provided by Merck. It is present in glacial form. It
is used as anion source in the formation of ionic liquid

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.

2.1.5 Nitric Acid


Nitric acid (65%) was purchased from Merck chemicals. It is available as
colorless liquid with pungent smell

2.1.6 Hydrofluoric Acid


Technical grade (38-40%) hydrofluoric Acid was supplied by Merck chemicals.
It was used as catalyst during gelation process of sol gel method.

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

2.1.8 Copper Nitrate


Copper nitrate is available as blue colored powder. It was used for in situ
synthesis of CuO nanoparticles on SiO2/C matrix. It was supplied by Merck chemicals.

2.1.9 Ethylene Glycol


It was purchased from Daejung chemicals Korea with purity 99%. It is available as a
colorless liquid with density of 1.11 g/cm3

2.1.10 Sodium Hydroxide


It is available in the form of pallets. It is a strong alkali. It was used in synthesis process
to maintain the pH of solution during in-situ immobilization of copper oxide CuO and
was also used as supporting electrolyte for electrochemical oxidation of catechol.
Analytical grade sodium hydroxide was provided by Sigma Aldrich chemicals.

2.1.11 Uric Acid


It is white crystalline solid. It is used for the interference study of catechol with
modified electrode. It was purchased from BDH chemicals with purity 98%.

2.1.12 Ascorbic Acid


It is commercially available as white solid. It was purchased from Daejung with purity
of 99%. It was also used for interference study to measure selectivity of proposed
electrode.

2.1.13 4 Amino Phenol


It is present in reddish black solid which is used in the interference study of electrodes
as a phenol. Its molar mass was 109 g/mol with a density of 1.13 g/cm provided by
Sigma- Aldrich.

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

2.2 Instrumentation and characterization techniques


Characterization of the samples was carried out by following techniques

2.2.1 Scanning Electron Microscope (SEM)


The morphology of the prepared samples was analyzed by scanning electron
microscope VEGA3 TESCAN in IRCBM. The instrument was operated at 10 kV. SEM
images were recorded in the range of 900 nm - 5 m. The porous nature was verified
by SEM images.

2.2.2 BET multipoint Technique


BET surface area and porosity analyzer (Micromemitics TriStar II 3020) was used for
calculating the surface area, porosity and pore size distribution.

2.2.3 Universal testing machine (UTM)


Pallets of synthesized material were prepared by universal testing machine (Testometric
UTM M500-50AT). 60mg of material was pressed under 6000-pound force in a 6 mm
diameter die. Disk was prepared using UTM.

2.2.4 Fourier Transform Infrared Spectroscopy (FTIR)


Functional group analysis was performed using FTIR. Thermo-Nicolet 6700 P FTIR
Spectrometer (USA) Range: 4000 to 400cm-1. Attenuated Total Reflectance (ATR) was
used for our liquid sample of ionic liquid.

2.2.5 Nuclear Magnetic Resonance


For structural analysis, 1H NMR and

13

C NMR was performed on a 500 MHz NMR

spectrometer from Malaysia.

13

2.2.6 Melting Point Apparatus


Melting point meter (MPM) was used to determine the melting point of ionic liquid in
capillary tubes. Model MPM-H2 was used having upper limit of melting point
calculation as 360 C.

2.2.7 Rotary Evaporator


BUCHI Rotavapor R -215 has been used to evaporate solvent under reduced pressure
and elevated temperature.

2.2.8 Potentiostat Machine:


Sensing properties of material were determined by potentiostat machine (Gamry
Reference-3000). Cyclic voltammetry was used for the measurement of oxidation
potential of sensor against catechol. By using amperometric technique, response of
sensor was recorded at different concentrations of catechol while electrochemical
impedance spectroscopy was performed to check the charge transfer resistance.

