Development of Alkaline Electrolyzer Electrodes and Their Characterization

Development of Alkaline Electrolyzer Electrodes and
Their Characterization in Overall Water Splitting
Tao JIANG
N° d’ordre : Année : 2020
Université de Technologie de Belfort-Montbéliard

Ecole doctorale Sciences Pour l’Ingénieur et
Microtechniques
THESE
Présentée pour obtenir le grade de
Docteur de l’Université de Technologie de Belfort-Montbéliard en
Sciences des Matériaux
Development of Alkaline Electrolyzer Electrodes and Their

Characterization in Overall Water Splitting
Tao JIANG
Defense expected 20 May 2020
With the jury composed of
Rapporteurs
Mr. Joris Proost, Professor, Université Catholique de Louvain
Mr. Raphael Schneider, Professor, Université de Lorraine
Examinateurs
Mr. Bernard Normand, Professor, INSA de Lyon
Mr. Fenineche Nour-Eddine, Professor, Université de Technologie de Belfort-Montbéliard
Mr. Syed-asif Ansar, Senior researcher (HDR), German Aerospace Center (DLR)
Mr. Hanlin Liao, Professor, Université de Technologie de Belfort-Montbéliard
Invité
Mr. Ghislain Montavon, Professor, Université de Technologie de Belfort-Montbéliard
General introduction
With a rising global population, increasing energy demands, and impending climate change, major
concerns have been raised over the security of our energy future. Developing sustainable, fossil-free
pathways to produce fuels and chemicals of global importance could play a major role in reducing
carbon dioxide emissions while providing the feedstocks needed to make the products, we use daily.
The share of renewable energy worldwide is expected to increase by 38% in the period between 2011
and 2035. Consequently, the share of energy from fluctuating energy sources, such as wind, sun and
ocean current, will escalate and new alternatives for energy conversion, energy storage and load
management will be needed. One prospective goal is to develop electrochemical conversion processes
that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-
value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable
energy. Hydrogen is one of the most valuable energy carriers, which can contribute to various forms of
energy, such as, production of electricity via fuel cells, fuel for internal combustion engines or gas
turbines, or as a raw material to produce synthetic fuels via Sabatier or Fischer-Tropsch process. In some
situations, it may be suitable to simply inject hydrogen into the existing natural gas-based infrastructure.
Producing hydrogen via water electrolysis technologies using surplus, low cost power from
renewables offers the possibility of increased production capacity and load management with no
greenhouse emissions. Alkaline electrolysis cell (AEC) is one of the most promising methods for
producing high purity hydrogen to be used as a clean and renewable energy carrier, meanwhile AEC is
also become the current standard (state-of-the-art) for industrial large-scale water electrolysis systems.
A basic AEC needs two electrodes: the anode and cathode supported with their respective oxygen
evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts. Of the two half-reaction,
OER is more energy-consuming due to the high thermodynamic potential required for water oxidation
(1.23 V vs RHE (reversible hydrogen electrode)) and the sluggish kinetic hindrance of the multi-electron
evolving charge-transfer reactions. Currently, noble transition metal oxides, such as RuO2 and IrO2, have
been regarded as the state-of-the-art oxygen evolution reaction electrocatalysts (OEEs), while their
large-scale applications were impeded by the scarcity, high cost, and poor durability.
Accordingly, in order to replace these noble metal-based electrocatalysts, extensive efforts have
been devoted to developing alternative OER electrocatalysts based on the inexpensive and earth-
abundant first-row transition-metal (e.g. Fe, Co, Ni, Cu), which are highly active and stable under OER
conditions, thus making water splitting more practically feasible. Although great progress has been made
in designing these types of non-noble metal based catalysts, the suboptimal intrinsic activity, the limited
active sites exposure and the inherently poor electronic conductivity are key problem to hamper further
catalytic performance enhancement of these catalysts. On the other side, complex preparation methods
and expensive conductive polymers as binder for electrode fabrication, minimize their potential
for practical applications. The in situ electrochemical activation (ECA) method has been mostly applied
for OER in alkaline condition, which is a novel electrochemical tuning access to enhance catalytic
performances in a facile, mild, green and controllable way. Such tuning strategy opens up a fresh new
pretreatment technique for electrocatalysts, which can not only obtain comparable excellent OEEs
I
without adopting complex chemical synthesis method, but also largely avoid use of expensive binder
and easy access to promising self-supporting electrocatalysts or even bifunctional electrocatalysts for
overall water splitting.
Moreover, OER is a process involved electrocatalytic reactions at the boundary of gas-liquid-solid
phases. Catalytic reactions take place at the interface of the catalyst and the electrolyte, catalytic activity
can also be restricted due to the lack of bubble transport channels. In practice, rational design of the
OER catalyst architecture can dramatically promote activity in electrocatalytic water splitting. Therefore,
ingenious designing the morphology, structure, and composition of the electrocatalysts is pivotal for
achieving high catalytic activity towards OER. To achieve effective ways of further promoting OER
performance at the three-phase boundary, the design of hierarchical porous supports with facile
charge/electrolyte/bubble migration and higher catalysts loading contributions to the catalytic OER
activity has to be further explored.
Currently, OER catalyst needs to meet the most stringent requirements in industrial applications
such as delivery of very high current density (≥ 500 mA cm-2) at low overpotentials (≤ 300 mV), and
certain mechanical robustness and prolonged durability during harsh oxidizing conditions and the
complicated mechanism of the OER. On the other hand, for large-scale industrial applications, AECs
also require the commodious scale production of large areal type electrodes (e.g. where the geometric
surface area of the electrode can reach several square meters). Currently, electrolytic codeposition and
high-velocity oxy-fuel spraying are two effective and potential avenues of fabricating large-sized
oxygen evolution electrode that meet industrial needs. Additionally, electrochemical activation (ECA)
strategy as an efficient technique for activating the integrated electrodes (precatalysts) to enhance
electrocatalytic performance and preparing self-supported OEEs, has been mostly applied.
Enlightened by the above discussion, engineering highly active and stable earth-abundant transition
metal-based OEEs with 3D porous architectures via electrolytic codeposition and high-velocity oxy-fuel
spraying in combination with in situ ECA, respectively, is the main objective of the present PhD study.
Furthermore, this dissertation gives more in-depth analysis of their catalytic activities, microstructure
evolution and reaction mechanism. In addition, inspired by the process of developing OEE, we initially
develop HER electrocatalysts (HEEs) by dynamic self-optimization of the same precatalysts as OEEs,
coupled with the obtained OEEs to form a two-electrode configuration of AEC, providing new
dimensions in the design of newly highly active, cost effective and stable electrocatalysts for overall
water splitting.
This thesis is divided into six chapters, as follows:
Chapter I provides a brief introduction about fundamentals of water electrolysis and water
electrolysis technologies, synthetic strategies of OER electrocatalytic anode material, including reaction
mechanism of OER electrocatalytic anode material, key performance parameters of OER
electrocatalytic anode material, AEC technology, industrial application parameters in AEC developers
and synthetic strategies of OER electrocatalytic anode material for AEC. Finally, the objectives of the
thesis, the originality and novelty of PhD study and thesis organization are presented.
Chapter II introduces physical characterizations and electrochemical characterizations, respectively.
Physical characterizations including Scanning electron microscope (SEM), X-ray diffraction (XRD),
Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and Transmission electron microscope
(TEM) are employed to test the morphologies, structures and chemical valences of the fabricated anode
II
catalytic layers. Brunauer-Emmett-Teller (BET, ASAP 2020 V4.00) analysis is conducted to study the
surface area and the porosity distribution of all the catalysts. Electrochemical characterizations,
including Electrochemical workstation (Metrohm Autolab PGSTAT-128N) equipped home-made three-
electrode air-tight alkaline electrolytic cell and Gas-chromatograph are used to characterize the catalytic
activity of the prepared anode material. Polarization curves and Cyclic voltammetry (CV) curves, Tafel
slopes, Electrochemical active surface area (ECSA) and double-layer capacitance (Cdl), electrochemical
impedance spectroscopy (EIS) and Chronopotentiometry are measured in electrochemical tests.
Chapter III includes a fundamental study of using one-step electrolytic codeposition as a novel
method for preparation of the hybrid electrocatalysts for OER by fabrication of high-efficient Co3O4 and
Graphene oxide (GO) on the porous framework. The commercial nickel foam (NF) with typical
micropores are researched as the framework during electrolytic codeposition process. The morphology
and microstructure of the hybrid catalysts deposited onto the surface of the NF are optimized by
adjusting additives and electrolytic codeposition parameters to produce OEEs with similar catalytic
performance and long-term stability as the noble metal-based catalysts (e.g. IrO2 and RuO2).
Subsequently, these pre-catalysts are activated upon in situ ECA. The morphological, structural and
chemical evolution of OEEs before and after activated via in situ ECA are investigated by SEM, XRD,
TEM, BET, Raman and XPS. Electrochemical performances of the finally obtained OEEs are evaluated
by Polarization curves and CV curves, Tafel slopes, Cdl, EIS and Chrono potentiometric methods. Finally,
the relationship between the OER performance and the morphological, structural and chemical evolution
of OEEs are discussed in detail.
Chapter IV mainly presents how high-velocity oxy-fuel (HVOF) spraying followed by chemical
activation (CA), combines with in situ ECA, as a versatile synthesis approach to producing hierarchical
porous core-shell structure with Jamborite (Ni(OH)2/NiOOH hybrid) nanosheets in situ generating. This
typical nanostructure owns highly intrinsic catalytic activity, large active surface areas and facile
charge/electrolyte/bubble migration, thus ensuring excellent OER performance comparable to the state-
of-the-arts noble metal-based electrocatalysts. This chapter introduces a novel process of preparing
OEEs, HVOF followed by CA, combining with in situ ECA, especially focuses on morphological,
structural and chemical evolution of the OEEs upon CA and in situ ECA by SEM, XRD, TEM, BET,
Raman and XPS. Finally, the OER catalytic mechanism of the core@shell/NiAl@ Jamborite
(Ni(OH)2/NiOOH hybrid) structure is revealed by combining the oxygen evolution activity tests, which
include Polarization curves and CV, Tafel slopes, Cdl, EIS and Chrono potentiometric methods.
Chapter V considers preparing promising HEEs (H-NF@CGO, H-HNA-CA ) once verified a way
possessing the potential to obtain excellent OEEs (O-NF@CGO, O-HNA-CA), coupling with which
form a two-electrode configuration (O-NF@CGO(+)||H-NF@CGO(-), O-HNA-CA(+)||H-HNA-CA(-)),
rivalling the integrated state-of-the-art IrO2/NF(+)||Pt foil(-) electrode in alkaline overall water splitting.
We hope our work can promote advanced development toward large-scale H2 production using excess
electrical power whenever and wherever available.
Chapter VI summarizes the conclusions and contributions of this research and provides
recommendations for the future work; put forward new exploration directions for future fabrication of
OEEs and HEEs, such as self-supported bifunctional transition metal compounds (TMC) via 3D printing
or Melting process in combination with in situ ECA, and developing the effective of magnetic field on
electrode fabrication and applications.
III
Content
Content
General introduction ................................................................................................................................. I

Content .................................................................................................................................................. IV
Abbreviation ......................................................................................................................................... VII
Chapter I Introduction of water electrolysis .......................................................................................... 1
1.1 Background .............................................................................................................................. 1
1.2 Fundamentals of water electrolysis .......................................................................................... 2
1.2.1 The principle ............................................................................................................................ 2
1.2.2 Reaction mechanism of OER catalysts in alkaline medium..................................................... 4
1.2.3 Performance parameters of OER catalysts in alkaline medium ............................................... 6
1.2.3.1 Electrode and electrolyte .......................................................................................................... 6
1.2.3.2 Onset overpotential and overpotential...................................................................................... 7
1.2.3.3 Electrochemical impedance spectrum analysis ........................................................................ 8
1.2.3.4 Tafel slope and exchange current density ................................................................................ 8
1.2.3.5 Electrochemical active surface area ......................................................................................... 9
1.2.3.6 Stability .................................................................................................................................... 9
1.2.3.7 Turnover frequency ................................................................................................................ 10
1.2.3.8 Faradic efficiency ................................................................................................................... 10
1.3 Water electrolysis technologies ...............................................................................................11
1.3.1 Alkaline electrolysis cell technology ..................................................................................... 12
1.3.2 Other methods of hydrogen production ................................................................................. 13
1.3.3 Industrial application parameters in alkaline electrolysis cell developers ............................. 14
1.4 Synthetic strategies of OER catalysts for alkaline medium ................................................... 15
1.4.1 Noble metals and their oxides as OER catalysts .................................................................... 16
1.4.2 First-row transition metal compounds as OER catalysts ....................................................... 17
1.4.2.1 Co-based transition metal compounds as OER catalysts ....................................................... 17
1.4.2.2 Fe-Based transition metal compounds as OER catalysts ....................................................... 18
1.4.2.3 Ni-Based transition metal compounds as OER catalysts ....................................................... 19
1.4.3 In situ electrochemical activation based OER catalysts ......................................................... 20
1.5 Objectives............................................................................................................................... 21
1.6 The originality and novelty of PhD study .............................................................................. 22
References of Chapter I ......................................................................................................................... 23
Chapter II Experimental details........................................................................................................... 39
2.1 Synthesis and fabrication approaches .................................................................................... 39
2.1.1 Electrolytic codeposition process ........................................................................................... 39
2.1.1.1 Materials................................................................................................................................. 40
2.1.1.2 Equipment of electrolytic codeposition process..................................................................... 41
2.1.2 High-velocity oxy-fuel spraying process ............................................................................... 42
2.1.2.1 Materials................................................................................................................................. 42
IV
Content
2.1.2.2 Equipment of high-velocity oxy-fuel spraying ...................................................................... 44

2.1.2.3 Chemical activation................................................................................................................ 45
2.1.3 In situ electrochemical activation........................................................................................... 45
2.2 Physical characterizations ...................................................................................................... 45
2.3 Electrochemical characterizations .......................................................................................... 46
References of Chapter II........................................................................................................................ 47
Chapter III Development of OER electrocatalysts by combining electrolytic codeposition and in situ
electrochemical activation ..................................................................................................................... 49
3.1 Introduction ............................................................................................................................ 49
3.2 Effect of additives in electrolytic codeposition on OER performance ................................... 51
3.3 Effect of current density in electrolytic codeposition on OER performance ......................... 52
3.4 In situ electrochemical activation of a codoped heterogeneous system as a highly efficient OER
electrocatalyst ........................................................................................................................................ 53
3.4.1 Synthesis strategy of the NF@CGO ...................................................................................... 53
3.4.2 Physical characterization of the activated NF@CGO ............................................................ 55
3.4.3 Electrocatalytic oxygen evolution at the activated NF@CGO............................................... 62
3.4.4 Discussion .............................................................................................................................. 67
3.5 Summary ................................................................................................................................ 69
References of Chapter III ...................................................................................................................... 70
Chapter IV Development of OER electrocatalysts by combining high-velocity oxy-fuel spraying and in
situ electrochemical activation .............................................................................................................. 77
4.1 Introduction ............................................................................................................................ 77
4.2 HNA-CA-ECA as a highly efficient OER electrocatalyst ...................................................... 78
4.2.1 Synthesis of the HNA-CA-ECA ............................................................................................ 78
4.2.2 Physical characterization of the HNA-CA-ECA .................................................................... 80
4.2.3 Electrocatalytic oxygen evolution at the HNA-CA-ECA ...................................................... 90
4.2.4 Discussion .............................................................................................................................. 96
4.3 Summary .............................................................................................................................. 100
References of Chapter IV .................................................................................................................... 100
Chapter V Electrochemical characterizations of dynamic self-optimized catalysts in hydrogen
evolution reaction and overall water splitting ..................................................................................... 107
5.1 Introduction .......................................................................................................................... 107
5.2 Electrochemical characterization of the activated NF@CGO electrocatalyst in HER and
overall water splitting .......................................................................................................................... 108
5.2.1 Electrocatalytic hydrogen evolution of the H-NF@CGO .................................................... 108
5.2.2 O-NF@CGO(+)||H-NF@CGO(-) electrocatalytic overall water splitting ...............................112
5.3 Electrochemical characterization of the activated HNA-CA electrocatalyst in HER and overall
water splitting .......................................................................................................................................114
5.3.1 Electrocatalytic hydrogen evolution of the H-HNA-CA.......................................................114
5.3.2 O-HNA-CA(+)||H-HNA-CA(-) electrocatalytic overall water splitting...................................119
References of Chapter V ..................................................................................................................... 120
Chapter VI Conclusions and perspectives ......................................................................................... 127
V
Content
6.1 Conclusions .......................................................................................................................... 127

