1.

INTRODUCTION
In recent years, serious environmental deterioration and rapid energy depletion have
changed modern society. With the rising demand and development of next-generation clean
and sustainable energy sources, it is paramount to exploit efficient energy storage and
conversion devices to make renewable energy as alternative to traditional fossil fuels. CO 2
emissions and the existing nature of fossil fuels have led to a rise in global warming and this
keeps us on developing technologies for clean energy production. Past decades have
experienced severe energy depletion and environmental pollution [1][2].

It is urged to develop environmentally friendly energy devices, such as metal-air batteries,

water electrolysis fuel cells, and so on. The consumption of excessive fossil energy and its
derived issue have aroused concerns worldwide and this leads us to make efforts to seek
applications of renewable and sustainable energies. The unrestricted consumption of traditional
fossil fuels not only aggravates the global energy crisis but also causes significant damage to
the natural ecological environment. Therefore, it is extremely urgent to push forward extensive
research into renewable clean energy sources, such as solar energy, wind energy, H 2 energy,
and so on, as alternatives for non-renewable fossil fuels[3].

To tackle the issues above, various measures have been applied to reduce the overpotential
and accelerate the reaction rate. Even though, designing a feasible route for synthesizing
electrocatalysts with excellent performance has become a research hotspot. Electrolytic water
splitting is a promising technique for the production of pure hydrogen and oxygen with zero
pollution. OER and HER, high-performing metal-based catalysts, are of supreme importance
for renewable energy technologies like batteries, fuel cells, and electrochemical water splitting.
HER and OER processes always require high overpotentials due to low reaction kinetics. Thus,
it is imperative to develop catalysts with high electrocatalytic activity[4].

By means of electrochemistry, the development of earth-abundant inexpensive

electrocatalysts is central to the generation of H 2 and O2. The breaking of H2O into its
constituent elements at two different compartments by electrochemical means with O 2
evolution reaction takes place at the anode (OER) and H2 liberation takes place at the cathode
(HER), where they involve two and four electron transfer processes. Diverse nonprecious HER
and OER catalysts derived from transition metal oxides or hydroxides, metal sulphides,
selenides, and carbides have shown to exhibit promising HER activity in acidic electrolytes.
Despite of these developments, it is highly desirable to perform both HER as well as OER

1
catalysis in alkaline electrolytes using a single electrocatalyst to accomplish the overall water
splitting [5].

Theoretically, under the thermodynamic potential of 1.23 V (ΔG = 237.2 kJ), one molecule
of H2O can be split into one molecule of H2 and one-half molecule of O2 completely.
Nevertheless, a larger overpotential (1.8–2.2 V) is needed to finish the strongly uphill reaction
for commercial electrolyzers at room temperature. The difference in driving force can be
attributed to the existence of intrinsic activation barriers on both anode (ηa) and cathode (ηc) in
the water electrolysis cell. Specifically, compared to the hydrogen evolution reaction (HER),
the oxygen evolution reaction (OER) is critical to efficient water splitting. To date, noble
metal–based electrocatalysts, such as Pt- and Ir/Ru-based oxides, exhibit the most efficient
activities for HER and OER, respectively. However, the scarcity of noble metals limits their
widespread application[6].

Recently as an economical and efficient replacement to these expensive metal precursors,

nickel–based electrocatalysts in the shape of nickel foam (NF), alloys, nitrides, phosphides,
oxides, metal-organic frameworks (MOFs), etc. have exhibited very promising electrocatalytic
activity and stability toward ORR, OER, and HER, as monofunctional or bifunctional
materials. The high synergistic effect between Ni and neighbouring hetero-atoms results in
much better surface adsorption properties which can be attributed to the enhancement in the
electrocatalytic properties of resulting materials. Due to low price, high elemental abundance,
strong strength, better ductility, high corrosion resistance, good heat conduction, and high
electrical conductivity, Ni–based materials have been widely studied for their electrochemical
applications[7][8].

2
CHAPTER-II
MECHANISM OF ELECTROCHEMICAL WATER SPLITTING REACTIONS
2. MECHANISM

Owing to the sluggish kinetics of alkaline water reduction and oxidation, it is crucial to
understand the mechanism of the hydrogen evolution reaction/oxygen evolution reaction
(HER/OER) and construct efficient electrocatalysts based on the structure–activity
relationship.