2.3 Synthetic procedures for the material preparation


2.3.1 Synthesis of SiO2/C by the solgel method
SiO2/C is prepared by following a reported method [23].The sol gel method was used
to prepare SiO2/C having amount of SiO2 and C in 2:1 ratio. Tetraethylorthosilicate
(TEOS) and ethanol were mixed in proportion 1:1 (v/v) TEOS/ethanol to make 50 ml
solution. Then 4.0 mL distilled water and 0.1 mL conc. HNO3 were added in the
solution and let it stir gently at a temperature of 80 oC for 3 hours. After that, graphite
3.3g, 4mL distilled water and 0.1 mL HF catalyst were added to pre-hydrolyzed TEOS
solution [44]. The amount of graphite added in the reaction mixture was 50% (w/w) of
SiO2, mixture was sonicated until gelation of the material occurred and then allowed to
rest. The rate of evaporation of solvent determines the distribution of porosity in the
xerogel. The gel obtained was dried at room temperature slowly for about 15 days and
then ground to powder and washed thoroughly, initially with deionized water and then
in soxhlet extractor for 3 h. Finally, the product was dried in oven at 393 K for 4 h [19].

14

Figure 2-1 Scheme of synthesis of SiO2/C by Sol Gel Method

2.3.2 Synthesis of CuO on SiO2/C matrix


Copper oxide nanoparticles were synthesized in situ on mesoporous SiO2/Cgraphite to form SiO2/C/CuO composite material by following a reported method [29]
. For this purpose, 0.35 g of copper nitrate was dissolved into 50 mL ethylene glycol in
a round bottom flask. 0.1M Sodium hydroxide (NaOH) solution was added dropwise,
if needed, to maintain the pH of solution at 9. Digital pH meter was used for monitoring
the pH. Then 5g SiO2/C powder was added into solution and let it stir for 30 min at a
rate of 300 rpm at room temperature so that the ingredients could be mixed properly.
Then the reaction mixture was heated at a temperature of 190 oC for 3 hours. After that
the reaction mixture was cooled down to room temperature and filtered. Blackish solid
product was dried at 150 oC. Finally, the product was annealed in air environment for
30 min to get mesoporous SiO2/C/CuO nanocomposite material as required product
[45].

15

2.3.3 Synthesis of Ionic Liquid


For the synthesis of ionic liquid, reported method was followed by a little modification
of reaction conditions [46]. Benzimidazolium-1-acetate was synthesized by mixing 2
grams of benzimidazole (16.9 mmol) in 10 mL of methanol in a round bottom flask.
The temperature was kept 80 oC so as to achieve refluxing. Equimolar acetic acid
volume (0.965 mL) was added in 15 minutes at a rate of 3 drops / min. The reaction
mixture was left for 24 hrs under reflux [47]. After that the reaction mixture was heated
at 100 oC at pressure of 50 mbar rotavapor. The product was obtained as yellow
transparent liquid. It is a room temperature ionic liquid.

Figure 2-2 Synthesis of Benzimidazolium-1-acetate

2.3.4 Synthesis of formamidines


Formamidines have been used as ionophores for the detection of many analyte
molecules.

The

condensation

reaction

between

4-aminophenazone

and

triethylorthoformate took place to synthesize formamidine using reported method [37].

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.

2.3.5 Fabrication of carbon ceramic electrode


For the preparation of working electrodes of SiO2/C, SiO2/C/CuO and SiO2/C/CuO/IL
materials, pallets of each material were prepared with UTM (Universal Testing
Machine) by pressing 60 mg of each sample at a rate of 20 mm/ min under the force of
6000-pound force. The resultant pallets, having dimensions of 6 mm dia, 1.5 mm
thickness and 0.28 cm2 of surface area of disk were glued at one end of glass tube
(diameter 6 mm, length 15.4 cm) using UHU and joint was wrapped with Teflon tape
to prevent the entry of solvent into the glass tube. Electrical connections were made by
inserting a copper wire in the glass tube with a small quantity of graphite powder so
that the Cu wire might be contacted with disk properly.

Figure 2-3 Schematics of carbon ceramic electrode of 6 mm surface area

17

2.3.6 Fabrication of carbon paste electrodes


First of all, carbon paste was prepared by mixing carbon- graphite powder for
conductance and silicon oil as binder. Copper was chemisorbed on formamidine by the
method reported [24]. Briefly 50 mg of formamidine was added in 0.01 mM solution
of CuCl2 in ethanol and let the solution to evaporate so that copper, which is an
electroactive specie, could form a complex with formamidine.
For the fabrication of CMCPE, carbon paste and formamidine complex were mixed in
agate mortar and pestle in a ratio of 4:6. After that the mixture was inserted in 3 mm
hole present in carbon paste electrode (ALS, the electrochemical company, Japan. Then
the electrode was left for drying with downside up for 24 hrs so that material might not
leach out of electrode during selective electrochemical study.