6.2 Perspectives .......................................................................................................................... 129
Abstract ............................................................................................................................................... 131
Résumé ................................................................................................................................................ 133
List of participation activities .............................................................................................................. 135
List of peer-reviewed publications ...................................................................................................... 135
VI
Abbreviation
Abbreviation
Abbreviation Explanations
AEC Alkaline electrolysis cell
PEMEC Proton exchange membrane electrolysis cell
SOEC Solid oxide electrolysis cell
OER Oxygen evolution reaction
HER Hydrogen evolution reaction
OEE Oxygen evolution reaction electrocatalyst
HEE Hydrogen evolution reaction electrocatalyst
BET Brunauer-Emmett-Teller
RHE Reversible hydrogen electrode
CV Cyclic voltammetry
ECSA Electrochemical active surface area
Cdl Double-layer capacitance
EIS Electrochemical impedance spectroscopy
Rct Charge transfer resistance
GO Graphene oxide
HVOF High-velocity oxy-fuel
TMC Transition metal compounds
ECA Electrochemical activation
NF Nickel foam
NF@N Nickle layer electrodeposited on NF
NF@GO Nickle layer and GO nanosheets electrodeposited on NF
NF@C Nickle layer and Co3O4 particles electrodeposited on NF
NF@CGO Nickle layer, GO nanosheets and Co3O4 particles electrodeposited on NF
H-NF@CGO NF@CGO followed by in situ ECA upon HER
O-NF@CGO NF@CGO followed by in situ ECA upon OER
NP Nickel plate
HVOF High-velocity oxy-fuel
CA Chemical activation
HNA Ni-Al alloy coating deposited on NP via HVOF
HNA-CA HNA followed by CA
HNA-CA-ECA/O-HNA-CA HNA-CA followed by in situ electrochemical activation (ECA) upon OER
H-HNA-CA HNA-CA followed by in situ electrochemical activation (ECA) upon HER
DSO Dynamic self-optimization
NP(+)||NP(-) Two-electrode configuration for comparison
(+) (-)
NF ||NF Two-electrode configuration for comparison
(+) (-)
IrO2/NF ||Pt State-of-the-art commercial two-electrode configuration for comparison
(+) (-)
O-NF@CGO ||H-NF@CGO Two-electrode configuration
VII
Abbreviation
O-HNA-CA(+)||H-HNA-CA(-) Two-electrode configuration
VIII
Chapter I Introduction of water electrolysis
1.1 Background
Hydrogen, as an energy carrier, has become increasingly important, mainly in the last two decades.
Presently, the technologies that dominate hydrogen production include reforming of natural gas,
gasification of coal and petroleum coke, as well as gasification and reforming of heavy oil. Although
water electrolysis has been known for around 200 years, it still contributes only a minor fraction of the
total hydrogen production (4 % of the worldwide hydrogen production).1-4 When compared to other
available methods, water electrolysis has the advantage of producing extremely pure hydrogen (>
99.9 %), ideal for some high value-added processes such as manufacture of electronic components.5
Simultaneously, exploiting safe, clean, and sustainable energy sources is a major societal and
technological challenge in the 21st century.6-8 Solar, wind and hydro energy, are in principle able to meet
a large portion of the global energy demand. However, they are intermittent and require efficient and
economic storage solutions. Among various storage solutions, the water splitting reaction is an attractive
solution as it enables the sustainable production of hydrogen, a desirable energy carrier. 8-11 The overall
concept of hydrogen produced by water electrolysis for distributed power generation routes is shown in
Figure 1-1.
Although offering an effective way to make high-purity hydrogen, the practical use of
electrochemical water splitting for mass hydrogen production is limited because it is a strongly uphill
reaction with a large overpotential (commercial electrolyzers typically operate at a cell voltage of 1.8-
2.0 V, much higher than the theoretical minimum value of 1.23 V).12 Many innovative processes have
been subject to intense research and some have already reached high efficiencies. Implementation of
electrocatalysts for OER and HER is an efficient way to overcome the large water-splitting
overpotentials, which makes the whole process more energy-efficient.11
1
Figure 1-1 The overall concept of hydrogen produced by water electrolysis for distributed power generation
routes.13
A variety of water electrolysis systems have been proposed developed and constructed over the
years. Among different methods of hydrogen production, AEC is considered to be the current standard
for large-scale water electrolysis systems, because of the highest production rate and the lowest
production cost.14 AECs hold many advantages in comparison to other systems. As cheaper, non-noble
metals are stable in alkaline media, the relatively low cost of the electrode materials is one of the main
advantages of alkaline systems over electrolyzers using proton-conducting electrolytes. Therefore, the
main part of published literature on alkaline electrolysis describes electrodes based on low cost materials
such as nickel for both anode and cathode. However, finding low cost electrode materials that are both
efficient and have long term stability is one of the remaining challenges with the field of AEC.
1.2 Fundamentals of water electrolysis
1.2.1 The principle

Water electrolysis is a process where electricity is used to decompose water into its components -
gaseous hydrogen and oxygen according to:
1
H2 O(l) → H2 (g) + 2 O2 (g) (1-1)
In detail, water electrolysis consists of two half-cell reactions: hydrogen evolution reaction (HER)
at the cathode (2H + (aq) + 2e− → H2 (g)) and oxygen evolution reaction (OER) (2H2 O(l) →
O2 (g) + 4H + (aq) + 4e− )) at the anode. Theoretically, the applied potential of electrolysis cell voltage
is 1.23 V under the standard condition (298 K, 1 atm = 1.013×105 Pa). In practice, the real water
electrolysis needs a much larger voltage to overcome unfavorable drawbacks such as high overpotentials
2
and sluggish kinetics, especially for OER. Thus, it is essential to gain insight into electrochemical
reaction process for providing guidelines of designing efficient catalysts.
Generally, the HER process is a two-electron transfer process in individual Volmer-Heyrovsky or
Volmer-Tafel mechanism, where the absorbed hydrogen (H ∗ ) as intermediate on the electrode surface
participates in the reaction pathways. The HER process highly depends on pH value of electrolytes. In
acid solution, the HER proceeds according to the following steps:
(i) Proton discharging to form an adsorbed hydrogen atom:
H + + e− → H ∗ (Volmer reaction) (1-2)
Subsequently, molecular H2 can be formed via the following two alternative steps depending on
the surface of electrodes.
(ii) The quick coupling of two adsorbed hydrogen atoms to generate a hydrogen molecule:
H ∗ + H ∗ → H2 (Tafel reaction) (1-3)
(iii) Combination of one adsorbed hydrogen atom with a proton to generate a hydrogen molecule:
H ∗ + H + → H2 (Heyrovsky reaction) (1-4)
In alkaline condition, molecular H2O participates in Volmer and Heyrovsky reactions due to the
low concentration of H + :
H2 O + e− → H ∗ + OH − (Volmer reaction) (1-5)
H ∗ + H2 O → H2 + OH − (Heyrovsky reaction) (1-6)
The free energy of hydrogen adsorption (ΔGH∗ ) is a crucial descriptor for the HER catalyst.15-17 The
negative ΔGH∗ represents favorable combination of H ∗ with the surface of electrode and Volmer step,
whereas too negative value may cause slow proceeding of subsequent Tafel or Heyrovsky steps. In
contrast, the positive value of ΔGH∗ leads to weaker interactions between protons and electrode surface
and thus an inefficiency of the entire process.
On the anode of OER process, it is a more complicated reaction containing four-electron transfer
and more surface-adsorbed intermediates. It is also a pH-dependent process (in alkaline or acid), where
the alkaline OER is mostly researched as shown in the following pathway18-20:
OH − + ∗→ OHads + e− (1-7)
OHads + OH − → Oads + H2 O + e− (1-8)
The ‘‘*” means active site of the catalyst and ‘‘ads” means the adsorption on the catalyst. The
generation of molecular O2 can be proceeded by two possible pathways as follows:
(i) The combination of two Oads intermediates to form O2:
Oads + Oads → O2 (1-9)
(ii) Oads coupling with OH − to form OOHads and subsequent combination with OH − to form O2:
Oads + OH − → OOHads + e− (1-10)
− −
OOHads + OH → O2 + H2 O + e (1-11)
In theory, the thermodynamic potential value of OER is 1.23 V at 298 K (vs. reversible hydrogen
3
electrode (RHE)). Actually, a much higher potential is required for OER because of activation barriers
and solution resistances, which will cause excessive energy consumption and decrease conversion
efficiency. In screening proper electrocatalysts for OER with low cost and high efficiency, first low
transition metals such as Ni, Co and Fe and their derivatives are demonstrated to be comparable to state-
of-the-art noble electrocatalyst of Ir/Ru species.21-23
A typical water electrolysis cell consists of two electrodes, a diaphragm, an electrolyte and a power
supply. The most common type of water electrolysis is AEC, as illustrated in Figure 1-2.
Figure 1-2 Conceptual set-up of an AEC.14

When current is applied to the system, hydrogen gas is formed at the cathode and oxygen gas at
the anode. The core of an electrolysis unit is an electrochemical cell, which is filled with electrolyte and
has two electrodes connected with an external power supply. At a certain voltage, which is called critical
voltage, between both electrodes, the electrodes start to produce hydrogen gas at the negatively biased
electrode and oxygen gas at the positively biased electrode. The amount of gases produced per unit time
is directly related to the current that passes through the electrochemical cell. The diaphragm is to hinder
the mixing of gasses developed at the two electrodes and allows the ions to pass. The gas produced can
be captured in their pure form when drifting up from the electrolyte. The reactions taking place at the
electrodes, i.e. the half-cell reactions, differ between the types of water electrolysis techniques applied.
1.2.2 Reaction mechanism of OER catalysts in alkaline medium

A general mechanism of OER on metal oxides in alkaline medium (red line) is described in Figure
9, 24, 25
1-3. Here the active site is simply drawn as “M”. In the first step, a hydroxyl radical is adsorbed
on the active site to give M-OH by 1 e− oxidation of hydroxide. Coupled proton and electron removals
from M-OH then gives M-O. In one pathway, nucleophilic attack of hydroxyl anion on M-O coupled
with 1 e− oxidation yields the hydroperoxide intermediate M-OOH. A further proton-coupled electron
transfer resulted in the release of O2 and the regeneration of the free active site. In another pathway,
combination of two M-O species gives directly O2 and M. The mechanism depicted here forms the
blueprint for the majority of proposed mechanisms, with the main variation being the number of electron
or proton transfer in individual steps. In some cases, proton and electron transfers are proposed to be
4
decoupled.26
Figure 1-3 The OER mechanism for alkaline conditions (the blue line refers to the acid conditions). The black
line indicates that the oxygen evolution involves the formation of a peroxide (M-OOH) intermediate (black line)
while another route for direct reaction of two adjacent oxo (M-O) intermediates (green) to produce oxygen is
possible as well.9
The relationship of current density (j) and overpotential (η) in an electrochemical reaction can be
described by the Butler-Volmer Eq. (1-12). Here 𝑗0 is change current density, n is the number of
transferred electrons, F is the Faraday's constant, R is the universal gas constant, T is the thermodynamic
temperature, 𝛼𝑎 and 𝛼𝑐 is the transfer coefficient of anodic reaction and cathodic reaction,
respectively. 𝛼𝑎 and 𝛼𝑐 are normally assumed to be 0.5. When the anodic overpotential is sufficiently
large, the cathodic current is negligible. Thus, Eq. (1-12) can be simplified into Eq. (1-13), the logarithm
form of which is the Tafel equation (Eq. (1-14)).9, 27 For a multi-step electrochemical reaction, the Tafel
slope (Eq. (1-15)) may provide information of the reaction mechanism. Assuming that a rate-
determining step (RDS) exists, the Tafel slope can be described as Eq. (1-16).11, 27
𝛼𝑎 𝑛𝐹𝜂 𝛼𝑐 𝑛𝐹𝜂
j = 𝑗0 [exp ( )− exp(− )] (1-12)
𝑅𝑇 𝑅𝑇
𝛼𝑎 𝑛𝐹𝜂
j = 𝑗0 [exp ( 𝑅𝑇
) (1-13)
𝜂
log 𝑗 = log 𝑗0 + 𝑏 (1-14)
∂η 2.303𝑅𝑇
b = ∂ log 𝑗 = 𝛼𝑛𝐹
(1-15)
𝑛𝑏
𝛼𝑎 = 𝑛𝑟 𝛽 + 𝑣
(1-16)
Where 𝑛𝑏 is the number of electrons transferred before the RDS, ν is the number of rate-
determining steps, 𝑛𝑟 is the number of electrons that participate in the rate-determining step, and β is
5
the transfer coefficient of the RDS (typically assumed to be 0.5). Eq. (1-16) provides a simple yet rapid
means to identify the RDS of OER. This simple treatment, however, is not sufficient to account for the
real kinetic behaviors of OER catalysts. The same Tafel values may originate from different reaction
pathways. Moreover, the treatment assumes a low coverage of the surface intermediate before the RDS,
which does not always hold especially at high overpotentials. The transfer coefficient can deviate from
0.5 when the reorganization energy is comparable to overpotential, or when there is a significant barrier
in the electron transfer.28, 29
Due to these limitations, a full kinetic analysis, including rate order
determinations, in addition to Tafel analysis, is necessary to establish the detailed reaction mechanism.26-
28
Another important tool is first-principle DFT simulations of Tafel kinetics, which gives fundamental
information about the reaction mechanism.27
1.2.3 Performance parameters of OER catalysts in alkaline medium
1.2.3.1 Electrode and electrolyte

The working electrodes/substrates play a critical role in determining the performance and greatly
influence the reaction rate due to their different structure, conductivity, degree of wettability and access
of catalyst to an electrolyte. On the basis of the structure and degree of electrolyte movement, electrode
supports are divided into two categories: flat surface electrode and 3D electrode.30
The flat surface electrodes, like glassy carbon (GC), Cu/Ti foil and indium doped tin oxide (ITO)
substrate, allow single-way penetration of electrolyte that limits the catalysis only on surface of catalyst,
while the 3D substrates, e.g. carbon cloth/paper (CC and CP) and Ni foam, allow multiple pathways for
electrolyte penetration from all sides of catalyst and involve all the material in catalytic reaction.31-33 All
these electrode substrates have their own advantages and limitations such as, GC electrode is easy to
handle and widely used in literature but offers a limited loading of catalyst (~1 mg cm-2).34 In addition,
GC electrode requires a binder to stabilize the catalysts, resulting in poor wettability, unwanted and
unescapable powder agglomeration. Furthermore, these binders also increase the resistance, block the
active sites and prevent diffusion of ions.35 Thus, to get rid of nonconductive binders, various research
groups make efforts to grow catalyst directly on the conductive substrates like Ni foam, CC, CP, which
also brings strong electrical connection among the catalyst and current collector. Importantly, 3D texture
comes from the Ni foam or graphene foam brings high gas diffusivity and easy penetration of electrolyte
and results in better catalysis. However, direct fabrication of catalyst on supportive substrate may lead
to the pealing of catalyst due to mismatched growth, resulting in poor stability, which may be resolved
by surface modification of substrate for better connection. Further, the control over the mass loading of
active materials through direct growth is difficult that may bring challenges for comparative
performance analysis. Recently Zhang et al. used three different electrodes i.e. Ni foam, Au (111)
electrode and gold-plated Ni foam to analyze their effect on the electrochemical performance of different
6
catalyst.18 The results show that gold plated Ni foam results much better electrocatalytic performance
compared to other two electrodes due to the higher conductivity.30
Different electrolytes such as alkaline or acid extremely influence the performance of electrode
material. The OER electrocatalysis in alkaline solution is more favorable but difficult in neutral
electrolytes and reaches at very low performance in acidic solution. Currently, most of the research is
focused on finding the OER electrocatalysts which are stable in alkaline conditions like carbon-based
materials, oxides or oxyhydroxides of transition metals, hybrids, complex ternary (spinel and
perovskites).30
1.2.3.2 Onset overpotential and overpotential

