RV Institute of Technology & Management ®

Module -1
Sensors and Energy Systems

Syllabus
Sensors: Introduction, working principle and applications of Conductometric
sensors,Electrochemical sensors, Thermometric sensors, and Optical sensors. Sensors for
themeasurement of dissolved oxygen (DO). Electrochemical sensors for the
pharmaceuticals,surfactants, hydrocarbons. Electrochemical gas sensors for SOx and NOx.
Disposablesensors in the detection of biomolecules and pesticides.

Energy Systems: Introduction to batteries, construction, working and applications of Lithium

ion and Sodium ion batteries. Quantum Dot Sensitized Solar Cells (QDSSC’s)-Principle,
Properties and Applications.

Self-learning: Types of electrochemical sensor, Gas sensor - O2 sensor, Biosensor –

Glucosesensors.

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Sensors
An overview of analytical chemistry development demonstrates that electrochemical
sensors represent the most rapidly growing class of chemical sensors. A chemical sensor
can be defined as a device that provides continuous information about its environment.
Ideally, a chemical sensor provides a certain type of response directly related to the
quantity of a specific chemical species. All chemical sensors consist of a transducer, with
transforms the response into a detectable signal on modern instrumentation, and a
chemically selective layer, which isolates the response of the analyte from its immediate
environment. They can be classified according to the property to be determined as:
electrical, optical, mass or thermal sensors and they are designed to detect and respond to
an analyte in the gaseous, liquid or solid state. Compared to optical, mass and thermal
sensors, electrochemical sensors are especially attractive because of their remarkable
detectability, experimental simplicity and low cost. They have a leading position among
the presently available sensors that have reached the commercial stage and which have
found a vast range of important applications in the fields of clinical, industrial,
environmental and agricultural analyses.

A sensor is a device that detects and responds to some type of input from the physical
environment. The input can be light, heat, motion, moisture, pressure or any number of
other environmental phenomena. The output is generally a signal that is converted to a
human-readable display at the sensor location or transmitted electronically over a
network for reading or further processing

A potentiometric sensor is a kind of electrochemical sensor that can be utilized to compute

the insightful grouping of certain logical gas or arrangement segments. Such sensors
measure an anode's electrical likely when there is no flow present. The impact of focus on
the equilibrium of redox responses happening at the anode electrolyte interface of an
electrochemical cell is used by potentiometric sensors.

The redox reaction takes on the electrode surface:

Oxidant + Ze- => Reduced product

Z is the number of electrons involved in the redox reaction

Principle: The signal is resolved between the working cathode and the reference terminal
as the likely contrast (voltage). The capability of the working cathode must be reliant on
the analyte focus in the gas or arrangement stage. To give a given reference potential, a
reference cathode is required.

Sensor

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A sensor is a device that in contact with a specific chemical or biological species, detects it
and produces the signal proportional to its quantity.

A chemical sensor is a device that is capable of giving real time analytical information
about a test sample. It interacts with a specific chemical or biological analyte, detects it
and produces the signal proportional to its quantity. Analyte is the target species which is
being detected and measured using a sensor.

Transducer
Transducer is used to convert the signal produced by the receptor-analyte interaction into
a readable value or measurable form physical quantity. In most chemical sensors, the
sensing element and the transducer are packaged together, in direct spatial contact, in the
same unit.

Actuator
Actuator is a device that converts the electrical signals into the physical events or
characteristics. It takes the input from the system and gives output to the environment.

For example, motors and heaters are some of the commonly used actuators.
Difference between Sensor and Actuator

SENSOR ACTUATOR

It converts physical characteristics into It converts electrical signals into physical

electrical signals. characteristics.

It takes input from output conditioning unit

It takes input from environment.
of system.

It gives output to input conditioning

It gives output to environment.
unit of system.

Sensor generates electrical signals. Actuator generates heat or motion.

It is placed at input port of the system. It is placed at output port of the system.

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It is used to measure the physical It is used to measure the continuous and

quantity. discrete process parameters.

It gives information to the system

It accepts command to perform a function.
about environment.

Example: Photo-voltaic cell which

Example: Stepper motor where electrical
converts light energy into electrical
energy drives the motor.
energy.

Electrochemical sensors
➢ Electrochemical sensors use electrodes as the transducer component.

➢ Electrochemical sensor consists of working or sensing electrode, electrolyte, counter

electrode and reference electrode.

➢ Its working is based on the monitoring and measuring of reduction or oxidation of the
analyte on the surface of the electrode.

➢ The sensing electrode has a chemically modified surface.

➢ The modification ensures the selectivity facilitating the reduction or oxidation of the
analyte.

➢ The electrolyte is part of the electric circuit of an electrochemical sensors system.

➢ The role of the electrolyte is to transport charge within the sensor, contact all electrodes
effectively, solubilize the reactants and efficient transport, and be stable chemically and
physically under all conditions of sensor operation.
Working Principle of Electrochemical Sensor
➢ Diffusion of the analyte to the electrode/electrolyte interface (in the liquid phase).

➢ Adsorption onto the electrode surface.

➢ Electrochemical reaction with electron transfer.

➢ Detection of potential change.

➢ Desorption of the products.