2.1 Mechanism of Hydrogen Evolution Reaction (HER)

In the HER process, the reduction of a proton or water molecule occurs to generate
molecular hydrogen in acidic and alkaline media, respectively, by applying minimum
external potential. Three main steps are involved in HER mechanistic path;

(a) electrochemical hydrogen adsorption (Volmer reaction),

(b) electrochemical desorption (Heyrovsky reaction),
(c) chemical desorption (Tafel reaction).
2.1.1 Volmer reaction:

H3O + + M + e − → M − H ∗ + H2O………………… (1) (in acidic media)

−
H2O + M + e → M − H ∗ + OH−…………………….(2) (in basic
media)
In the first step, protons combine with electrons to generate adsorbed hydrogen
atoms (H*) on the electrode material surface (M). The proton sources for the HER process
are the hydronium cation (H3O+) and the water molecule in acidic and alkaline electrolytes,
respectively. Then molecular hydrogen is produced either by Heyrovsky or Tafel reaction or
both. In the Heyrovsky step, another proton combines with the adsorbed species (H*) and
then reacts with a second electron to produce H2.
2.1.2 Heyrovsky reaction:

H + + e − + M − H ∗ → H2 + M ………………………… (3) (in acidic

media) H2O + e − + M − H ∗ → H2 + OH− + M…………………. (4) (in basic
media)
In the Tafel step, two adsorbed species come closer to combine on the surface of the
electrode to evolve H2
2.1.3 Tafel reaction:

2M − H∗ → H2 + 2M …………………. (5) (Both media)

3
 Scheme 1 Schematic pathways for hydrogen evolution reaction under acidic and
alkaline conditions [ [9] B. Wang et al,.]
The overall mechanical path in acidic and alkaline media in different pH is given in
Scheme 1. The slopes representing the intrinsic nature of the catalyst are derived from the
polarization curves by plotting the log of reduction current density against the overpotential
(called the Tafel plot). It has been considered that for the Tafel, Heyrovsky, and Volmer rate-
determining step, the slopes are ~29 mV/dec, ~39, and ~118 mV/dec respectively. The
Heyrovsky and Volmer step is considered the rate-determining step in the case of the acid
medium and the alkaline medium, respectively [9].

2.2 Mechanism of Oxygen Evolution Reaction (OER)

Oxygen evolution reaction (OER) is another key reaction for the overall electricity-driven
water splitting to produce hydrogen. OER is a complex multistep reaction involving the O-H
bond breaking and the O-O bond formation.

Oxygen evolution reaction (OER) is a four-electron transfer process with a very slow
reaction rate that severely limits oxygen production, thus, the reaction process of OER is
relatively complicated. Three different intermediates are involved in the reaction process.
Therefore, O2 can be produced in two different ways in acidic or alkaline solutions. At present,
the generally recognized reaction mechanisms of OER can be illustrated as follows

4
In acidic electrode:

* + H2O  *OH + H+ + e- ................................................................ (6)

*OH-  *O + H+ + e-..................................................................... (7)

*O + H2O  *OOH + H+ + e-................................................................ (8)

*OOH  * + O2 + H+ + e ........................................... (9)

in which * represents the active sites of catalysts, and O*, OH*, OOH* denote adsorbed
intermediates. Similarly, the reaction pathways can be shown as the following elementary steps
in basic electrode.

In basic electrode:

* + OH-  *OH + e- ....................................................................... (10)

*OH  *O + H2O + e ......................................... (11)

*O + OH-  *OOH + e- ...................................................................... (12)

*OOH + OH- * + O2 + H2O + e ......................................... (13)

OER is often the rate-limiting step because of the sluggish kinetics associated with the O–
H bond breaking and the consequent O-O bond formation, as well as the 4-electron–proton-
coupled process. The development of active and stable OER electrocatalysts is, therefore,
imperative to improve the overall water splitting performance. Various strategies have been
devised toward the design of efficient OER materials from the aspects of binding energy
modulation, electronic structure optimization, and surface engineering. In addition, the lattice
oxygen mechanism has also been proposed and observed on several metal oxides, which further
lowered the overpotential for oxygen evolution [10].

5
Scheme 2 Schematic illustration of oxygen evolution reaction (OER) in alkaline (red
route inside the circle) and acidic (blue route outside the circle) conditions, [[10] .N.
Yuan et al,.]