The onset overpotential is the applied potential with apparent anodic currents. However, it is
difficult to determine the precise potential values. Usually, the onset overpotential is calculated at current
density of 0.5 or 1 mA cm-2. Overpotential is another important criterion, which is the additional
potential (beyond the thermodynamic requirement) to drive a reaction at a certain rate. According to the
equation Eelectroysis = Ereversible + ΔEirreversible + iR, Ereversible represents the theoretical decomposition voltage,
iR expresses the voltage drop caused by the electrolyte, wires and contact point, and ΔEirreversible is the
overpotential for OER. Based on the origins of Polarization on the electrode, the overpotential mainly
includes concentration overpotential and electrochemical overpotential, which are caused by
concentration Polarization and electrochemical Polarization, respectively. As for concentration
Polarization, it can be reduced by vigorously stirring or raising the operating temperature to accelerate
the ion diffusion. The electrochemical Polarization can be significantly lowered using appropriate
electrocatalysts. A useful method to eliminate the effect of IR drop toward OER is iR compensation.
Much modern electrochemical equipment frequently includes circuitry for electronic compensation of
the iR. iR-compensation can exclude the effect of the resistance from the solution and electrode.
However, the current density obtained without iR compensation can give the integral catalytic system
and actual HER performance of the electrodes. Furthermore, the resistance between the tip of the Luggin
capillary and the surface of the working electrode can be effectively reduced by placing the electrode
surface close to the tip of the Luggin capillary.
In order to quantitatively compare the performance of the catalysts, the overpotential value for the
current density of 10 mA cm-2 (i.e., the current density expected for a 12.3% efficient solar water-
splitting device) is regarded as an important reference. An ideal electrocatalyst can deliver higher current
density with lower overpotential. As for carbon-based composites, due to their high electrochemical
surface area, it tends to cause high capacitive current during the test process. An effective method to
reduce the capacitive current is to set up a low sweep rate in linear-sweep voltammetry (LSV)
experiment (such as 1 or 2 mV s-1).
All the potentials are referenced to RHE in current studies. While, potentials are often measured
7
and quoted with respect to reference electrodes other than the RHE, which is not very convenient from
an experimental standpoint. The common references are the saturated calomel electrode (SCE) or silver-
silver chloride electrode. In order to unify the standard of evaluation, the potentials in the final graphs
should be converted to the potentials versus the RHE according to the calculation:
E (vs RHE) = E (vs SCE) + E0SCE +0.0592* pH (1-17)
(E0SCE = 0.242 V)
E (vs RHE) = E (vs Ag/AgCl, saturated KCl) + E0 (Ag/AgCl, saturated KCl) + 0.0592* pH (1-18)
E0 (Ag/AgCl, saturated KCl) = 0.197 V
However, if the Hydrogen Reference Electrode (HRE, i.e., HydroFlex, which is produced by
Gaskatel GmbH from Germany) is used as the reference electrode. The potential measured using this
HRE as the reference electrode don’t require any complex conversion to RHE, as in the case allowing
any test temperature and pH of the electrolyte, namely ERHE = EHRE. Furthermore, HRE is suitable for
the full pH-range from -2 to 16 and temperature-range from -303 K to 473 K.
1.2.3.3 Electrochemical impedance spectrum analysis

Electrochemical impedance spectrum (EIS) analysis under operating conditions is conducted to
probe the OER kinetics and the electrode/electrolyte interface reactions. The charge transfer resistance
(Rct) is related to the interface charge-transfer process of the electrode, which can be obtained from the
diameter of the semicircles in the high frequency zone. The lower Rct value indicates a faster reaction
rate. Notably, the larger the overpotential is, the smaller Rct will be. In addition, the semicircles in the
low frequency zones stand for the adsorption of oxidized species on the electrode surface, namely
adsorption resistance (Rad). Because the onset potential is associated with Rad, the smaller Rad is, the
more positive of the onset potential will be. Before the impedance spectrum test, the open circuit voltage
should be tested. After being stable in the open circuit voltage, impedance spectrum should be conducted
under oxygen evolution voltage, which always corresponds to the potential at 10 mA cm-2. EIS
measurements are carried out in the configuration from the frequency range of 105-0.01 Hz.13
1.2.3.4 Tafel slope and exchange current density

The reaction kinetics for OER can be revealed by Tafel slopes, which can be obtained by the
following three methods: 1) measure directly by electrochemical workstation; 2) convert from
Polarization curves; 3) obtain from the impedance data. In the first way, the applied voltage range should
cover the potential of the water reduction reaction. Normally, the voltage range remains consistent with
that of the LSV test. The second method is the most common way to achieve the Tafel slope value. In
brief, the Polarization curves are replotted as overpotential vs log (current density). Owing to the large
amounts of O2 bubbles produced at high overpotential, the log (current density) usually deviates from
linear relation at such potential range. So, the Tafel slope is determined by the linear portions at low
overpotential fitted to the calculation:
8
η = blog j + a (Tafel equation) (1-17)

Where η is overpotential, j is the current density, and b is the Tafel slope). As for the last method,
the Tafel slopes are calculated from the linear fitting plots of log (Rct) vs overpotential, in which Rct
represents the charge transfer resistance in the equivalent circuit fitted in impedance spectroscopy. 36
Compared with the first two methods, Tafel slopes gained by this approach can purely reflect the charge
transfer kinetic of the electrode reaction. Regardless of which method you use, the linearity of the linear
part of the fitting curve reaches at least 99.9%, at which point the data is accurate. 13 Exchange current
density (J0) serves as a key descriptor to appraise the catalytic efficiency, which depends on electrode
materials, electrode surface state, electrolyte composition and experimental temperature. It can be
calculated by extrapolating the Tafel plots to the x-axis. According to Eq. (1-17), the J0 can be obtained
assuming η is zero. It should be mentioned that J0 is considered to be proportional to the catalytically
active surface area. The large J0 indicates the large surface area, fast electron transfer rate, and favorable
OER kinetics.
1.2.3.5 Electrochemical active surface area

The electrochemical double-layer capacitance (Cdl) is measured to investigate the electrochemical
active surface area (ECSA). An efficacious way to evaluate the Cdl is to measure the capacitance of the
double layer at the solid-liquid interface employing CV. CV is performed in a certain potential window
without the faradaic processes.37 First, the CV experiments are operated under a series of sweep speeds
(10-200 mV s-1), and usually 5-10 successive points are selected. With the increase in scanning speed,
the obtained CV curves may deviate from the rectangle. In order to ensure the linear relationship of the
final data, it requires a suitable scanning speed to be chosen. Next, the differences in current density
variation (ΔJ = Ja − Jc ) at overpotential (intermediate value of the applied potential range) are to be
plotted against scan rate. The plotted lines can be fitted by linear regression enabling the estimation of
Cdl, where the slope is twice Cdl. The large Cdl manifests more exposed surface reactive sites and much
higher current density. Noticeably, for carbon composites, the Cdl mainly comes from carbon supports.
For this reason, Cdl does not accurately assess the activity of this kind of material, and some other factors
need to be emphasized.
1.2.3.6 Stability
Long-term stability is one of the most important parameters for OER catalysts. Generally speaking,
there are two kinds of assessment methods, namely, CV and chronoamperometry (current -time curve)
or Chronopotentiometry test (potential-time curve). With regard to CV test, potential cycles usually are
consonant with that of LSV range. The stability is evaluated by comparing the Polarization curves before
and after the continuous CV cycles (normally 500-10000 cycles). If the Polarization curves almost
exactly overlay with the initial one or the overpotential slightly increases less than 10 % compared with
the original values, it suggests good endurance. Chronoamperometry or Chronopotentiometry test is
9
measured for a certain hour with applied potential or a given current density. In most cases,
Chronopotentiometry test is more popular among the researchers, and the potential is usually related to
10 mA cm-2, while much larger current densities, such as 50, 100, 500, 800 and 1000 mA cm-2 are
employed as a criterion for evaluating stability based on industrial application recently. Normally, 10
hours or much longer is regard as a benchmark for comparison.31, 38-42 In addition, along with the O2
bubbles from accumulation to release, the measured i-t curves will present in a typical serrate shape.
The generated O2 bubbles not only cover the catalytic sites for oxygen production, but also may lead the
electrode materials falling off from the electrode surface in the process of bubble release, although the
negative influence of O2 bubbles can be partially weakened by stirring. More interestingly, the anode
material is inevitably oxidized 31, 43 and slightly strained during the OER process from oxygen generation
to release.
1.2.3.7 Turnover frequency

Up to now, the evaluation of catalytic activity mainly depends on comparison of the overpotential
under the same current density. However, different tests are always with different electrocatalysts
loading mass, which makes it difficult to judge the catalytic performance. In order to address this issue,
turnover frequency (TOF) gradually becomes a crucial detector to evaluate the catalytic ability. TOF is
defined by the transformation of the number of reactant molecules on per active site in unit time. The
high TOF value shows the outstanding catalytic activity. For TOF calculations, the number of active
sites is determined by CVs data, which gathered from 1.2 to 1.7 V vs RHE in 0.1 or 1.0 M KOH aqueous
solution with a scan rate of 10-80 mV s-1. The oxidation peak current of redox species shows linear
dependence on the scan rate.44 The slope of the line can be calculated based on the formula:
𝑠𝑙𝑜𝑝𝑒 = 𝑛2 𝐹 2 𝐴Γ0 /4𝑅𝑇 (1-18)
Where n is number of electrons transferred, F is Faraday’s constant; A is surface area of electrode;
Γ0 is surface concentration of active sites (mol cm-2), R and T are ideal gas constant and absolute
temperature, respectively.45
TOF values can be calculated from the formula:
JA
TOF = 4Fm (1-19)
Where J is the current density at certain an overpotential, A is the area of electrode, indicates the
mole of electrons consumed for evolving one mole of O2 from water, F is Faraday’s constant (96485 C
mol-1) and m is the number of the moles of active sites. The factor 1/4 in the equation represents that
four electrons are required to form one oxygen molecule from four protons.46
1.2.3.8 Faradic efficiency

Faradaic efficiency (FE) describes the transfer efficiency of electric charge in an electrochemical
reaction system, and it is the ratio between the utilized charge by reactants and the amount of total charge
10
of the external circuits. FE plays a vital role in detecting the complete decomposition of water. FE losses
may occur when heat or by-products formed during the reaction. The FE of the OER process is
calculated by comparing the amount of experimentally quantified O2 (gas chromatography or a water-
gas displacing method) with theoretically calculated O2 (galvanostatic or potentiostatic electrolysis by
integration).
1.3 Water electrolysis technologies

The water electrolysis technique is not at all a new invention. The technique was developed over
two centuries ago by the two companions Nicholson and Carlisle. Up to now, the main water electrolysis
technologies available are AEC, which represents the most mature technology and has been applied for
large-scale hydrogen production in the MW-scale already in the beginning of the 20th century. The other
main water electrolysis technologies are proton exchange membrane electrolysis cell (PEMECC, also
named solid polymer electrolysis (SPE)) and solid oxide electrolysis cell (SOEC). Figure 1-4 depicts
the technology set-up of PEMEC and SOEC.
Figure 1-4 Conceptual set-up of PEMEC and SOEC.14
AEC and PEMEC have both reached commercialization while SOEC is still in the development
stage. Commercial AEC and PEMEC electrolyzers are typically operated at temperatures below 100°C
while SOEC is operated at gas phase conditions at temperatures in the range of 800-1,000°C. The
advantage of the high operation temperature is a significant reduction in the electrical energy demand
for hydrogen production. Consequently, developers of water electrolysis systems are increasingly
looking in the direction of higher operation temperatures. The drawbacks of working at elevated
temperatures are however greater challenges regarding the decomposition of materials, which often
causes corrosion of metals and the degradation of polymers used for sealing and etc., which in fact are
the main reasons for the SOEC still being at the R&D stage.
For the commercially available electrolyzers, PEMEC electrolyzers display the best efficiencies at
higher current densities. The investment cost for PEMEC is much larger than for their alkaline
counterparties. The capital cost for commercial electrolyzers are estimated to be 1000-1200 € kWel -1for
-1
the largest alkaline systems compared to 1860-2320 € kWel for small PEMEC electrolyzers.
11
Additionally, the durability of the materials for PEMEC is much less than for alkaline electrolysis. The
lifetime of commercial alkaline electrolyzers is said to be about 60,000-90,000 hours compared to
20,000-60,000 hours for PEMEC electrolyzers. Table 1 summarizes component materials as well as
performance and cost parameters. There are other two methods of hydrogen production, steam
electrolysis and the chlor-alkali production, from which hydrogen is the byproduct.
As seen from the Table 1-1, AECs have by far the largest power capacity and are available up to
the 6 MW range, compared to the maximum of 2 MW for PEMEC. The low power consumption and,
thus, low production rate for PEMEC makes AEC the current standard for large-scale hydrogen
production techniques.
Table 1-1 Main characteristics of AEC, PEMEC and SOEC systems.14

Parameters AEC PEMEC SOEC
Electrolyte Aq. potassium hydroxide (20- Polymer membrane (e.g. Yttria stabilized Zirconia
40 wt.% KOH) 5 Nafion) 47 (YSZ) 48
Cathode Ni, Ni-Mo alloys 5 Pt, Pt-Pd 47 Ni/YSZ 48
Anode Ni, Ni-Co alloys 5 RuO2, IrO2 47 LSMb/YSZ 48
Current density (A cm-2) 0.2-0.4 47 0.6-2.0 47 0.3-2.0 48
Cell voltage (V) 1.8-2.4 47 1.8-2.2 47 0.7-1.5 48
Cell area (m2) <4 14 <0.3 14 <0.01 14
Operating Temp. (℃) 60-80 47 50-80 47 650-1000 48
Operating Pressure (bar) <30 14 <200 14 <25 14
Production RateC (m3H2h-1) <760 14 <40 14 <40 14
Gas purity (%) >99.5 5 99.99 5 99.9 a
Stack Lifetime (h) 60,000-90,000 5 20,000-60,000 5 <10,000 a
Maturity Mature Commercial Demonstration a
Capital Cost (€ kWel -1) 1000-1200 5 1860-2320 5 >2000 5
Power (kW) 2-6000 49 1.8-2000 49 N.A.d

a Where no reference is provided, data were derived during expert elicitations.
b Perovskite-type lanthanum strontium manganese (La0.8Sr0.2MnO3).
c
Refers to norm cubic meter of hydrogen (at standard conditions) and respective electrical energy consumption (kWhel)
if applicable.
d N.A: information not available
1.3.1 Alkaline electrolysis cell technology

Alkaline electrolysis cell (AEC) is the incumbent water electrolysis technology and widely used
for large-scale industrial applications since 1920.50 AEC systems are readily available, durable and
exhibit relatively low capital cost due to the avoidance of noble metals and relatively mature stack
components.5, 47 The principle layout of AEC is shown in Figure 1-5. The electrodes are immersed in a
liquid electrolyte separated by a diaphragm. The electrolyte is usually a 25-30 % KOH aqueous solution.
12
It is circulated for the removal of product gas bubbles and heat either by pumps or by natural circulation
due to temperature gradients and buoyancy of the gas bubbles. The electrolyte is stored in two separated
drums for each product gas (O2 and H2) which serve also as gas-liquid-separator. The product gas quality
after drying is typically in the range of 99.5-99.9 % for H2 and 99-99.8 % for O2 which can be increased
to above 99.999 % by catalytic gas purification (deoxidizer).51 The partial reaction at the electrodes is
given by:
2H2 O + 2e− = H2 + 2OH− Cathode (1.3.1.1)
1
2OH− = 2 O2 + H2 O + 2e− Anode (1.3.1.2)
As seen, water is consumed on the cathode side while water is produced on the anode side. As a
result, the lye streams of both sides must be mixed before entering the electrolyzer to prevent a respective
dilution or concentration of the electrolyte streams. This results in a contamination of product gases due
to the electrolyte streams carrying dissolved gases, as the separators can only remove the gas bubbles.
A critical contamination (flammable mixture) in part load has to be avoided by a proper control of the
lye circulation, which is automatically the case for natural circulation.51, 52
However, low current density and operating pressure negatively impact system size and hydrogen
production costs. Also, dynamic operation (frequent start-ups and varying power input) is limited and
can negatively affect system efficiency and gas purity. Therefore, development is focused on increasing
current density and operating pressure, as well as system design for dynamic operation, to allow
operation with intermittent renewable sources, for example.5, 14, 47
Figure 1-5 Layout of AEC system.51
1.3.2 Other methods of hydrogen production

