Electrocatalytic Water Splitting

ELECTROCATALYTIC WATER SPLITTING
WITH PRUSSIAN BLUE ANALOGUES UNDER

EXTERNAL STIMULI
A THESIS SUBMITTED TO
THE GRADUATE SCHOOL OF ENGINEERING AND SCIENCE OF

BILKENT UNIVERSITY
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE

DEGREE OF
MASTER OF SCIENCE
IN
CHEMISTRY
By
Waqar Ahmad
September 2023
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ELECTROCATALYTIC WATER SPLITTING WITH PRUSSIAN
BLUE ANALOGUES UNDER EXTERNAL STIMULI
By Waqar Ahmad
September 2023
We certify that we have read this thesis and that in our opinion it is fully adequate, in scope
and in quality, as a thesis for the degree of Master of Science.
_____________________________
Ferdi Karadaş (Advisor)
__________________________
Burak Ülgüt
__________________________
Emren Nalbant
Approved for the Graduate School of Engineering and Science
_________________________
Orhan Arıkan
Director of the Graduate School
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ABSTRACT
Electrocatalytic Water Splitting with Prussian Blue Analogues
Under External Stimuli
Waqar Ahmad
M.S. in Chemistry
Advisor: Ferdi Karadaş
September 2023
The development of long-lasting and efficient catalysts for water splitting is crucial for the
advancement of a carbon emission-free world. A well-known class of compounds called
Prussian blue analogues (PBAs) offers several advantages such as high stability, diversity, and
simple synthesis for the development of sustainable water-splitting devices. This thesis
investigates the construction of PBA-based overall water-splitting electrolytic cells assisted
with external stimuli.
Alsac et al. investigated the oxygen evolution reaction (OER) efficiency of various PBAs and
concluded that Co-Co exhibits the best performance as an OER catalyst among the Co-M
PBAs. Ahmad et al. studied the hydrogen evolution reaction (HER) performance of various
PBAs and observed that Co-Ni stands out in performance. Furthermore, Chalil Oglou et al.
elucidated the effect of the magnetic field on the OER catalytic activity of Co-Fe PBA
electrodeposited on the surface of the FTO. His findings unveiled an enhanced catalytic activity
under the influence of a magnetic field. To further explore these concepts, we aim to move one
step ahead and combine all these studies to investigate overall water splitting (OWS) under the
influence of magnetic field and solar light irradiation.
In this thesis, [Co-Co] was used for the OER reaction, while [Co-Ni] was utilized for the HER
reaction. Both electrodes were prepared involving a two-step electrodeposition method and
comprehensively characterized with SEM, EDAX, P-XRD, XPS, and ATR-FTIR. SEM images
unveiled threat-like and needle-like grown particles with uniform sizes of 1-2 µm for [Co-Co]
and [Co-Ni] formed on the fluorine-doped tin oxide (FTO) electrode respectively. The
oxidation states of the pristine and post-catalytic electrodes and the stability during the
electrocatalytic process were confirmed with XPS and FTIR studies.
The electrochemical characterization of these catalysts was thoroughly investigated with linear
sweep voltammetry (LSV), chronoamperometry (CA), and cyclic voltammetry (CV) profiles.
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The electrochemical performance was investigated in three chapters; OER, HER, and overall
water splitting under magnetic and solar light irradiation.
(i) OER performance of FTO/[Co-Co] was evaluated with LSV, which shows prominent
enhancement peaks under the influence of external stimuli. Under the influence of the
magnetic field, it illustrated an enhancement of 11.9% with an overpotential of 949 mV,
while in the presence of solar light, it showed an augmentation of 10.7% with an
overpotential of 949 mV. CA profiles, recorded under magnetic field showed that there
is a direct relation between magnetic field strength and the enhancement in the current
density. On the contrary, an opposite trend is observed with the CA profiles under solar
light irradiation, which suggests that the origin of the enhancement under the magnetic
field is different from the one under solar light irradiation.
(ii) Similar to OER studies, HER activity of FTO/[Co-Ni] was investigated under the effect
of solar light irradiation and magnetic field. The LSV profile showed enhancement only
in the case of solar light, while no significant enhancement was observed under the
magnetic field, contrary to the previous studies. Similar to OER, the CA profiles of
FTO/[Co-Ni] illustrated the opposite trend with respect to overpotential applied. In the
case of HER, CA under a magnetic field showed a small enhancement (1.4%) with an
overpotential of 300 mV, which was attributed to the magnetohydrodynamic effect.
(iii) Two and three-electrode systems were used to conduct the investigation into overall
water splitting. To achieve a current density of 1 mA/cm2 in the two-electrode having
FTO/[Co-Co] on the working/working sense electrode (W/WS) and FTO/[Co-Ni] on
the counter/reference electrode R/C configuration, the system required an overpotential
of roughly 1013 mV. The subsequent analysis of each electrode's unique voltage
contributions helped explain this observation. OER takes around 1.3 V while it is 0.6
V for the HER side.
On the other hand, in the three-electrode configuration, the working electrode was
FTO/[Co-Co], the counter electrode was FTO/[Co-Ni], and the reference electrode was
Ag/AgCl. The observed profile notably showed significant improvement seen when
solar light and magnetic fields were present.
Overall, this study indicates that there is still plenty of room for enhancement in catalysis, with
slight modification in reaction conditions from another perspective i.e., external stimulus. This
thesis takes a progressive step by raising the bar and adding a new dimension to the challenge
of using PBAs in catalytic applications, building on earlier efforts.
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Keywords: Prussian Blue Analogues, Oxygen Evolution Reaction, Hydrogen Evolution
Reaction, Coordination Chemistry, External Stimuli, Spin Crossover, Magnetohydrodynamic,
Overall Water Splitting, Photocatalysis,
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ÖZET
Prusya Mavisi Analoglarıyla Dış Uyarıcıların Desteğinde

Eletrokatalitik Suyun Parçalanması
Waqar Ahmad
Kimya Bölümü, Yüksek Lisans
Tez Danışmanı: Ferdi Karadaş
Eylül 2023
Suyun parçalanması için uzun ömürlü ve verimli katalizörlerin geliştirilmesi, karbon
emisyonlarından arınmış bir dünyanın ilerlemesi için kritik bir öneme sahiptir. Prusya mavisi
analogları olarak bilinen bir bileşik sınıfı (PBAs), yüksek kararlılık, çeşitlilik ve sürdürülebilir
su bölünme cihazlarının geliştirilmesi için basit sentez gibi birçok avantaja sahiptir. Bu tez, dış
uyarıcılar ile desteklenen PBA tabanlı genel su bölünme elektrolitik hücrelerinin inşasını
araştırmaktadır.
Alsac ve iş arkadaşları, çeşitli PBAs'ın oksijen evrim reaksiyonu (OER) verimliliğini inceledi
ve Co-Co'nun Co-M PBAs içinde en iyi performansı sergilediğini göstediler. Ahmad ve iş
arkadaşları, çeşitli PBAs'ın hidrojen evrim reaksiyonu (HER) performansını incelemiş ve Co-
Ni'nin performansta öne çıktığını gözlemlemişdiler. Ayrıca, Chalil Oglou ve iş arkadaşları,
FTO yüzeyine elektrodepozite edilen Co-Fe PBA'nın OER katalitik aktivitesi üzerinde
manyetik alanın etkisini açıklamaya çalıştılar. Bulguları, manyetik alan etkisi altında artan bir
katalitik aktiviteyi öne sürmüştür. Bu fenomeni daha iyi anlayabilmek için, bu çalışmada
manyetik alan ve güneş ışığı ışınımının etkisi altında tam su bölünme (OWS) olayını
araştırmayı amaçlıyoruz.
Bu tezde, [Co-Co] OER reaksiyonu için kullanılmıştır, [Co-Ni] ise HER reaksiyonu için
kullanılmıştır. Her iki elektrot da iki aşamalı bir elektro-depo yöntemi kullanılarak hazırlanmış
ve SEM, EDAX, P-XRD, XPS ve ATR-FTIR ile kapsamlı olarak karakterize edilmiştir. SEM
görüntüleri, [Co-Co] ve [Co-Ni] için sırasıyla florlu kalay oksit (FTO) elektrot üzerinde oluşan
tehdit benzeri ve iğne benzeri büyüyen partiküllerin homojen boyutlarını ortaya koymaktadır.
Pratik ve post-katalitik elektrotların oksidasyon durumları ve elektro-katalitik süreç sırasındaki
kararlılıkları XPS ve FTIR çalışmaları ile doğrulanmıştır.
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Bu katalizörlerin elektrokimyasal karakterizasyonu lineer tarama voltametrisi (LSV),
kronoamperometri (CA) ve dönüşümlü voltametri (CV) profilleri ile ayrıntılı olarak
incelenmiştir. Elektrokimyasal performans, OER, HER ve manyetik veya güneş ışığı ışınımı
altında tam su bölünmesi olarak üç bölümde incelenmiştir.
(i) FTO/[Co-Co] OER performansı LSV ile değerlendirilmiştir ve dış uyarıcıların etkisi altında
belirgin artış pikleri gösterilmiştir. Manyetik alan etkisi altında, aşırı gerilim 949 mV ile %
11.9'luk bir artış gösterirken, güneş ışığı varlığında, aşırı gerilim 949 mV ile% 10.7'lik bir artış
göstermiştir. Manyetik alan altında kaydedilen CA profilleri, manyetik alanın şiddeti ile akım
yoğunluğu artışı arasında doğrudan bir ilişki olduğunu göstermiştir. Tersine, güneş ışığı ışınımı
altında kaydedilen CA profillerinde ters bir eğilim gözlemlenmiştir, bu da manyetik alan
altında görülen artışın güneş ışığı ışınımı altındakinden farklı olduğunu önermektedir.
(ii) OER çalışmalarına benzer şekilde, FTO/[Co-Ni]'nin HER aktivitesi güneş ışığı ışınımı ve
manyetik alanın etkisi altında araştırılmıştır. LSV profili, yalnızca güneş ışığının etkisi altında
artış göstermiş olup manyetik alan altında ise önemli bir artış göstermemiştir. Önceki
çalışmaların aksine HER için CA profilleri, manyetik alan altında küçük bir artış (1.4%)
göstermiştir ve aşırı gerilim 300 mV'a ayarlanmıştır.
(iii) İki ve üç elektrotlu sistemler, tam su bölünme çalışmalarını yürütmek için kullanılmıştır.
Bu çalışmada, iki elektrotlu sistem kullanılmıştır. İş-çalışma duyusu elektrodunda FTO/[Co-
Co] ve karşı/referans elektrodunda FTO/[Co-Ni] kullanmak ve 1 mA/cm2'lik bir akım
yoğunluğu elde etmek için sisteme yaklaşık olarak 1013 mV'luk bir aşırı gerilim uygulanmıştır.
Her elektrodun benzersiz voltaj katkılarının analizi, bu gözlemi açıklamaya yardımcı olmuştur.
OER için yaklaşık 1.3 V gözlemlenirken, HER tarafı için bu değer 0.6 V'tur.
Öte yandan, üç elektrotlu yapıda çalışma elektrodu FTO/[Co-Co], karşı elektrot FTO/[Co-Ni]
ve referans elektrodu Ag/AgCl’dir. Gözlemlenen profil, güneş ışığı ve manyetik alanın
varlığında önemli bir iyileşme gösterdi.
Genel olarak, bu çalışma, katalizde hala iyileştirme için geniş bir alan bulunduğunu ve dış
etkenler gibi reaksiyon koşullarındaki hafif değişikliklerin katalizdeki göstermektedir. Bu tez,
katalitik uygulamalarda Prusya mavisi analoglarının kullanımı konusundaki mevcut çabaları
temel alarak, çıtayı yükselterek ve zengin bir boyut ekleyerek bu zorluğa yeni bir boyut
kazandırmaktadır.
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Acknowledgment
I would like to dedicate my whole work to Seher, without whose support it was
almost impossible for me to complete the project. She has a very responsible and
important role in my master’s degree. I extend my heartfelt thanks to her, for
unwavering support, patience, and understanding. Her constant belief in my
abilities and continuous encouragement has been a constant source of strength.
Besides that, I would like to express my heartfelt gratitude to the foundational

pillars of my life, my parents, with a special mention of my father, for their
unconditional love, support, and encouragement throughout my academic
journey. Your belief in me has been an invaluable source of motivation.
I am deeply indebted to my esteemed supervisor, Dr. Ferdi Karadas, for his

invaluable guidance, expert insights, patience, and relentless dedication to
nurturing my intellectual growth. Your mentorship has played a pivotal role in
shaping the direction of this thesis and my academic pursuits. Besides that, I
would like to show my humble gratitude towards Dr Halil Okur, and Dr Burak
Ulgut. Indeed, their help and support were very much crucial in achieving this.
I extend my appreciation to the members of my Karadas research group with

special thanks to Dr. Ruby, Ramadan, Sina, and Dr. Sara. Emir, Huseyin, and
Yaren were helpful. The collaborative spirit has enriched my research experience.
Your constructive feedback and shared insights have been instrumental in
refining my work.
Lastly, to all my Pakistani, Bangladeshi, Turkish, and Arab friends, your

companionship, and encouragement have provided solace during the demanding
phases of this endeavor. Your presence has illuminated both my academic and
personal journey. Special thanks to Hamid, Faruk, Muzaffar, Ahmad, Hilal,
Wissam, Fahaar, Yunus, Yusuf and Ilyas.
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This achievement is a result of the collective efforts, guidance, and support of all
those mentioned and many others who have played a role in my academic voyage.
Your contributions have enriched my life and academic pursuits immeasurably.
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Contents
Chapter 1: Introduction ..................................................................................... 1
1.1. Current Trends in Energy Technologies and Catalysis ............................ 1
1.2. Water Splitting under Electricity and Light ............................................. 2
1.2.1. Water Splitting in an Acidic Medium ................................................... 3
1.2.2. Water Splitting in Basic/Neutral Medium ............................................ 4
1.3. Prussian Blue Analogues .......................................................................... 6
1.4. OER Mechanism on the Cobalt Site ........................................................ 8
1.5. HER Mechanism on the Cobalt Site ...................................................... 12
1.6. Magnetic Field-Assisted Catalysis ......................................................... 13
1.7. The Motivation of This Thesis Study ..................................................... 18
Chapter 2: Methods and Instrumentations .................................................... 23
2.1. Synthesis Procedure For FTO/[Co-M], (M = Co, Ni)............................ 23
2.1.1. Chemicals ............................................................................................ 23
2.1.2. Preparation of FTO/[Co-Co] and FTO/[Co-Ni] .................................. 23
2.2. Scanning Electron Microscopy (SEM) Coupled with Energy Dispersive