Figure 1 Schematic-diagram of an electrochemical-water-splitting-system

6
CHAPTER- III
3. Standard parameters for the catalytic evolution process
1. Overpotential
2. Tafel slope
3. Electrochemically active surface area
4. Nyquist plot
5. Cyclic stability

3.1 Overpotential
In electrochemical water splitting, either hydrogen or oxygen evolution is
thermodynamically not feasible in the standard condition of temperature and pressure. So,
this process needs some extra energy. According to the Nernst equation, 1.23 V (vs.
SHE) water oxidation and 0 V (Vs SHE) require for water reduction, respectively.
In HER process H + (aq) + 2e- → H2 (g), E0 (HER): = 0.00 V

In OER process 2H2O (l) → 4 H+ (aq) + O2 (g) + 4e-, E0 (OER): = 1.23 V

However, this does not happen as these calculations are theory-based. The
sluggish reaction kinetics of these reactions require additional energy to overcome the
activation barrier. Therefore, overpotential is the difference of potential between
experimentally observed and thermodynamic one of a particular electrochemical
reaction. Strictly speaking, materials with a higher value of overpotential lower will be
its activity and vice-versa. This overpotential depends on parameters like reaction
activation, series resistance, and diffusion of charge carriers. A suitable catalyst with
proper loading can activate the reaction properly by reducing overpotential.

Figure 2 Schematic LSV diagram of finding onset potential and

overpotential [ [13] C. D, Gu et al,.]

7
 In earlier years η was measured at defined current or potential required to 15
produce some of the current density or onset potential. In recent years, so far 10 mA cm-
2 has been used as a benchmark, which is minimal for the production of synthetic fuel,
with a solar-to-fuel conversion efficiency of 12.5%.
3.2 Tafel slope
To evaluate the intrinsic activity of the electrocatalyst, the Tafel slope is an essential
parameter. It entails the reaction kinetics of the catalytic process. It shows the relation
between overpotential and current density (both are iR corrected) as follows-

𝑑𝑙𝑜𝑔(𝑗) / 𝑑ƞ = 2.303𝑅𝑇/ 𝛼𝑛F ..........................................(14)

The equation shows that the Tafel slope is inversely proportional to the diffusion
coefficient. It becomes a common parameter to evaluate electrocatalysts. Simply plotting
the log of current density and overpotential Tafel plot can be obtained. After that, fitting
the linear portion, the Tafel slope can be obtained by using the following equation

ƞ = 𝑎 + 𝑏 log j.......................................... (15)

Where ƞ is the overpotential, a and b are the Tafel constants, Tafel slope, and j is the
obtained current density.

3.3 Electrochemically active surface area (ECSA)

The actual surface area of the catalyst can be evaluated either by the in-situ or ex-situ
method. In the in-situ method, the surface area can be obtained by BET gas adsorption,
and the particle size can be determined by scanning electron microscopy. However, the
percentage of accuracy is found to be less than the average surface area obtained from
these methods. Secondly, all the surfaces need not be electrochemically active, so a better
method should be chosen. The ECSA value can be obtained by evaluating the double-
layer capacitance (Cdl) from the non-faradic region of a static cyclic voltammetry (CV)
curve. Non-faradic region means a portion where neither oxidation nor reduction occurs.
The current getting from the CV curve is directly proportional to the scan rate and
double-layer capacitance (Cdl) from the equation as follows

𝑖 = 𝜐𝐶𝑑𝑙…………………………………… (16)
Moreover, ECSA can be calculated by dividing double-layer capacitance and specific
capacitance given in the equation as follows-

𝐸𝐶𝑆𝐴 = 𝐶𝑑𝑙 𝐶𝑠………………………………… (17)

Cs, the specific capacitance, depends upon the nature of the electrolyte and varies from
20-60 µF. If ECSA is divided further with the geometrical surface area of electrode
roughness factor (Rf) can be obtained. The equation is given as follows-

8
 𝑅𝑓 = 𝐸𝐶𝑆𝐴 𝑆𝑔𝑒𝑜 ……………………………………(18)
ECSA also has been predicted from the non-faradic potential region of electrochemical
impedance spectroscopy.

3.4 Cyclic stability

An electrocatalyst's practical application and commercialization always depend upon
its stability or durability. Frankly, the catalytic performance is measured by long cyclic
stability. The long-cycle stability is measured by mostly chronopotentiometry (CP) and
chronoamperometry (CA). Chronopotentiometry is the measurement of the variation of
current density over a period of time at a particular overpotential, whereas
chronoamperometry is the measurement of the change of overpotential over a time
period at constant current density. It can also be evaluated by performing continuous CV
in a potential window. The recorded LSV 20 polarisation curve after and before stability
also tells the change in overpotential. Moreover, a further shift in diffraction angle, change
in surface morphology, and change in oxidation state also reveal the post-stability results.

3.5 Electrochemical Impedance Spectroscopy (EIS)

During water splitting, solution resistance (Rs), charge transfer resistance (RCT), and
mass transfer activity are observed. To investigate these terms, electrochemical
impedance spectroscopy or Nyquist plot is necessary. In the desired electrolyte, the
imaginary axis (Z") Vs real axis (Z') is known as the Nyquist plot. Applying a particular
potential due to charge transfer between the electrode surface and electrolyte generates
response conduct from lower to higher. A lower charge transfer resistance refers to higher
conductivity of electrode material and vice versa. Therefore, the electrocatalyst showing
better water splitting has low charge transfer resistance. Randles circuit observed from
Nyquist plot from which Rs, Rct is clearly calculated [11].