PEMEC systems are based on the solid polymer electrolyte (SPE) concept for water electrolysis
that was first introduced in the 1960s by General Electric to overcome the drawbacks of AECs.50 The
technology is therefore less mature than AEC and mostly used for small-scale applications. Key
13
advantages are high power density and cell efficiency, provision of highly compressed and pure
hydrogen, and flexible operation.47 Disadvantages include expensive platinum catalyst and fluorinated
membrane materials, high system complexity due to high pressure operation and water purity
requirements, and shorter lifetime than AEC at present. Current development efforts are therefore
targeted at reducing system complexity to enable system scale-up and reducing capital costs through
less expensive materials and more sophisticated stack manufacturing processes.47
SOEC is the least developed electrolysis technology. It is not yet widely commercialized, but
50
systems have been developed and demonstrated on laboratory scale and individual companies are
currently aiming to bring this technology to market. SOECs use solid ion-conducting ceramics as the
electrolyte, enabling operation at significantly higher temperatures. Potential advantages include high
electrical efficiency, low material cost and the options to operate in reverse mode as a fuel cell or in co-
electrolysis mode producing syngas (H2 + CO) water steam (H2O) and carbon dioxide (CO2). A key
challenge is severe material degradation because of the high operating temperatures. Thus, current
research is focused on stabilizing existing component materials, developing new materials and lowering
the operation temperature to 773-973 K (from 923 to 1273 K) to enable the commercialization of this
technology.14, 48
Steam electrolysis is a technology that reaches higher total energy efficiency compared to AEC and
PEMEC. From the thermodynamic viewpoint of water decomposition, it is more advantageous to
electrolyze water at high temperature (1073-1273 K) because the energy is supplied in mixed form of
electricity and heat. The main advantage is that a substantial part of the energy needed for the electrolysis
process is added as heat, which is much cheaper than electric energy.53
Hydrogen, as a byproduct, also can be produced from Chlor-alkali industry. The main product of
the chlor-alkali electrolysis process, which uses NaCl as a raw material, is chlorine. The industrially
used electrolysis cells are the mercury, the diaphragm and the membrane cell.53
1.3.3 Industrial application parameters in alkaline electrolysis cell
developers
Table 1-2 compares cell operating conditions for the alkaline water electrolysis in five companies:
De Nora S.A.P., Norsk Hydro, Electrolyzer Corp. Ltd., Teledyne Energy systems and General Electric.
Only Electrolyzer Corp. Ltd. uses monopolar cell type, while all others are using bipolar cell type. The
PTFE bonded noble metals are cathodes and anodes in the cells of General Electric (operating at 500
mA cm-2 with the cell voltage of 1.7 V), while others are using either Ni-coated steel, or activated Ni-
coated steel. The operation current density varies from 134 mA cm-2 to 200 mA cm-2 with the operating
cell voltage varying from 1.75 V to 1.9 V.5, 54
14
Table 1-2 Water electrolyzer developers and cell operating conditions.5

Parameter De Nora S.A.P Norsk Hydro Electrolyzer Teledyne Energy General Electric
Corp. Ltd. systems
Cell type B-FP B-FP M-T B-FP B-FP
Anode Expanded Ni-plated Activated Ni- Ni-coated Steel Ni screen PTFE-bonded
Mild steel coated Steel Noble metal
Cathode Activated Ni-plated Activated Ni- Steel Ni screen PTFE-bonded
Steel coated Steel Noble metal
Pressure (MPa) Ambient Ambient Ambient 0.2 0.4
Temperature (℃) 80 80 70 82 80
Electrolyte 29 % KOH 25 % KOH 28 % KOH 35 % KOH Nafion
Current density (A m-2) 1500 1750 1340 2000 5000
Cell voltage (V) 1.85 1.75 1.9 1.9 1.7
Current efficiency (%) 98.5 98.5 >99 NR NR
Oxygen purity (%) 99.6 99.3-99.7 99.3-99.7 >98.0 >98.0
Hydrogen purity (%) 99.9 98.9-99.9 99.9 99.99 >99.0
1.4 Synthetic strategies of OER catalysts for alkaline medium

Oxygen evolution reaction (OER) has been historically one of the most important reactions in the
realm of electrochemistry due to the fundamental and industrial importance of the electrolysis of water.
To date, some noble metals and their oxides, such as Ru, Ir, RuO2, and IrO2, are recognized to be the
best OER electrocatalysts in aqueous acidic and alkaline solutions since their lowest overpotential for
the OER at practical current densities.10, 55 However, their widespread commercial applications are
limited significantly because of their low abundance and high cost. Therefore, some researchers also try
to build Ru- or Ir-based ternary metal oxides to reduce the amount of the noble metals required while
gaining their excellent performance in reducing the OER overpotential. However, commercial
electrolyzers operate in highly conductive medium, that is, either in acidic or alkaline conditions.
Unfortunately, RuOx, IrOx, and their composites exhibit substantial stability in only acidic medium, that
is, they are not stable in alkaline media, due to forming unstable film.56, 57 Consequently, there is an
active quest for finding inexpensive electrocatalysts to efficiently conduct OER with a minimum
overpotential. Accordingly, extensive efforts have been devoted to the design, synthesis, and
characterization of alternative OER electrocatalysts based on first-row transition metal compounds
(TMC) that are low cost, highly active, and stable long-term under oxidizing conditions, thus making
the overall water splitting more practically feasible.58-68
In fact, we should not only focus on the development of the best performing catalysts. In addition,
developing catalyst assembly and subsequent activation processes, investigating the evolution of the
structure and OER performance for the integrated electrode in commercial AEC during long-term
service, are the keys to determine whether the newly developed catalytic materials have the potential to
15
replace the existing commercial electrodes, for the reason that these outstanding catalysts are almost
synthesized with unsupported structure, such as nanoparticle, nanosheet, core-shell nanostructure, and
other ingenious nanostructures. However, they must assemble with their supports to form an integrated
electrode in actual industrial service. It's hard to fully play the inherent performance for the original
catalysts once they are assembled as integrated electrode for service in commercial AEC, often with the
loss of activity and stability.
Meanwhile, OER is a surface reaction (or more precisely within an ultrathin film), rational design
of the electrode architecture can dramatically promote activity in the electrochemical performance.69-72
Therefore, in order to achieve effective ways of further improving electrocatalytic reactions at the three
phase boundary, the design of 3D electrodes/supports with facile charge/electrolyte/bubble migration
and higher catalyst loading contributions to the catalytic activity are widely explored.73, 74
In situ ECA strategy as an efficient activation technique for the integrated electrodes to enhance
OER performance has been mostly applied.75-82 The electrode surfaces are modified from bulk phase
upon ECA treatment, which can tune local electronic structures, create more active species, enlarge
surface area and thus improve the OER performances.77, 83, 84 Meanwhile, this technique can couple the
atomic, electronic structures with electrocatalysis mechanisms for water splitting. 75, 76, 82 Compared to
traditional chemical treatment, the in situ electrochemical activation has superior advantages such as
facile operation, mild environment, variable control, high efficiency and flexibility.85
1.4.1 Noble metals and their oxides as OER catalysts

Noble metals as well as their oxides are the most studied catalysts due to their excellent
performance towards OER. It is experimentally proved that iridium (Ir) and ruthenium (Ru) materials
are more active towards OER as compared to platinum (Pt) and palladium (Pd) (Pt < Pd < Ir < Ru).56, 86,
87
Thus, researchers mainly focus on Ir and Ru based catalysts. Ir and Ru are still considered as the state-
of-the-art OER electrocatalysts with relatively low overpotential and Tafel slope and particularly
superior stability.88-90 Additionally, alloying noble metals together can result in a synergetic effect while
the ordered uniform structure of metallic lattice is somewhat altered by the arrangement of two or more
atoms with different sizes. This approach has shown potential results for improving the electrocatalytic
activities of noble metal for various electrochemical reactions including OER.91-100
For oxides, iridium oxide (IrO2) and ruthenium oxide (RuO2) catalysts are commonly considered
as benchmark electrocatalysts for OER owing to their high electrocatalytic activities toward OER in
both acidic and alkaline solution.101-107 As be reported earlier, RuO2 is unstable under high anodic
potential and is going to deteriorate (dissolve) during OER, while IrO2 is a more stable catalyst than
RuO2, but less active than RuO2 for OER.108 To further optimize the activity and stability of RuO2 and
IrO2, Ru-Ir based oxides have been synthesized with the high surface area by co-precipitation method
in ethanol medium.109 It was found that the Ru0.9Ir0.1O2 presents activity close to that of RuO2,
16
importantly with the significant improvement of the stability.30
1.4.2 First-row transition metal compounds as OER catalysts

As mentioned earlier, noble metal as well as their oxides are well-known OER electrocatalysts with
high activity but suffer from high cost and low abundance. Hence considerable efforts have been devoted
to developing cost-effective OER catalysts derived from earth-abundance elements. First-row TMC
mainly including Co-based-,110-116 Fe-based-,113, 114, 117, 118 and Ni-based-,111, 117-121 are the mostly studied
noble-free metal OER catalysts. Among these compounds, the metal oxides,110, 117 (oxy) hydroxides,111,
118
phosphates,112 phosphides,113, 114, 119 sulfides,120 selenides,115, 121 and nitrides116 display some of the
most outstanding OER performance. Noteworthy, recent studies reveal that the essential active sites of
the metal phosphides, sulfides, and selenides for OER are likely the surface oxides, (oxy) hydroxides
species formed during the electrochemical oxidation process.76, 77, 81, 122 With this in mind, the synthetic
and structural tuning of metal oxides, (oxy) hydroxides toward enhanced activity and stability has been
a focus in OER electrocatalysis.
1.4.2.1 Co-based transition metal compounds as OER catalysts

Co-based TMC have emerged as a promising candidate for investigating the OER in an alkaline
medium owing to their environmental friendliness, abundant reserves, thermal stability, and low cost.82,
123-145
Hence, synthesis and fine structural optimization of cobalt-based catalysts and a deep
understanding of their structure-property relationships in the OER have been actively pursued. Generally,
these cobalt-based TMC OER catalysts can be classified into oxides/(oxy) hydroxides, phosphides and
sulfides. All these three kinds of OER catalysts will be discussed in detail below and are summarized in
Table 1-3.
Table 1-3 The electrocatalytic activity of Co-based TMC OER catalysts.

Catalysts Methods Electrolyte 𝜂10𝑚𝐴/𝑐𝑚2 (mV Tafel (mV/dec)
O-vacancy-rich Co3O4146 Mild solvothermal reduction 1 M KOH NA 49.1
Co3O4-250147 Anodization 1 M KOH 275 NA

148
Co3O4/rGO nanocomposites Electrostatic interaction/induced growth 1 M KOH 346 47
149
Pd@PdO-Co3O4 Nano-cubes Thermal decomposition 1 M KOH 310 70
150
3D urchin-like Co3O4 Hydrothermal reaction 1 M KOH 410 65
151
Nano-porous Zn-doped Co3O4 Hydrothermal method 0.1 M KOH 172 34
NiO/Co3O4@ NC152 Thermal annealing 1 M KOH 240 73
Co3O4/Co-Fe DSNBs153 Thermal annealing 1 M KOH 297 61

154
Co-Nx/C NRA Decomposition 1 M KOH 300 62.3
155
Co/Co9S8@NSOC-800 One-step pyrolysis 1 M KOH 373 80
156
Ni-Co-S/NF Hydrothermal and calcination synthesis 1 M KOH NA 133.8
17
Mn-Co-P@MnCo2O4/Ti157 Cathodic Polarization 1 M KOH 269 102

158
Ni-Co-P HNBs A rapid microwave-assisted method 1 M KOH 270 76
Co9S8/C NSs159 Hydrothermal method 0.1 M KOH 434 119
Co3O4@MoS2160 Two-step hydrothermal method 1 M KOH 269 58

161
CF-NG-Co A simple impregnation-pyrolysis method 1 M KOH 400 60
162
Co-P/Co-N-C/NPC Polymerization and pyrolysis 1 M KOH 374 92
163
NiCo/NLG-270 LI-PLI method 1 M KOH 310 87
164
Fe@BIF-91 Reaction method 1 M KOH 350 71
(Ni, Co)0.85Se165 Electrosynthesis method 1 M KOH NA 86.75
FeCoNiP166 Chemical reduction 1 M KOH 200 70

167
C-MOF-C2-900 Pyrolysis 1 M KOH 350 79
168
CoOOH nanosheets “Atomic-scale phase-transformation” 1 M KOH 300 38
169
Ni-Co-O@Ni-Co-S nanoarray Hydrothermal and thermal annealing 1 M KOH NA 79
1.4.2.2 Fe-Based transition metal compounds as OER catalysts

Iron offers significant advantages in comparison with precious metals and even other transition
metals. Firstly, iron is the second most abundant metal in the Earth’s crust, and thus is far more
inexpensive than other metals often used for constructing water-splitting electrocatalysts.170 Secondly,
iron is relatively less toxic and is present as a key element in various biological systems. 171, 172 Thirdly,
iron-based catalysts are known to effectively mediate some important biological processes in nature.
Meanwhile, iron also has multiple valence state, and has become a highly visible material for OER.173,
174
Compared with other transition metals such as Co and Ni, Fe based OER electrocatalysts have not
been as broadly investigated, especially for pure Fe (oxy)hydroxides. Generally, Fe is particularly well
known to be incorporated as a dopant/impurity into Ni-/Co-based OER catalysts, dramatically
improving their OER performances. Interestingly, some recent studies proposed that Fe is the active site
and that the Ni or Co (oxy)hydroxide primarily provides an electrically conductive, chemically
stabilizing, and high-surface area host. Some related work has been summarized in Table 1-4.
Table 1-4 The electrocatalytic activity of Fe-based TMC OER catalysts.

FeOOH2nm/LDH175 Hydrothermal method 1 M KOH 174 27

176
Co2-Fe-B Chemical method 1 M KOH 298 62.6
177
Fe7S8 nanosheet Modified liquid exfoliation 1 M KOH 270 43
178
NiFeS/NF Hydrothermal sulfidation process 1 M KOH 65 119.4
179
Ni1.5Fe1.5-O Chemical dealloying 1 M KOH 244 39
Fe3O4/Co3S4180 Hydrothermal and calcination 1 M KOH 270 56
Iron-rich V-Co-Fe181 Chemical method 1 M KOH 307 36
Ni-Fe(OxHy)182 Physically mixing 1 M KOH 298 37

183
Fe-N-CIG Heat treatment 0.1 M KOH 390 96
18
NiO/NiFe2O4184 Calcination 1 M KOH 303 58.5

185
Ni-Fe PBA Self-templating 1 M KOH 240 24
Fe-N4 SAs/NPC186 Polymerization and pyrolysis 1 M KOH 430 95
N-HMSC (FePc)187 Template 0.1 M KOH 490 117

188
Fe3-Co2-Al2-AE Doping-etching route 1 M KOH 284 100.6
189
Fe@C-NG/NCNTs Pyrolysis strategy 1 M KOH 450 163
114
Co0.63Fe0.21P0.16 One-step solvothermal process 1 M KOH 217 40
190
NiFe LDHs-VNi Hydrothermal and etching method 1 M KOH 229 62.9
Fe-doped NiOx nanotubes191 Template 1 M KOH 310 49
Fex%-NiO/NF192 Solvothermal synthesis 1 M KOH 206 49.7

193
Ni-Fe LDH hollow prisms Self-templated strategy 1 M KOH 280 49.4
194
Fe/Fe2O3@Fe-N-C-1000 Pyrolysis 0.1 M KOH 690 77.5
195
Co-Fe oxyphosphide MTs Hydrothermal and phosphidation 1 M KOH 280 53
196
NiFe-LDH@NiCu Polyol-assisted reduction process 1 M KOH 218 66
Fe-O2cat197 Solvothermal synthesis 1 M KOH 238 82.7
1.4.2.3 Ni-Based transition metal compounds as OER catalysts

Currently, Ni-based OER catalysts are arousing increasing research interest due to their earth-
abundant nature and theoretically high catalytic activity. Generally, such catalysts mainly include Ni-
based oxides, and Ni-based hydroxides/oxyhydroxide (see Table 1-5Table 1-5). From an industrial
perspective, nickel is typically used as the promising electrode material in commercial electrocatalytic
electrolysis units in highly alkaline electrolytes owing to its relatively high stability and favorable
activity. Particularly, nickel foam (NF) with a long range ordered porous framework, which not only
exposes more reaction active sites but also accelerate fast ion and electron transport, is the most widely
used conductive substrate for the construction of three-dimensional (3D) catalysts.198-202
Table 1-5 The electrocatalytic activity of Ni-based TMC OER catalysts.