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➢ Diffusion of the products away from the reaction zone to the bulk of electrolyte or gas
phase.
Application of Electrochemical sensors
➢ Varieties of electrochemical sensors in unique geometries or structures for large
number of chemicals are available.

➢ They are used in diverse areas as industrial safety, biochemistry, clinical chemistry,
health and medicine, agriculture, food safety, environmental protection, automobile
technology, space exploration, military threat detection, and process control.

➢ The oxygen sensor is used for detection of dissolved oxygen in water boiler and to
monitor dissolved oxygen concentration in metal melts, glasses and in hydrogen fuel.

➢ They are used in security and defence application like detection of toxic gases, warfare
agents etc.

➢ They are used in water analysis and environmental monitoring, like measurement of
toxic metal concentration in water, detection of oxides of nitrogen and sulphur, pH of
water etc.

➢ They are used in diagnostic and health-care applications, like in situ monitoring of
glucose serum, uric acid, blood Ca2+, Fe2+, Acetylcholine etc.

➢ They are used in soil parameter analysis, evaluation, and in agriculture applications.

Advantages of electrochemical sensors:

It could be interesting to a particular gas or fume in the scope of parts per million. The
level of selectivity relies upon the kind of sensor, the sensor is worked to distinguish, the
objective gas, and the gas focus. Straight performance, low necessities for force and great
goal. Remarkable repeatability and accuracy. The sensor can give an exact perusing of a
repeatable objective gas once adjusted to a known fixation. Doesn't get harmed by other
gases. The presence of other surrounding fumes would not abbreviate or restrict the
sensor 's life. Less expensive than most different advances for gas detection.
Electrochemical sensors are practical, not normal for infrared and PID innovations.

Limitations of electrochemical sensors:

Limited or confined scope of temperatures. They are temperature touchy, so the sensors
are regularly temperature remunerated inside. It is more secure to keep the temperature of
the example as consistent as could be expected under the circumstances.

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Short or confined rack life. Depending on the gas to be distinguished and the climate in
which it is utilized, an electrochemical sensor regularly has a timeframe of realistic
usability of a half year to one year.
Cross-affectability of different gases. In spite of the fact that this is an advantage, it tends
to be a disadvantage too. A few sensors are fit for meddling with different gases. To know
about conceivable bogus readings, it is critical to understand what gases can cause
impedance with your sensor.
The more prominent the objective gas presentation, the more limited the existence span. A
one-to three-year future is typically characterized. Low mugginess and high temperatures
can make the electrolytes of the sensors dry out. The electrolyte is likewise depleted by
presentation to target gas or cross-affectability gases.

Conductometric Sensor
➢ Conductometric senor is considered as a type of electrochemical sensor, even though it
is not used to measure electrochemical change.

➢ An electrochemical sensor measures the electrochemical processes (redox reactions) at

the surface of electrodes.

➢ But, a conductometric sensor is based on measurements of physical properties of a

homogeneous bulk solution like electrolytic conductance by aqueous electrolyte
solutions.

➢ In conductometric sensor, determination of the concentration of analyte is based on

measurement of changes that occur in electrolyte solution.

➢ Here the electrodes are just used to measure change in electrolytic conduction of an
electrolyte and they do not provide surface for any reaction. Therefore, their surface is
generally not modified.

➢ Electrode used in conductometric sensor is called as conductivity cell.

➢ It is used to measure the change in electrolytic conductance of the solution during

replacement of ions of a particular conductivity by ions of different conductivity.

➢ It is made of two platinum foils with unit cross sectional area and unit distance
between them. Volume between two electrodes is 1 cm3.

➢ Conductance of unit volume of the solution is called as specific conductance.

➢ There will be change in specific conductance of solution when there is change in

number of ions or type of ion. This change is measured using conductivity cell.

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➢ The conductivity cell is dipped in the electrolytic solution taken in a beaker and it is
connected to a conductance measuring device called as conductivity meter.
Application of Conductometric sensors
1. Conductometric sensor can be used to monitor any chemical which can change the
electrolytic conductance of solution on chemical reaction.

2. It is used to estimate acids, bases and their mixtures in a sample.

3. It is used to check the amount of ionic impurities in water samples.

4. It is used in measuring acidity or alkalinity of sea water and fresh water.

5. Conductometric biosensors are used in biomedicine, environment monitoring, bio-

technology and agriculture related applications.

Optical sensors
An optical sensor converts light rays into an electronic signal. The purpose of an optical
sensor is to measure a physical quantity of light and, depending on the type of sensor,
then translates it into a form that is readable by an integrated measuring device.
Optical Sensors are used for contact-less detection, counting or positioning of parts as
shown in figure 1.3. Optical sensors can be either internal or external. External sensors
gather and transmit a required quantity of light, while internal sensors are most often
used to measure the bends and other small changes in direction. The measurands possible
by different optical sensors are Temperature, Velocity Liquid level, Pressure,
Displacement (position), Vibrations, Chemical species, Force radiation, pH- value, Strain,
Acoustic field and Electric field.
Types of Optical Sensors
There are different kinds of optical sensors (Fig.1.1), the most common types which we
have been using in our real-world applications as given below. Photoconductive devices
used to measure the resistance by converting a change of incident light into a change of
resistance.