Figure 3 Schematic diagram of Nyquist plot [[11] D. Li et al,.]

9
 CHAPTER-IV

4. Strategy for using MOF as electrocatalysts

The benchmark noble metal-based OER/HER catalysts of IrO2, RuO2, and Pt/C are
rare in abundance, high cost, and instability under the long-term reaction conditions
limiting the large-scale commercialization of the water splitting process. Significant
efforts are underway to develop efficient, earth-abundant materials for the production of
clean energy at cost-effectiveness. Transition metal-based MOF are used as
electrocatalysts.

The desirable feature of MOF electrocatalysts includes:

1) Lower η with high specific and selective catalytic activity towards OER/HER.

2) Longer and more stable performance under different reaction conditions.

3) Desirable substrate compatibility.

4) Ease of synthesis and their commercialization.

MOFs represent an intriguing class of porous materials formed through the coordination of

metal ions or clusters with organic ligands[12]. These materials display exceptional structural

versatility and high surface areas, rendering them suitable for various applications, including

gas storage, catalysis, and sensing[13].

MOFs boast highly ordered and customizable porous structures. The capacity to engineer and

produce MOFs with specific functional groups allows for their targeted use, particularly in

electrochemical sensing applications where selectivity and sensitivity are crucial.

The term MOF was introduced to describe materials that consist of metal centers linked

together by organic ligands to form two- or three-dimensional networks(Figure 4). In these

structures, the metal centers serve as nodes, while

the organic molecules act as bridges connecting these nodes[14]. The ability to

tailor both the metal ions and the organic linkers allows for the creation of materials with

specific pore sizes, shapes, and functionalities[15]. By modifying the metal ion or cluster

and the organic linker, researchers can engineer MOFs with targeted chemical and physical
10
properties suitable for specific applications, such as detecting food additives or contaminants.

One of the key attributes of MOFs is their controllable porosity, making them suitable for

gas storage, contaminant filtration, and immobilization of target molecules for sensing

applications[16]. Additionally, their ability to integrate functional groups into the pores

enables MOFs to exhibit selective behavior in molecule adsorption. The combination of high

porosity, large surface area, and customizable chemical environment makes MOFs well-suited

for applications requiring high sensitivity and selectivity, such as electrochemical

sensing[17].

Figure 4 Schematic representation of the Formation of MOFs

4.1 History and Development of MOFs

The history and development of MOFs extend back to the late 1990s, marking a

significant advancement in materials science. Early leaders in the field, including Omar

Yaghi and others, focused on creating frameworks that were not only porous but also stable

for practical applications[18]. Since then, the field of MOFs has experienced rapid growth,

with thousands of different structures synthesized for diverse applications(Figure 5).

Initially developed for gas storage, MOFs have now found expanded utility in various

other areas. Their high surface area allows for the adsorption of substantial gas volumes

such as hydrogen and methane, making them promising candidates for energy storage

technologies[19]. In catalysis, MOFs have been employed as heterogeneous catalysts. The

metal centers within MOFs can serve as catalytic sites, while the porous structure permits
11
the diffusion of reactants and products. This makes MOFs particularly valuable for reactions

requiring high surface area and selectivity[20].

Figure 5 History and Development of MOFs[35]

In recent years, MOFs have emerged as a significant material in the field of

electrochemical sensing, particularly for detecting antioxidants and dyes in food samples[35].

The large surface area and customizable pore structures of MOFs make them ideal for

creating sensitive and selective sensors.

4.2 Importance of MOFs in Modern Chemistry

Due to their structural flexibility and high surface area, MOFs have emerged as one of

the most significant materials for various advanced technologies. They are also considered

environmentally friendly materials, as their synthesis often avoids the use of toxic

solvents and harsh conditions. In the field of electrochemical sensing, MOFs have become

an indispensable tool for detecting various food toxins including antioxidants and dyes in

food samples at low concentrations.

4.3 The Structure of MOFs

MOFs consist of two primary components: the metal ion or metal cluster and the

organic ligand. The metal serves as a node, while the organic ligand acts as a

12
linker, establishing a three-dimensional network. The interactions between the metal nodes

and organic linkers determine the overall stability and porosity of the structure[36]. This

adjustability makes MOFs highly customizable for distinct purposes, including

electrochemical detection and catalysis.