X-Ray Analysis (EDAX) ................................................................................. 25
2.3. Powder X-ray Diffraction (P-XRD) Analysis ........................................ 25
2.4. Xray-Photoelectron Spectroscopy (XPS) Analysis ................................ 25
2.5. Fourier Transform Infrared Spectroscopy (ATR-FTIR) Analysis ......... 25
2.6. Electrochemical Setup ............................................................................ 26
2.7. Magnetic Setup ....................................................................................... 28
2.8. Photocatalytic Setup ............................................................................... 29
2.9. Calculating Surface Concentration of the Active Catalyst ................... 29
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Chapter 3: Results Section ............................................................................... 30
3.1. Synthesis Procedure For FTO/[Co-M], (M = Co, Ni)............................ 30
3.1.1. Hydrothermal technique: ..................................................................... 30
3.1.2. Electrodeposition technique: ............................................................... 30
3.2. FTO/[Co-M] (M = Co, Ni) Characterization ......................................... 31
3.2.1. Scanning Electron Microscopy and EDAX Analysis ......................... 31
3.2.2. XRD Analysis ..................................................................................... 35
3.2.3. XPS Analysis....................................................................................... 36
3.2.4. ATR-FTIR Analysis ............................................................................ 37
3.2.5. Calculating the Surface Concentration of the Catalyst ....................... 38
Chapter 4: Electrocatalytic water oxidation under magnetic and light field

with FTO/[Co-Co] ............................................................................................. 40
4.1. Magnetic Field-Assisted OER Studies ................................................... 41
4.1.1. Linear Sweep Voltammetry Studies ................................................... 41
4.1.2. Chronoamperometric Studies .............................................................. 43
4.2. Solar Light-Assisted Studies .................................................................. 45
4.2.1. Linear Sweep Voltammetry Studies Under Light Irradiation ............. 45
4.2.1.1. Relative LSV Profile ........................................................................ 47
4.2.2. Chronoamperometric Studies Under Solar Light Irradiation.............. 48
4.2.2.1. Catalyst Stability .............................................................................. 51
4.2.3. Temperature Profile for CA Under Solar Light Irradiation ................ 53
Chapter 5: Electrocatalytic hydrogen evolution reaction (HER) studies

under magnetic field and solar light irradiation with FTO/[Co-Ni] ............ 55
5.1. Magnetic Field-Assisted HER Studies ................................................... 55
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5.1.1. Linear Sweep Voltammetry Studies ................................................... 55
5.2. Solar Light Assisted HER Studies ......................................................... 56
5.2.1. Linear Sweep Voltammetry Studies Under Light Irradiation ............. 56
Chapter 6: Electrochemical overall water splitting (OWS) under magnetic

field and solar light irradiation ........................................................................ 61
6.1. Novel Experimental Configuration for Conducting Oxygen and

Hydrogen Evolution Reaction in One Setup Studies....................................... 61
6.1.1. Two Electrode System ........................................................................ 62
6.1.2. Three-Electrode System ...................................................................... 65
6.2. Magnetic Field-Assisted Studies ............................................................ 66
6.2.1. CA Profile Of FTO/[Co-Co] And FTO/[Co-Ni] For OWS ................ 66
6.3. Solar Light Irradiated Studies ................................................................ 69
Chapter 7: Conclusion ...................................................................................... 72
References .......................................................................................................... 75
xiv
Table of Figures
Fig 1.1 Spin state of O2 is different from H2O and OH−. ..................................... 5
Fig 1. 2 Illustration of cyanide ion HOMO LUMO molecular orbital diagram... 7
Fig 1. 3 Chemical structure of PBA FTO/[Co-M], (M = Co/Ni) illustrating the

effect of σ donation and π back donation on bond length in [Co-M], (M
=Co/Ni). .......................................................................................................... 7
Fig 1. 4 Schematic diagram illustrating σ donation and π back donation. ........... 8
Fig 1. 5 Schematic diagram illustrating OER reaction on Co2+. [Reprinted with

permission from ref [58] (Alsaç et. al., Chem. Eur. J, 2018, 24(19), 4856-
4863) WILEY-VCH verlag GmbH & Co. KGaA, Weinheim]. .................... 9
Fig 1. 6 Schematic diagram illustrating spin crossover effect from low-spin to

intermediate- spin. ........................................................................................ 10
Fig 1. 7 Schematic diagram illustrating the assistance of spin-crossover in water
splitting. [Reprinted with permission from ref [63] (Hegner. F. et. al., J. Phys.
Chem. Lett. 2022, 13, 18, 4104-41102). Copyright (2022) American
Chemical Society]. ........................................................................................ 12
Fig 1. 8 Schematic diagram illustrating HER mechanism on cobalt complexes.

[Reprinted with permission from ref [64] (L. Dempsey et. al., Acc. Chem.
Res. 2009, 42, 12, 1995–2004). Copyright (2009) American Chemical
Society]. ........................................................................................................ 12
Fig 1. 9 Scheme illustrating the importance of spin crossover effect for Cobalt-
based catalyst during a water splitting reaction. ........................................... 16
Fig 1. 10 Summary of the possible effect of magnetic field on the enhanced
catalysis......................................................................................................... 19
Fig 1. 11 Relative activity of PBAs comparing OER current density. [Reprinted
with permission from ref [58] (Alsaç et- al., Chem. Eur. J, 2018, 24(19),
4856-4863) WILEY-VCH verlag GmbH & Co. KGaA, Weinheim]. ........ 20
Fig 1. 12 Relative activity of PBAs comparing HER evolution. Reprinted with
permission from ref [59] with permission of Royal Society of Chemistry,
London. ......................................................................................................... 21
Fig 1. 13 Investigation of overall water splitting under solar light irradiation +
magnetic field to enhance the catalytic activity featuring the 1)
semiconducting effect and 2) spin crossover effect. .................................... 22
xv
Fig 2. 1 Schematic diagram illustrating 3 electrode system for electrochemical
deposition of PBA on FTO surface. ............................................................. 24
Fig 2. 2 a) Electrochemical set up with gamry featuring b) working electrode and

c) reference electrode. (Karadas Research Group) ....................................... 27
Fig 2. 3 Magnetic Setup utilized for our experiment (Karadas Research group)
....................................................................................................................... 28
Fig 3. 1 CA profile of FTO/[Co-Ni] illustrating relatively low current density and

undesired peaks. ............................................................................................ 30
Fig 3. 2 SEM images of FTO/[Co] (a) 20,000x magnification and (b) 40,000x
magnification. ............................................................................................... 31
Fig 3. 3 EDAX analysis of FTO/[Co]................................................................. 32
Fig 3. 4 SEM images of fresh FTO/[Co-Co] (a) 10,000x magnification, (b)

40,000x magnification and SEM images of fresh FTO/[Co-Ni] (c) 20,000x
magnification, (d) 80,000x magnification. ................................................... 33
Fig 3. 5 EDAX analysis, the elemental insights of FTO/[Co-Co] ..................... 33
Fig 3. 6 EDAX analysis, the elemental profile of FTO/[Co-Ni] ........................ 34
Fig 3. 7 XRD patterns compared to FTO and FTO/[Co] for (a) FTO/[Co-Co],
and (b) FTO/[CoNi] ...................................................................... 35
Fig 3. 8 XPS analysis for pristine and post-catalytic FTO/[Co-Co] (a) C-1s and
K-2p peaks and (b) Co-2p3/2 and Co-2p1/2 peaks. ......................................... 36
Fig 3. 9 XPS analysis for pristine and post FTO/[Co-Ni] (a) Cobalt peaks and (b)
Nickel peaks.................................................................................................. 37
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Fig 3. 10 ATR-FTIR spectrum of FTO/[Co-Co] and FTO/[Co-Ni] featuring
prominent stretches. ...................................................................................... 38
Fig 3. 11 Statistical data relating current (I) and sweep voltage aimed to measure
Active surface area with equation 2 Chapter 2.9 .......................................... 39
Fig 4. 1 Image of the 3D-printed stage for all the HER and OER reactions under
magnetic field. .............................................................................................. 41
Fig 4. 2 LSV Profile of FTO/[Co-Co] illustrating magnetic enhancement (Inset:

Magnified image of the enhancement zone) ................................................ 42
Fig 4. 3 Tafel slope FTO/[Co-Co] under magnetic field .................................... 43
Fig 4. 4 CA profile obtained for FTO/[Co-Co] OER at η = 949 mV ................. 44
Fig 4. 5 CA Profile obtained for FTO/[Co-Co] at different overpotential (Insets:

zoomed images of graphs that are not clear in the main graph) ................... 44
Fig 4. 6 CA profile obtained for FTO/[Co-Co] OER at η = 859 mV various

magnetic field. .............................................................................................. 45
Fig 4. 7 LSV Profile of FTO/[Co-Co] with and without solar light irradiation
(Inset: Magnified the enhancement zone) .................................................... 46
Fig 4. 8 Tafel slope FTO/[Co-Co] under magnetic field .................................... 47
Fig 4. 9 Relative LSV profile of FTO/[Co-Co] with and without solar Light
irradiation. ..................................................................................................... 48
Fig 4. 10 CA profile of FTO/[Co-Co] under light irradiation. .......................... 49
Fig 4. 11 CA Profile of FTO/[Co-Co] illustrating Light enhancement at different

overpotentials(inset: Showing the red graph enhancement which is not very
prominent in the main graph) ....................................................................... 50
xvii
Fig 4. 12 CA Profile of FTO/[Co-Co] illustrating the combined effect of light
and magnet. ................................................................................................... 51
Fig 4. 13 CA profile of FTO/[Co-Co] under light for 2 h and dark 6 h ............. 52
Fig 4. 14 LSV profile of FTO/[Co-Co] before and after 8 h experiment ........... 53
Fig 4. 15 Temperature recorded profile during (FTO/Co-Co) CA..................... 54
Fig 5. 1 LSV Profile of FTO/[Co-Ni] with and without magnet field ............... 55
Fig 5. 2 CA profile of FTO/[Co-Ni] for HER reaction ...................................... 56
Fig 5. 3 LSV Profile of FTO/[Co-Ni] illustrating enhancement under solar light

irradiation (Inset: Magnified the enhancement zone) ................................... 57
Fig 5. 4 CA Profile of FTO/[Co-Ni] under solar light irradiation ..................... 58
Fig 5. 5 CA profile of FTO/[Co-Ni] at various overpotentials........................... 59
Fig 6. 1 Compilation and Overview of Current Research Findings ................... 61
Fig 6. 2 Novel Experimental Setup for Conducting Overall Water-Splitting

Experiments .................................................................................................. 62
Fig 6. 3 CA profile obtained for OWS in a two-electrode system ..................... 63
Fig 6. 4 a) Images of overpotential reading at working electrode displayed on the

screen b) Image of overpotential displayed between counter and reference
electrode with potentiometer. ....................................................................... 64
Fig 6. 5 a) Images of overpotential reading at working electrode displayed on the

screen b) Image of overpotential displayed between counter and reference
electrode with potentiometer. ....................................................................... 65
xviii
Fig 6. 6 Three-electrode system real image planted inside the magnetic field, with
a schematic representation. ........................................................................... 65
Fig 6. 7 Schematic diagram illustrating the three-electrode system utilized for

OWS a) Face-to-face configuration for studies under magnetic field b) Side-
by-side configuration for solar light irradiated studies ................................ 66
Fig 6. 8 CA profile obtained for FTO/[Co-Co] W/WS and FTO/[Co-Ni] C for

OWS.............................................................................................................. 67
Fig 6. 9 CA profile obtained for FTO/[Co-Co] as W/WS and FTO/[Co-Ni] as C

for OWS at various overpotentials (inset: Magnified picture of lower
enhancements in the main graph) ................................................................. 68

for OWS at various magnetic field strengths (inset: Magnified picture of
lower enhancements in the main graph) ....................................................... 69
Fig 6. 11 LSV profile obtained for FTO/[Co-Co] as W/WS and FTO/[Co-Ni] as

C for OWS .................................................................................................... 70

for OWS at various overpotential under solar light irradiation (inset:
Magnified picture of lower enhancements in the main graph) ..................... 71
xix
LIST OF TABLES
Table 1. 1 Summary of Magnetic Field Assisted Water Splitting catalysis ...... 17
Table 4. 1 Summary of solar irradiated and under magnetic field OER studies54
Table 5. 1 Summary of solar irradiated OER studies ........................................ 60
Table 6. 1 Summary of solar irradiated and under magnetic field OWS studies
....................................................................................................................... 71
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Chapter 1: Introduction
1.1. Current Trends in Energy Technologies and Catalysis
The demand for energy is a critical factor in development and prosperity. Our conventional
reliance on hydrocarbons as principal energy reservoirs has been beset by limitations
particularly because of their finite nature and emission of polluting, gases, which deteriorate
the decorum of our environment [1]. Energy is necessary for industrial activities, vehicle
propulsion, residential institutions, medical facilities, and a variety of other vital life cycles,
among many other life cycles [2]. Future energy resources should be renewable and
sustainable, and should not generate methane, CO2 [3, 4], etc. such as solar, hydroelectric, or
wind energy. Thus, finding and establishing alternative energy sources is crucial to meet future
energy demands with renewable and sustainable resources [4].
To address the aforementioned issues, catalysis is crucial in tackling the soaring energy needs
of contemporary society [5]. The development of efficient catalysis using transition metals and
photosensitizers is an attractive solution to address the world's energy demands sustainably [6].
This approach has shown promising results in converting solar energy into chemical energy,
which can be stored and utilized in the future [7, 8]. Additionally, this technology can
potentially replace conventional energy sources and reduce carbon emissions, mitigating the
adverse effects of climate change [9]. Therefore, further research and development in this field
are crucial to achieving a sustainable energy future.
Catalysis, which is a fundamental process in chemical transformations, provides detailed