The photovoltaic cell (solar cell) converts an amount of incident light into an output
voltage. The Photodiodes convert an amount of incident light into an output current.
Phototransistors are a type of bipolar transistor where the base-collector junction is
exposed to light. This results in the same behaviour of a photodiode, but with an internal
gain. The operating principle is the transmitting and receiving of light in an optical sensor,
the object to be detected reflects or interrupts a light beam sent out by an emitting diode.
Depending on the type of device, the interruption or reflection of the light beam is

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evaluated. This makes it possible to detect objects independently of the material they are
constructed from (wood, metal, plastic or other). Special devices even allow for a detection
of transparent objects or those with different colours or variations in contrast

Fig.1.1. Different types of Optical Sensor

Temperature sensors
Temperature sensors are devices that detect and measure coolness and hotness and
convert it into an electrical signal. Temperature sensors are utilized in our daily lives, be it
in the form of domestic water heaters, thermometers, refrigerators, or microwaves. There
is a wide range of applications of temperature sensors, including the geotechnical
monitoring field and others as shown in the below diagram.

Temperature sensors

Working of temperature sensors

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The working principle of a temperature sensor is the voltage across the terminals of the
diode. If there is an increase in the voltage, the temperature also increases. This is
followed by a drop in the voltage between the terminals of the transistor of base and
emitter in a diode. There are also temperature sensors that work on the principle of stress
change caused by changes in temperature.

In a vibrating wire temperature meter, dissimilar metals have different linear coefficients
of expansion. It mainly consists of a magnetic stretched wire of high tensile strength with
two ends fixed to any dissimilar metal so that any temperature change will directly affect
the tension in the wire and its natural vibration frequency.

The dissimilar metal can be made from aluminium since it has a larger linear expansion
coefficient than steel. When the conversion of the temperature signal into frequency
occurs, the very same read-out unit that is used for other vibrating wire sensors can also
be utilized in the monitoring of temperature also.

The specially built vibrating wire sensor is the one that senses the temperature change and
then the temperature change is converted into an electrical signal which is then
transmitted to the read out the unit as a frequency.

Sensors for the measurements of dissolved oxygen (DO)

Molecular free oxygen, O2 is slightly soluble in water. Only about 8mg of oxygen is
soluble in 1litre of water. This oxygen present in water in dissolved form is called as
Dissolved oxygen. It is an important water quality parameter. Because aquatic living
beings depend upon this dissolved oxygen for their survival. Concentration of dissolved
oxygen in boiler feed water plays an important role in corrosion of water boiler. In many
industries monitoring concentration of dissolved oxygen in metal melts and other
materials is highly essential. Since, measurements of dissolved oxygen by classical
titration procedures Is tedious, sensors for dissolved oxygen measurement plays an
important role.
Two types of sensors are commonly used foe measurements of dissolved oxygen:
1.Optical sensor
2.Electrochemical sensor
1. Optical sensor for measurement of dissolved oxygen
Main components of an optical DO sensor are semipermeable membrane, sensing
element, light-emitting diode (LED) and photodetector. The sensing element contains a
luminescent dye that is immobilized on a gel matrix.

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When this dye is exposed to blue light, it moves to excited state and while returning back
to ground state, it emits light with known intensity. When the dissolved oxygen crosses
the semipermeable membrane, and interacts with the dye, it reduces the intensity of light
emitted by dye. The intensity of light emitted by the dye is inversely proportional to DO
concentration. Therefore, DO can be measured by measuring decrease in intensity of light
emitted by luminescent dye using a photodetector.

Optical DO sensor requires more power and take two to four times longer to acquire a
reading than an electrochemical DO sensor. These sensors are also heavily dependent on
temperature.

2. Electrochemical sensor for measurement of dissolved oxygen

In an electrochemical DO sensor, two electrodes used are of dissimilar metals. Zinc or
Lead is used as anode and silver metal is used as inert cathode. The difference in potential
between the anode and the cathode should be more than 0.5V to reduce dissolved oxygen
without an external applied potential. The electrolyte solution used is Sodium chloride, or
any other inert electrolyte.

When the electrode assembly is dipped in water to measure its Do, anode undergoes
oxidation liberating electrons.

2 Zn → 2 Zn2+ + 4e-

At cathode.DO undergoes reduction. Ag cathode is inert, it only passes electrons to

oxygen for reduction.

O2 + 2 H2O + 4e- → 4 OH-

Overall reaction is

Zn2+ + O2 + 2 H2O → 2 Zn(OH)2

The current produced by the reduction of oxygen at cathode is proportional to the partial
pressure of oxygen in the water sample, The zinc hydroxide that is produced by these
reactions is precipitated out into the electrolyte solution. This will gradually affect the
sensor’s performance. When the sensor readings are not stabilized, then the electrolyte
solution and Zinc anode have to be replaced to bring the sensor back to working
condition.