Figure 2-4 Schematic of carbon paste electrode of 3 mm diameter of hole

18

Chapter 3

Results and Discussion

19

Results and Discussion

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.

3.1.2 Synthesis of benzimidazolium-1-acetate


The reaction was performed between benzimidazole and acetic acid at a refluxing
temperature of 80 oC. The results were tremendous as we obtained a room temperature
ionic liquid after the evaporation of methanol in rotary evaporator. Acetic acid
protonated the benzimidazole and also acted as anion source.

3.2 SEM Analysis


3.2.1

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

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

Figure 3-3 SEM image of SiO2/C-graphite with the magnification of 25 kx and 50 kx

22

3.2.2 SiO2/C/CuO Material


Figure 3-4 to Figure 3-6 showed SEM images of SiO2/C/CuO material obtained at 10
kV with magnification of 5-50 kx. These images showed the high compactness of
material and small gaps between some flakes. There was no phase segregation there.
These images exhibited high strength because of composite nature of material. The pore
size was confirmed by BET multipoint analyzer and homogeneity of material was
confirmed by EDX elemental analysis.

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

Figure 3-6 SEM image of SiO2/C/CuO with the magnification of 25 kx and 50 kx

3.2.3 SiO2/C/CuO/IL Material


Figure 3-7 to Figure 3-9 show the SEM images obtained at 10 kV with magnification
of 5-50 kx. Ionic Liquid was added in 25 % by weight of SiO2/C/CuO. Small flakes on
some micro sized agglomerates showed the physisorption of ionic liquid on
SiO2/C/CuO surfaces. These images showed the compactness of material and small
pores in between.

24

Figure 3-7 SEM image of SiO2/C/CuO/IL with the magnification of 5 kx

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

3.3 Energy Dispersive X-rays Spectroscopy (EDX)


3.3.1 EDX analysis of SiO2/C/CuO
Synthesis of copper oxide nanoparticles was confirmed by EDX analysis. Figure 3-10
showed high intensity peaks at 0.1, 0.6 and 1.7 kV. These peaks were assigned to
graphite (C), oxygen (O) and silicone (Si) in the matrix respectively. One high intensity
peak at 1 kV and low intensity peak of Cu appeared at 8 kV confirmed the presence of
Cu. This study provided the information about weight % of these elements present in
material.

Figure 3-10 EDX spectrum of SiO2/C/Cu

Table of Composition of Elements in SiO2/C/CuO


Element
C
O
Si
Cu
Total

Weight%
45.83
37.91
15.27
0.98
100.00

Atomic%
56.58
35.13
8.06
0.23
100.00

Figure 3-11 Weight percentage of elements present in Sensor

26

3.3.2 EDX color mapping of material SiO2/C/CuO


Figure 3-12 shows the EDX color mapping. It can be concluded from these figure that
Si, O, C and Cu particles are homogeneously dispersed in the matrix. Copper is in
smaller amount. The uniform dispersion and distribution of elements is associated to
the compactness of material.

Figure 3-12 Color mapping of Cu, Si, O and C

27

3.4 BET (Brunauer Emmett Teller) surface area and porosity


analysis
The pore size, pore volume and surface area of SiO2/C-graphite matrix was investigated
by BET multipoint surface area and porosity analyzer. Figure 3-13 shows adsorptiondesorption isotherm of nitrogen. The isotherm shows hysteresis adsorption and
desorption which is typical for mesoporous materials. The shape of isotherm is similar
to H3-type hysteresis loop as defined by International Union of Pure and Applied
Chemistry (IUPAC) in 1985. The surface area and pore volume of material was
calculated by software itself by BJH method. The surface area (SBET) and pore volume
(pv) of material is 99.87 m/g and 0.3104 cm/g respectively. Figure 3-14 shows pore
size distribution of material. Pore distribution region of sample is maximum at 14.15
which depicts that the material is in mesoporous range i.e. 2 - 50 nm.