Fe11%-NiO/NF192 Solvothermal synthesis 1 M KOH 206 49.4

203
NiO-Ni3S2/NF Sulfidation treatment 1 M KOH 340 75
204
Elox_H2S_NF Thermal sulfurization 1 M KOH 256 41
205
Ni0.82Co0.18O@C/NF Pyrolysis 1 M KOH 190 65
NiO/Ni206 Laser ablation 1 M KOH 294 41
NiB0.45-250/Cu207 Electroless plating method 1 M KOH 296 58

208
Ni3N Hydrothermal method 1 M KOH 277 118
209
NiCoON NSAs/NF Hydrothermal method 1 M KOH 247 35
210
(Zn)Ni-LDH/N-rGO Solvothermal process 1 M KOH 290 44
211
Ni-Fe LDH Hydrothermal method 1 M KOH 174 27
Ce-NiO-E212 Sol-gel method and annealing 1 M KOH 382 118.7
NiSxPy213 Hydrothermal reaction 1 M KOH 192 95
19
Ni0.75Fe0.25-P/PO3@fCNT214 Decoration and phosphorization 1 M KOH 239 34.4

215
γ-NiOOH/NiNPS In situ activation 1 M KOH - 46
NiO@MoO3/VC216 Hydrothermal treatment 1 M KOH 280 64.5
holey Ni(OH)2217 Etching method 1 M KOH 293 65

209
NiCoO2/CoO/Ni3N Hydrothermal method 1 M KOH 247 35
218
PANiO Phosphorized method 1 M KOH 138 36
219
RuO2/NiO/NF Hydrothermal and calcination 1 M KOH 250 50.5
220
Fe-Ni(OH)2/NF Hydrothermal 1 M KOH 235 51.5
Ni/NiO@G-SH221 Reduction method 0.1 M KOH 270 46
Ni@NiO222 Mild etching 1 M KOH 382 103

223
NiP120 Electroless deposition and robocasting 1 M KOH 286 75.1
224
NiCo2O4/Ni2P Deposition and phosphorization 1 M KOH 250 58
+ 225
N -5e15 Irradiation 0.1 M KOH 400 136
84
NiOOH-NiCr2O4/NF In situ electrochemical conversion 1 M KOH - 104
1.4.3 In situ electrochemical activation based OER catalysts

The in situ ECA method has been mostly applied for OER in alkaline condition, which is a novel
electrochemical tuning access to enhance catalytic performances in a facile, mild, green and controllable
way. It has been first explored by Cui’s group to synthesize transition metal (e.g., Co, Ni and Fe) oxides
(TMOs) from sulfides (TMS). The electrodeposited TMOs on carbon fiber cloth were first transferred
to TMS followed by in situ ECA back to TMOs (referred as ECT-TMOs). Different from traditional
electrodeposited TMO nanosheets, ECT-TMOs became porous and composed of small grains with
decreased crystalline degree.226 Such small grains created more defects and surface catalytic sites for
OER, which can be verified by increased current densities, lower onset potentials and larger ECSA.227-
230
Furthermore, the enhanced OER activities of binary, ternary or quaternary ECT-TMOs can also be
observed under identical electrochemical tuning. One explanation for enhanced OER properties is the
higher oxidation state of metals under anodic potentials, which can facilitate the multi-electron transfer
in water oxidation.231, 232 In addition, the low-crystalline, porous nanostructures containing abundant
defects and surface sites contribute to high OER performance.75 Recently, induced lattice distortion upon
in situ ECA for efficiently triggering water splitting by enhancing intrinsic activity were gradually
realized by researchers.233, 234
Such tuning strategy opens up a fresh new pretreatment technique for electrocatalysts, which is
quite distinguished from traditional chemical treatment always requiring harsh and polluted conditions.
These works (as shown in Table 1-6) greatly motivated peer workers to investigate more available
transition metal materials under electrochemical activation and gain deeper insight into activation
mechanism.
20
Table 1-6 The electrocatalytic activity of In situ ECA based OER electrocatalysts.
Catalysts Methods Electrolyte 𝜂10𝑚𝐴/𝑐𝑚2 (mV) Tafel (mV/dec)
75
ECT-S-Co0.37Ni0.26Fe0.37O In situ ECA 1 M KOH 232 37.6
83
Fe0.33Co0.67OOHPNSAs/CFC In situ ECA 1 M KOH 266 30
CoTeNR/NF82 In situ ECA 1 M KOH 202 75
NiOOH-NiCr2O4/NF84 In situ ECA 1 M KOH - 104
CoP/C122 In situ ECA 0.1 M KOH 360 66

81
NixFe1-xSe2-DO In situ ECA 1 M KOH 195 28
157
Mn-Co-P@MnCo2O4/Ti In situ ECA 1 M KOH 269 102
235
E-CoOx/CF In situ ECA 1 M KOH 249 50
MnGa4/NF236 In situ ECA 1 M KOH 291 98
Fe1Ni1 LDH237 In situ ECA 1 M KOH 253 34
MoOx@N3-doped MoS2-x238 In situ ECA 1 M KOH 270 61
1.5 Objectives
In order to obtain promising OEEs withstand extremely high current density (≥ 500 mA cm-2) which
is required practically for commercial industrial electrolyzers, the OEEs should fulfill multiple criteria
simultaneously: (i) high intrinsic activity for OER, (ii) huge ECSA, (iii) facile charge/electrolyte/bubble
migration at the same time, and (iv) high tolerance against corrosion under strong oxidizing conditions.
Additionally, the catalytically active phase must also have a strong adhesion to its framework, and
thereby it can be prevented from peeling off during long-term electrocatalysis. In this case, a long-time
steady catalytic output at large current densities is generally unrealizable due to the presence of the
common problem of catalyst peeling during electrocatalysis as well as the large interfacial resistance
between the catalyst and its framework. Meanwhile, in order to facilitate the OEEs commercialization,
it is not negligible to discover a manufacturing method capable of realizing large-size (≤ 4 m2) and high
production efficiency of the electrode. However, to date, it is still quite difficult to design versatile OEEs
that can meet all the above standards.
Thus, designing hierarchical porous OEEs with cost effective, high catalytic reactivity, high
structural stability, and high electronic conductivity via suitable synthesis approaches, eventually
become objectives of my PhD work and deserve to be strongly pursued, toward meeting our goal of
making efficient OEEs at large current densities. Additionally, we also consider preparing promising
HEEs at the same time while discovering a way to have the potential to obtain excellent OEEs, coupling
with which form a two-electrode configuration for the commercial AEC, in order to achieve efficient
overall water splitting.
In details:
(1) Engineering hybrid pre-catalysts by fabrication of additives (Co3O4 and GO) with high
efficient OER activity on the typical commercial nickel foam (NF) via electrolytic codeposition is the
21
first step of our goals to obtain promising OEEs. The second step is to activate these pre-catalysts upon
in situ ECA by in situ oxidation of Ni crystals to wrinkled Ni(OH)2/NiOOH nanosheets, thus, obtaining
a versatile OEE (denoted as the activated NF@CGO).
(2) High-velocity oxy-fuel (HVOF, a common thermal spray process) followed by chemical
activation (CA) is employed to design a promising hierarchical porous OEE, to achieve huge ECSA,
and facile charge/electrolyte/bubble migration. Subsequently, Jamborite (Ni(OH)2/NiOOH hybrid)
nanosheets are in situ generate on the surface of the pre-catalysts upon in situ ECA, eventually formation
of a promising OEE with high intrinsic activity (denoted as HNA-CA-ECA).
(3) Preparing HEEs with the same approach while OEEs are made, coupling with the obtained
OEEs and forming a two-electrode configuration, rivalling the integrated state-of-the-art IrO2(+)||Pt(-)
electrode in alkaline overall water splitting. We hope our work can promote advanced development
toward large-scale H2 production using excess electrical power whenever and wherever available.
1.6 The originality and novelty of PhD study

(1) Both of the methods, electrolytic codeposition and HVOF followed by CA, are simple and are
two of the few methods that are conducive to commercial production of OEEs based on the fact both of
these have the potential to achieve large-scale, high efficient production of OEEs with large dimensions
for AEC.
(2) The application of the in situ activation process makes the two kinds of OEEs abovementioned
self-supported and binder-free architectures, which is not only easy to operate, but also can generate
robust and highly active nanostructures on the surface of the pre-catalysts, avoiding the additional
resistance between the catalyst powders and current collector (e.g., glassy carbon) within the powder-
based electrodes, and long-lasting OER performance gradually deteriorated when bearing extremely
large current density, if electrical insulating binding agents (e.g., Nafion) are utilized.
(3) For the activated NF@CGO, such a remarkable performance can benefit from the self-assembly
of the introduced OER catalysts deposited on NF, in situ-generated Ni(OH)2/NiOOH nanoflakes, and
their synergistic effects. A catalytic layer with an arbitrary thickness, excellent electrical conductivity,
and highly efficient catalytic activity for OER can be obtained. While maintaining the sufficiently high
performance, this uniform catalytic layer also allows us to maintain long-term durability of OEE without
significant deterioration during harsh and oxidative OER operation conditions, which is one of the
drastic requirements necessary for industrial applications.
(4) For HNA-CA-ECA, the micro-voids retained in resulting coatings by HVOF can not only
increase the ECSA, but also facilitate the appearance of macropores with de-alloying of the precursor
coatings upon CA process. The micro-voids and macropores combine with mesopores upon subsequent
in situ ECA, forming the hierarchical porous architecture, which is not only conducive to electron/ion
transport and the formation of oxygen, but also facilitates the oxygen bubble detachment, consequently,
22
promoting reaction kinetics of OER. The increasement of intrinsic activity is mainly achieved by lattice-
distorted Jamborite nanosheets.
References of Chapter I
[1]. S. Dunn, Hydrogen futures: toward a sustainable energy system. . Int. J. Hydrogen Energy, 2002, 27,
235-264.
[2]. D. L. Stojić, Marčeta, M. P., Sovilj, S. P., & Miljanić, Š. S. , Water electrolysis: who first? J. Electroanal.
Chem., 2003, 476, 315-319.
[3]. R. F. de Souza, J. C. Padilha, R. S. Gonçalves, M. O. de Souza and J. Rault-Berthelot, Electrochemical
hydrogen production from water electrolysis using ionic liquid as electrolytes: Towards the best device. J. Power
Sources, 2007, 164, 792-798.
[4]. D. L. Stojić, M. P. Marčeta, S. P. Sovilj and Š. S. Miljanić, Hydrogen generation from water electrolysis-
possibilities of energy saving. J. Power Sources, 2003, 118, 315-319.
[5]. K. Zeng and D. Zhang, Recent progress in alkaline water electrolysis for hydrogen production and
applications. Prog. Energy Combust. Sci., 2010, 36, 307-326.
[6]. N. D. G. Lewis N S, Powering the planet: Chemical challenges in solar energy utilization. Proceedings
of the National Academy of Sciences 2006, 103, 15729-15735.
[7]. S. Chu, Majumdar, A., Opportunities and challenges for a sustainable energy future. Nature, 2012, 488,
294-303.
[8]. T. R. Cook, Dogutan, D. K., Reece, S. Y., Surendranath, Y., Teets, T. S., & Nocera, D. G. , Solar Energy
Supply and Storage for the Legacy and Nonlegacy Worlds. Chem. Rev., 2010, 110, 6474-6502.
[9]. N. T. Suen, Hung, S. F., Quan, Q., Zhang, N., Xu, Y. J., Chen, H. M., Electrocatalysis for the oxygen
evolution reaction: recent development and future perspectives. Chem. Soc. Rev., 2017, 46, 337-365.
[10]. E. L. W. Michael G. Walter, James R. McKone, Shannon W. Boettcher, Qixi Mi, Elizabeth A. Santori,
and Nathan S. Lewis., Solar Water Splitting Cells. Chem. Rev., 2010, 110, 6446-6473.
[11]. F. Song, Bai, L., Moysiadou, A., Lee, S., Hu, C., Liardet, L., Hu, X., Transition Metal Oxides as
Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance.
JACS, 2018, 140, 7748-7759.
[12]. J. Wang, W. Cui, Q. Liu, Z. Xing, A. M. Asiri and X. Sun, Recent Progress in Cobalt-Based
Heterogeneous Catalysts for Electrochemical Water Splitting. Adv. Mater., 2016, 28, 215-230.
[13]. J. Wang, F. Xu, H. Jin, Y. Chen and Y. Wang, Non-Noble Metal-based Carbon Composites in Hydrogen
Evolution Reaction: Fundamentals to Applications. Adv. Mater., 2017, 29, 1605838.
[14]. O. Schmidt, A. Gambhir, I. Staffell, A. Hawkes, J. Nelson and S. Few, Future cost and performance of
water electrolysis: An expert elicitation study. Int. J. Hydrogen Energy, 2017, 42, 30470-30492.
[15]. W. I. Choi, B. C. Wood, E. Schwegler and T. Ogitsu, Site-Dependent Free Energy Barrier for Proton
Reduction on MoS2 Edges. J. Phys. Chem. C, 2013, 117, 21772-21777.
[16]. B. Hinnemann, Moses, P. G., Bonde, J., Jørgensen, K. P., Nielsen, J. H., Horch, S. & Nørskov, J. K. ,
Biomimetic Hydrogen Evolution: MoS2 Nanoparticles as Catalyst for Hydrogen Evolution. JACS, 2005, 127,
5308-5309.
[17]. J. Greeley, T. F. Jaramillo, J. Bonde, I. B. Chorkendorff and J. K. Norskov, Computational high-
throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater., 2006, 5, 909-913.
23
[18]. L. C. Seitz, Dickens, C. F., Nishio, K., Hikita, Y., Montoya, J., Doyle, A. & Jaramillo, T. F. , A highly
active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction. Science, 2016, 353, 1011-1014.
[19]. C. C. McCrory, S. Jung, I. M. Ferrer, S. M. Chatman, J. C. Peters and T. F. Jaramillo, Benchmarking
hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J. Am.
Chem. Soc., 2015, 137, 4347-4357.
[20]. M. E. Lyons and S. Floquet, Mechanism of oxygen reactions at porous oxide electrodes. Part 2-Oxygen
evolution at RuO2, IrO2 and Ir(x)Ru(1-x)O2 electrodes in aqueous acid and alkaline solution. Phys. Chem. Chem.
Phys, 2011, 13, 5314-5335.
[21]. J. X. Feng, H. Xu, Y. T. Dong, S. H. Ye, Y. X. Tong and G. R. Li, FeOOH/Co/FeOOH Hybrid Nanotube
Arrays as High-Performance Electrocatalysts for the Oxygen Evolution Reaction. Angew.Chem. Int. Ed., 2016, 55,
3694-3698.
[22]. J. Liu, D. Zhu, T. Ling, A. Vasileff and S.-Z. Qiao, S-NiFe2O4 ultra-small nanoparticle built nanosheets
for efficient water splitting in alkaline and neutral pH. Nano Energy, 2017, 40, 264-273.
[23]. T. Ling, D. Y. Yan, H. Wang, Y. Jiao, Z. Hu, Y. Zheng, L. Zheng, J. Mao, H. Liu, X. W. Du, M. Jaroniec
and S. Z. Qiao, Activating cobalt(II) oxide nanorods for efficient electrocatalysis by strain engineering. Nat.
Commun., 2017, 8, 1509.
[24]. H. Dau, C. Limberg, T. Reier, M. Risch, S. Roggan and P. Strasser, The Mechanism of Water Oxidation:
From Electrolysis via Homogeneous to Biological Catalysis. Chem. Cat. Chem., 2010, 2, 724-761.
[25]. J. O. M. Bockris, Kinetics of Activation Controlled Consecutive Electrochemical Reactions: Anodic
Evolution of Oxygen. J. Chem. Phys., 1956, 24, 817-827.
[26]. R. L. Doyle and M. E. G. Lyons, Kinetics and Mechanistic Aspects of the Oxygen Evolution Reaction
at Hydrous Iron Oxide Films in Base. J. Electrochem. Soc., 2013, 160, H142-H154.
[27]. Y.-H. Fang and Z.-P. Liu, Tafel Kinetics of Electrocatalytic Reactions: From Experiment to First
Principles. ACS Catalysis, 2014, 4, 4364-4376.
[28]. M. E. G. Lyons and M. P. Brandon, A comparative study of the oxygen evolution reaction on oxidised
nickel, cobalt and iron electrodes in base. J. Electroanal. Chem., 2010, 641, 119-130.
[29]. R. E. Meyer, Cathodic Processes on Passive Zirconium. J. Electrochem. Soc., 1960, 107, 847-853.
[30]. M. Tahir, L. Pan, F. Idrees, X. Zhang, L. Wang, J.-J. Zou and Z. L. Wang, Electrocatalytic oxygen
evolution reaction for energy conversion and storage: A comprehensive review. Nano Energy, 2017, 37, 136-157.
[31]. X. Lu and C. Zhao, Electrodeposition of hierarchically structured three-dimensional nickel-iron
electrodes for efficient oxygen evolution at high current densities. Nat. Commun., 2015, 6, 6616.
[32]. P. Zhang, L. Li, D. Nordlund, H. Chen, L. Fan, B. Zhang, X. Sheng, Q. Daniel and L. Sun, Dendritic
core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation. Nat.
Commun., 2018, 9, 381.
[33]. S. Sultan, J. N. Tiwari, A. N. Singh, S. Zhumagali, M. Ha, C. W. Myung, P. Thangavel and K. S. Kim,
Single Atoms and Clusters Based Nanomaterials for Hydrogen Evolution, Oxygen Evolution Reactions, and Full
Water Splitting. Adv. Energy Mater., 2019, 9.
[34]. Y. Jiao, Y. Zheng, M. Jaroniec and S. Z. Qiao, Design of electrocatalysts for oxygen-and hydrogen-
involving energy conversion reactions. Chem.Soc.Rev., 2015, 44, 2060-2086.
[35]. J. Masa, P. Weide, D. Peeters, I. Sinev, W. Xia, Z. Sun, C. Somsen, M. Muhler and W. Schuhmann,
Amorphous Cobalt Boride (Co2B) as a Highly Efficient Nonprecious Catalyst for Electrochemical Water Splitting:
Oxygen and Hydrogen Evolution. Adv. Energy Mater., 2016, 6.
24
[36]. H. Vrubel, T. Moehl, M. Gratzel and X. Hu, Revealing and accelerating slow electron transport in
amorphous molybdenum sulphide particles for hydrogen evolution reaction. Chem. Commun., 2013, 49, 8985-
8987.
[37]. M. R. Gao, J. X. Liang, Y. R. Zheng, Y. F. Xu, J. Jiang, Q. Gao, J. Li and S. H. Yu, An efficient
molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation. Nat. Commun.,
2015, 6, 5982.
[38]. Z. Lu, W. Xu, W. Zhu, Q. Yang, X. Lei, J. Liu, Y. Li, X. Sun and X. Duan, Three-dimensional NiFe
layered double hydroxide film for high-efficiency oxygen evolution reaction. Chem. Commun., 2014, 50, 6479-
6482.
[39]. S. Niu, Jiang, W. J., Wei, Z., Tang, T., Ma, J., Hu, J. S., & Wan, L. J. , Se-Doping Activates FeOOH for
Cost-Effective. JACS, 2019, 141, 7005-7013.
[40]. J. Zhang, T. Wang, P. Liu, Z. Liao, S. Liu, X. Zhuang, M. Chen, E. Zschech and X. Feng, Efficient
hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics. Nat. Commun., 2017, 8,
15437.
[41]. T. Ling, D. Y. Yan, Y. Jiao, H. Wang, Y. Zheng, X. Zheng, J. Mao, X. W. Du, Z. Hu, M. Jaroniec and S.
Z. Qiao, Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior
electrocatalysis. Nat. Commun., 2016, 7, 12876.
[42]. Z.-Y. Yu, C.-C. Lang, M.-R. Gao, Y. Chen, Q.-Q. Fu, Y. Duan and S.-H. Yu, Ni-Mo-O nanorod-derived
composite catalysts for efficient alkaline water-to-hydrogen conversion via urea electrolysis. Energy Environ. Sci.,
2018, 11, 1890-1897.
[43]. R. D. Smith, Prévot, M. S., Fagan, R. D., Zhang, Z., Sedach, P. A., Siu, M. K. J. & Berlinguette, C. P. ,
Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis. Science,
2013, 340, 60-63.
[44]. Y. Li, L. Zhang, X. Xiang, D. Yan and F. Li, Engineering of ZnCo-layered double hydroxide nanowalls
toward high-efficiency electrochemical water oxidation. J. Mater. Chem. A, 2014, 2.
[45]. S. Pintado, S. Goberna-Ferron, E. C. Escudero-Adan and J. R. Galan-Mascaros, Fast and persistent
electrocatalytic water oxidation by Co-Fe Prussian blue coordination polymers. J. Am. Chem. Soc., 2013, 135,
13270-13273.
[46]. M. Gong, Y. Li, H. Wang, Y. Liang, J. Z. Wu, J. Zhou, J. Wang, T. Regier, F. Wei and H. Dai, An advanced
Ni-Fe layered double hydroxide electrocatalyst for water oxidation. J. Am. Chem. Soc., 2013, 135, 8452-8455.
[47]. M. Carmo, D. L. Fritz, J. Mergel and D. Stolten, A comprehensive review on PEM water electrolysis.
Int. J. Hydrogen Energy, 2013, 38, 4901-4934.
[48]. M. A. Laguna-Bercero, Recent advances in high temperature electrolysis using solid oxide fuel cells: A
review. J. Power Sources, 2012, 203, 4-16.
[49]. R. J. Lempert, & Schlesinger, M. E. , ROBUST STRATEGIES FOR ABATING CLIMATE CHANGE.
Clim. Change, 2000, 45, 387-401.
[50]. X. Zhang, S. H. Chan, H. K. Ho, S.-C. Tan, M. Li, G. Li, J. Li and Z. Feng, Towards a smart energy
network: The roles of fuel/electrolysis cells and technological perspectives. Int. J. Hydrogen Energy, 2015, 40,
6866-6919.
[51]. A. Buttler and H. Spliethoff, Current status of water electrolysis for energy storage, grid balancing and
sector coupling via power-to-gas and power-to-liquids: A review. Renew. Sust. Energ. Rev., 2018, 82, 2440-2454.
[52]. C. A. Schug, Operational characteristics of high-pressure, high-efficiency water-hydrogen-electrolysis.
25
Int. J. Hydrogen Energy, 1998, 23, 1113-1120.