Oxygen Sensor

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Monitoring of oxygen is required in many areas of industries, health care, safety and
environmental concerns. In few cases, high purity oxygen is used. For example, oxygen
cylinders for welding contain a minimum of 99.5 vol% O2. There are few applications
where oxygen tolerance is in low ppm range. For example, hydrogen to be used as fuel in
Polymer Electrolyte Membrane fuel cell vehicles, the maximum allowable oxygen level
should be 5ppm. The oxygen content in air is typically given as 20.9 vol%. The minimum
oxygen content in breathing air must be mandatorily above 19.5 vol%. Thus, depending
on the application, oxygen measurements can be required from low ppm levels to nearly
100 vol% and also at concentrations in between these two extremes.

Several major sensor technologies are currently and routinely used for gas phase oxygen
measurements. The most common oxygen sensor types are clark electrode, galvanic
oxygen sensor and the zirconia oxygen sensor. These all offer the ability for on-site, real-
time detection of oxygen over a broad range of concentrations and conditions.
Clark electrode
Earliest technology developed for oxygen measurements is the clark electrode. It was first
developed to measure dissolved oxygen in water. In the clarkelectrode,Ag/AgCl electrode
is used as anode and Pt or Gold metal as cathode(Fig. 1.2). KCl is used as electrolyte. A
thin oxygen-permeable membrane made of Teflon covers the electrode assembly.
Dissolved oxygen is extracted from the test solution on to the surface of Pt electrode
through oxygen-permeable membrane.

Fig.1.2. Schematic of the Clark electrode.

Reactions
At working electrode (the cathode) reaction: O2 + 2 H2O + 4e- → 4 OH-

At counter electrode (the anode) reaction: 4Ag → 4Ag+ + 4e-

4 Ag+ + 4 Cl- → 4 AgCl

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Net cell reaction:

4Ag + O2 + 2 H2O + 4 Cl- → 4 AgCl + 4 OH-

Reduction of oxygen at the cathode is carried out at fixed applied potential of 0.8V.
Current generated due to flow of electrons from oxidation of Ag to reduction of Oxygen is
measured. The magnitude of current is directly proportional to the concentration of
oxygen molecules. The clark electrode is an excellent sensor for the determination of
oxygen aqueous environments. However, it is not suitable for direct gas phase
determinations. For this Galvanic oxygen sensor and Zirconia oxide oxygen sensors are
used.
Galvanic oxygen sensor
In this sensor, one end of the working electrode(cathode) is Pt or Gold is covered with
oxygen permeable Teflon membrane and another end is in contact with electrolyte. Lead
is used as anode and acetate solution is used as electrolyte (Fig. 1.3).

Gaseous oxygen is directly supplied to cathode. Reduction of oxygen at the cathode is

carried out at fixed applied potential of 0.8V.

O2 + 4 e- → 2O2-

The magnitude of current generated is directly proportional to the concentration of

oxygen molecules.

Both of the above methods are amperometric methods, which are based on the
measurements of current produced at fixed applied voltage.

Fig.1.3. Schematic of galvanic oxygen sensor.

Electrochemical gas sensor

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Electrochemical gas sensor (Fig. 1.4) is used in monitoring of concentration of gaseous

analytes. They are used mainly to monitor the concentration of air pollutants, detection of
leakage of chemicals I industries, and in defence, military and space applications.

Fig.1.4. Schematic of a typical gas sensor.

The following are the main components of an electrochemical sensor:

1. Filter: The filter is used to prevent unwanted contaminants, mainly particulate matter
from entering in to sensor.

2. Gas-permeable membrane: is used to regulate the gas flow into the sensor. It selectivity
allows only the analyte gas to pass and also acts as a barrier to prevent leakage of the
electrolyte for the interior of the sensor. Hydrophobic porous membranes are used with
aqueous electrolytes. These pores are not wetted by the aqueous solution but allow the
transport of dissolved gases to the electrode-electrolyte interface. The sensitivity and
response time of the sensor mainly depends on the nature of membrane, its pore size and
thickness.

3. Electrodes: Two or three electrode system is used based on the requirement. Working or
sensing electrode, Counter electrode, and reference electrodes are used.

4. Electrolyte: Electrolyte used should be a good ionic conductor, and chemically and
physically stable under operation condition of sensor. Main role of the electrolyte is to
transport charge within the sensor, contact all electrodes effectively, solubilize the
reactants and products for efficient transport.

Working principle of an electrochemical gas sensor

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The following steps are involved in the working of a typical electrochemical gas sensor:

1.The Diffusion of gas analyte through filter, membrane and then finally through
electrolyte on to the surface of sensing electrode.

2.Adsorption of analyte gas molecule on the surface of sensing electrode

3.Oxidation of analyte on the surface of sensing electrode, liberating electrons. Transfer of

liberated electrons from anode to cathode through external circuit, the surface of sensing
electrode is the active part of the electrode, it is modified by coating with appropriate
catalysts which can selectively interact with analyte gas and carry out its chemical change.

4.Desorption of the products from the electrode surface.

5.Diffusion of the products away from the reaction zone from the reaction zone to the bulk
of electrolyte or gas phase.

Electrochemical Gas sensors for SOx and NOx

Electrochemical sensors are used to measure the concentration of gases like NO, SO2 and
NO2. In principle, any gaseous compound which can undergo redox reaction on the
surface of electrode can be measured with an electrochemical sensor. Design of the sensor
for each gas can be unique but the component (membranes, electrolytes, and electrodes)
and working principle is same as discussed in previous section.