control over the reaction paths, and energy demands, resulting in accelerated and manipulatable
controls over chemical reactions [10]. There are many parameters to manipulate while dealing
with catalysis, and any small variation in the catalysis process has a great impact on its
performance [11]. In turn, this makes it easier to produce the materials and energy carriers
required for a variety of applications [12]. Catalytic processes enable energy-efficient
technology by producing chemicals and fuels from renewable sources and purifying
hydrocarbons [4]. In addition to its contributions to energy production, catalysis has numerous
uses in a variety of scientific fields. Catalytic converters reduce harmful pollutants from vehicle
exhaust [13] in the field of environmental science [14, 15], while catalysis allows the
production of complex medicinal compounds in the field of pharmaceuticals [16]. Similarly,
they play a role in the degradation of harmful organic dye pollutants and microbes to clean
water [17]. A great deal of work is going on in regard to enhancing the performance of catalysis.
1
Solar energy is an abundant and renewable unlimited energy source that holds great potential
for addressing the world's energy demands [18]. It uses photovoltaic and solar thermal
technologies to capture sunlight and transform it into electricity and heat without creating any
emissions. There is great work going on, in catalysis in regard to utilizing semiconducting
properties with the help of solar light irradiation [19].
Moreover, catalysis has been studied for illustrating enhancement under the influence of
magnetic fields. This section is discussed in detail in topic 1.3. Magnetic field-assisted
Catalysis.
1.2. Water Splitting under Electricity and Light
Hydrogen is proposed as a future energy carrier due to its abundant nature, whose biggest
precursor can be water, which covers 75% of our planet Earth [20]. Hydrogen as an energy
carrier is also supported by the fact that this source is renewable [21]. Moreover, hydrogen is
not only used as a fuel to produce heat but also can be used to generate electricity when treated
with oxygen in optimized conditions producing water as a byproduct [22]. In addition to that,
hydrogen also has low viscosity, which makes it easy to be transported through storage or
pipeline systems [23, 24].
There are many ways to generate hydrogen e.g., steam methane reforming [25], and coal
gasification [26] in which methane gas or carbon respectively is treated with water to produce
carbon dioxide and hydrogen gas, but the drawback of this method is that it is carried out at a
very high temperature, i.e., 1000 ᵒC and that it gives carbon dioxide, which is harmful to our
environment [27]. Although water splitting could be a benign approach toward green energy.
It is a highly energy-demanding process, which should be overcome with an external stimulus
thermochemical water splitting can require up to 2000 °C [28, 29].
Water-splitting has the potential to provide a sustainable path to produce hydrogen [30], which
can simply be described as electrochemical [31] photocatalytic or photoelectrochemical
conversion [32] of water into hydrogen and oxygen gases [33]. These reactions are made easier
by catalytic materials since they can dramatically lower the activation energy barriers, speed
up the reactions, and regulate the reaction paths. Catalytic materials play a key role in the
corresponding anodic and cathodic half-reactions of the oxygen evolution reaction (OER) and
hydrogen evolution reaction (HER). The development of effective catalysts for these processes,
2
such as transition metal oxides [34], metal chalcogenides, Prussian blue analogues, and
molecular complexes [35], has advanced significantly in recent years [36].
Electrochemical water splitting has been regarded as one of the most convenient and efficient
ways to get hydrogen with high purity and minimum pollution. This approach has shown
promising results in converting solar energy into chemical energy, which can be stored and
utilized in the future. The general demand for water splitting is 1.23 V or above with reference
to Ag/AgCl electrodes as reference. Given the difficulty of this 4e− process, the development
of an efficient catalyst is critical to address the water-splitting process.
Platinum takes the crown for being the state of art catalyst for cathode/hydrogen production,
while IrO2/RuO2 performs the best anodic reaction under basic conditions. However, the
problem with catalysts such as Pt, IrO2 Pt, IrO2, and RuO2 is that they are scarce and expensive.
Electrochemical water splitting consists of two half-reactions, called hydrogen evolution

reaction HER and oxygen evolution reaction OER. Based on the medium of the reaction, the
water-splitting reaction mechanism is different in an acidic medium than neutral or basic
medium. In an acidic medium the reaction advents from the anode where the water molecule
loses electrons and splits into two protons and an oxygen molecule, which is liberated.
1.2.1. Water Splitting in an Acidic Medium
I. Oxygen Evolution Reaction (OER)
Water molecules adhere to active sites on the catalyst (*), leading to their transformation into
hydroxide ions (OH−) and the release of an electron (e−). These hydroxide ions (OH−) then
convert into oxygen ions (O), simultaneously emitting an electron (e−). The oxygen ions (O*)
interact with water molecules, producing oxygen gas (O2) and releasing an electron (e−).
1. H2O + *
(Active site) OH* + H+ + e− (1)
2. OH* O* + H+ + e− (2)
3. O* + H2O OOH* + H+ + e− (3)
4. OOH* O2 + *(Active site) + H+ + e− (4)
II. Hydrogen Evolution Reaction (HER)
In this procedure, electrons are removed from the liquid to attach hydrogen atoms (also known
as adsorbed hydrogen atoms, or Hads) that interact with the catalyst's active sites. These
adsorbed hydrogen atoms react with incoming protons and electrons to form hydrogen gas
3
when only a small number of them are present. On the other hand, if there are too many
hydrogen atoms adsorbed, they can combine to form hydrogen gas through a collective process.
The HER reaction may proceed in two different ways,
➢ Volmer Step
The proton goes to the cathode, receives an electron, and gets itself adsorbed.
H+ + e Hads (5)
➢ Heyrovsky step
Another proton comes and in the presence of an electron binds with the adsorbed hydrogen to
form a hydrogen molecule.
Hads + H+ + e− H2 (6)
1.2.2. Water Splitting in Basic/Neutral Medium
I. Oxygen Evolution Reaction in Basic/Neutral Medium
In basic or neutral media, the OER goes through the following steps series of phases. OH,
interacts with surface sites (*), releasing electrons (e−). Then, through an electron transfer
reaction, OH* combines with more OH to form surface-bound oxygen species (O*) and water
(H2O). The surface-bound per oxo species (OOH*) produced by this (O*) species' interaction
with OH releases an electron (e−). In the long run, OOH* reacts with OH to produce molecular
oxygen (O2), regenerate active surface sites (*), and release water (H2O), while electron
transport takes place. The OER reaction in basic media.
1. OH + * OH* + e− (7)
2. OH* + OH O* + H2O + e− (8)
3. O* + OH OOH* + e− (9)
4. OOH* + OH O2 + *(active sites) + H2O + e− (10)
II. Hydrogen Evolution Reaction in Basic/Neutral Medium
Water molecules (H2O) and electrons (e−) combine to produce hydrogen gas (H2) and
hydroxide ions (OH−).In the context of the basic medium, the reaction’s modality varies as
follows.
4
➢ Volmer step
H2O + e− Hads + OH− (11)
➢ Heyrovsky step
Hads + H2O + e− H2 + OH− (12)
In case Hads is highly concentrated, the Hads react with another Hads.
Hads + Hads H2 (13)
Subsequently, the protons leave for the cathode, where they receive 2 electrons and are
adsorbed on the anode surface and quickly convert into hydrogen molecules, which liberate
from the anode. On the contrary, in a basic medium, the reaction begins with receiving 2
electrons from the cathode, forming hydrogen molecules and 2 OH− ions [37].
In a heterogeneous catalytic system, the fermi level of the system can be raised high by
applying the potential difference, which makes it easier to induce electron transfer into the
conduction band of the catalyst [38].
In water splitting, comparatively, the OER part requires more overpotential due to the
following three reasons [39].
i. The spin state of the O2 molecule is a triplet as shown in Fig 1.1, however, the spin
state of OH− and H2O both are singlet, which makes the kinetics of this reaction
slower [40].
Fig 1.1 Spin state of O2 is different from H2O and OH−.
ii. The electrons taken by the adsorbate during the OER reaction must flow through
areas like electrocatalysts and external circuits [41].
iii. Electrical conductivity of the catalyst plays a vital role in the increased demand of
overpotential for OER [42].
5
OER reactions in water splitting have been investigated with numerous numbers of inorganic
catalysts, including simple structures like metal oxides [43], selenides [44], and some
complicated structures like MOF [45], perovskites structures [46], and recently structures with
surfactants [47] and liposomes [48] are introduced recently with enhanced electrochemical
activity performance.
1.3. Prussian Blue Analogues
Prussian blue analogues (PBAs) are cyanide-based polymeric compounds that connect two
metals through a cyanide bridge. The story of cyanide-based compounds back to 1704 when
the first coordination compound was discovered by German Artist Diesbach [49]. The major
precursor of cyanide-based coordination polymers, potassium ferrocyanide, or K4[Fe(CN)6], is
laboriously isolated by mixing animal waste with sodium carbonate in a pot of iron to produce
Prussian blue [50].
Computational studies investigated the electronic distribution, their binding characteristics, and
the resulting metal-ligand interactions in cyanide ligands. Because carbon-based HOMO and
LUMO orbitals predominate, the monodentate binding nature of cyanide to metal centers is
usually established through carbon [51]. As indicated by examples like iron in [Fe(CN)6]4 and
cobalt in (PPN)2[Co(CN)]4, cyanide is categorized as a high-field ligand [52]. Due to HOMO
and LUMO interactions, this interaction produces relatively weak π bonds, when they receive
electrons from metal as shown in Fig 1.2, while also producing strong σ bonds with electron
transfer from the ligand to the metal.
6
Fig 1. 2 Illustration of cyanide ion HOMO LUMO molecular orbital diagram.
Through FT-IR and X-ray diffraction spectroscopic techniques, the π back bonding can be well
understood. Cyanide coordination with metal ions displays a shorter M-CN bond with more π
back donation as illustrated in Fig 1.3 [53].
Fig 1. 3 Chemical structure of PBA FTO/[Co-M], (M = Co/Ni) illustrating the effect of σ