Figure 3-13 BET nitrogen adsorption-desorption isotherm of SiO2/C-graphite matrix

28

0.6

dv / dlog(w) (cm /g)

0.5

0.4

0.3

0.2

0.1

0.0
2

10

12

14

16

18

20

22

Pore Width (nm)

Figure 3-14 BET pore size distribution of SiO2/C-graphite material

3.5 Fourier transform infrared spectroscopy (FTIR) study of


[BzIm]OAc
Function group analysis was performed using FTIR- ATR. The IR spectrum of
Bendimidazolium-1-acetate is shown in Figure 3-15. Less intensive peak at 665.05
showed out of plane bending of CC bond, strong peak at 738.023, 862.13 and weak
peak at 936.28 cm-1 showed CH out of plane bending. While peak at 1004.74 cm-1
showed the trigonal bending of CC. Peak at 1147.45 cm-1 showed CH in plane
bending while peak at 1238.09 cm-1 showed CC stretching and peak at 1363.44 cm1

CN stretching, peak at 1620.90 showed C= C stretching, peak at 1687.43 showed

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

Wave number (cm-1)

Figure 3-15 IR spectrum of [BzIm]OAc

3.6 Nuclear Magnetic Resonance (NMR)


To confirm the structure of benzimidazolium-1-acetate ionic liquid, NMR was
performed using DMSO-d6 solvent. Its spectroscopy data is 1HNMR (500 MHz,
DMSO): = 2.690 (s, 3H), 7.547-7.566 (d, 2H), 7.709-7.771 (d, 2H), 9.166 (s, 1H).
13

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

3.7 Electrochemical analysis of carbon ceramic electrodes:


Electrochemical analysis was done to test the sensing properties of working electrodes.
For this purpose, three electrode system was used. Saturated Calomel electrode (SCE),
Platinum wire electrode and SiO2/C-Graphite, SiO2/C/CuO and SiO2/C/CuO/IL
electrodes were used as reference, auxiliary and working electrodes respectively.
Pressed disks of 6mm diameter, made from synthesized materials i.e., SiO2/C-Graphite,
SiO2/C/CuO and SiO2/C/CuO/IL were used to synthesize the working electrodes.
Sodium Hydroxide (NaOH) 0.1 M was used as supporting electrolyte to carry out
electrochemical reactions throughout this research work. Three techniques which were
used to study electrochemical sensing properties of electrodes as sensor are i.e. cyclic
voltammetry, chronoamperometry, Electrochemical Impedance Spectroscopy (EIS)

3.7.1 Cyclic voltammetry:


Cyclic voltammetry was used to measure the redox potentials of the working electrodes.
Reactions on electrodes usually involve electrons transfer on surface which is
influenced by electrode potential [51]. In cyclic voltammetry, the electrode potential
changes linearly vs time. The rate of voltage change per unit time is known as the scan
rate (mV/s). For our case, it is 20 mV/sec. The potential difference is applied between
the working electrode (WE) and the reference electrode (RE) which is SCE while the
current is measured between the working electrode (WE) and the auxiliary/counter
electrodes (CE) respectively [52]. A wide potential window (-0.2 to 0.8 V) was applied
during electrochemical measurement and changes in current was recorded against
voltage. Figure 3-16 and Figure 3-17 shows the cyclic voltammograms of three
different electrodes i.e. SiO2/C, SiO2/C/CuO and SiO2/C/CuO/IL in the Blank solution
0.1 M NaOH (absence of analyte) and in the presence of 4mM Catechol (CC)
respectively. It can be seen that the SiO2/C/CuO/IL electrode shows good
electrochemical response and higher current as compared to SiO2/C and SiO2/C/CuO
electrodes. SiO2/C /CuO/IL electrode shows an oxidation peak of catechol at 0.6 V
volts. However, SiO2/C-graphite and SiO2/C/CuO electrodes do not show any oxidation
peak for glucose. By comparing these results, it is proved that the material
(SiO2/C/CuO/IL) shows good electrochemical response towards catechol.