But receptor coated on surface of sensing electrode (working electrode) is different for
each gas. Reaction that occurs on surface of the electrode is also different for each case.

Detection of NO2 is an amperometric gas sensor in aqueous electrolyte is based on the

following electrochemical reduction reaction on the surface of sensing electrode. Au,
Pf/Nafion sensing electrode with 10M H2SO4 is used as electrolyte.

NO2 + 2H+ + 2 e- → NO + H2O

Detection of NO in an amperometric gas sensor in aqueous electrolyte is based on the

following electrochemical oxidation reaction on the surface of sensing electrode.
Au/NASICON-NaNO2 is used as sensing electrode and electrolyte.

NO + 2 H2O → NO32- + 4H+ + 3 e-

Detection of SO2 in an amperometric gas sensor in aqueous electrolyte is based on the

following electrochemical oxidation reaction on the surface of sensing electrode.
Au/Nafion sensing electrode with 0.5M H2SO4 is used as electrolyte.

SO2 + 2 H2O → SO42- + 4H+ + 2 e-

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Disposable sensor
Disposable sensors are low-cost and easy-to-use sensing devices intended for short-term
or rapid single-point measurements.

In the analysis of samples from healthcare, food, industrial, and environmental fields,
portable sensors with the capability of on -the-spot analysis is required. Further, they
should be economical, easy to use, with small quantity of sample. Therefore, to meet these
requirements, several portable, disposable sensors have been developed. Portable
Glucometer used in monitoring of blood sugar level at home with disposable strips is an
example of such disposable biosensor.

Disposable strip of a biosensor is a special type of paper over which receptor and
electrodes are coated. They are coated in the form of thin film strip using screen printing
technology. In such systems, all the electrodes namely reference, working and counter
electrodes and a bio receptor are printed on a single platform as shown in Figure. These
electrodes are called as screen-printed electrodes and are main components of a
disposable biosensor. These strips can be inserted into the portable systems and used for
on-site sample analysis.

Disposable electrodes in the detection of biomolecules

Monitoring of levels of biomolecule like carbohydrates, proteins, lipids, nucleic acids,
enzymes, hormones, etc. is very essential to maintain a healthy body. Because, any
deficiency or excess of these molecule may result biological disorders such as Alzheimer’s
disease, Parkinson’s disease, diabetes, heart attack, pregnancy complications,
osteoporosis, etc resulting in decreased average life-span of the humans. Several types of
disposable biosensor have been developed for continuous monitoring of these bioanalytes.

Disposable, pre-activated screen-printing electrodes have been developed (Fig.1.5) for on

spot analysis of glucose, ascorbic acid, uric acid, creatinine, lactic acid and dopamine in
human blood samples.

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Fig. 1.5. Disposable screen-printed electrode.

Detection of Ascorbic acid
Chemical name of Vitamin-C, a water-soluble vitamin is Ascorbic acid. It is an antioxidant
essential for life and aids in protecting the body against oxidative stress. It is abundantly
available in fruits, and vegetables. Its content varies from source to source. Thus, the
electrochemical biosensor which can detect ascorbic acid in various samples in lower
concentration are developed. These sensors are fast, low-cost, and sensitive and use
disposable strips. These sensors can be used for on the spot analysis. In the disposable
strip, active materials of the sensing electrode, counter electrode and reference electrode
are printed on the disposable paper strip using Screen printing technology. Active
material coated on sensing electrode must be capable of oxidizing ascorbic acid on its
surface. Several active materials are available for ascorbic acid oxidation. The ascorbate
oxidase enzyme immobilized on a screen-printed carbon electrode with poly (ethylene
glycol) and diglycidyl ether as a crosslinking agent can be used as sensing(working)
electrode in ascorbic acid disposable biosensor. It oxidizes ascorbic acid in to
dehydroascorbic acid. Concentration of ascorbic acid is determined from the change in
potential of the oxidation process.

Oxidation reaction involved in the detection of AA.

Disposable electrodes in the detection of Pesticides

With the development of science and technology, to improve yield and protect crops,
farmers have started using several pesticides. These synthetic chemical pesticides are
supposed to be used in very low concentration of ppm/ppb level. But, due to lack of

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proper knowledge they are often used in large quantities without caution. This has
resulted in accumulation of pesticides in soil as well in agricultural produces. Pesticides
can induce a number of diseases such as asthma, diabetes, birth defects, reproductive
dysfunction, etc. Therefore, monitoring the level of pesticides in soil, water and cultivated
agro-products is one of the best ways to detect the abuse of pesticides.

Enzyme modified screen printed disposable paper strip electrodes are playing an
important role in the detection of pesticides. These electrodes are coated with enzymes.
Pesticides interact with the immobilized enzymes and leads to the formation of
electroactive species. This results in decreased enzyme activity which can be measured
quantitatively.
Detection of Glyphosate
Glyphosate [N-(phosphonomethyl)glycine] is an organophosphorus pesticide. It is
extensively used as herbicide in agriculture. Its residues are present in large amounts in
agricultural products and entering in to ecosystem in large quantity. Glyphosate is
classified as a potential carcinogen to humans. Therefore, there is a need to develop a
rapid, reliable, and sensitive approach for analysing glyphosate in environmental samples.