donation and π back donation on bond length in [Co-M], (M =Co/Ni).
7
The cyanide bond is further weakened by coordination through nitrogen atoms because
nitrogen's lone pair is antibonding. In infrared spectra, as illustrated by Fig 1.4 ν(CN) stretches
that reflect electronic characteristics and are unable to pull off the electron pair due to
electronegativity, coordination number, and metal oxidation state are reflected [54]. PBAs
exhibit a variety of structural variations with promise for use in electrochromics [55],
biosensing [56], energy conversion, and storage [57], among other fields. The active cobalt
sites and switchable characteristics of cobalt hexacyanometallates make them adaptable
candidates for photomagnetism- and catalysis.
Fig 1. 4 Schematic diagram illustrating σ donation and π back donation.
PBAs offer a wide surface area, tunable metal active sites, and a vast variety of framework
structures that make them very attractive for water-splitting technologies. [ [58, 59, 49].
The electronic configuration of the cyanide ion (1σ)2 (2σ)2 (3σ)2 (4σ)2 (1π)4 (5σ)2, making it
isoelectronic with molecular species like N2, CO, and NO+. This isoelectronic resemblance is
explained by the occurrence of a triple bond formation with a bond distance of 1.16 Å between
the carbon and nitrogen atoms in the structure [49, 60].
1.4. OER Mechanism on the Cobalt Site
The advancement of the OER encounters limitations due to the problems like linear scaling
relationships [61] and high overpotential demand as discussed above inherent in its reaction
intermediates. Several complicated factors play a role in the behavior of cobalt sites during
water-splitting events. For coordination compounds, the cyanide group's vibration can serve as
a distinctive marker. We can determine the cyanide group's connection, assess the oxidation
states of metal ions, and comprehend their electron densities by examining changes in this
vibration. The cyanide vibration moves to higher frequencies as the metal's oxidation state
rises, showing electron shortages in CoII centers [53]. Fig 1.5 shows how we can arrange the
electron densities at CoII sites in particular structures using this information. In turn, the
8
electron densities shed light on the rate-determining step (r.d.s.) in the catalysis of water
oxidation. The oxidation stage and the water's nucleophilic attack have been identified as two
competing steps. The [CoII-CoIII] analog stands out as an effective catalyst among the many
structures examined because of its reduced electron density. This correlation shows that the
rate-determining step is the water's nucleophilic attack on the intermediate [58]. It is significant
to notice that the difference in electron densities persists even when the electrical characteristics
of the catalyst change when a voltage is applied. The study's conclusions are important.
Fig 1. 5 Schematic diagram illustrating OER reaction on Co2+. [Reprinted with permission
from ref [58] (Alsaç et. al., Chem. Eur. J, 2018, 24(19), 4856-4863) WILEY-VCH verlag
GmbH & Co. KGaA, Weinheim].
An important factor that has a significant impact on the electrocatalytic process of water
oxidation is the electron density of CoII. It is now clear that there is a direct correlation between
the structural configuration and the electrical characteristics when the type of
hexacyanometallates group is changed. The complicated interaction between oxidation state
and electron density is strengthened as the metal's oxidation state is increased since this causes
a decrease in electron density at CoII sites. The nucleophilic attack of water on the cobalt-oxo
intermediate is likely the rate-regulating step in water oxidation catalysis, highlighting the
significance of this interaction pathway [58].
9
There are four crucial steps for the OER process as shown in (Equations 17-20). These steps
are accompanied by transferring of protons and electrons between the molecules to produce
oxygen ultimately. Here the most challenging step is equation 2, where a molecule with a
negatively charged oxygen atom and a positively charged hydrogen atom (referred to as *Co–
OH) transforms into a molecule with a negatively charged oxygen atom and a neutral hydrogen
atom (referred to as *Co–O). This step is energetically demanding and requires a relatively
high voltage to proceed.
Fig 1.6 shows the spin crossover effect is found to assist the OER reaction in step 2. The term
"spin" describes the intrinsic angular momentum, or "spinning" motion, of electrons. Spin
crossover is a phenomenon in which the spin states of the electrons alter because of outside
influences such as temperature, pressure, or an applied magnetic field. Some chemicals
involved in the OER may behave differently as a result of the SCO effect [62].
The SCO effect is proposed to occur between two spin states of a molecule called *Co–OH. In
its initial state, this molecule has a certain spin configuration called the low-spin (LS) state.
Through the SCO effect, it can transition to another spin configuration called the intermediate-
spin (IS) state. This transition happens because of changes in the molecule's electronic
environment caused by factors like an external electric field.
Fig 1. 6 Schematic diagram illustrating spin crossover effect from low-spin to intermediate-
spin.
The IS state of the *Co–OH molecule is found to be more favorable for the OER process. In
this state, the molecule is more efficient at transferring electrons during the OER, which makes
the overall reaction require less energy.
10
This SCO-assisted pathway provides a new way to make the OER more efficient. By
controlling the spin states of molecules involved in the reaction, scientists can reduce the
energy needed for the OER to occur. This is a novel approach to improving electrocatalysis
and enhancing the efficiency of processes like water splitting for clean energy production.
Equations 17-20 illustrate how the oxygen evolution reaction (OER) takes place in a series of
steps, with a challenging step 2. It introduces the concept of spin crossover (SCO), where the
spin states of certain molecules involved in the OER can change, leading to more efficient
reactions. This SCO-assisted pathway offers a new strategy to enhance the efficiency of OER
and other electrocatalytic processes.
To address the overpotential and linear scaling relationship issues, stimuli like solar irradiation
(favoring semi-conducting effect) and magnet (involving the manipulation of spin
configurations) in water oxidation intermediates offer a means to surmount these constraints.
Franziska et al. explained cobalt hexacyanoferrate (CoFe−PB), which not only demonstrates
as a proficient and resilient water oxidation catalyst [58] but also presents magnetic switching
capabilities. Capitalizing on its versatile electronic structure, CoFe−PB emerges as a promising
contender for magnetic modulation of the OER.
This study employs first-principles density functional theory calculations to expound on the
OER dynamics within two distinct CoFe−PB model systems and assesses the potential for spin-
crossover (SCO) phenomena as shown in Fig 1.7 in their stable states. The findings unveiled a
remarkable prospect: the incorporation of SCO during OER can appreciably decrease the
overpotential by 0.7 V, resulting in an overpotential hovering around 0.3 V, which is in good
agreement with experimental measurements. Moreover, under the influence of an external
potential surpassing 1.5 V vs SHE, the SCO-assisted pathway garners substantial favor [63].
11
Fig 1. 7 Schematic diagram illustrating the assistance of spin-crossover in water splitting.
[Reprinted with permission from ref [63] (Hegner. F. et. al., J. Phys. Chem. Lett. 2022, 13, 18,
4104-41102). Copyright (2022) American Chemical Society].
1.5. HER Mechanism on the Cobalt Site
Similar to OER reactions, the cobalt complexes can transform into different forms and interact
with various external stimuli including acids and light to generate hydrogen in various ways.
Based on various forms of cobalt, the HER reaction may proceed in various ways as follows.
Fig 1.8 illustrates the formation of hydrogen through multiple sets of reactions, in which the
cobalt acquires various oxidation states.
Fig 1. 8 Schematic diagram illustrating HER mechanism on cobalt complexes. [Reprinted with
permission from ref [64] (L. Dempsey et. al., Acc. Chem. Res. 2009, 42, 12, 1995–2004).
Copyright (2009) American Chemical Society].
12
• The cobalt complexes undergo reduction from Co3+/ Co2+ to Co1+ which enable it to be
protonated to become Co3+H. After the formation of Co3+H, the reaction may proceed
through different pathways, a) Homolytic path: this hydride can be treated with another
hydride (Co3+H) to liberate H2 indicated by the red path in Fig 1.9. b) Heterolytic path:
Another way for the reaction to proceed is by getting extra hydrogen to form H2 while
Co3+H is converted into Co3+.
• Co3+H can also be turned into Co2+H which again can be treated with Co2+H to get H2
following a similar path as above.
• Another scenario is, that if Co1+ is not provided with hydrogen, it can be reduced directly
to Co0 which in turn can get hydrogen to be converted into Co2+H, which can undergo a
similar path mentioned above.
According to this study, an acidic medium accelerates this reaction, as this reaction is
continuously consuming hydrogen which makes an acidic environment favorable for such
reactions. The reaction may be controlled with the amount and concentration of the acid, the
reaction can be manipulated. The reaction path followed in the case of strong and weak acids
is very different.
Apart from medium, another factor that can potentially change the reaction parameters is light
energy.
Since, the cobalt complexes for HER reaction lack the step where (Co-OH) to (CoO−), where
the spin state is convertible from low spin to intermediate spin, the reaction cannot undergo
spin crossover, and there will be no enhancement under the effect of the magnetic field [64].
1.6. Magnetic Field-Assisted Catalysis
The pursuit of improved catalyst materials has been coupled with the emergence of innovative
strategies involving external fields such as gravity, light, ultrasound, and electric fields. These
external stimuli have demonstrated the capability to enhance mass transfer at the electrode
surface and alter reaction kinetics, opening new avenues in electrochemistry. Particularly
intriguing is the recent exploration of coupling magnetic fields with electrochemistry [65],
presenting a promising and novel approach to boost electrochemical reactions [66]. The effect
of the magnetic field on catalysis has been known for decades, the effect of which has been
under debate [67]. Magnetic fields can affect intricate electrocatalytic systems in a variety of
13
ways. For instance, forces like the Lorentz force and Kelvin force allow them to directly affect
the electrolyte's electric currents and specific magnetic particles. Furthermore, the localized
heating that can result from a rapidly changing magnetic field can actually aid electrochemical
reactions. The behavior of electrochemical reactions can also be affected by other magnetic
field effects, such as the Maxwell stress effect and the spin selectivity effect [68].
First studies indicate that the enhancement mainly roots due to the Lorentzian force [69], which
describes the force experienced by a charged particle moving through an electromagnetic field,
backed by the diffusion of reagents or gas bubbles liberation but necessarily it cannot always
increase the efficiency, but also can negatively affect the catalytic activity [70, 71] This was
immediately rejected when some technical explanations were put forward [72].
The magnetohydrodynamic (MHD) effect, magnetothermal effect, spin polarization effect, and
magnetoresistance (MR) effect are able to improve the diffusion, surface temperature of the
catalysts, reaction path, and spin electrons transport efficiency, respectively, in a variety of
electrochemical reactions [73]. Later, much study has been pursued in order to find out the real
nature of catalysis and magnetic field relation [74]. The theories behind this enhancement are
briefly discussed herein.
1) Magnetohydrodynamic effect: In processes like OER or HER, electrogenerated bubbles

present a significant problem because they affect energy and mass transfer in gas-evolving
electrodes. The reaction at the electrode surface that causes the solution to become
supersaturated and subsequently bubble formation and growth is linked to the development
of gas bubbles. These bubbles may enclose active areas, interfere with the distribution of
current, and result in undesirable outcomes like significant overpotentials [75]. Strategies
for removing bubbles have been investigated as a means of reducing these effects [76].
These strategies can be divided into two types: those requiring an additional energy source
to change behaviour and those that use external sources like magnetic fields. Investigations
into the impact of magnetic fields on bubble dynamics have revealed increased
electrocatalytic activity [77]. Applying an external magnetic field can help remove bubbles,
reduce overpotentials, and improve electrocatalytic performance. This magnetic-field-
induced bubble removal affects ohmic resistance and overall electrocatalysis, driven by
forces like Lorentz and Kelvin forces, and even by current distortion within the catalysts
themselves [77]. MHD effect mainly enhances mass transport on the catalytic interface
needed during the catalytic process under the magnetic field [77]. Contrary to initial
14
expectations, empirical evidence suggests that the observed OER enhancement is not
predominantly attributed to the Lorentzian force. This conclusion is substantiated through
two primary lines of investigation. Firstly, the study examines non-ferromagnetic catalysts,
specifically Co3O4 and IrO2, where the Lorentzian movement is not pronounced due to
weak magnetic interactions. Secondly, there was hardly any difference observed in the
OER performance of Co(acac)2 and Fe(acac)3 with and without a magnetic field. However,
species like OH− and H3O+ partake in transport through sequential proton transfer
processes, known as the Grotthuss dynamics/magnetohydrodynamic effect [78].
2) Spin Polarization effect: In this study, spins with preferential orientation exhibit a more
dominated direction in which both the possible states may not be equally populated. The
effects of a magnetic field on the ferromagnetic and non-ferromagnetic materials CoFe2O4
(spin polarizer), Co3O4, and IrO2 were investigated. In comparison to Co3O4 and IrO2,
which showed little magnetic susceptibility, CoFe2O4 among them showed improved
performance when exposed to a magnetic field. Notably, the Tafel slope of CoFe2O4
significantly decreased, dropping from about 120 to 90 mV.dec−1. This improvement was
attributed to the catalyst's ability to act as a spin polarizer when a magnetic field is present.
This ferromagnetic catalyst promotes the production of oxygen with parallel spins by
aligning electron spins. The underlying cause of this phenomenon is "quantum spin-
exchange interactions." These interactions lead to the oxygen evolution reaction (OER)
experiencing facilitation, where the initial step of the reaction Fig 1.9, which was
previously rate-determining under a magnetic field, is no longer the limiting factor [79, 80].
This important finding highlights the need of maintaining total spin on active sites during
OER, a key idea that makes use of quantum spin-exchange interactions to enhance reaction
kinetics [63, 81, 82, 83]. Galan-Mascaros et a. studied the growth of catalytic materials
(magnetic or non-magnetic) on magnetic substrates such as Ni foam has shown promise in
enhancing reactions like the Oxygen Evolution Reaction (OER) attributing the effect to
spin polarization effect [84].
3) Spin Crossover effect: The process of switching between configurations distinguished by

d4 and d7 electron counts within a metal complex from the first two rows of the periodic
table is subject to modification by outside forces like magnetic fields, variations in
temperature, or shifts in pressure. This phenomenon also involves the conversion of the
spin state of the metal complexes, either high-spin (HS) or low-spin (LS). Co-Fe Prussian
15
blue analogues are prone to undergo spin crossover easily. Co-NC-Fe is a switchable
molecular magnet that can function in a wide pH range and in step 2 of OER reactions as
shown in (Eq. 18) [63]. Besides this, a similar study was pursued by Ramadan et al. who
found a 10.7 % enhancement in OER reaction under magnetic field.
Fig 1. 9 Scheme illustrating the importance of spin crossover effect for Cobalt-based catalyst
during a water splitting reaction.
The application of magnetic fields to catalytic processes has garnered significant attention due
to their potential to enhance various reaction aspects. Table 1 provides a comprehensive
summary of catalytic processes that can be augmented through magnetic field assistance,
accompanied by the underlying rationales. In the context of the HER, the application of a
magnetic field is anticipated to enhance HER activity. This enhancement is usually due to
mechanical changes in the reaction particularly MHD, or Lorentz force, resulting in higher
catalytic activity. Similarly, the OER (being spin dependent reaction) can benefit from
magnetic field assistance, primarily due to its influence on oxygen adsorption and activation,
and also influencing the reaction mechanism through spin pining/polarization or spin crossover
effect, thereby facilitating quicker oxygen evolution kinetics. Furthermore, charge transfer
processes are influenced by magnetic fields, which can lead to altered charge transfer rates and
16
mechanisms. This effect is attributed to the magnetic field's capability to influence charge
distribution and modify electron transfer mechanisms in redox reactions.
Table 1. 1 Summary of Magnetic Field Assisted Water Splitting catalysis

S. First Material Catalytic Credit for Enhanceme Yea
N Author Activity enhancement nt r
o
1 Yuanyuan NiFe- OER Synergy Decrease of 2022

LDH/Co3O4/ overpotential
NF by 25 mV
2 Steven R. Pt and Au Electrochemical Magnetic 100% 1996
Ragsdale, microdisk reduction of field-induced efficient
electrodes acetophenone convective
(AP) fluid flow
altering mass
transfer
3 Liang Cai Fe–Co–Ni– HER Lorentz 27% increase 2022
P–B interaction in current
magnetic enhancing density at 20
catalyst charge- mT
transfer
efficiency
4 Jose NiZnFe4Ox Alkaline water Spin Current 2019
Ramon on Ni Foam electrolysis Polarization density
100% /
intrinsic
activity 40%
5 Liju Elias Electroactive HER MHD-induced Reduction in 2017
Ni–W alloy convection high
coating with and H2 bubble overvoltage
a specific disentangleme towards HER
composition nt
6 Lorena M Fe, Co, Zn ORR Zn MHD, Zn = 3% 2012
A electrodeposi
Fe, Co Lorentz Fe = 12%
ted on
interaction
(PANI) Co = 8%
coated gold
electrodes
17
7 Yuanyuan (Ni(OH)2, OER MR + MHD + Overpotentia 2022
Zhang NiO, and Ni) Charge l decrease by
transfer 20 mV to
produce 10
mA/cm2
8 Xiao Ren CoFe2O4, OER Spin Tafel 2021
Co3O4, and Polarization decrease
IrO2 during 1st step from
of OER
109 mV/dec
to about 87.8
mV/dec
9 Jiawei Che NiFe2O4@M HER Lorents + Overpotentia 2020
n OF-74 MHD l decreased
by 31 mV for
10 mA, 7.7%
enhancement
1.7. The Motivation of This Thesis Study
While various electrochemical reactions have exhibited positive responses to magnetic fields
through mechanisms like the magnetohydrodynamic effect and spin polarization effect,
challenges still persist. Common magnetic materials suffer from issues like agglomeration and
limited active sites, impacting their catalytic activity. Many "magnetization effect" catalysts
struggle to ensure both catalytic activity and magnetic field enhancement. Additionally, the
precise mechanism underlying the enhancement of catalysts supported on magnetic substrates
under magnetic fields remains unclear. As there could be three possible reasons for the
enhancement under magnetic field, mentioned as MHD effect, spin polarization effect, and
spin crossover effect as summarized in Fig 1.10.
18
Fig 1. 10 Summary of the possible effect of magnetic field on the enhanced catalysis.
To address these challenges, our work takes a comprehensive approach, focusing on taking full
advantage of the external stimulus but combing HER and OER making an over-all water
splitting reaction under the influence of magnetic field using PBAs, which are one of the finest
IMCT , and spin crossover effect illustrating catalyst [85]. This architecture leverages enhanced
conductivity and increases catalytic performance resulting in promising OWS activity.
Co-Fe PBAs, have recently been shown to be active catalysts for numerous applications, i.e.,
CO2 conversion, alcohol splitting, HER and OER, etc. Alsac et al. investigated a series of PBAs
for the OER process as summarized in Fig 1.11 and found that FTO/[Co-Co] gave the highest
productivity in OER generation. The study is minimized in the following graph, which
compares the OER activity of various Prussian blue analogues [58]. From this graph, it is
obvious that [Co-IICoIII] is the best OER catalyst reaching over 3.7 mA/cm2 of current density.
According to the study,- [Co-II-CoIII] reaching 1 mA current density with the lowest
overpotential compared to other PBAs of 565 mV, has the highest TOF of 5.0 x 10−2/s.
19
Fig 1. 11 Relative activity of PBAs comparing OER current density. [Reprinted with
permission from ref [58] (Alsaç et- al., Chem. Eur. J, 2018, 24(19), 4856-4863) WILEY-VCH
verlag GmbH & Co. KGaA, Weinheim].
Furthermore, Ahmad et al. investigated a series of PBAs for the photocatalytic HER process
shown in Fig 1.12. In this study [Co-Ni] PBA, which has a two-dimensional network structure,
exhibits a high HER activity in the presence of a ruthenium photosensitizer. In this study,
photocatalytic hydrogen evolution was performed in a three-component system that included
the catalyst, the photosensitizer [Ru(bpy)3]Cl2, and the sacrificial electron donor ascorbic acid.
This was done in an aqueous medium with a pH of 5.0. A noteworthy aspect was the [Co-Ni]
catalyst's extraordinary hydrogen evolution reaction (HER) efficacy, which was measured at
4229 µmol/gh. This performance is about 20 times better than that of [Co-Fe] (216 µmol/gh)
and [Co-Co] (617 µmol/gh).
20
Fig 1. 12 Relative activity of PBAs comparing HER evolution. Reprinted with permission from
ref [59] with permission of Royal Society of Chemistry, London.
Chalil Oglou et al. advanced one step ahead and investigated the catalytic properties of PBAs
for the application of oxygen evolution reaction of cobalt nickel Prussian blue analogues
FTO/[Co-Fe]. He observed an interesting property of Prussian blue analogues, that is, some
PBAs show enhancement in OER reactions under the influence of a magnetic field.
Cobalt and nickel-based catalysts are the two famous non-platinum grouped metal (PGM)
based catalysts explored. Previous studies indicate that cobalt surfaces have a high propensity
for the Tafel/Heyrovsky processes, which concludes that the recombination of 2 hydrogen
atoms on the cobalt surface to make a hydrogen molecule is a very feasible process. Water
dissociation from oxygen and hydrogen is a challenging and rate-determining step.
Given the aforementioned studies, my thesis focus is on catalysts synthesized with elements
that are abundant on Earth, such as cobalt and nickel [86, 87, 88]. The main goal is to build an
integrated experimental framework that combines the knowledge gained from the mentioned
research projects. Notably, by including the simultaneous analysis of the hydrogen evolution
reaction (HER) and oxygen evolution reaction (OER), this work adds a new dimension to
external stimuli-assisted water-splitting devices as summarized in Fig 1.13. Beyond this, a
ground-breaking step is performed by researching the whole process of water splitting in the
context of external stimulants like solar light irradiation and magnetic fields, successfully
addressing both HER and OER.
21
Fig 1. 13 Investigation of overall water splitting under solar light irradiation + magnetic field
to enhance the catalytic activity featuring the 1) semiconducting effect and 2) spin crossover
effect.
22
Chapter 2: Methods and Instrumentations
All the necessary characterizations were pursued at UNAM and the Chemistry Department of
Bilkent University.
2.1. Synthesis Procedure For FTO/[Co-M], (M = Co, Ni)