4.4 Chemical and Physical Properties

MOFs possess several distinctive properties that make them valuable across a wide

range of fields.

High Porosity: The most remarkable characteristic of MOFs is their extensive internal

surface area. Certain MOFs have surface areas as substantial as 10,000 m²/g, enabling them

to adsorb significant quantities of molecules.

Adjustable Pore Sizes: The pore size in MOFs can be manipulated by varying the

metal-ligand combinations. This enables Scientists to tailor MOFs for specific

applications, such as adsorbing particular gases or detecting specific chemicals.

Thermal and Chemical Stability: Depending on the metal utilized, many MOFs

exhibit high thermal stability and can endure temperatures of several

hundred degrees Celsius. However, chemical stability may vary based on the ligands and

the operating environment. While many MOFs remain stable in organic solvents, some

may degrade in the presence of water.

Structural Flexibility: Unlike conventional porous materials like zeolites or silica,

MOFs can display structural flexibility. This means that they can undergo

reversible structural changes in response to external stimuli such as pressure, temperature, or

the presence of guest molecules.

13
 Fig. 6 Properties of MOFs

4.5 Types of MOF

MOFs can be categorized into various types based on their structure, flexibility, and

the types of metal ions and ligands used. Understanding these distinctions is crucial for

tailoring MOFs to specific applications, such as detecting antioxidants and dyes in food

samples.

4.5.1 Porous MOFs

Porous MOFs are the most prevalent type of metal-organic frameworks. They are

distinguished by their exceptionally large internal surface areas, making them

14
suitable for gas storage and molecule adsorption[21]. Porous MOFs are synthesized by

selecting metal ions and organic linkers that form rigid, open structures with cavities or

channels large enough to capture guest molecules.

Porous MOFs are primarily utilized in gas storage, separation technologies, and

chemical sensing[22]. Their high porosity enables them to entrap molecules within their

framework, which can then be detected electrochemically. This makes them particularly

valuable in the detection of small molecules such as antioxidants in food samples.

Furthermore, the adjustability of porous MOFs allows for selective adsorption,

meaning that certain MOFs can be designed to preferentially adsorb specific molecules over

others. For instance, specific MOFs have been engineered for the selective adsorption of

carbon dioxide in gas separation processes.

4.5.2 Flexible MOFs

Flexible MOFs, also referred to as "breathing" MOFs, have structures that can dynamically

change in response to external stimuli like temperature, pressure, or the presence of guest

molecules[23]. This flexibility enables these MOFs to adapt to varying environmental

conditions, making them suitable for applications requiring dynamic sensing.

Flexible MOFs are particularly valuable in sensing applications due to their ability to alter
their structure, which can enhance detection sensitivity [24]. For instance, in electrochemical
sensors, flexible MOFs can change their conformation upon contact with the target
molecule, resulting in a detectable signal change. This property i s highly advantageous
for detecting low concentrations o f antioxidants or dyes in food samples, where the
dynamic nature of the MOF can amplify its sensitivity.
4.5.3 Rigid MOFs

In contrast to flexible MOFs, rigid MOFs maintain a fixed structure regardless of

external conditions. This rigidity is crucial for applications requiring long-term structural

integrity, such as in industrial processes or long-term storage applications[25].

15
 Rigid MOFs are frequently utilized in applications where stability is more critical than

flexibility. They are commonly employed in gas storage and separation technologies,

where they can adsorb and release gases without significant structural changes[26]. In

electrochemical sensing, rigid MOFs are used when a stable, predictable response is

necessary, such as in the repeated detection of specific molecules in complex environments

like food samples.

4.5.4 3D MOFs

Three-dimensional MOFs (3D MOFs) are a type of MOFs with extensive spatial

networks. These MOFs are highly stable and exhibit remarkable structural integrity[27]. Their

3D structure increases their surface area, making them beneficial for applications requiring

significant molecule capture or adsorption capabilities.

Due to their enhanced surface areas, 3D MOFs are particularly useful in catalysis and

gas separation. In electrochemical sensing, 3D MOFs offer the advantage of a large surface

for interaction with target molecules, which can lead to enhanced sensitivity[28]. These

materials are therefore highly sought after in the detection of dyes and antioxidants in

food samples.

4.5.5 2D and 1D MOFs

In addition to 3D MOFs, there are also two-dimensional (2D) and one- dimensional (1D)

MOFs. These MOFs are characterized by their lower dimensionality, which often leads to

different electronic and chemical properties compared to their 3D counterparts[29].