Various analytical methods based on electrochemical biosensor have been designed and
used for glyphosate determination. Glycine oxidase can catalyse the oxidative
deamination of various amines and cleave the C-N bond in glyphosate. The glycine
oxidase enzyme immobilized on a screen-printed carbon electrode can be used as
sensing(working) electrode in glyphosate disposable biosensor. It oxidizes glyphosate I to
amidomethylphosphonic acid (AMPA) and glyoxylate. Concentration of glyphosate is
determined from the change in potential of the oxidation process.

Reaction involved in the detection of Glyphosate.

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Energy Systems
Battery

John Bannister Goodenough (born July 25, 1922)

Is an American materials scientist, a solid-state physicist, and
a Nobel laureate in chemistry. He is a professor of mechanical
engineering and materials science at the University of Texas at
Austin. He is widely credited with the identification and
development of the lithium-ion battery, for developing
the Goodenough–Kanamori rules in determining the sign of the
magnetic super-exchange in materials, and for seminal
developments in computer random access memory.

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Battery is a collection of cells connected either in series or in parallel to get required

amount of energy.

Classification of Batteries
Primary

Secondary

Reserved.

Primary Batteries: These are the batteries which serve as a source of energy only as long as
the active chemical species are present in the battery or in the cell. The cell reactions are
irreversible. These are designed for only single discharge and cannot be charged again.

Ex: Dry Cell, Zn – HgO cell, Zn-Ag2O cell etc.,

Secondary Batteries: These batteries are chargeable and can be used again and again. The
cell reactions are reversible and are often called reversible batteries. During discharging
the cell acts like voltaic cell converting chemical energy into electrical energy. During
charging the cell acts like electrolytic cell by converting electric energy into chemical
energy, hence these batteries are called as storage battery.

Ex: Lead acid Battery, Ni-cd battery etc.

Reserved Batteries: The batteries which can be stored in an active state and made ready for
use by activating them prior to the applications (usage) are called as reserved batteries.
The key components of the batteries such as electrolyte etc., is separated from the battery.
And the battery is stored for a longer time. The electrolyte if filled before its usage. The
advantages of the reserved batteries are, Batteries can be stored for a longer period.

To prevent corrosion at contact points during storage.

Self-discharging reactions during storage can be eliminated or avoided.

They can be used whenever they are required.

Ex: Mg – water activated batteries, Zn-Ag2OBatteries etc.

Lithium ion Battery

The three primary functional components of a lithium-ion battery are the positive and
negative electrodes and electrolyte (Fig.1.6). Generally, the negative electrode of a
conventional lithium-ion cell is made from carbon. The positive electrode is a metal oxide,
and the electrolyte is a lithium salt in an organic solvent. The electrochemical roles of the

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electrodes reverse between anode and cathode, depending on the direction of current flow
through the cell.

The most commercially popular anode (negative electrode) is graphite. The positive
electrode is generally one of three materials: a layered oxide (such as lithium cobalt oxide),
a polyanion (such as lithium iron phosphate) or a spinel (such as lithium manganese
oxide). Recently, graphene-based electrodes (based on 2D and 3D structures of graphene)
have also been used as electrodes for lithium batteries.

The electrolyte is typically a mixture of organic carbonates such as ethylene

carbonate or diethyl carbonate containing complexes of lithium ions. These non-
aqueous electrolytes generally use non-coordinating anion salts such as lithium
hexafluorophosphate (LiPF6), lithium hexafluoro arsenate monohydrate (LiAsF6), lithium
perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), and lithium triflate (LiCF3SO3).

Fig.1.6. Schematic of Li-ion battery.

The anode half reaction is

The Cathode half-reaction is

Overall reaction

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Overcharge up to 5.2 V leads to the synthesis of cobalt (IV) oxide

Uses: Lithium-ion batteries are common in consumer electronics, with a high energy
density, no memory effect, and only a slow loss of charge when not in use.

LIBs are also growing in popularity for military, electric vehicle and aerospace
applications.

Mechanism involved in the working of Li-ion battery.

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Sodium ion Battery

Na-ion battery is a type of rechargeable battery. The three primary functional components
of a lithium-ion battery are the positive and negative electrodes and electrolyte (Fig.1.7).
Layered transition metal dioxides, NaMO2, where M = Fe, Ni, Mn, Co etc., exist in O3 and
P2 crystallographic versions. In the O3-NaMO2 phase, Na resides in octahedral sites, while
in the P2-phase Na is in prismatic sites. Generally, the negative electrode of a conventional
Sodium-ion cell is made from carbon. Most commercially popular negative electrode
(anode) is graphite. The electrolyte is a sodium salt in an organic solvent. Electrolyte is
typically a mixture of organic carbonates such as ethylene carbonate or diethyl.
carbonate containing complexes of sodium ions. These non-aqueous electrolytes generally
use non-coordinating anion salts such as sodium hexafluorophosphate (NaPF6), sodium
hexafluoro arsenate monohydrate (NaAsF6), sodium perchlorate (NaClO4), sodium
tetrafluoroborate (NaBF4) and sodium triflate (NaCF3SO3).