2.1.1. Chemicals
All the chemicals were purchased from established commercial suppliers and used without any
further purification. Potassium hexacyanoferrate(III) (K3Fe(CN)6), potassium
hexacyanoferrate(II) trihydrate (K4Fe(CN)6·3H2O), and potassium chloride (KCl) were
acquired from Sigma Aldrich. Cobalt(II) nitrate hexahydrate (Co(NO3)2.6H2O) was sourced
from Fischer Scientifics and Alfa Aesar. The precursors of potassium phosphate buffer solution
(PBS), Potassium phosphate monobasic (KH2PO4), and Potassium phosphate dibasic
(K2HPO4) were sourced from Sigma Aldrich. For all the experiments discussed below
Millipore deionized water with a resistivity of 18 MΩ.cm. was utilized. The glass substrates
utilized in the experiments were covered with fluorine-doped tin oxide (FTO), having a sheet
resistance of 20 Ω/sq. and 2mm thickness.
All the experiments are performed with a three-electrode system, Gamry software. In this setup
the FTO is connected to the working electrode, Ag/AgCl is used reference electrode while the
counter electrode is platinum (Pt) wire of 15 cm. This Pt wire was provided in the official
package of Gamry.
2.1.2. Preparation of FTO/[Co-Co] and FTO/[Co-Ni]
Before FTO/PBA preparation, an FTO electrode cleaning operation is carried out. Each FTO
electrode is sequentially submerged for 15 minutes in a sonication fluid made up of deionized
water, acetone, and ethanol. Then, for one hour prior to usage, the FTO electrode is maintained
at 100 ᵒC.
FTO/[Co-Co] and FTO/[Co-Ni] electrodes were prepared with two methods:
i) Hydrothermal technique: [89] In this method, a 30 mL 20 mM cobalt nitrate solution was

mixed well with 30 mL 0.1 M hexacyanocobaltate solution with the help of a sonicator at room
temperature. An aqueous solution of PBA and FTO electrode having its conducting side
downwards is immersed in a Teflon-lined stainless-steel autoclave. The sealed autoclave was
kept in the oven for 1 h at 120 °C. The autoclave was left to cool down to room temperature,
23
and the FTO was collected and rinsed multiple times with deionized water. The as-prepared
FTO was dried for 24 h at 50 ᵒC.
ii) Electrodeposition technique: [90] The 2-step electrodeposition method was employed to
prepare FTO/PBA. After experimenting with a spectrum of parameters, the following
procedure is developed:
First, 30 mL of 20 mM cobalt nitrate solution, supplemented with a supporting electrolyte KCl

(0.1 M) was prepared in a 50 mL beaker and the solution is treated with cathodic bias of −0.9
VAg/AgCl for a time span of 200 s to deposit metallic Cobalt on FTO electrode. A blue color on
the FTO surface is obtained which indicates the formation of FTO[Co] Fig 2.1. Subsequently,
the FTO electrode is rinsed thoroughly to eliminate any residue of KCl or any other potential
impurity, and FTO[Co] was immersed in 0.1 M hexacyanocobaltate solution with KCl (0.1 M)
under an anodic potential of 0.9 VAg/AgCl for FTO/Co-Co, or in 0.1 M tetracyanonickelate with
KCl (0.1 M) under the anodic potential of 1.02 VAg/AgCl for FTO/CoNi. Both, the FTO/[Co-Co]
and FTO/[Co-Ni] give brown color. The whole process is summarized in Fig 2.1. From SEM
studies we concluded that this approach provides a controlled and refined method related to the
roughness of the surface.
Fig 2. 1 Schematic diagram illustrating 3 electrode system for electrochemical deposition of

PBA on FTO surface.
24
2.2. Scanning Electron Microscopy (SEM) Coupled with Energy
Dispersive X-Ray Analysis (EDAX)
SEM-EDAX, combining scanning electron microscopy with energy dispersive X-ray

spectroscopy, was skilfully utilized to provide an insight into surface morphology of the
microscale characteristics of FTO/[Co-Co] and FTO/[Co-Ni] and measure the atomic ratio
respectively. These analyses were executed through FEI – Quanta 200 FEG at 5 kV for SEM
and 15 kV for EDAX analysis. For each study, multiple points were chosen, to get uniform
analysis.
2.3. Powder X-ray Diffraction (P-XRD) Analysis
X-ray diffraction (XRD) analysis was investigated to elucidate the structural characteristics of
the FTO/[Co-Co] composites and compared them to FTO and FTO[Co] samples. To employ
these analyses Panalytical X’pert Multi-Purpose apparatus was utilized. This study aimed to
elucidate the phase structures and attributed phase structures of FTO and electrodeposited PB
composites on FTO.
2.4. Xray-Photoelectron Spectroscopy (XPS) Analysis
Xray-Photoelectron Spectroscopy (XPS), with Al K-Alpha radiation and a photon energy (hʋ)
of 1486.6 eV was used in the survey mode with an activated flood gun to neutralize the surface
charge to determine the sample's elemental composition. The pass energy and step size for the
flood gun were 30 eV and 0.1 eV, respectively. Peak positions were calibrated precisely by
reference to the location of the C1s peak at 284.8 eV and then adjusting other peaks throughout
the spectrum in accordance.
2.5. Fourier Transform Infrared Spectroscopy (ATR-FTIR) Analysis
This analytical method makes use of a Bruker ALPHA Platinum-ATR spectrometer, which can
record spectra with wavenumbers between 4000 and 400 cm−1. With a noteworthy resolution
of 4 cm−1, the spectral acquisition was carried out, ensuring precise spectral feature
discrimination. To improve the reliability and precision of the data, 64 scans were gathered
while the measurement was being done. The thorough examination of the FTIR spectra
revealed important information about the complex chemical interactions and structural changes
related to the development of the FTO/[Co-Co] and FTO/[Co-Ni].
25
2.6. Electrochemical Setup
To carefully investigate the water splitting performance of FTO/[Co-M], (M = Co,Ni), a broad

spectrum of electrochemical techniques was utilized. These methods included two-electrode
and three-electrode system electrocatalysis studies, cyclic voltammetry (CV), linear sweep
voltammetry (LSV), chronoamperometry (CA), and cyclic voltammetry (CV) A Gamry
Instruments Interface 1000 Potentiostat/Galvanostat was utilized in the electrochemical setup
Fig 2.2a.
In this configuration, the reference electrode (RE) was Ag/AgCl (sat. ), the counter electrode
(CE) was 15 cm Pt wire in the official package with Gamry, and the working electrode (WE)
was FTO/[Co-Co] for OER reactions and FTO/[Co-Ni] for HER reactions. Notably, all
potentials were designated as VAg/AgCl and referred against Ag|AgCl|KCl(sat.) as shown in (Fig
2.2b and c). Electrochemical studies were performed at pH 7, maintained by 0.1 M PBS
solution as their electrolytic medium, together with 0.5 M KCl as a supporting electrolyte.
To account for the standardization, the potentials were converted into values relative to the
reversible hydrogen electrode (RHE), abbreviated as VRHE, using the Nernst equation to
adjust for standardization:
𝑉𝑅𝐻𝐸 = 𝑉𝐴𝑔/𝐴𝑔𝐶𝑙 (𝑉) + 0.059 × 𝑝𝐻 + 𝑉𝑜𝐴𝑔/𝐴𝑔𝐶𝑙 (𝑉) (21)
Here, VAg/AgCl (V) stands for the standard potential applied vs the Ag/AgCl reference electrode,
VRHE stands for the potential applied vs RHE, and VoAg/AgCl (V) stands for the standard potential
of the reference electrode, which is measured at (0.197 VRHE).
26
Fig 2. 2 a) Electrochemical set up with gamry featuring b) working electrode and c) reference
electrode. (Karadas Research Group).
27
2.7. Magnetic Setup
Vibrating sample magnetometer (VSM) technology shown in (Fig 2.3) was utilized to conduct
the study of catalyst performance under a magnetic field using the physical properties
measuring system (PPMS-Quantum Design). The measurements of temperature-dependent
magnetization (M-T) were made using an applied magnetic field of 500 Oe and temperatures
ranging from 2 K to 300 K. The magnetic field strength provided by the system could range
from 30 mT to 290 mT, and we studied a vast spectrum of investigation for Oxygen Evolution
Reaction, (OER), Hydrogen Evolution Reaction, (HER) and Overall Water Splitting (OWS).
Fig 2. 3 Magnetic Setup utilized for our experiment (Karadas Research group).
28
2.8. Photocatalytic Setup
A 300 W Xenon lamp and an AM 1.5 global filter were installed in the solar light simulator
(Sciencetech, Model SLB-300B) used in the experiment. This simulator was carefully
calibrated to emit light at a rate of 100 milliwatts per square centimeter (mW/cm2), representing
the brightness of one sun. This arrangement was created to look at how sunlight affects the
efficiency of the catalytic process.
Notably, no new filter was added at any point during the experimental processes. The Oxygen
Evolution Reaction (OER), Hydrogen Evolution Reaction (HER), and Oxygen-Water Splitting
(OWS) were among the reactions that used this arrangement. To establish repeatability and
validate the recyclability of the experimental system, each of these reactions was carried out in
a minimum of three cycles.
2.9. Calculating Surface Concentration of the Active Catalyst
By examining the relationship between the oxidation peak current (I) in milliamperes (mA)
and the sweep rate (v) in millivolts per second (mV s1), the surface concentration of active
catalytic sites present on the electrodes was identified. This was accomplished using a
computation based on the equation below.
𝑛2 𝐹 2 𝐴 𝜞
𝑆𝑙𝑜𝑝𝑒 = (22)
4𝑅𝑇
In the provided equation
• n: Indicates how many electrons are involved in the redox process. It is set to 1 in this
situation, denoting a one-electron transfer.
• F: the Faraday constant, has a value of 96485 s A/mol. It describes the electric charge
that one mole of electrons carries.
• A: Refers to the coated electrode surface area, measured in square centimeters (cm2). It
indicates the extent of the electrode's active surface available for catalytic reactions.
• Γ: Signifies the surface concentration of active catalytic sites on the electrode's surface,
expressed in moles per square centimeter (mol/cm2).
• R: Ideal gas constant, has a value of 8.314 Kg m2 s−2 K−1 mol−1
• T: Temperature of the reaction, which is 298, the room temperature.
29
Chapter 3: Results Section
3.1. Synthesis Procedure For FTO/[Co-M], (M = Co, Ni)