2D MOFs have been studied for their use in energy storage devices such as batteries and

supercapacitors. Their layered structures allow for better ion diffusion, which is beneficial in

electrochemical applications[30]. 1D MOFs, while less common, are being explored for their

potential in catalysis and molecular sensing due to their linear arrangements of metal and

organic components[31].
16
4.6 Synthesis of MOF

The synthesis of MOFs is a crucial process that significantly impacts the properties of

the final material. Various methods are employed to create MOFs, each offering different

degrees of control over the structure, size, and morphology of the material. The selection

of a method for the synthesis depends on the intended application, as each method can

affect the crystallinity, porosity, and functionalization of the MOF. The key methods used

for MOF synthesis are as follows:

4.6.1 Microwave Synthesis

The microwave-assisted method is a rapid technique used to synthesize MOFs. In this

method, microwave radiation is applied to the reaction mixture to provide the energy

necessary for the reaction to occur[32]. This approach is known for its ability to produce

MOFs with high crystallinity in a short period of time. Microwave radiation rapidly heats the

reaction mixture, allowing for faster crystallization and shorter duration of time for the

synthesis. The uniform heating provided by microwave radiation ensures that the reaction

occurs evenly throughout the mixture, leading to highly crystalline MOFs with well-defined

shapes. Due to their high crystallinity, MOFs synthesized using microwave- assisted

methods are often used in applications requiring high performance, such as in

electrochemical sensors[33]. The enhanced crystallinity improves the conductivity and

sensitivity of the material, making it ideal for detecting trace amounts of contaminants in food

samples.

Wang [Link], used the microwave-assisted method to synthesize a Cu-MOF in just 15

minutes, achieving high crystallinity as shown in Figure 7. The uniform heating provided by

microwave radiation resulted in well-defined crystalline

structures[34].

17
 Fig. 7 Microwave Synthesis of Cu-MOF[50]

Mahmoud [Link], reported the rapid synthesis of a Zr-MOF using the microwave

method. The reaction was completed in 7 minutes, and the resulting Zr-MOF exhibited

excellent crystallinity[35].

Taylor [Link], synthesized a Mn-MOF using microwave radiation, which shortened the

reaction time to 10 minutes. The Mn-MOF displayed high crystallinity and uniform

morphology[36].

Jhung [Link], utilized microwave-assisted synthesis to fabricate a Cr-MOF. The synthesis

took only 40 minutes, and the Cr-MOF displayed well-ordered crystalline structures[37].

4.6.2 Solvothermal Synthesis

Solvothermal synthesis is a commonly used method in which the reaction takes place

in a sealed vessel at elevated temperatures and pressures[38]. Organic solvents such as

dimethylformamide (DMF) or ethanol are employed to dissolve the metal precursors and

organic linkers, facilitating the formation of crystalline MOF structures. This method

allows for the control of particle size and shape, making it ideal for producing MOFs with

specific properties for applications such as sensing and catalysis[39].

Manaswini [Link], synthesized a Ni-MOF using the solvothermal method, where DMF

18
was used as the solvent. The reaction resulted in highly crystalline structures with uniform

morphology as depicted in Figure. 8 [40].

Fig. 8 Solvothermal Synthesis of Ni-MOF[56]

Su [Link], utilized the solvothermal approach to synthesize a Zr-MOF. The reaction was

carried out in a DMF solvent at 120°C for 24 hours, resulting in well- defined polyhedral

crystals[41].

Prettencia [Link], studied the synthesis of a Mn-MOF using a solvothermal method. The

Mn-MOF was synthesized in ethanol at 180°C for 12 hours, and the resulting material

displayed high crystallinity with controlled particle size[42].

Wang [Link], synthesized a In-MOF composite via solvothermal synthesis at 100°C for

3 days using DMF as the solvent. The reaction produced highly crystalline In-MOF

particles with uniform size[43].

4.6.3 Hydrothermal Synthesis

Hydrothermal synthesis is similar to solvothermal synthesis, but it specifically involves

water as the solvent. This method is particularly useful for creating MOFs with unique

structural properties, as water can interact with the metal ions and organic linkers in a way

that other solvents cannot[44]. The reaction takes place at high temperatures and

19
pressures, typically inside an autoclave or pressure vessel. Water is a non-toxic,

environmentally friendly solvent, making hydrothermal synthesis a greener alternative

compared to other methods that use organic solvents like DMF or ethanol. Similar to

solvothermal synthesis, hydrothermal methods enable precise control over the size and shape

of the MOF crystals. Hydrothermal synthesis is highly versatile, allowing for the synthesis

of a wide range of MOFs with different metal ions and linkers. Hydrothermal MOFs are

widely utilized in environmental applications due to the eco-friendly nature of the

synthesis process. They are also employed in catalysis, gas storage, and electrochemical

sensing. In food safety, hydrothermal MOFs have shown promise for detecting contaminants

such as antioxidants and synthetic dyes, particularly because the water-based synthesis results

in highly stable materials that perform well in aqueous environments[45].