Fig.1.7. Schematic of Na-ion battery.

The anode half reaction

The Cathode half-reaction

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Overall reaction

Quantum Dot Sensitized Solar cells (QDSSC’s)

Construction
A QDSSC’s consists of three components:

a)Photo anode: Photoanode is the working electrode in the cell. It is a conducting glass,
over which a wide-band gap semiconductor like TiO2, Nb2O5, ZnO, SnO2 is coated with
thickness of 10 mm and a porosity of 50%-60%. Outer layer of photoanode is coated with
sensitizer, quantum dots (QD’s) in colloidal form.

b)Electrolyte: Photo anode is in contact with a redox electrolyte. It is a hole conductor.

Polysulphide redox couple S2-/ Sx2- which can effectively take up holes from QD’s is
used as an electrolyte.

c)Cathode electrode (CE): cathode electrode is used to regenerate electrolyte and complete
the circuit.

A QDSC is composed of a QD-sensitized photoanode, an electrolyte, and a counter

electrode.
Working
A QDSC is composed of a QD-sensitized photoanode, an electrolyte, and a counter
electrode.

Charge generation: Upon light irradiation, the QDs absorb solar energy and electrons in
the valence band (VB) of the QDs are excited to the conduction band (CB), generating
electron–hole pairs.

Charge separation: Then, electrons in the CB of the QDs are quickly injected into the CB of
a metal oxide (generally TiO2) electron acceptor under the driving force of the energetic
difference in the CB between the QDs and metal oxide.

Charge transportation: The electrons transfer through the TiO2 mesoporous film to the
transparent electrode and then to the counter electrode through an external circuit.

Regeneration: Meanwhile, the oxidized QDs are regenerated by reduced species of the
redox couple in the electrolyte, while the oxidized species of the redox couple are reduced
by the electrons from the external circuit under the catalysis of CE.

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Fig. 1.8. Schematic of QDSSC.

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Additional information
Electrochemical sensors for the Pharmaceuticals
Pharmaceuticals are basically organic compounds, which are used extensively by human
beings as a solution for various health issues. After usage they are excreted or washed off
their hosts and enter into the environment through effluents of waste water. Even though
use of pharmaceuticals for various health conditions are well understood and
documented, there is limited knowledge about their unintended effects in the
environment. Majority of these are complex organic molecules with lower bio-
degradability. Therefore, it is necessary to use sensors for the detection of pharmaceuticals
to monitor their concentration and know their toxic effects. Several electrochemical
sensors are available for the detection of pharmaceuticals in lower concentrations. These
sensors are fast, low-cost, and sensitive and use disposable strips. These sensors can be
used for on the spot analysis. One example is the electrochemical sensor used for detection
of Diclofenac.

Electrochemical sensor for detection of Diclofenac

Diclofenac with chemical name 2-(2—((2,6-dichiorophenyl) amino) phenyl) acetic acid, is
one of the most frequently prescribed non-steroidal anti-inflammatory drugs (NSAID)
with antipyretic and analgesic effects. It is safe in prescribed dose, but may cause adverse
effects at higher doses. Due to wide usage and poor biodegrability, it can have serious
effects on the ecosystem. Electrochemical sensor can be used to detect diclofenac in lower
concentrations.

Three electrode system, i.e. modified working electrode, counter electrode and reference
electrode is used. In the electrochemical sensor, the working electrode is glassy carbon
electrode coated with multi walled carbon nanotubes (MWCNT) and gold nanoparticles.
When the sample containing diclofenac is put in the sensor, the following oxidation
reaction of diclofenac occurs on the surface of the sensing electrode. The change in current
at about 0.8 V as a result of the reaction can be correlated with the concentration of
diclofenac (10.1016/j.msec.2015.09.097).

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Probable electrochemical reaction of Diclophenac on modified working electrode

Increase in current response of the sensor with increased concentration of the

Diclophenac. Inset shows the calibration graph of I (A) vs. Diclophenac concentration.

Electrochemical sensors for hydrocarbons

Among the dangerous hydrocarbons pollutants, polycyclic aromatic hydrocarbons
(PAHs) are widely found in the air, water, soil and food. PAHs are known carcinogenic
and mutagenic compounds. They can enter the human body mainly through respiration,
and diet. Detection of PAHs is essential to monitor their toxicity and carcinogenic risk.
After entering the body, some PAHs are metabolized into hydroxyl PAHs (OH-PAHs),
which are excreted with urine. 1-hyroxypyrene is a commonly found hydroxyl PAH in
urine sample. Therefor concentration of 1-hydroxypyrene is used as a biomarker to
evaluate PAH exposure levels in the human body, ITS concentration in urine,
quantitatively reflect the extent of recent exposure to PAHs. Conventional methods used
for estimation of 1-hydroxypyrene like HPLC-MS, GC-MS, and LC-MS/MS use large,
expensive, and difficult to operate instruments. It also requires more time for laborious
sample pre-treatment and analysis,

Therefore, electrochemical sensors are being developed for detection of 1-hydroxypyrene

in urine sample. These sensors are fast, low-cost, and sensitive and use disposable strips.
These sensors can be used for on the spot analysis.