3.1.1. Hydrothermal technique:
FTO/PBA prepared through hydrothermal technique [89] method affords an uneven

coating of PBA on the FTO surface. (Fig 3.1) depicts the unnecessary peaks and low
current density due to the rough surface of the catalyst on FTO posing the challenges.
-0.3
FTO/[Co-Ni]
-0.4 Hydrothermal synthesis
-0.5
j (mA/cm2)
-0.6
-0.7
-0.8
-0.9
-1.0
-1.1
0 1000 2000 3000 4000
Time (s)
Fig 3. 1 CA profile of FTO/[Co-Ni] illustrating relatively low current density and

undesired peaks.
3.1.2. Electrodeposition technique:
FTO/[Co-M], prepared through the electrodeposition technique [90] afforded a

relatively smoother, uniform, and high-activity catalyst, compared to those prepared by
the hydrothermal method. This is confirmed by all the characterization techniques and
all the electrochemical experiments coming up in chapters 3, 4, 5, and 6. Therefore, all
the electrodes used in this thesis are prepared with the electrodeposition method.
30
3.2. FTO/[Co-M] (M = Co, Ni) Characterization
In order to comprehend the electronic and surface morphological attributes inherent in the
FTO/[Co-Co] and FTO/[Co-Ni] electrodes, a number of characterization techniques including
SEM, EDAX, XRD, ATR-FTIR, and XPS were employed.
3.2.1. Scanning Electron Microscopy and EDAX Analysis
Fig 3.2 shows scanning electron microscopy (SEM) pictures of the FTO electrode with
electrodeposited metallic cobalt coating, abbreviated as FTO/[Co]. A highly developed
microporous flower-like morphology with layered layers was revealed by the SEM
investigation. These structures had sub-micron diameters between 1 and 2 µm, and they were
evenly distributed across the whole FTO surface. FTO/[Co] preparation step is similar in both
FTO/[Co-Co] and FTO/[Co-Ni] cases. EDAX analysis of FTO/[Co] illustrated in Fig 3.3
confirms the presence of cobalt.
Fig 3. 2 SEM images of FTO/[Co] (a) 20,000x magnification and (b) 40,000x magnification.
31
Fig 3. 3 EDAX analysis of FTO/[Co].
SEM images for electrodeposited PBA FTO/[Co-Co] illustrated in Fig 3.4a and b and PBA
FTO/[Co-Ni] Fig 3.4c and d were achieved to probe the surface morphology. They showed
uniformity in particle size ranging from 1-2 μm and layered structures grown in thread-like
shapes. On the contrary, for FTO/[Co-Ni], porous needle-like structures were grown with a
huge range of 100 nm to 3 µm. The EDAX analysis shown for FTO/[Co-Co] in Fig 3.5 and for
FTO/[Co-Ni] in Fig 3.6 respectively confirms the presence of cobalt in FTO/[Co-Co], and Co
and Ni in FTO/[Co-Ni] in the equimolar ratio of 3.21% Co to 3.34% Ni, between the two
elements.
32
Fig 3. 4 SEM images of fresh FTO/[Co-Co] (a) 10,000x magnification, (b) 40,000x
magnification and SEM images of fresh FTO/[Co-Ni] (c) 20,000x magnification, (d) 80,000x
magnification.
Fig 3. 5 EDAX analysis, the elemental insights of FTO/[Co-Co].
33
Fig 3. 6 EDAX analysis, the elemental profile of FTO/[Co-Ni].
34
3.2.2. XRD Analysis
All the electrodes exhibit characteristic diffraction patterns of FTO labeled as circles. Notably,
the metallic cobalt exhibits two relatively weaker diffraction features at 11° and 29°. In
contrast, these features are not observed for FTO/[Co-Co] and FTO/[Co-Ni], indicating that
the metallic cobalt is completely oxidized to yield [Co-Co] PBA (CoII-CoIII). Remarkably the
asterisk-annotated peaks shown by FTO/[Co-Co] in Fig 3.7a and FTO/[Co-Ni] in Fig 3.7b,
correspond to the characteristic patterns of cubic Prussian blue structure. XRD profiles thus
confirm the formation of face-centered cubic (fcc) PB lattice structure, closely aligned with the
Fm3m space group. The XRD pattern of the FTO[Co-Ni] discernible diffraction peaks
occurring at approximately 25°, 32°, 36°, and 43°. These distinctive peaks are ascribed to the
diffraction characteristics of the Co-Ni PBA [26]. Similarly, XRD patterns of FTO/[Co-Co]
features prominent peaks around 17°, 24°, 35°, 39°, 51°, 58° and 60° are attributed to Co-Co
PBA[ [58, 59].
Fig 3. 7 XRD patterns compared to FTO and FTO/[Co] for (a) FTO/[Co-Co], and
(b) FTO/[CoNi].
35
3.2.3. XPS Analysis
To check the oxidation states of the elements in the materials XPS analysis (X-ray
Photoelectron Spectroscopy) was performed for FTO/[Co-Co] and FTO/[Co-Ni].
Fig 3.8a illustrates the XPS spectra of C-1s and K-2p while Fig 3.8b represents the Co-2p. Our
focus was on researching the metal sites in a networked structure connected by cyanide groups.
Previous studies have demonstrated that there is typically a partial oxidation effect when metal
ions are connected by cyanide bridges [76]. The metals in PBA i.e., cobalt and nickel feature
their 2p peaks in the binding energy region of 770 eV to 880 eV [91]. C-1s and K-2p give
prominent peaks in the binding energy regions of 285 eV and 293.4 eV. Two distinct peaks at
energies 781 eV and 797 eV, which correspond to various cobalt states, can be seen in the Co-
2p spectrum. The research reveals that the material's structure is preserved throughout the
electrochemical process in the instance of the PB (Prussian Blue) layer in FTO/[CoFe] [92].
Fig 3. 8 XPS analysis for pristine and post-catalytic FTO/[Co-Co] (a) C-1s and K-2p peaks
and (b) Co-2p3/2 and Co-2p1/2 peaks.
Similarly, XPS analyses were performed for the FTO/[Co-Ni] before and after the catalytic
performance as shown in Fig 3.9a and b. Fig 3.9a corresponds to the Co-2p peaks in the binding
energy region of 782 eV in Co-2p3/2 and 796 for Co-2p1/2. However, Fig 3.9b features the
characteristic peaks for Ni 2p3/2 at around 856 eV and Ni-2p1/2 at around 874 eV [93].
36
Fig 3. 9 XPS analysis for pristine and post FTO/[Co-Ni] (a) Cobalt peaks and (b) Nickel peaks.
3.2.4. ATR-FTIR Analysis
A systematic FTIR-ATR analysis was executed to confirm the synthesis of FTO/[Co-Co] and
FTO/[Co-Ni] PBA as depicted in Fig 3.10. The FT-IR data unveils distinct peaks at around
2176 cm−1 attributed to the CoII-CN-CoIII in FTO/[Co-Co] and 2164 cm−1 attributed to the CoII-
CN-NiIII in FTO/[Co-Ni] coordination motif within the structural arrangement. The peak at
around 1610 cm−1 and broadband at 3385 cm−1 observed by both samples are ascribed to H2O
bending modes and O-H bending modes, respectively. Notably, the presence of sharp peaks
within the fingerprint region at around in ATR spectra at around 580 cm−1 and 430 cm−1
correspond to the CoII-N and CoIII-C/NiII-C bond stretches distinctly elucidating the chemical
connectivity within the structure [90].
37
FTO/[Co-Co]
FTO/[Co-Ni]
Transmittance (a.u.)
M-N
H2O M-C
CN H2Obending
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Fig 3. 10 ATR-FTIR spectrum of FTO/[Co-Co] and FTO/[Co-Ni] featuring prominent

stretches.
3.2.5. Calculating the Surface Concentration of the Catalyst
The surface of the catalyst is consistently maintained to be 1 cm2 throughout the thesis,
however, the actual parameter to understand the catalytic performance is the surface
concentration of the active catalyst on the surface of FTO/[Co-Co]. By investigating the
relation between current (I), and sweep rate, (equation 2 chapter 2.9) we were able to find the
active surface concentration to be, 53.01 nmol/cm2 for FTO/[Co-Co] and 63.41 nmol/cm2 for
FTO/[Co-Ni] which is comparatively better than previously reported electrodeposition
depending upon the size of ligands for example Ahmad et al. synthesized the catalysts through
co-precipitation techniques the active surface concentration to be 0.53, 10.01 and 0.32
nmol/cm2 for [Cobpy-Fe], [Co-Fe], and [Cophen-Fe] [94]. Fig 3.11 illustrates the
aforementioned values of current (I) and sweep rate potential in mV for both FTO/[Co-Co] and
FTO/[Co-Ni]. Similarly, Chalil Oglou et al. through electrodeposition method achieved almost
similar active surface concentration of 49 nmol/cm2, 34 nmol/cm2 and 43 nmol/cm2 for
38
FTO/[Co−FeII−NO], FTO/[Co−FeII] und FTO/[Co−FeIII] because of following the same
*protocols [85].
Fig 3. 11 Statistical data relating current (I) and sweep voltage aimed to measure Active surface
area with equation 2 Chapter 2.9.
39
Chapter 4: Electrocatalytic water oxidation under magnetic and
light field with FTO/[Co-Co]
A three-electrode setup was employed in the experimental technique for the oxygen evolution
reaction (OER) studies. All the experiments were performed at pH 7, in a phosphate buffer
solution (PBS 0.1 M) KCl was used as an electrolyte at room temperature. In all three-electrode
experiments, Pt wire is used as the counter electrode, and an Ag/AgCl electrode was used as
the reference electrode, which was used to create a constant electrochemical potential reference
point so that the working electrode and counter electrode could have their electrochemical
behavior quantitatively compared. The prepared FTO electrodes are used as working
electrodes.
The stability of the FTO electrode presented a substantial difficulty during our electrocatalytic
studies that were carried out under the influence of a magnetic field. A solution was required
since our FTO electrode is inherently vulnerable to magnetic field displacement. We came up
with a unique 3D-printed stage to solve this problem, which is shown in Fig 4.1. This stage's
careful positioning and construction ensured the electrode's immobility throughout the trial.
Notably, the stage's measurements were adjusted to ensure that the electrode would fit
perfectly. The height of the 3D-printed stage is 0.2 centimeters, which is the same as the
electrodeposit we were using to cover the electrode's 1-centimeter height.
40
Fig 4. 1 Image of the 3D-printed stage for all the HER and OER reactions under magnetic field.
4.1. Magnetic Field-Assisted OER Studies

4.1.1. Linear Sweep Voltammetry Studies
Linear sweep voltammetry (LSV) curves were obtained to acquire distinct profiles as shown in
Fig 4.2 in which the black trace depicts the OER current density in the absence of the magnetic
field the red profile indicates the catalysis under a magnetic field of 200 mT (milli tesla). This
investigation encompasses a potential range from 0.2 V to 1.6 V. There is an enhancement of
0.34 mA/cm2 at an overpotential of 997 mV (which is 1.6 V, the LSV limit for our studies) in
the current under the magnetic [63]. The overpotential required to achieve 1 mA/cm2 current
density is recorded as 570 mV and remains the same under the magnetic field of 200 mT as
well. Overall, an enhancement of 3.3% is achieved under magnetic field.
41
Fig 4. 2 LSV Profile of FTO/[Co-Co] illustrating magnetic enhancement (Inset: Magnified
image of the enhancement zone).
Similarly, the enhanced current density was also confirmed through the Tafel slope shown in
Fig 4.3, which is 88 mV/dec for FTO/[Co-Co] with no stimulus, and 87 mV/dec under the
influence of magnetic field. Tafel plots were constructed for OER mechanisms by conducting
LSV measurements under different external stimuli Fig 4.3 and Fig 4.8, aiming to figure out
the nature of enhancement from the two external stimuli is different.
Notably, we observed a linear correlation between the logarithms of steady-state current

densities and over-potentials, spanning the overpotential range of 560 mV to 580 mV. Within
this range, we calculated Tafel slopes, which fell within the range of 88 to 95 mV per decade
illustrating the lowest for solar light irradiated LSV.
Comparing our obtained Tafel slopes for FTO/[Co-Co] and FTO/[Co-Ni] with those previously
reported by Alsac et al. [58] We observed minute differences. These disparities can largely be
attributed to distinct preparation methods, Specifically, PBA-modified electrodes on FTO
surface, prepared method exhibited slightly lower Tafel slopes.
42
0.58
FTO/[Co-Co] H OFF
FTO/[Co-Co] H ON
H OFF
0.58
95 mV/dec
Over potential (V)

0.57
0.57
H ON
0.56
93 mV/dec
0.56
-3.10 -3.08 -3.06 -3.04 -3.02 -3.00 -2.98 -2.96
2
logA (log(A/cm )
Fig 4. 3 Tafel slope FTO/[Co-Co] under magnetic field.
4.1.2. Chronoamperometric Studies
Chronoamperometry measurements were performed to investigate the stability of the catalyst

and to further investigate the effect of the magnetic field on the catalytic activity. An
overpotential of 949 mV was applied for 2100 seconds. As could be seen from Fig 4.4, the CA
profile initially reveals a steady state current density for around 500 seconds, and a magnetic
field of 200 mT was applied for 300 seconds. This process was repeated subsequently, and the
pattern of CA measurements continued until the experimental endpoint at 2100 seconds. A
steady profile obtained indicates the stability of the catalyst. The maximum current density
achieved during this CA profile at 949 mV overpotential was 4.6 mA/cm2. From the given
profile it is evident that the results are reproducible and an enhancement of 10.7 % is achieved.
43
Fig 4. 4 CA profile obtained for FTO/[Co-Co] OER at η = 949 mV.
Following this, CA profiles as shown in Fig 4.5 were investigated at various overpotentials
under a magnetic field of 200 mT under the same conditions. Interestingly we observed that as
the overpotential decreases, the relative enhancement in the current density also decreases.
Fig 4. 5 CA Profile obtained for FTO/[Co-Co] at different overpotential (Insets: zoomed

images of graphs that are not clear in the main graph).
44
After this, a CA measurement profile was obtained at varying magnetic fields shown in Fig
4.6, which reveals a direct relationship between the applied magnetic field and current density.
Fig 4. 6 CA profile obtained for FTO/[Co-Co] OER at η = 859 mV various magnetic field.
4.2. Solar Light-Assisted Studies

4.2.1. Linear Sweep Voltammetry Studies Under Light Irradiation
Linear sweep voltammetry profile was performed to investigate the effect of solar light on the
catalytic performance of FTO/[Co-Co] as shown in Fig 4.7. The experiment was performed
from 0.2 V to 1.6 V vs Ag/AgCl. A xenon lamp (300 W-100 mW/cm2) was used as the light
source. Under solar light irradiation, an enhancement of 0.74 mA/cm2 is achieved in the current
density while the overpotential required to achieve 1 mA/cm2 current density is 570 mV. The
peak at around 1 V is attributed to the Co+2/+3 redox process [58].
45
Fig 4. 7 LSV Profile of FTO/[Co-Co] with and without solar light irradiation (Inset: Magnified
the enhancement zone).
As the similar Tafel slopes indicate similar OER kinetics, we observed difference in Tafel
slopes for the one under magnet and solar light, as could be seen in Fig 4.8. This indicates that
the OER reaction kinetics under solar light are different and faster from the one under magnetic
field.
46
800
FTO/[Co-Co] OER (h) h OFF
93 mV/dec
Overpotential (mV)
600
h ON
88 mV/dec
400
200
-2.99 -2.98 -2.97 -2.96
log A (log (A/cm2))