[53]. E. Zoulias, Varkaraki, E., Lymberopoulos, N., Christodoulou, C. N., & Karagiorgis, G. N. , A review on
water electrolysis. Tcjst, 2004, 4, 41-71.
[54]. V. D. Jović, B. M. Jović, U. Č. Lačnjevac, N. V. Krstajić, P. Zabinski and N. R. Elezović, Accelerated
service life test of electrodeposited NiSn alloys as bifunctional catalysts for alkaline water electrolysis under
industrial operating conditions. J. Electroanal. Chem., 2018, 819, 16-25.
[55]. Y. Lee, J. Suntivich, K. J. May, E. E. Perry and Y. Shao-Horn, Synthesis and Activities of Rutile IrO2
and RuO2 Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions. J. Phys. Chem.Lett. , 2012, 3, 399-
404.
[56]. T. Reier, M. Oezaslan and P. Strasser, Electrocatalytic Oxygen Evolution Reaction (OER) on Ru, Ir, and
Pt Catalysts: A Comparative Study of Nanoparticles and Bulk Materials. ACS Catalysis, 2012, 2, 1765-1772.
[57]. M. Oezaslan, F. Hasché and P. Strasser, Pt-Based Core-Shell Catalyst Architectures for Oxygen Fuel
Cell Electrodes. J. Phys. Chem. Lett., 2013, 4, 3273-3291.
[58]. J. Landon, E. Demeter, N. İnoğlu, C. Keturakis, I. E. Wachs, R. Vasić, A. I. Frenkel and J. R. Kitchin,
Spectroscopic Characterization of Mixed Fe-Ni Oxide Electrocatalysts for the Oxygen Evolution Reaction in
Alkaline Electrolytes. ACS Catalysis, 2012, 2, 1793-1801.
[59]. X. Zou, J. Su, R. Silva, A. Goswami, B. R. Sathe and T. Asefa, Efficient oxygen evolution reaction
catalyzed by low-density Ni-doped Co3O4 nanomaterials derived from metal-embedded graphitic C3N4. Chem.
Commun., 2013, 49, 7522-7524.
[60]. X. Yu, Z. Sun, Z. Yan, B. Xiang, X. Liu and P. Du, Direct growth of porous crystalline NiCo 2O4 nanowire
arrays on a conductive electrode for high-performance electrocatalytic water oxidation. J. Mater. Chem. A, 2014,
2, 20823-20831.
[61]. E. Detsi, J. B. Cook, B. Lesel, C. Turner, Y. L. Liang, S. Robbennolt and S. H. Tolbert, Mesoporous
Ni60Fe30Mn10-alloy based metal/metal oxide composite thick films as highly active and robust oxygen evolution
catalysts dagger. Energy Environ. Sci., 2016, 9, 540-549.
[62]. S. Chen and S. Z. Qiao, Hierarchically porous nitrogen-doped graphene-NiCo2O4 hybrid paper as an
advanced electrocatalytic water-splitting material. ACS Nano, 2013, 7, 10190-10196.
[63]. S. Mao, Z. Wen, T. Huang, Y. Hou and J. Chen, High-performance bi-functional electrocatalysts of 3D
crumpled graphene-cobalt oxide nanohybrids for oxygen reduction and evolution reactions. Energy Environ. Sci.,
2014, 7, 609-616.
[64]. H. Liang, F. Meng, M. Caban-Acevedo, L. Li, A. Forticaux, L. Xiu, Z. Wang and S. Jin, Hydrothermal
continuous flow synthesis and exfoliation of NiCo layered double hydroxide nanosheets for enhanced oxygen
evolution catalysis. Nano Lett., 2015, 15, 1421-1427.
[65]. M. W. Louie and A. T. Bell, An investigation of thin-film Ni-Fe oxide catalysts for the electrochemical
evolution of oxygen. JACS, 2013, 135, 12329-12337.
[66]. X. Deng and H. Tüysüz, Cobalt-Oxide-Based Materials as Water Oxidation Catalyst: Recent Progress
and Challenges. ACS Catalysis, 2014, 4, 3701-3714.
[67]. Y. Li, P. Hasin and Y. Wu, NixCo3-xO4 nanowire arrays for electrocatalytic oxygen evolution. Adv. Mater.,
2010, 22, 1926-1929.
[68]. L. Han, S. Dong and E. Wang, Transition-Metal (Co, Ni, and Fe)-Based Electrocatalysts for the Water
Oxidation Reaction. Adv. Mater., 2016, 28, 9266-9291.
[69]. L. Wang, X. Huang, S. Jiang, M. Li, K. Zhang, Y. Yan, H. Zhang and J. M. Xue, Increasing Gas Bubble
26
Escape Rate for Water Splitting with Nonwoven Stainless Steel Fabrics. ACS Appl. Mater. Interfaces, 2017, 9,
40281-40289.
[70]. Z. Lu, W. Zhu, X. Yu, H. Zhang, Y. Li, X. Sun, X. Wang, H. Wang, J. Wang and J. Luo, Ultrahigh
hydrogen evolution performance of under‐water “superaerophobic” MoS2 nanostructured electrodes. Adv.
Mater., 2014, 26, 2683-2687.
[71]. A. E. Dorfi, A. C. West and D. V. Esposito, Quantifying losses in photoelectrode performance due to
single hydrogen bubbles. J. Phys. Chem. C, 2017, 121, 26587-26597.
[72]. J. Deng, H. Li, J. Xiao, Y. Tu, D. Deng, H. Yang, H. Tian, J. Li, P. Ren and X. Bao, Triggering the
electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS2 surface via single-atom metal
doping. Energy Environ. Sci., 2015, 8, 1594-1601.
[73]. S. Chang, Huang, X., Ong, C. Y. A., Zhao, L., Li, L., Wang, X., & Ding, J. , High loading accessible
active sites via designable 3D-printed metal architecture towards promoting electrocatalytic performance. J. Mater.
Chem. A, 2019, 7, 18338-18347.
[74]. X. Huang, S. Chang, W. S. V. Lee, J. Ding and J. M. Xue, Three-dimensional printed cellular stainless
steel as a high-activity catalytic electrode for oxygen evolution. J. Mater. Chem. A, 2017, 5, 18176-18182.
[75]. W. Chen, Y. Liu, Y. Li, J. Sun, Y. Qiu, C. Liu, G. Zhou and Y. Cui, In Situ Electrochemically Derived
Nanoporous Oxides from Transition Metal Dichalcogenides for Active Oxygen Evolution Catalysts. Nano Lett.,
2016, 16, 7588-7596.
[76]. C. Hu, Q. Ma, S.-F. Hung, Z.-N. Chen, D. Ou, B. Ren, H. M. Chen, G. Fu and N. Zheng, In Situ
Electrochemical Production of Ultrathin Nickel Nanosheets for Hydrogen Evolution Electrocatalysis. Chem, 2017,
3, 122-133.
[77]. X. Li, G. Q. Han, Y. R. Liu, B. Dong, W. H. Hu, X. Shang, Y. M. Chai and C. G. Liu, NiSe@NiOOH
Core-Shell Hyacinth-like Nanostructures on Nickel Foam Synthesized by in Situ Electrochemical Oxidation as an
Efficient Electrocatalyst for the Oxygen Evolution Reaction. ACS Appl. Mater. Interfaces, 2016, 8, 20057-20066.
[78]. Z. Qiu, C.-W. Tai, G. A. Niklasson and T. Edvinsson, Direct observation of active catalyst surface phases
and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting. Energy
Environ. Sci., 2019, 12, 572-581.
[79]. T. Shinagawa, M. T. Ng and K. Takanabe, Boosting the Performance of the Nickel Anode in the Oxygen
Evolution Reaction by Simple Electrochemical Activation. Angew. Chem. Int. Ed. Engl., 2017, 56, 5061-5065.
[80]. X. Xiong, D. Ding, D. Chen, G. Waller, Y. Bu, Z. Wang and M. Liu, Three-dimensional ultrathin
Ni(OH)2 nanosheets grown on nickel foam for high-performance supercapacitors. Nano Energy, 2015, 11, 154-
161.
[81]. X. Xu, F. Song and X. Hu, A nickel iron diselenide-derived efficient oxygen-evolution catalyst. Nat.
Commun., 2016, 7, 12324.
[82]. L. Yang, H. Xu, H. Liu, D. Cheng and D. Cao, Active Site Identification and Evaluation Criteria of In
Situ Grown CoTe and NiTe Nanoarrays for Hydrogen Evolution and Oxygen Evolution Reactions. Small, 2019, 3,
1900113.
[83]. S. H. Ye, Z. X. Shi, J. X. Feng, Y. X. Tong and G. R. Li, Activating CoOOH Porous Nanosheet Arrays
by Partial Iron Substitution for Efficient Oxygen Evolution Reaction. Angew. Chem. Int. Ed. Engl., 2018, 57, 2672-
2676.
[84]. J. Zhao, X. Ren, Q. Han, D. Fan, X. Sun, X. Kuang, Q. Wei and D. Wu, Ultra-thin wrinkled NiOOH-
NiCr2O4 nanosheets on Ni foam: an advanced catalytic electrode for oxygen evolution reaction. Chem. Commun.,
27
2018, 54, 4987-4990.