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

SiO2/C/CuO/ILin 4mM cat


SiO2/C/CuO 4mM cat
SiO2/C in 4mM cat

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

Response of electrode was also checked for higher concentration of catechol to


calculate the linear range. Figure 3-20 shows the amperogram at higher concentration
of catechol. After addition of 1mM catechol in 0.1 M NaOH solution after 50 seconds,
electrode exhibits good linear response. The response of electrode was very excellent
up to 10mM Catechol which proved that synthesized material had very wide linear
range.

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

SiO2/C/CuO/IL with 0.2mM & 0.38 mM CC


Current

Plot

No Weighting

Weight

1600
1400

Intercept

122.92255 19.089

Slope

191.87101 3.7019

Residual Sum of Squares

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

1000 1100 1200 1300 1400 1500 1600 1700

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

3.7.4 Interference study and selectivity:


Interference study was done using other analytes in same concentration. To evaluate
the selectivity of modified electrode sensor interfering substances such as 4-amino
phenol, L-cysteine, uric acid, ascorbic acid, sodium nitrate and dopamine were added
after 50 sec as shown in self-explanatory Figure 3-22. The sensor did not show any
response to these interfering species even in the same concentration with catechol.
Hence, modified electrode SiO2/C/CuO/IL showed good selectivity towards catechol.

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.

3.7.5 Real Samples Analysis:


Response of the proposed sensor was checked towards catechol in the real samples. The
effluent water from pharmaceutical, dyeing and insecticides industry contain certain
amount of dissolved catechol. For this purpose, the effluent water from Monnoo Yarn
Dyeing was collected and 0.5 mL of water was added after every 50 secs in 50 ml of
38

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

3.7.6 Electrochemical Impedance Spectroscopy:


EIS can be characterized in two regions i.e. a semicircular part at low frequencies and
a straight line at higher frequencies. The electron transfers resistance (Rct) at the
electrode surface is directly related to the diameter of the semicircle and the inclined
line is related to the diffusion limit step [45]. Here in Figure 3-24, SiO2/C is showing
maximum charge transfer resistance as it has large semicircle diameter.
The order of semi-circle diameter was SiO2/C > SiO2/C/CuO > SiO2/C/CuO/IL which
shows that the maximum electrons transferred from SiO2/C/CuO/IL electrode and
higher current achieved which is specific for ionic liquids i.e. better electrical
conductors [53].

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.

3.8 Electrochemical Analysis of Chemically modified carbon paste


electrodes (CMCPE- CP/Cu/FA)
For electrochemical study of chemically modified carbon paste electrode which is
CP/Cu/FA carbon paste electrode made from copper formamidine complex [Cu/FA],
we performed CV as well as amperometry. But the sensitivity and selectivity were not
good for catechol.

3.8.1 Cyclic voltammetry of CMCPE- CP/Cu/FA


Cyclic voltammetry was performed to find the redox potential of CMCPE, the potential
window (-0.2 0.8 V), there was a linear change in peak current with the increase in
concentration as illustrated in Figure 3-25. There was no sharp peak observed, just
change in current was seen with increase in concentration. The change in current was
maximum at 0.6 V.

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)

Figure 3-25 CV of CMCPE- CP/Cu/FA with increasing conc. of CC from 0 to 6 mM

3.8.2 Amperometry of CMCPE- CP/Cu/FA


Current response vs concentration was observed using amperometry. Potential was
fixed at 0.6 V. There was a little increase in current by adding 1mM CC after 50 sec.
The sensitivity, limit of detection and linear response range were not good.
y = a + b*x

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)

Figure 3-26 Amperogram of CMCPE-CP/Cu/FA with successive addition of 1 mM catechol (CC) in


0.1 M NaOH solution

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

The direct electro-oxidation of electrode against catechol was characterized by cyclic


voltammetry. The sensing ability of electrode was further verified using amperometry.
EIS exhibited that ionic liquid modified electrode has lowest charge transfer resistance.
The sensor showed excellent sensitivity and detection range for catechol. Moreover, the
synthesized materials were characterized with Scanning Electron Microscopy (SEM)
and BET surface area analyzer, FTIR and NMR.

43

Chapter 4
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44

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