Fig 4. 8 Tafel slope FTO/[Co-Co] under magnetic field.
4.2.1.1. Relative LSV Profile
Under solar light irradiation, we observed a permanent enhancement in the catalytic

performance of PBA FTO/[Co-Co]. This fact is in good agreement with Fig 4.8 where the last
LSV profile (rightmost) illustrates the difference between i) the black-colored LSV without
light, ii) the orange with light, and iii) the red without light after a long CA measurement. This
behavior is backed by the CA profile of FTO/[Co-Co] shown in Fig 4.8 and 4.10
47
Fig 4. 9 Relative LSV profile of FTO/[Co-Co] with and without solar Light irradiation.
4.2.2. Chronoamperometric Studies Under Solar Light Irradiation
In order to investigate the stability and long-term behavior of solar light irradiation, a CA
profile was obtained with FTO/[Co-Co] at 859 mV overpotential shown in Fig 4.9. The CA
profile was initially stabilized in the first 500 seconds and then the system was exposed to solar
light. The profile showed an average enhancement of 9.03% and the results are reproducible
as could be seen from the three repeated cycles.
48
Fig 4. 10 CA profile of FTO/[Co-Co] under light irradiation.
CA experiments at varying overpotentials were performed, which interestingly reveals an

inverse relationship between the overpotential and the relative enhancement. Furthermore, a
permanent enhancement due to solar light irradiation is obtained, which indicates that the
catalytic activity of the post-catalytic electrode is enhanced Fig 4.10. This effect was not seen
when the catalyst was exposed to the magnetic field. The results are summarized in Table 4.1.
49
Fig 4. 11 CA Profile of FTO/[Co-Co] illustrating Light enhancement at different
overpotentials(inset: Showing the red graph enhancement which is not very prominent in the
main graph)
We also performed a long-term chronoamperometric experiment to combine the effect of both

stimuli. As can be seen from Fig 4.11 with a magnet, an average enhancement of 10.7% is
achieved under a magnetic field of 200 mT, while it is 11.9% under solar irradiation
Furthermore when the light was switched on during the application of magnetic field i.e., at
3400 seconds, the profile clearly indicates that they exhibit a combined effect to yield an overall
enhancement of 22.5%.
50
Fig 4. 12 CA Profile of FTO/[Co-Co] illustrating the combined effect of light and magnet.
4.2.2.1. Catalyst Stability
In order to evaluate the catalyst's stability and confirm the catalyst’s continued improvement
in catalytic performance a long-term experiment was designed. As could be seen in Fig 4.12
The duration of this prolonged experiment included two hours of light exposure followed by
six hours of no light. This experiment was carried out at a rather low overpotential of 570 mV,
which was specifically designed to give the catalyst plenty of time to improve its effectiveness.
This tactical decision was influenced by earlier research as shown in Fig 4. 10, which showed
an inverse relationship between the magnitude of the overpotential, and the degree of the
enhancement attained under solar light irradiation.
Exciting results were achieved from the entire study's findings. In particular, a striking net
improvement of 193%, as graphically shown in Fig 4.12, was unquestionably attained. The
continuous nature of this improvement, as shown by the constant current attained over an
extended period, is particularly significant. It was noted that the attained current density did
51
not return to its initial value, which is significant since it shows that the FTO/[Co-Co] system's
catalytic performance has continued to improve.
Fig 4. 13 CA profile of FTO/[Co-Co] under light for 2 h and dark 6 h.
These results were confirmed by the LSV profile as seen in Fig 4.13, where the black LSV
profile leads the rest as it was done after a long time CA profile.
52
Fig 4. 14 LSV profile of FTO/[Co-Co] before and after 8 h experiment.
4.2.3. Temperature Profile for CA Under Solar Light Irradiation
In order to thoroughly examine how solar light irradiation affects the reaction's temperature
dynamics, and thereby gain deeper insights into the underlying mechanisms governing light-
induced enhancement, the temperature of the reaction at 570 mV overpotential was monitored
using the previous experimental procedure that consists of two hours of exposure to light and
six hours of darkness as illustrated by Fig 4.14. The principal findings of this experiment are
that when the catalytic system was exposed to light, the temperature showed a gradual,
unidirectional increase of about 5 to 6 ᵒC, which was then followed by a decrease when the
light source was blocked. An obvious correlation between temperature changes and reaction
kinetics was established by the phase of temperature elevation, which stood out for exhibiting
noticeably accelerated kinetics. Additionally, the overall temperature changed from the initial
25 ᵒC to a maximum of 31 ᵒC lowered back to 26 ᵒC instead of 25 ᵒC. A consistent improvement
of 36% persisted even after the solar light was stopped, highlighting the significant impact that
53
temperature has on reaction kinetics. The complex interaction between temperature and the
underlying reaction dynamics is the reason for the persistent increase in current density.
1.8 40
FTO/[Co-Co] 39
1.7 Temperature (°C)
38
1.6 37
36
1.5 35
34
Temperature (°C)
1.4
33
1.3
j (mA/cm2)
32
1.2 31
30
1.1 29
1.0 28
27
0.9 26
0.8 25
24
0.7 23
22
0.6
21
0.5 20
0 1 2 3 4 5 6 7 8
Time (h)
Fig 4. 15 Temperature recorded profile during (FTO/Co-Co) CA.
Table 4. 1 Summary of solar irradiated and under magnetic field OER studies.
Ƞ (mV/cm2) jm mA/cm2 jm/j×100, % js mA/cm2 js/j×100, %
997 (LSV) 0.34 3.3 0.74 7.1
949 (CA) 4.91 10.7 5.69 11.9
859 (CA) 2.42 9.5 3.96 14.1
570 (CA) 7.2 5.8 2.68 26.1
54
Chapter 5: Electrocatalytic hydrogen evolution reaction (HER)
studies under magnetic field and solar light irradiation with
FTO/[Co-Ni]
A three-electrode system utilized for OER reaction was used, also for HER studies. The FTO
electrode was used as a working electrode and Pt wire was used as a counter electrode.
Similarly, Ag/AgCl was used as a reference electrode. All experiments were conducted in KCl
(0.5 M) solution as a supporting electrolyte at pH 7 in PBS (0.1 M) solution.
5.1. Magnetic Field-Assisted HER Studies

5.1.1. Linear Sweep Voltammetry Studies
The LSV profile was obtained to investigate the difference between the catalyst performance
with and without a magnetic field. LSV profile was obtained from 0 to −1.6 V vs Ag/AgCl as
illustrated in Fig 5.1. In both cases, i.e., the current density reached −1 mA/cm2 at an
overpotential of 114 mV. However, there is nearly no enhancement under the magnetic field.
1
H OFF
0 H ON
-1
-2
j (mA/cm )
2
-3
H OFF
-4 H ON
-4 -5
j (mA/cm )
2
-6
-5
-7
-6 -8
-1.4 -1.2
E (V) vs. RHE
-7
-8
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
E (V) vs. RHE
Fig 5. 1 LSV Profile of FTO/[Co-Ni] with and without magnet field.
55
Unlike OER reactions, an enhancement under a magnetic field was not anticipated since the
HER process does not involve a spin crossover effect [80]. To confirm this, a long-term
experiment of 2100 seconds was performed at a constant overpotential of 300 mV as shown in
Fig 5. 2. There was a very small change of 1.4% in the current density under the magnetic field,
which is attributed to the magnetohydrodynamic effect caused by the random accelerated
motion of ions under the influence of the magnetic field [73]. Similar study was pursued by
Hang-bo et al. by utilizing directly ferromagnetic materials such as CoNi@C as catalyst and
discovered very small and unstable enhancements in catalytic activity [94]. Moreover, Jiawei
et al. attributed the magnetic effect of HER enhancement under magnetic effect to using
ferromagnetic material [95].
Fig 5. 2 CA profile of FTO/[Co-Ni] for HER reaction.
5.2. Solar Light Assisted HER Studies

5.2.1. Linear Sweep Voltammetry Studies Under Light Irradiation
56
As shown in Fig. 5.3, linear sweep voltammetry (LSV) curves were used to acquire distinct
profiles, with the black trace representing the HER current density in the absence of solar light
irradiation, and the red profile representing catalysis under solar light irradiation. The potential
range for this investigation is between −0.2 and −1.6 volts against Ag/AgCl. The current under
solar light irradiation is enhanced by 0.42 mA/cm2 at a 42 V overpotential (which was the
selected zone for HER LSV’s) [63]. 54 mV is recorded as the overpotential needed to achieve
−1 mA/cm2 current density, and in the presence of solar light due to the early reduction of Ni
from Ni2+ to Ni1+, the overpotential was very slightly less than without solar light with a
difference of decimals as could be seen in Fig 5.3. Under solar light irradiation, 6.2%
enhancement was achieved in HER activity.
0
-6.80 mA/cm2 h OFF
-1 -7.22 mA/cm2 h ON
-2
j (mA/cm2)
-3
j (mA/cm2)
-4
-7
-5
-6 -1.6
E (V) vs. RHE
-7
-8
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2
E (V) vs. RHE
Fig 5. 3 LSV Profile of FTO/[Co-Ni] illustrating enhancement under solar light irradiation
(Inset: Magnified the enhancement zone).
57
Unlike the magnetic field profile for HER, we were expecting enhancement for HER profile
under solar light irradiation due to the semiconducting nature of PBA. Initially, a current
density of −0.11 mA/cm2 with −0.7 V, corresponds to an overpotential of 100 mV as could be
seen in Fig 5.4. The current density was led to stabilize within 500 seconds which was later
exposed to solar light irradiation. The solar light irradiation was subsequently switched off, and
the CA pattern was allowed to continue, until the experimental endpoint at 2100 seconds. From
the graph, it is evident that an enhancement is under light irradiation which is reversible.
Furthermore, similar to FTO/[Co-Co] an enhancement under solar irradiation (38%) is
obtained, which is reversible.
Fig 5. 4 CA Profile of FTO/[Co-Ni] under solar light irradiation.
58
Following this, once again the photocatalytic activity of the FTO/[Co-Ni] was investigated at
various overpotentials as illustrated in Fig 5.5. Similarly, when the overpotential increases, %
enhancement decreases revealing an inverse relationship between % enhancement and
overpotential.
Fig 5. 5 CA profile of FTO/[Co-Ni] at various overpotentials.
Table 5.1 summarizes the FTO/[Co-Ni] HER activity depicting the negative trend in
overpotential vs solar light irradiated catalytic performance.
59
Table 5. 1 Summary of solar irradiated HER studies.
Ƞ (mV/cm2) js mA/cm2 js/j×100, %
433 (LSV) -0.42 6.7
300 (CA) -1.28 12
200 (CA) -0.61 14
100 (CA) -0.24 38
60
Chapter 6: Electrochemical overall water splitting (OWS) under
magnetic field and solar light irradiation
After studying carefully OER and HER with FTO/[Co-Co] and FTO/[Co-Ni] respectively, we
concluded that the spin cross-over effect exclusively takes place in OER reactions. Since the
gamry potentiostat is built in a design to prioritize the working electrode, thus allowing it to
experience any level of overpotential compared to the counter electrode. Fig 6.1 summarizes
the previous findings obtained in chapters 4 and 5.
In this chapter, we aimed to combine these findings to build a magnetic field and light-assisted
overall water-splitting device, which has not been reported up to now.
Fig 6. 1 Compilation and Overview of Current Research Findings.
6.1. Novel Experimental Configuration for Conducting Oxygen and

Hydrogen Evolution Reaction in One Setup Studies
The design of the OWS was one of the most challenging parts of this thesis since two 3D-
printed electrode holders were used in the OWS experiment rather than one electrode holder
for OER and HER experiments. Keeping the electrode holders, firm and static under a magnetic
field was difficult. It should also be noted that alligators are also sensitive to magnetic fields.
In our optimization experiment, we found out magnetic field-assisted experiments reveal the
highest activity when the electrodes are face to face (f2f) while for solar light-assisted studies,
electrodes are placed side by side to ensure that both electrodes are exposed to solar light also
illustrated in Fig 6.7.
61
Another additional concern was regarding the experimental setup. The issue was that if we
remove the 3D-printed stage Fig 4.1, which was used to hold electrodes firmly under magnetic
field studies, the experiment is not possible, since the electrodes held by alligators are prone to
moving under magnetic field studies, and due to these reasons, we decided to use nonmagnetic
conducting set up.
To address this issue, we tied platinum wires to the FTO electrode and stuffed it with extra
platinum foil, to maximize the conductivity as shown in Fig.6.2.
Fig 6. 2 Novel Experimental Setup for Conducting Overall Water-Splitting Experiments.
To perform the experiments, we came up with 2 designs, a two-electrode system, and a three-
electrode system.
6.1.1. Two Electrode System
In a two-electrodes system, the reference electrode was removed, and combined the alligator
of the reference electrode with the counter electrode. This Reference/Counter electrode was
used to accommodate FTO/[Co-Ni] while on the working electrode we put FTO/[Co-Co] as
shown in Fig 6.3. In 2 electrode system, gamry potentiostat adds the overpotential of both
electrodes and combines them providing a very high overpotential. In our experimental setup,
we used 2 V of potential which corresponds to an overpotential of 1013 mV with respect to the
working electrode to get the following graph. To understand each electrode is taking how much
62
overpotential, we tried to run a chronopotentiometry experiment in which 1 mA/cm2 current
density was selected to be pursued. Hereby, we pursued 2 experiments.
Fig 6. 3 CA profile obtained for OWS in a two-electrode system.
A) In the first experiment, FTO/[Co-Co] was accommodated as a working electrode, and

FTO/[Co-Ni] as a counter electrode, with Ag/AgCl as a reference electrode. During the
chronoamperometry experiment, a current density of 1 mA/cm2 was pursued at 1.35 V,
which corresponds to the potential between the working electrode and the reference
electrode. By looking at the 2-electrode experiment, it should be a a potential difference
of 0.54 V between the reference electrode and counter electrode Fig 6.4.
63
a) b)
Fig 6. 4 a) Images of overpotential reading at working electrode displayed on the screen b)

Image of overpotential displayed between counter and reference electrode with potentiometer.
B) To confirm this, the electrodes were swapped, i.e., the FTO/[Co-Co] was shifted to the
counter electrode, however, the FTO/[Co-Ni] was shifted to the working electrode and
a negative current density of −1 mA/cm2 was given in chronopotentiometry study. This
time the gamry was showing 0.6 V of potential difference, and to make sure, the
potential difference between the reference and the counter was measured to be 1.298 V
with a potentiometer. Hence confirmed, that the OER part was taking 1.3 V, however,
HER is taking 0.6 V potential to achieve 1 mA/cm2 of current density. The stats are
displayed in Fig 6.5.
64
a) b)
Fig 6. 5 a) Images of overpotential reading at working electrode displayed on the screen b)