[85]. X. Shang, B. Dong, Y.-M. Chai and C.-G. Liu, In-situ electrochemical activation designed hybrid
electrocatalysts for water electrolysis. Science Bulletin, 2018, 63, 853-876.
[86]. Y. Jiao, Y. Zheng, M. Jaroniec and S. Z. Qiao, Design of electrocatalysts for oxygen-and hydrogen-
involving energy conversion reactions. Chem. Soc. Rev., 2015, 44, 2060-2086.
[87]. N. Danilovic, R. Subbaraman, K.-C. Chang, S. H. Chang, Y. J. Kang, J. Snyder, A. P. Paulikas, D.
Strmcnik, Y.-T. Kim and D. Myers, Activity-stability trends for the oxygen evolution reaction on monometallic
oxides in acidic environments. J. Phys. Chem. Lett., 2014, 5, 2474-2478.
[88]. Y. Pi, N. Zhang, S. Guo, J. Guo and X. Huang, Ultrathin laminar Ir superstructure as highly efficient
oxygen evolution electrocatalyst in broad pH range. Nano Lett., 2016, 16, 4424-4430.
[89]. Y. Pi, N. Zhang, S. Guo, J. Guo and X. Huang, Ultrathin Laminar Ir Superstructure as Highly Efficient
Oxygen Evolution Electrocatalyst in Broad pH Range. Nano Lett., 2016, 16, 4424-4430.
[90]. J. Shan, C. Guo, Y. Zhu, S. Chen, L. Song, M. Jaroniec, Y. Zheng and S.-Z. Qiao, Charge-Redistribution-
Enhanced Nanocrystalline Ru@IrOx Electrocatalysts for Oxygen Evolution in Acidic Media. Chem, 2019, 5, 445-
459.
[91]. L. Yuan, Z. Yan, L. Jiang, E. Wang, S. Wang and G. Sun, Gold-iridium bifunctional electrocatalyst for
oxygen reduction and oxygen evolution reactions. Journal of energy chemistry, 2016, 25, 805-810.
[92]. M. T. Koper, Thermodynamic theory of multi-electron transfer reactions: Implications for
electrocatalysis. J. Electroanal. Chem., 2011, 660, 254-260.
[93]. S. St. John, R. W. Atkinson III, R. R. Unocic, T. A. Zawodzinski Jr and A. B. Papandrew, Ruthenium-
alloy electrocatalysts with tunable hydrogen oxidation kinetics in alkaline electrolyte. J. Phys. Chem. C, 2015, 119,
13481-13487.
[94]. Y. Wang, G. Wang, G. Li, B. Huang, J. Pan, Q. Liu, J. Han, L. Xiao, J. Lu and L. Zhuang, Pt-Ru catalyzed
hydrogen oxidation in alkaline media: oxophilic effect or electronic effect? Energy Environ. Sci., 2015, 8, 177-
181.
[95]. Y. Li and Y. Huang, Low-temperature, seed-mediated synthesis of monodispersed hyperbranched PtRu
nanoparticles and their electrocatalytic activity in methanol oxidation. J. Mater. Chem., 2012, 22, 12461-12464.
[96]. Z. Liu, E. T. Ada, M. Shamsuzzoha, G. B. Thompson and D. E. Nikles, Synthesis and activation of PtRu
alloyed nanoparticles with controlled size and composition. Chem. Mater., 2006, 18, 4946-4951.
[97]. K. Neyerlin, G. Bugosh, R. Forgie, Z. Liu and P. Strasser, Combinatorial study of high-surface-area
binary and ternary electrocatalysts for the oxygen evolution reaction. J. Electrochem. Soc., 2009, 156, B363-B369.
[98]. J. Pei, J. Mao, X. Liang, C. Chen, Q. Peng, D. Wang and Y. Li, Ir-Cu nanoframes: one-pot synthesis and
efficient electrocatalysts for oxygen evolution reaction. Chem. Commun., 2016, 52, 3793-3796.
[99]. D. A. Cullen, K. L. More, L. L. Atanasoska and R. T. Atanasoski, Impact of IrRu oxygen evolution
reaction catalysts on Pt nanostructured thin films under start-up/shutdown cycling. J. Power Sources, 2014, 269,
671-681.
[100]. J. Tymoczko, F. Calle-Vallejo, W. Schuhmann and A. Bandarenka, Making the hydrogen evolution
reaction in polymer electrolyte membrane electrolysers even faster. Nat. Commun., 2016, 7, 10990.
[101]. R. Frydendal, E. A. Paoli, B. P. Knudsen, B. Wickman, P. Malacrida, I. E. Stephens and I.
Chorkendorff, Benchmarking the stability of oxygen evolution reaction catalysts: the importance of monitoring
mass losses. ChemElectroChem, 2014, 1, 2075-2081.
[102]. Y. Lee, J. Suntivich, K. J. May, E. E. Perry and Y. Shao-Horn, Synthesis and activities of rutile
28
IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett., 2012, 3,
399-404.
[103]. S. Trasatti, Electrocatalysis by oxides-attempt at a unifying approach. J. Electroanal. Chem., 1980,
111, 125-131.
[104]. K. A. Stoerzinger, R. R. Rao, X. R. Wang, W. T. Hong, C. M. Rouleau and Y. Shao-Horn, The Role
of Ru Redox in pH-Dependent Oxygen Evolution on Rutile Ruthenium Dioxide Surfaces. Chem, 2017, 2, 668-
675.
[105]. R. Ge, L. Li, J. Su, Y. Lin, Z. Tian and L. Chen, Ultrafine Defective RuO2 Electrocatayst Integrated
on Carbon Cloth for Robust Water Oxidation in Acidic Media. Adv. Energy Mater., 2019, 9.
[106]. H.-S. Park, J. Yang, M. K. Cho, Y. Lee, S. Cho, S.-D. Yim, B.-S. Kim, J. H. Jang and H.-K. Song,
RuO2 nanocluster as a 4-in-1 electrocatalyst for hydrogen and oxygen electrochemistry. Nano Energy, 2019, 55,
49-58.
[107]. W. Sun, Z. Wang, W. Q. Zaman, Z. Zhou, L. Cao, X. Q. Gong and J. Yang, Effect of lattice strain
on the electro-catalytic activity of IrO2 for water splitting. Chem. Commun., 2018, 54, 996-999.
[108]. S. Cherevko, S. Geiger, O. Kasian, N. Kulyk, J.-P. Grote, A. Savan, B. R. Shrestha, S. Merzlikin,
B. Breitbach and A. Ludwig, Oxygen and hydrogen evolution reactions on Ru, RuO 2, Ir, and IrO2 thin film
electrodes in acidic and alkaline electrolytes: A comparative study on activity and stability. Catal. Today, 2016,
262, 170-180.
[109]. T. Audichon, E. Mayousse, S. Morisset, C. Morais, C. Comminges, T. W. Napporn and K. B.
Kokoh, Electroactivity of RuO2-IrO2 mixed nanocatalysts toward the oxygen evolution reaction in a water
electrolyzer supplied by a solar profile. Int. J. Hydrogen Energy, 2014, 39, 16785-16796.
[110]. L. Xu, Q. Jiang, Z. Xiao, X. Li, J. Huo, S. Wang and L. Dai, Plasma‐engraved Co3O4 nanosheets
with oxygen vacancies and high surface area for the oxygen evolution reaction. Angew. Chem. Int. Ed., 2016, 55,
5277-5281.
[111]. H. Y. Wang, Y. Y. Hsu, R. Chen, T. S. Chan, H. M. Chen and B. Liu, Ni 3+‐Induced Formation of
Active NiOOH on the Spinel Ni-Co Oxide Surface for Efficient Oxygen Evolution Reaction. Adv. Energy Mater.,
2015, 5, 1500091.
[112]. Y. Surendranath, M. W. Kanan and D. G. Nocera, Mechanistic studies of the oxygen evolution
reaction by a cobalt-phosphate catalyst at neutral pH. JACS, 2010, 132, 16501-16509.
[113]. A. Mendoza‐Garcia, H. Zhu, Y. Yu, Q. Li, L. Zhou, D. Su, M. J. Kramer and S. Sun, Controlled
Anisotropic Growth of Co‐Fe‐P from Co‐Fe‐O Nanoparticles. Angew. Chem. Int. Ed., 2015, 54, 9642-9645.
[114]. T. Wang, C. Wang, Y. Jin, A. Sviripa, J. Liang, J. Han, Y. Huang, Q. Li and G. Wu, Amorphous Co-
Fe-P nanospheres for efficient water oxidation. J. Mater. Chem. A, 2017, 5, 25378-25384.
[115]. Y. Liu, H. Cheng, M. Lyu, S. Fan, Q. Liu, W. Zhang, Y. Zhi, C. Wang, C. Xiao and S. Wei, Low
overpotential in vacancy-rich ultrathin CoSe2 nanosheets for water oxidation. JACS, 2014, 136, 15670-15675.
[116]. P. Chen, K. Xu, Z. Fang, Y. Tong, J. Wu, X. Lu, X. Peng, H. Ding, C. Wu and Y. Xie, Metallic
Co4N porous nanowire arrays activated by surface oxidation as electrocatalysts for the oxygen evolution reaction.
Angew. Chem. Int. Ed., 2015, 54, 14710-14714.
[117]. M. Gong, Y. Li, H. Wang, Y. Liang, J. Z. Wu, J. Zhou, J. Wang, T. Regier, F. Wei and H. Dai, An
advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation. JACS, 2013, 135, 8452-8455.
[118]. L. Trotochaud, S. L. Young, J. K. Ranney and S. W. Boettcher, Nickel-iron oxyhydroxide oxygen-
evolution electrocatalysts: the role of intentional and incidental iron incorporation. JACS, 2014, 136, 6744-6753.
29
[119]. L.-A. Stern, L. Feng, F. Song and X. Hu, Ni2P as a Janus catalyst for water splitting: the oxygen
evolution activity of Ni2P nanoparticles. Energy Environ. Sci., 2015, 8, 2347-2351.
[120]. W. Zhou, X.-J. Wu, X. Cao, X. Huang, C. Tan, J. Tian, H. Liu, J. Wang and H. Zhang, Ni 3S2
nanorods/Ni foam composite electrode with low overpotential for electrocatalytic oxygen evolution. Energy
Environ. Sci., 2013, 6, 2921-2924.
[121]. C. Tang, N. Cheng, Z. Pu, W. Xing and X. Sun, NiSe nanowire film supported on nickel foam: an
efficient and stable 3D bifunctional electrode for full water splitting. Angew. Chem. Int. Ed., 2015, 54, 9351-9355.
[122]. J. Ryu, N. Jung, J. H. Jang, H.-J. Kim and S. J. Yoo, In Situ Transformation of Hydrogen-Evolving
CoP Nanoparticles: Toward Efficient Oxygen Evolution Catalysts Bearing Dispersed Morphologies with Co-
oxo/hydroxo Molecular Units. ACS Catalysis, 2015, 5, 4066-4074.
[123]. J. Huang, J. Chen, T. Yao, J. He, S. Jiang, Z. Sun, Q. Liu, W. Cheng, F. Hu and Y. Jiang, CoOOH
nanosheets with high mass activity for water oxidation. Angew. Chem. Int. Ed., 2015, 54, 8722-8727.
[124]. W. Yuan, M. Zhao, J. Yuan and C. M. Li, Ni foam supported three-dimensional vertically aligned
and networked layered CoO nanosheet/graphene hybrid array as a high-performance oxygen evolution electrode.
J. Power Sources, 2016, 319, 159-167.
[125]. V. Artero, M. Chavarot‐Kerlidou and M. Fontecave, Splitting water with cobalt. Angew. Chem.
Int. Ed., 2011, 50, 7238-7266.
[126]. G. Mattioli, P. Giannozzi, A. Amore Bonapasta and L. Guidoni, Reaction pathways for oxygen
evolution promoted by cobalt catalyst. JACS, 2013, 135, 15353-15363.
[127]. D. K. Zhong and D. R. Gamelin, Photoelectrochemical water oxidation by cobalt catalyst (“Co−
Pi”)/α-Fe2O3 composite photoanodes: oxygen evolution and resolution of a kinetic bottleneck. JACS, 2010, 132,
4202-4207.
[128]. T.-L. Wee, B. D. Sherman, D. Gust, A. L. Moore, T. A. Moore, Y. Liu and J. C. Scaiano,
Photochemical synthesis of a water oxidation catalyst based on cobalt nanostructures. JACS, 2011, 133, 16742-
16745.
[129]. J. Tian, H. Li, A. M. Asiri, A. O. Al‐Youbi and X. Sun, Photoassisted preparation of cobalt
phosphate/graphene oxide composites: a novel oxygen‐evolving catalyst with high efficiency. Small, 2013, 9,
2709-2714.
[130]. S.-X. Guo, Y. Liu, A. M. Bond, J. Zhang, P. E. Karthik, I. Maheshwaran, S. S. Kumar and K. L. N.
Phani, Facile electrochemical co-deposition of a graphene-cobalt nanocomposite for highly efficient water
oxidation in alkaline media: direct detection of underlying electron transfer reactions under catalytic turnover
conditions. Phys. Chem. Chem. Phys., 2014, 16, 19035-19045.
[131]. L. D. Rafailović, C. Gammer, C. Rentenberger, T. Trišović, C. Kleber and H. P. Karnthaler,
Enhanced oxygen evolution and reduction reactions of porous ternary NiCoFe foam electrodes prepared by
dynamic hydrogen template deposition. Nano Energy, 2013, 2, 523-529.
[132]. M. Xing, L.-B. Kong, M.-C. Liu, L.-Y. Liu, L. Kang and Y.-C. Luo, Cobalt vanadate as highly
active, stable, noble metal-free oxygen evolution electrocatalyst. J. Mater. Chem. A, 2014, 2, 18435-18443.
[133]. A. Han, H. Jia, H. Ma, S. Ye, H. Wu, H. Lei, Y. Han, R. Cao and P. Du, Cobalt porphyrin electrode
films for electrocatalytic water oxidation. Phys. Chem. Chem. Phys., 2014, 16, 11224-11232.
[134]. M.-R. Gao, Y.-F. Xu, J. Jiang, Y.-R. Zheng and S.-H. Yu, Water oxidation electrocatalyzed by an
efficient Mn3O4/CoSe2 nanocomposite. JACS, 2012, 134, 2930-2933.
[135]. P. Poizot, S. Laruelle, S. Grugeon, L. Dupont and J. Tarascon, Nano-sized transition-metal oxides
30
as negative-electrode materials for lithium-ion batteries. Nature, 2000, 407, 496.