In the electrochemical sensor used to detect 1-hydroxypyrene

(10.1021/acsomega.1c04765): The sensing (working electrode is graphite carbon coated
with chromium containing metal organic framework (Cr-MOF) and graphene oxide. This

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material has excellent chemical and hydrothermal stability, a large surface area, large pore
windows, and numerous unsaturated chromium sites, making it suitable sensing material
for electrochemical sensors. The 1-hydroxypyrene structure contains electrochemically
active hydroxyl groups, which can be oxidized by the anode active material. This is used
for electrochemical detection. In the detection, along with sensing electrode, counter
electrode and reference electrodes are used. When the sample containing 1-
hydroxypyrene is put in the sensor, the following oxidation reaction of 1-hydroxypyrene
occurs on the surface of the sensing electrode.

Probable mechanism for the electrochemical behaviour of 1-hydroxypyrene

Figure ... shows the typical electrochemical response (diffential pulse voltammograms,
DPVs) for the different 1-OHPyr concentrations. Reduction current response increases
with increasing concentration of 1-OHPyr. Inset of the Figure ... shows calibration graph
for the two linear ranges.

Figure ... DPVs of 1-OHPyr in a concentration range of 0.1–6.0 μM at electrochemical

sensor under optimum conditions. The inset is the linear calibration plots of peak currents
vs the concentrations of 1-OHPyr.

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BIOSENSOR
Introduction

Biosensors are devices that are used to detect and measure bioanalytes. They are used in
qualitative and quantitate analysis of biomolecules, biological structures, microorganism
etc. Number of biosensors are used in healthcare, food, industrial, and environmental
various fields for the detection of various bio analytes like glucose, cholesterol, ethanol,
creatinine etc, they are playing a crucial role in screening of diseases, monitoring of
human health, quality of food, water, and air.
Working of a Bio sensor
Main component of a biosensor is a receptor which can selectively interact with bioanalyte
and produce a signal corresponding to the interaction. Receptor contains immobilized
biomaterials like enzymes, antibodies, nucleic acids, hormones, organelles on its surface.
Signal produced is detected and transformed to appropriate physical, chemical or
electrical signal form by a transducer.

Biosensors provide excellent sensitivity and selectivity, continuous reliability and

portability. Therefore, they are identified as superior analytical tools. The desired
biomolecules such as enzyme, antibodies etc. are immobilized via
physisorption/chemisorption, which will cause an intimate contact with the transducer.
The analyte of interest will selectively bind with the biomaterial that produces the
measurable electronic response.

Glucose Sensors
The glucose sensor is one of the most widely used biosensor for monitoring blood sugar
levels in diabetic patients. Blood glucose sensors account for 85% of the current world
market for biosensor and are the most widely studied and commercialized of all
biosensors. In this sensor, Glucose oxidase (GOx) is immobilized on the electrode to
measure the glucose level in blood. A disposable single-use glucose sensor this can be
used effectively, with a high degree of reliability and fast response measurement, is very
desirable. These needs, however, require the biosensor to be highly uniform and
reproducible, and still be manufactured at a modest cost.

Blood glucose monitoring is achieved in several ways. The traditional method of testing
the blood glucose involves pricking the finger with a lancet (a small, sharp needle),
putting a drop of blood on a test strip and then placing the strip into a meter that displays

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the blood glucose level. Meters vary in features, readability, portability, speed, size and
cost. Some of the most recent developed meters allow the patient to test sites other than
the fingerstrio, including sites such as the upper arm, forearm, base of the thumb and
thigh.

Working principle of a Glucose sensor

Even though, many methods of transductions are available for a glucose biosensor,
because of the sensitivity, reproducibility and inexpensive manufacture, electrochemical
method is the most widely used method. The most commonly employed electrochemical
method is amperometry, which relies on the application of a fixed potential between two
electrodes and the measurement of the resultant current flow.

Clark oxygen electrode is the amperometric cell used in glucose biosensor. It is a three
electrode cell, composed of a reference electrode, typically Ag/AgCl electrode, a working
electrode, which is usually made of a noble metal or carbon and a counter or auxiliary
electrode. Pt working electrode is immobilized with Glucose oxidase (GOx) .

GOx is a FAD (flavin adenine dinucleotide) enzyme, which very specifically oxidises β-D-
glucose. It oxidizes glucose to Glucolactone and accepts electrons and gets reduced.

Glucose + GOx (FAD) → Glucolactone + GOx (FADH2)

Reduced, deactivated enzyme consumes oxygen from the electrolyte, transfers electrons to
it and reduces it to hydrogen peroxide. Thus, the amount of oxygen consumed is
proportional to concentration of glucose. The concentration of glucose can be measured
from decrease in oxygen concentration.

GOx (FADH2) + O2 → GOx (FAD) + H2O2

Glucose concentration can also be measured from the amount of hydrogen peroxide
formed. Hydrogen peroxide is oxidized amperometrically at fixed voltage of 0.7V and
current generated is measured. Measured current is proportional to concentration of
glucose.

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Images sources:
The images in this material are taken form google images, authors of the images are
acknowledged

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