Yao [Link], utilized hydrothermal synthesis to produce a Zn-MOF in water at 100°C for

5 days. The resulting MOF showed excellent crystallinity and square pyramidal

morphology[46].

Fu [Link], synthesized a Sn-MOF using the hydrothermal method at 180°C in a sealed

autoclave for 24 hours. The Sn-MOF exhibited a well-defined crystal structure and high

stability was depicted in Figure 9[47].

20
 Fig. 9 Hydrothermal Synthesis of Sn-MOF[63]

Li [Link], reported the hydrothermal synthesis of a Co-MOF using water at 125°C for 12

hours. The resulting Co-MOF particles displayed uniform size distribution and high

crystallinity[48].

Deore [Link], used hydrothermal synthesis to fabricate a Fe-MOF at 110°C for 24 hours.

The Fe-MOF exhibited high crystallinity and well-defined morphology, with water

playing a crucial role in controlling the particle shape[49].

4.6.4 Co-precipitation Method

The co-precipitation method is a straightforward technique for synthesizing MOFs. It

involves combining a metal salt solution with an organic linker solution at room

temperature or under mild heating conditions[50]. As the metal ions and ligands react, the

MOF material precipitates out of the solution, forming the desired framework. This method

is relatively inexpensive and uncomplicated compared to other methods, making it well-suited

for large-scale production. The method can often be performed at room temperature,

simplifying the experimental setup and reducing energy consumption. MOF formation

via co-

precipitation is typically fast, with reaction times ranging from minutes to hours,

21
depending on the reactants used. MOFs synthesized using the co-precipitation method are

commonly used in applications requiring large quantities of material, such as gas storage or

water treatment. Moreover, co-precipitated MOFs can still be effective for electrochemical

sensing applications, particularly when high surface area is more important than

crystallinity[51].

Negash [Link], synthesized a Zn-MOF using the co-precipitation method at room

temperature for 24 hours. The process resulted in fast precipitation, yielding a Zn-MOF

with moderate crystallinity but high surface area[52].

Li [Link], employed co-precipitation to produce a Cu-MOF in ethanol. Although the Cu-

MOF exhibited relatively low crystallinity, the low energy consumption during synthesis

was a notable advantage[53].

Ferey [Link], synthesized a Cr-MOF using co-precipitation, combining chromium nitrate

with benzene dicarboxylic acid at room temperature for 8 hours. The Cr-MOF precipitated

quickly, forming a material with moderate crystallinity and good electrochemical

properties[54].

Snowlin [Link], utilized the co-precipitation method to synthesize a Zn-MOF at room

temperature(Figure 10), yielding a material with low crystallinity but sufficient surface

area for catalysis and sensing applications[55].

22
 Fig. 10 Co-precipitation Synthesis of Zn-MOF[55]

4.6.5 Sonication Method

Sonication, which involves the use of ultrasound waves to agitate particles in a

solution, is a popular technique for synthesizing MOFs[56]. In this method, ultrasonic waves

are applied to the reaction mixture containing metal ions and organic ligands, leading to faster

reaction rates and more uniform particle distribution. The sonication method offers several

advantages, including faster reaction times and better control over the size and morphology

of the MOF crystals. The energy provided by the ultrasonic waves breaks down the solution

into smaller particles, increasing the surface area for reaction and promoting more uniform

crystal growth[57]. MOFs synthesized via sonication often have smaller, more uniform

crystals, making them ideal for applications that require precise control over material

properties, such as electrochemical sensing. In particular, sonicated MOFs have shown

improved performance in detecting food contaminants like antioxidants and dyes due to their

enhanced surface areas and uniformity.

23
 Yang [Link], synthesized a Mg-MOF using the sonication method, where ultrasonic

waves were applied to a magnesium nitrate and 2,5-dihydroxybenzene 1-carboxylic acid

solution. The sonication process reduced reaction time significantly, producing small,

uniform spherical crystals[58].

Li [Link], used sonication to prepare a Cu-MOF, resulting in rapid crystal formation and

uniform distribution. The smaller, more uniform crystals contributed to better sensor

sensitivity[59].

Razavi [Link], employed sonication to fabricate a Zn-MOF, which exhibited better

electrochemical performance than MOFs synthesized using conventional methods. The faster

reaction time also contributed to the efficiency of the synthesis[60].

Eliwa [Link], synthesized a Pb-MOF using the sonication method as shown in Figure 11.