Image of overpotential displayed between counter and reference electrode with potentiometer.
6.1.2. Three-Electrode System
In three electrodes same protocols as used for separate OER and HER reactions were followed,
however, the counter electrode C was replaced by FTO/[Co-Ni] instead of platinum wire while
FTO/[Co-Co] was used in the working/working sense W/WS electrode. Fig.6.6 and 6.7
illustrates the three-electrode design utilized for the OWS.
Fig 6. 6 Three-electrode system real image planted inside the magnetic field, with a schematic
representation.
65
Fig 6. 7 Schematic diagram illustrating the three-electrode system utilized for OWS a) Face-
to-face configuration for studies under magnetic field b) Side-by-side configuration for solar
light irradiated studies.
6.2. Magnetic Field-Assisted Studies

6.2.1. CA Profile Of FTO/[Co-Co] And FTO/[Co-Ni] For OWS
Chronoamperometric measurements were made to evaluate the catalyst's stability, how a

magnetic field affected it, and how well it performed as a catalyst. Over the course of 2100
seconds, a 949 mV of overpotential was applied. The chronoamperometric (CA) profile, shown
in Fig 6.8, shows a steady current density for the first 500 seconds or so. After that, a 200 mT
magnetic field was applied for 300 seconds. CA measurements continued throughout this
sequential process of iterations until the experiment's predetermined endpoint at 2100 seconds.
The catalyst's ongoing stability is indicated by the profile's consistency throughout. Under the
949 mV overpotential condition, the CA profile's peak current density was 5.1 mA/cm2. The
profile displays an impressive level of reproducibility in the findings, demonstrating an
enhancement of 9.2%.
66
Fig 6. 8 CA profile obtained for FTO/[Co-Co] W/WS and FTO/[Co-Ni] C for OWS.
The chronoamperometric (CA) profile was thoroughly explored after the aforementioned
investigations, this time with different overpotentials, while maintaining a constant magnetic
field intensity of 200 mT. The relationship between overpotential values and the relative
increase in current density was assessed. This showed a direct relationship where the
overpotential values were systematically decreased, and a corresponding decrement in relative
enhancement was observed as shown in Fig 6.9. The dependence of enhancement on
overpotential suggests that complex mechanisms (spin crossover effect) that control the
interaction between the magnetic field and electrocatalytic processes exist which is not similar
to what we observed in solar light irradiated experiment.
67
Fig 6. 9 CA profile obtained for FTO/[Co-Co] as W/WS and FTO/[Co-Ni] as C for OWS at
various overpotentials (inset: Magnified picture of lower enhancements in the main graph).
Subsequent to this analysis, a comprehensive chronoamperometric (CA) measurement profile

was achieved encompassing distinct magnetic field strengths. As visually represented in Fig
6.10. This experiment revealed a conspicuous and direct relationship between the magnitude
of the applied magnetic field and the resulting current density. The observable pattern
generated by these experiments highlights the potential for manipulating the magnetic field to
enhance and regulate catalytic performance.
68
various magnetic field strengths (inset: Magnified picture of lower enhancements in the main
graph).
6.3. Solar Light Irradiated Studies

In order to investigate thoroughly the stability and the extended performance of solar light
irradiation CA profile was obtained. This experiment was conducted using FTO/[Co-Co] as
the working electrode for OER, and FTO/[Co-Ni] as the counter electrode for HER reaction.
859 mV of overpotential was applied as shown in Fig 6.11 to achieve 36 % of the enhancement
mentioned in Fig 6.9. As shown by the figure, the CA profile, following a well-defined
stabilization period of an initial 500 seconds, underwent a significant transformation upon
exposure to solar light irradiation. The profile was recyclable and very stable in nature.
69
Fig 6. 11 LSV profile obtained for FTO/[Co-Co] as W/WS and FTO/[Co-Ni] as C for OWS.
Similar to our previous studies, (CA) experiments were conducted with a diverse range of
overpotentials to investigate the effect of overpotential on the catalytic performance as shown
in Fig 6.12. These experiments yielded a discernible pattern illustrating an inverse relationship
between the overpotential and relative enhancement in the current density. Significantly, this
effect was conspicuously opposite, when the catalyst was subjected to the influence of the
magnetic field, underscoring the distinct nature of these two external stimuli and their
differential impact on the electrochemical landscape.
70
various overpotential under solar light irradiation (inset: Magnified picture of lower
enhancements in the main graph).
Table 6.1 summarizes the FTO/[Co-Ni] + FTO/[Co-Co] OWS activity depicting the direct
relation between overpotential and % enhancement and negative trend in overpotential vs solar
light irradiated catalytic performance.
Table 6. 1 Summary of solar irradiated and under magnetic field OWS studies.
Ƞ (mV/cm2) jm mA/cm2 jm/j×100, % js mA/cm2 js/j×100, %
949 (CA) 5.1 9.2 4.6 4.4
859 (CA) 3.0 5.6 2.0 17.9
570 (CA) 1.6 5.2 0.6 36.2
71
Chapter 7: Conclusion
In conclusion, the search for long-lasting and potent catalysts is of utmost importance in the
effort to create a world with sustainable energy resources and clean environment. Prussian Blue
Analogues (PBAs), a thoroughly researched class of substances, offer a flexible toolkit for
designing powerful catalysts with exceptional functionality and reusability. This thesis
explores novel findings resulting from the use of FTO/[Co-M], (M = Co-Ni), PBAs to hasten
the overall water splitting (OWS) process while subjected to previously unresearched external
stimuli.
The important work by Alsac et al. who carefully assessed the (OER) activity of various PBAs,
served as the foundation for this investigation. They came up with the conclusion that Co-Co
exhibits highest performance as an OER catalyst. The (HER) was then explored by Ahmad et
al. who identified Co-Ni as the top performer in this context. By exploring the effect of
magnetic fields on OER catalytic activity within the framework of PBA Co-Fe electrodeposited
on the FTO surface, Ramadan et al. added to this discussion by expanding it to new levels.
Their research revealed an increased magnetic field-catalyzed catalytic activity.
This study advances the conversation by gathering these investigations and exploring OWS in
the context of external stimuli. This was accomplished by using FTO/[Co-Co] for OER
reactions and FTO/[Co-Ni] as the catalyst for HER reactions. These electrodes were
meticulously characterized using methods like SEM, EDAX, P-XRD, XPS, and ATR-FTIR
after being carefully synthesized using a two-step electrodeposition procedure. The fascinating
flower-like morphology of FTO/[Co], thread like growth of FTO/[Co-Co] and needle-like
dimensions of FTO/[Co-Ni] respectively, showed uniform particle of 1-2 µm in size.
Additionally, EDAX analysis confirmed an equimolar ratio of 3.21% Co and 3.34% Ni in
FTO/[Co-Ni], confirming the presence of the respective elements in the expected ratios. P-
XRD analyses confirmed the samples with their characteristic peaks.
The electrochemical studies performed on these catalysts revealed the following results.
Through LSV, the OER performance of FTO/[Co-Co] was revealed, and the enhancement
peaks in response to external stimuli painted a clear picture. Solar light produced a stronger
7.1% enhancement while the magnetic field produced a 3.3% augmentation. Fascinatingly, CA
profiles under the influence of varying overpotentials and magnetic field strengths revealed a
direct correlation between the overpotential and the magnetic field strength. On the contrary,
72
the CA profile under solar light irradiation, in sharp contrast, showed a trend that was the
opposite of the magnetic fields. The enhancement under magnetic fields was attributed to the
spin crossover effect, while the enhancement under solar light irradiation was attributed to the
semiconducting effect, according to the studies and insights from the body of existing literature.
Under the influence of solar light irradiation and magnetic fields, the HER efficacy of
FTO/[Co-Ni] was examined. The LSV profile revealed enhancement only under solar light
irradiation, the unanticipated boost was not brought about by magnetic fields. Similar to OER,
the FTO/[Co-Ni] CA profiles showed the opposite trend in terms of the applied overpotential.
Surprisingly, the magnetohydrodynamic effect resulted in a marginal 1.4% improvement in the
HER CA profile.
Both a two- and a three-electrode setup was used for the investigation into overall water
splitting. FTO/[Co-Co] served as the working electrode in the two-electrode configuration, and
FTO/[Co-Ni] served as the counter electrode. For the system to produce a current density of 1
mA, a significant 1013 mV overpotential (2 V against Ag/AgCl) was required. Then, by
analysing the various voltage contributions from each electrode, this phenomenon was
explained. Notably, HER required 0.6 V while the OER process used about 1.3 V.
The working electrode in the three-electrode configuration, however, was FTO/[Co-Co], the
counter electrode was FTO/[Co-Ni], and the reference electrode was Ag/AgCl. In this
configuration, the profile clearly showed a significant improvement when both solar light and
magnetic fields were present.
Based on PBA properties, we concluded that It's possible that the energy from photons could
excite the electrons in the PBAs during solar light irradiation, resulting in improved charge
transfer and reactivity. The PBAs' semiconducting characteristics might enable them to absorb
and use solar energy for catalysis. On the other hand, the spin crossover effect could certainly
play a role in the OER enhancement under magnetic fields, as it can influence the electronic
and magnetic properties of the catalyst. Magnetic fields can alter the spin states of the metal
ions in the PBAs, potentially affecting their reactivity and catalytic performance.
In conclusion, this study supports the idea that catalysis offers unexplored opportunities for
improvement through subtle changes to reaction conditions that add an external stimulus
dimension. This study should serve as a springboard for future research projects that explore
cutting-edge technological techniques like Mott-Schottky analysis, Electrochemical
Impedance Spectroscopy (EIS), and the use of in-situ characterization methods. These
73
analytical methods are intended to offer thorough understandings of the specific contributions
of magnet-related phenomena, such as magnetohydrodynamic effects, spin polarization effects,
or spin crossover effects, to the overall catalytic enhancement seen in this investigation.
Furthermore, our prospective investigations should encompass an expanded spectrum of
catalytic applications, subjecting the catalyst to diverse external stimuli. This multifaceted
approach seeks to uncover novel techniques for manipulating catalysis and harnessing its
potential in various domains. In essence, the future work outlined here underscores the need
for a deeper understanding of the intricate mechanisms at play within catalytic systems, thereby
advancing the frontiers of catalysis research. The current thesis advances the field by raising
the bar and adding a new level of complexity to the effort of using PBAs in catalytic
applications while building on earlier efforts.
74
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ELECTROCATALYTIC WATER SPLITTING

WITH PRUSSIAN BLUE ANALOGUES UNDER

THE GRADUATE SCHOOL OF ENGINEERING AND SCIENCE OF

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE

Approved for the Graduate School of Engineering and Science

Prusya Mavisi Analoglarıyla Dış Uyarıcıların Desteğinde

Besides that, I would like to express my heartfelt gratitude to the foundational

I am deeply indebted to my esteemed supervisor, Dr. Ferdi Karadas, for his

I extend my appreciation to the members of my Karadas research group with

Lastly, to all my Pakistani, Bangladeshi, Turkish, and Arab friends, your

Chapter 1: Introduction ..................................................................................... 1

1.1. Current Trends in Energy Technologies and Catalysis ............................ 1

1.2. Water Splitting under Electricity and Light ............................................. 2

1.2.1. Water Splitting in an Acidic Medium ................................................... 3

1.2.2. Water Splitting in Basic/Neutral Medium ............................................ 4

1.3. Prussian Blue Analogues .......................................................................... 6

1.4. OER Mechanism on the Cobalt Site ........................................................ 8

1.5. HER Mechanism on the Cobalt Site ...................................................... 12

1.6. Magnetic Field-Assisted Catalysis ......................................................... 13

1.7. The Motivation of This Thesis Study ..................................................... 18

Chapter 2: Methods and Instrumentations .................................................... 23

2.1. Synthesis Procedure For FTO/[Co-M], (M = Co, Ni)............................ 23

2.1.1. Chemicals ............................................................................................ 23

2.1.2. Preparation of FTO/[Co-Co] and FTO/[Co-Ni] .................................. 23

2.2. Scanning Electron Microscopy (SEM) Coupled with Energy Dispersive

2.3. Powder X-ray Diffraction (P-XRD) Analysis ........................................ 25

2.4. Xray-Photoelectron Spectroscopy (XPS) Analysis ................................ 25

2.5. Fourier Transform Infrared Spectroscopy (ATR-FTIR) Analysis ......... 25

2.6. Electrochemical Setup ............................................................................ 26

2.7. Magnetic Setup ....................................................................................... 28

2.8. Photocatalytic Setup ............................................................................... 29

2.9. Calculating Surface Concentration of the Active Catalyst ................... 29

3.1. Synthesis Procedure For FTO/[Co-M], (M = Co, Ni)............................ 30

3.1.1. Hydrothermal technique: ..................................................................... 30

3.1.2. Electrodeposition technique: ............................................................... 30

3.2. FTO/[Co-M] (M = Co, Ni) Characterization ......................................... 31

3.2.1. Scanning Electron Microscopy and EDAX Analysis ......................... 31

3.2.2. XRD Analysis ..................................................................................... 35

3.2.3. XPS Analysis....................................................................................... 36

3.2.4. ATR-FTIR Analysis ............................................................................ 37

3.2.5. Calculating the Surface Concentration of the Catalyst ....................... 38

Chapter 4: Electrocatalytic water oxidation under magnetic and light field

4.1. Magnetic Field-Assisted OER Studies ................................................... 41

4.1.1. Linear Sweep Voltammetry Studies ................................................... 41

4.1.2. Chronoamperometric Studies .............................................................. 43

4.2. Solar Light-Assisted Studies .................................................................. 45

4.2.1. Linear Sweep Voltammetry Studies Under Light Irradiation ............. 45

4.2.1.1. Relative LSV Profile ........................................................................ 47

4.2.2. Chronoamperometric Studies Under Solar Light Irradiation.............. 48

4.2.2.1. Catalyst Stability .............................................................................. 51

4.2.3. Temperature Profile for CA Under Solar Light Irradiation ................ 53

Chapter 5: Electrocatalytic hydrogen evolution reaction (HER) studies

5.1. Magnetic Field-Assisted HER Studies ................................................... 55

5.1.2. Chronoamperometric Studies .............................................................. 56

5.2. Solar Light Assisted HER Studies ......................................................... 56

5.2.1. Linear Sweep Voltammetry Studies Under Light Irradiation ............. 56

5.2.2. Chronoamperometric Studies .............................................................. 58

Chapter 6: Electrochemical overall water splitting (OWS) under magnetic

6.1. Novel Experimental Configuration for Conducting Oxygen and