The ultrasonic waves led to uniform particle distribution, improving the material's

electrochemical properties[61].

Fig. 11 Sono-chemical Synthesis of Pb-MOF[61]

24
CHAPTER-V
5. Metal Organic Framework (MOF) based catalysts for Electrochemical water
splitting reactions

Tao et al. reported MOF-derived FeNi alloy embedded in N-doped carbon as an

efficient bifunctional electrocatalyst for water splitting. The catalyst exhibited excellent
HER activity with a low overpotential of ~77 mV and OER activity at ~300 mV to reach 10
mA cm⁻². The enhanced performance was attributed to synergistic metal interactions and
high conductivity [62].

Fig 12. Schematic illustration of synthesizing carbon-coated metal nanoparticles

derived from metal–organic frameworks for catalyzing HER and OER.

Singh et al. developed a MOF-derived Fe–Co oxide/Co@NC heterostructure that

showed enhanced HER and OER activity in alkaline media. The catalyst demonstrated
improved charge transfer kinetics and long-term stability. The superior activity was due to
defect-rich active sites and Fe–Co synergistic effects [63].

Wang et al. developed Ni-MOF-based electrodes exhibiting efficient bifunctional

catalytic activity for HER and OER. The catalyst showed low overpotential and good
stability under alkaline conditions. In situ studies confirmed the formation of active NiOOH
species during OER [64].

Zhang et al. synthesized bimetallic Fe/Mn-MOF electrocatalysts via a hydrothermal

method for efficient OER. The catalyst exhibited a low overpotential of ~232 mV at 10 mA
cm⁻² with excellent durability. The improved performance was attributed to electronic
modulation between Fe and Mn centers [65].

25
 Fig 13. Schematic diagram of the preparation method for MOF-derived catalysts

Li et al. reported Co-MOF nanoflakes with high surface area for efficient overall water
splitting. The catalyst showed excellent HER and OER activity with good stability in
alkaline electrolyte. The enhanced catalytic activity was due to abundant active sites and
improved electron transport [66].

Fig 14. Representation of Co-MOF preparation

Chen et al. reviewed MOF-based electrocatalysts for water splitting and highlighted
their tunable porosity, high surface area, and adjustable metal centers. The study
emphasized strategies such as heterostructure formation and carbonization to enhance
HER/OER performance [67].

26
CHAPTER-VI
6. Conclusion
In conclusion, the growing concerns over environmental degradation, fossil fuel
depletion, and global warming have accelerated the search for sustainable and clean energy
alternatives. Electrochemical water splitting has emerged as a promising and eco-friendly
approach for hydrogen production, offering high purity hydrogen with zero carbon emissions.
However, the practical implementation of this technology is largely limited by sluggish
reaction kinetics of HER and OER, which demand efficient and cost-effective electrocatalysts.
Metal–organic frameworks (MOFs) have gained significant attention as advanced
electrocatalytic materials due to their unique structural features such as high surface area,
tunable porosity, and versatile chemical composition. The ability to precisely control metal
nodes and organic linkers enables the design of catalysts with enhanced activity, selectivity,
and stability. Various synthesis methods including hydrothermal, solvothermal, microwave-
assisted, co-precipitation, and sonochemical approaches provide flexibility in tailoring the
morphology and physicochemical properties of MOFs for specific electrochemical applications.
The mechanistic understanding of HER and OER reveals that the catalytic efficiency strongly
depends on adsorption energies of intermediates, electron transfer kinetics, and active site
availability. Parameters such as overpotential, Tafel slope, ECSA, and charge transfer
resistance play a crucial role in evaluating catalyst performance. The development of
bifunctional electrocatalysts capable of efficiently driving both HER and OER in a single
system is particularly important for achieving overall water splitting.
Recent studies demonstrate that MOF-derived and MOF-based catalysts, especially those
incorporating transition metals such as Ni, Co, Fe, and Cu, exhibit remarkable electrocatalytic
performance. The synergistic interaction between bimetallic centers, improved conductivity
through carbonization, and hierarchical porous structures significantly enhances catalytic
activity and durability. Furthermore, nickel-based MOFs stand out due to their low cost,
abundance, and excellent electrochemical properties, making them strong candidates for large-
scale applications.
Despite these advancements, challenges such as the poor intrinsic conductivity of pristine
MOFs, long-term stability under harsh conditions, and the scalability of synthesis remain
critical. Future research should focus on designing hybrid structures, improving electrical
conductivity, and understanding structure–activity relationships at the atomic level. Overall,
MOF-based electrocatalysts represent a highly promising class of materials for next-generation
energy conversion technologies..

27
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