[136]. L. Wu, Q. Li, C. H. Wu, H. Zhu, A. Mendoza-Garcia, B. Shen, J. Guo and S. Sun, Stable cobalt
nanoparticles and their monolayer array as an efficient electrocatalyst for oxygen evolution reaction. JACS, 2015,
137, 7071-7074.
[137]. W. Xu, Z. Lu, X. Lei, Y. Li and X. Sun, A hierarchical Ni-Co-O@ Ni-Co-S nanoarray as an
advanced oxygen evolution reaction electrode. Phys. Chem. Chem. Phys., 2014, 16, 20402-20405.
[138]. A. Indra, U. Paik and T. Song, Boosting Electrochemical Water Oxidation with Metal Hydroxide
Carbonate Templated Prussian Blue Analogues. Angew. Chem. Int. Ed., 2018, 57, 1241-1245.
[139]. Y. Li, C. Zhong, J. Liu, X. Zeng, S. Qu, X. Han, Y. Deng, W. Hu and J. Lu, Atomically Thin
Mesoporous Co3O4 Layers Strongly Coupled with N-rGO Nanosheets as High-Performance Bifunctional Catalysts
for 1D Knittable Zinc-Air Batteries. Adv. Mater., 2018, 30.
[140]. S. Zhao, B. Rasimick, W. Mustain and H. Xu, Highly durable and active Co 3O4 nanocrystals
supported on carbon nanotubes as bifunctional electrocatalysts in alkaline media. Applied Catalysis B:
Environmental, 2017, 203, 138-145.
[141]. H. Y. Wang, S. F. Hung, H. Y. Chen, T. S. Chan, H. M. Chen and B. Liu, In Operando Identification
of Geometrical-Site-Dependent Water Oxidation Activity of Spinel Co3O4. J. Am. Chem. Soc., 2016, 138, 36-39.
[142]. P. W. Menezes, A. Indra, V. Gutkin and M. Driess, Boosting electrochemical water oxidation
through replacement of Oh Co sites in cobalt oxide spinel with manganese. Chem. Commun., 2017, 53, 8018-8021.
[143]. L. Zhang, T. Mi, M. A. Ziaee, L. Liang and R. Wang, Hollow POM@MOF hybrid-derived porous
Co3O4/CoMoO4 nanocages for enhanced electrocatalytic water oxidation. J. Mater. Chem. A, 2018, 6, 1639-1647.
[144]. S. Wan, J. Qi, W. Zhang, W. Wang, S. Zhang, K. Liu, H. Zheng, J. Sun, S. Wang and R. Cao,
Hierarchical Co(OH)F Superstructure Built by Low-Dimensional Substructures for Electrocatalytic Water
Oxidation. Adv. Mater., 2017, 29.
[145]. L. An, J. Feng, Y. Zhang, Y.-Q. Zhao, R. Si, G.-C. Wang, F. Cheng, P. Xi and S. Sun, Controllable
tuning of Fe-N nanosheets by Co substitution for enhanced oxygen evolution reaction. Nano Energy, 2019, 57,
644-652.
[146]. Z. Cai, Y. Bi, E. Hu, W. Liu, N. Dwarica, Y. Tian, X. Li, Y. Kuang, Y. Li, X.-Q. Yang, H. Wang and
X. Sun, Single-Crystalline Ultrathin Co3O4 Nanosheets with Massive Vacancy Defects for Enhanced
Electrocatalysis. Adv. Energy Mater., 2018, 8.
[147]. G. Cheng, T. Kou, J. Zhang, C. Si, H. Gao and Z. Zhang, O 22-/O- functionalized oxygen-deficient
Co3O4 nanorods as high performance supercapacitor electrodes and electrocatalysts towards water splitting. Nano
Energy, 2017, 38, 155-166.
[148]. M. Leng, X. Huang, W. Xiao, J. Ding, B. Liu, Y. Du and J. Xue, Enhanced oxygen evolution
reaction by Co-O-C bonds in rationally designed Co3O4/graphene nanocomposites. Nano Energy, 2017, 33, 445-
452.
[149]. H.-C. Li, Y.-J. Zhang, X. Hu, W.-J. Liu, J.-J. Chen and H.-Q. Yu, Metal-Organic Framework
Templated Pd@PdO-Co3O4 Nanocubes as an Efficient Bifunctional Oxygen Electrocatalyst. Adv. Energy Mater.,
2018, 8.
[150]. R. Li, D. Zhou, J. Luo, W. Xu, J. Li, S. Li, P. Cheng and D. Yuan, The urchin-like sphere arrays
Co3O4 as a bifunctional catalyst for hydrogen evolution reaction and oxygen evolution reaction. J. Power Sources,
2017, 341, 250-256.
[151]. X. Liu, W. Xi, C. Li, X. Li, J. Shi, Y. Shen, J. He, L. Zhang, L. Xie, X. Sun, P. Wang, J. Luo, L.-
31
M. Liu and Y. Ding, Nanoporous Zn-doped Co3O4 sheets with single-unit-cell-wide lateral surfaces for efficient
oxygen evolution and water splitting. Nano Energy, 2018, 44, 371-377.
[152]. M. Tahir, L. Pan, R. Zhang, Y.-C. Wang, G. Shen, I. Aslam, M. A. Qadeer, N. Mahmood, W. Xu,
L. Wang, X. Zhang and J.-J. Zou, High-Valence-State NiO/Co3O4 Nanoparticles on Nitrogen-Doped Carbon for
Oxygen Evolution at Low Overpotential. ACS Energy Letters, 2017, 2, 2177-2182.
[153]. X. Wang, L. Yu, B. Y. Guan, S. Song and X. W. D. Lou, Metal-Organic Framework Hybrid-
Assisted Formation of Co3O4 /Co-Fe Oxide Double-Shelled Nanoboxes for Enhanced Oxygen Evolution. Adv.
Mater., 2018, 30, 1801211.
[154]. I. S. Amiinu, X. Liu, Z. Pu, W. Li, Q. Li, J. Zhang, H. Tang, H. Zhang and S. Mu, From 3D ZIF
Nanocrystals to Co-Nx/C Nanorod Array Electrocatalysts for ORR, OER, and Zn-Air Batteries. Adv. Funct. Mater.,
2018, 28.
[155]. J. Du, R. Wang, Y. R. Lv, Y. L. Wei and S. Q. Zang, One-step MOF-derived Co/Co9S8 nanoparticles
embedded in nitrogen, sulfur and oxygen ternary-doped porous carbon: an efficient electrocatalyst for overall water
splitting. Chem. Commun., 2019, 55, 3203-3206.
[156]. Y. Gong, Z. Xu, H. Pan, Y. Lin, Z. Yang and J. Wang, A 3D well-matched electrode pair of Ni-Co-
S//Ni-Co-P nanoarrays grown on nickel foam as a high-performance electrocatalyst for water splitting. J. Mater.
Chem. A, 2018, 6, 12506-12514.
[157]. J. Han, S. Hao, Z. Liu, A. M. Asiri, X. Sun and Y. Xu, In situ development of amorphous Mn-Co-
P shell on MnCo2O4 nanowire array for superior oxygen evolution electrocatalysis in alkaline media. Chem.
Commun., 2018, 54, 1077-1080.
[158]. E. Hu, Y. Feng, J. Nai, D. Zhao, Y. Hu and X. W. Lou, Construction of hierarchical Ni-Co-P hollow
nanobricks with oriented nanosheets for efficient overall water splitting. Energy Environ. Sci., 2018, 11, 872-880.
[159]. L. Li, L. Song, H. Guo, W. Xia, C. Jiang, B. Gao, C. Wu, T. Wang and J. He, N-Doped porous
carbon nanosheets decorated with graphitized carbon layer encapsulated Co 9S8 nanoparticles: an efficient
bifunctional electrocatalyst for the OER and ORR. Nanoscale, 2019, 11, 901-907.
[160]. J. Liu, J. Wang, B. Zhang, Y. Ruan, H. Wan, X. Ji, K. Xu, D. Zha, L. Miao and J. Jiang, Mutually
beneficial Co3O4@MoS2 heterostructures as a highly efficient bifunctional catalyst for electrochemical overall
water splitting. J. Mater. Chem. A, 2018, 6, 2067-2072.
[161]. Z. Pei, Z. Tang, Z. Liu, Y. Huang, Y. Wang, H. Li, Q. Xue, M. Zhu, D. Tang and C. Zhi,
Construction of a hierarchical 3D Co/N-carbon electrocatalyst for efficient oxygen reduction and overall water
splitting. J. Mater. Chem. A, 2018, 6, 489-497.
[162]. S. Wang, H. Jang, J. Wang, Z. Wu, X. Liu and J. Cho, Cobalt-Tannin-Framework-Derived
Amorphous Co-P/Co-N-C on N, P Co-Doped Porous Carbon with Abundant Active Moieties for Efficient Oxygen
Reactions and Water Splitting. ChemSusChem, 2019, 12, 830-838.
[163]. X. R. Wang, J. Y. Liu, Z. W. Liu, W. C. Wang, J. Luo, X. P. Han, X. W. Du, S. Z. Qiao and J. Yang,
Identifying the Key Role of Pyridinic-N-Co Bonding in Synergistic Electrocatalysis for Reversible ORR/OER.
Adv. Mater., 2018, 30, e1800005.
[164]. T. Wen, Y. Zheng, J. Zhang, K. Davey and S. Z. Qiao, Co (II) Boron Imidazolate Framework with
Rigid Auxiliary Linkers for Stable Electrocatalytic Oxygen Evolution Reaction. Adv. Sci., 2019, 6, 1801920.
[165]. K. Xiao, L. Zhou, M. Shao and M. Wei, Fabrication of (Ni,Co)0.85Se nanosheet arrays derived from
layered double hydroxides toward largely enhanced overall water splitting. J. Mater. Chem. A, 2018, 6, 7585-7591.
[166]. J. Xu, J. Li, D. Xiong, B. Zhang, Y. Liu, K. H. Wu, I. Amorim, W. Li and L. Liu, Trends in activity
32
for the oxygen evolution reaction on transition metal (M = Fe, Co, Ni) phosphide pre-catalysts. Chem. Sci., 2018,
9, 3470-3476.
[167]. M. Zhang, Q. Dai, H. Zheng, M. Chen and L. Dai, Novel MOF-Derived Co@N-C Bifunctional
Catalysts for Highly Efficient Zn-Air Batteries and Water Splitting. Adv. Mater., 2018, 30.
[168]. J. Huang, J. Chen, T. Yao, J. He, S. Jiang, Z. Sun, Q. Liu, W. Cheng, F. Hu, Y. Jiang, Z. Pan and S.
Wei, CoOOH Nanosheets with High Mass Activity for Water Oxidation. Angew. Chem. Int. Ed. Engl., 2015, 54,
8722-8727.
[169]. Hierarchical Ni-Co-O@Ni-Co-S Nanoarray as Advanced Oxygen Evolution Reaction Electrode.
Phys. Chem. Chem. Phys., 16, 20402-20405.
[170]. Y. Wu, M. Chen, Y. Han, H. Luo, X. Su, M. T. Zhang, X. Lin, J. Sun, L. Wang and L. Deng, Fast
and Simple Preparation of Iron‐Based Thin Films as Highly Efficient Water‐Oxidation Catalysts in Neutral
Aqueous Solution. Angew. Chem. Int. Ed., 2015, 54, 4870-4875.
[171]. S. Enthaler, K. Junge and M. Beller, Sustainable metal catalysis with iron: from rust to a rising star?
Angew. Chem. Int. Ed. Engl., 2008, 47, 3317-3321.
[172]. I. Bauer and H. J. Knolker, Iron catalysis in organic synthesis. Chem. Rev., 2015, 115, 3170-3387.
[173]. R. D. Smith, M. S. Prévot, R. D. Fagan, S. Trudel and C. P. Berlinguette, Water oxidation catalysis:
electrocatalytic response to metal stoichiometry in amorphous metal oxide films containing iron, cobalt, and nickel.
JACS, 2013, 135, 11580-11586.
[174]. J. A. Haber, C. Xiang, D. Guevarra, S. Jung, J. Jin and J. M. Gregoire, High‐Throughput Mapping
of the Electrochemical Properties of (Ni‐Fe‐Co‐Ce)Ox Oxygen‐Evolution Catalysts. ChemElectroChem,
2014, 1, 524-528.
[175]. J. hen, Zheng, F., Zhang, S. J., Fisher, A., Zhou, Y., Wang, Z., ... & Sun, S. G., Interfacial Interaction
between FeOOH and Ni-Fe LDH to Modulate the Local Electronic Structure for Enhanced OER Electrocatalysis.
ACS Catalysis, 2018, 8, 11342-11351.
[176]. H. Chen, S. Ouyang, M. Zhao, Y. Li and J. Ye, Synergistic Activity of Co and Fe in Amorphous
Cox-Fe-B Catalyst for Efficient Oxygen Evolution Reaction. ACS Appl. Mater. Interfaces, 2017, 9, 40333-40343.
[177]. S. Chen, Z. Kang, X. Zhang, J. Xie, H. Wang, W. Shao, X. Zheng, W. Yan, B. Pan and Y. Xie,
Highly Active Fe Sites in Ultrathin Pyrrhotite Fe7S8 Nanosheets Realizing Efficient Electrocatalytic Oxygen
Evolution. ACS Cent. Sci., 2017, 3, 1221-1227.
[178]. B. Dong, X. Zhao, G.-Q. Han, X. Li, X. Shang, Y.-R. Liu, W.-H. Hu, Y.-M. Chai, H. Zhao and C.-
G. Liu, Two-step synthesis of binary Ni-Fe sulfides supported on nickel foam as highly efficient electrocatalysts
for the oxygen evolution reaction. J. Mater. Chem. A, 2016, 4, 13499-13508.
[179]. C. Dong, T. Kou, H. Gao, Z. Peng and Z. Zhang, Eutectic-Derived Mesoporous Ni-Fe-O Nanowire
Network Catalyzing Oxygen Evolution and Overall Water Splitting. Adv. Energy Mater., 2018, 8, 1701347.
[180]. J. Du, T. Zhang, J. Xing and C. Xu, Hierarchical porous Fe 3O4/Co3S4 nanosheets as an efficient
electrocatalyst for the oxygen evolution reaction. J. Mater. Chem. A, 2017, 5, 9210-9216.
[181]. T. Gao, Z. Jin, M. Liao, J. Xiao, H. Yuan and D. Xiao, A trimetallic V-Co-Fe oxide nanoparticle as
an efficient and stable electrocatalyst for oxygen evolution reaction. J. Mater. Chem. A, 2015, 3, 17763-17770.
[182]. M. Gorlin, P. Chernev, P. Paciok, C. W. Tai, J. Ferreira de Araujo, T. Reier, M. Heggen, R. Dunin-
Borkowski, P. Strasser and H. Dau, Formation of unexpectedly active Ni-Fe oxygen evolution electrocatalysts by
physically mixing Ni and Fe oxyhydroxides. Chem. Commun., 2019, 55, 818-821.
[183]. D. He, Y. Xiong, J. Yang, X. Chen, Z. Deng, M. Pan, Y. Li and S. Mu, Nanocarbon-intercalated
33
and Fe-N-codoped graphene as a highly active noble-metal-free bifunctional electrocatalyst for oxygen reduction
and evolution. J. Mater. Chem. A, 2017, 5, 1930-1934.
[184]. B. K. Kang, M. H. Woo, J. Lee, Y. H. Song, Z. Wang, Y. Guo, Y. Yamauchi, J. H. Kim, B. Lim and
D. H. Yoon, Mesoporous Ni-Fe oxide multi-composite hollow nanocages for efficient electrocatalytic water
oxidation reactions. J. Mater. Chem. A, 2017, 5, 4320-4324.
[185]. J. Nai, Y. Lu, L. Yu, X. Wang and X. W. D. Lou, Formation of Ni-Fe Mixed Diselenide Nanocages
as a Superior Oxygen Evolution Electrocatalyst. Adv. Mater., 2017, 29.
[186]. Y. Pan, S. Liu, K. Sun, X. Chen, B. Wang, K. Wu, X. Cao, W. C. Cheong, R. Shen, A. Han, Z.
Chen, L. Zheng, J. Luo, Y. Lin, Y. Liu, D. Wang, Q. Peng, Q. Zhang, C. Chen and Y. Li, A Bimetallic Zn/Fe
Polyphthalocyanine-Derived Single-Atom Fe-N4 Catalytic Site:A Superior Trifunctional Catalyst for Overall
Water Splitting and Zn-Air Batteries. Angew. Chem. Int. Ed. Engl., 2018, 57, 8614-8618.
[187]. M. Y. Song, D.-S. Yang, K. P. Singh, J. Yuan and J.-S. Yu, Nitrogen-doped hollow carbon spheres
with highly graphitized mesoporous shell: Role of Fe for oxygen evolution reaction. Applied Catalysis B:
Environmental, 2016, 191, 202-208.
[188]. Y. Sun, Y. Xia, L. Kuai, H. Sun, W. Cao, M. Huttula, A. P. Honkanen, M. Viljanen, S. Huotari and
B. Geng, Defect-Driven Enhancement of Electrochemical Oxygen Evolution on Fe-Co-Al Ternary Hydroxides.
ChemSusChem, 2019, 12, 2564-2569.
[189]. Q. Wang, Y. Lei, Z. Chen, N. Wu, Y. Wang, B. Wang and Y. Wang, Fe/Fe 3C@C nanoparticles
encapsulated in N-doped graphene-CNTs framework as an efficient bifunctional oxygen electrocatalyst for robust
rechargeable Zn-air batteries. J. Mater. Chem. A, 2018, 6, 516-526.
[190]. Y. Wang, M. Qiao, Y. Li and S. Wang, Tuning Surface Electronic Configuration of NiFe LDHs
Nanosheets by Introducing Cation Vacancies (Fe or Ni) as Highly Efficient Electrocatalysts for Oxygen Evolution
Reaction. Small, 2018, 14, 1800136.
[191]. G. Wu, W. Chen, X. Zheng, D. He, Y. Luo, X. Wang, J. Yang, Y. Wu, W. Yan, Z. Zhuang, X. Hong
and Y. Li, Hierarchical Fe-doped NiOx nanotubes assembled from ultrathin nanosheets containing trivalent nickel
for oxygen evolution reaction. Nano Energy, 2017, 38, 167-174.
[192]. Z. Wu, Z. Zou, J. Huang and F. Gao, Fe-doped NiO mesoporous nanosheets array for highly
efficient overall water splitting. J. Catal., 2018, 358, 243-252.
[193]. L. Yu, J. F. Yang, B. Y. Guan, Y. Lu and X. W. D. Lou, Hierarchical Hollow Nanoprisms Based on
Ultrathin Ni-Fe Layered Double Hydroxide Nanosheets with Enhanced Electrocatalytic Activity towards Oxygen
Evolution. Angew. Chem. Int. Ed. Engl., 2018, 57, 172-176.
[194]. Y. Zang, H. Zhang, X. Zhang, R. Liu, S. Liu, G. Wang, Y. Zhang and H. Zhao, Fe/Fe 2O3
nanoparticles anchored on Fe-N-doped carbon nanosheets as bifunctional oxygen electrocatalysts for rechargeable
zinc-air batteries. Nano Research, 2016, 9, 2123-2137.
[195]. P. Zhang, X. F. Lu, J. Nai, S. Q. Zang and X. W. D. Lou, Construction of Hierarchical Co-Fe
Oxyphosphide Microtubes for Electrocatalytic Overall Water Splitting. Adv. Sci., 2019, 6, 1900576.
[196]. Y. Zhou, Z. Wang, Z. Pan, L. Liu, J. Xi, X. Luo and Y. Shen, Exceptional Performance of
Hierarchical Ni-Fe (hydr)oxide@NiCu Electrocatalysts for Water Splitting. Adv. Mater., 2019, 31, e1806769.
[197]. X. Zou, Y. Wu, Y. Liu, D. Liu, W. Li, L. Gu, H. Liu, P. Wang, L. Sun and Y. Zhang, In Situ
Generation of Bifunctional, Efficient Fe-Based Catalysts from Mackinawite Iron Sulfide for Water Splitting. Chem,
2018, 4, 1139-1152.
[198]. X. Zheng, Y. Zhang, H. Liu, D. Fu, J. Chen, J. Wang, C. Zhong, Y. Deng, X. Han and W. Hu, In
34
Situ Fabrication of Heterostructure on Nickel Foam with Tuned Composition for Enhancing Water-Splitting
Performance. Small, 2018, 14, e1803666.
[199]. Z. Xu, H. Pan, Y. Lin, Z. Yang, J. Wang and Y. Gong, Constructing a hexagonal copper-coin-shaped
NiCoSe2@NiO@CoNi2S4@CoS2 hybrid nanoarray on nickel foam as a robust oxygen evolution reaction
electrocatalyst. J. Mater. Chem. A, 2018, 6, 18641-18648.
[200]. X. Xu, X. Tian, Z. Zhong, L. Kang and J. Yao, In-situ growth of iron/nickel phosphides hybrid on
nickel foam as bifunctional electrocatalyst for overall water splitting. J. Power Sources, 2019, 424, 42-51.
[201]. H. Sun, Y. Lian, C. Yang, L. Xiong, P. Qi, Q. Mu, X. Zhao, J. Guo, Z. Deng and Y. Peng, A
hierarchical nickel-carbon structure templated by metal-organic frameworks for efficient overall water splitting.
Energy Environ. Sci., 2018, 11, 2363-2371.
[202]. Y. Li, F.-M. Li, X.-Y. Meng, X.-R. Wu, S.-N. Li and Y. Chen, Direct chemical synthesis of ultrathin
holey iron doped cobalt oxide nanosheets on nickel foam for oxygen evolution reaction. Nano Energy, 2018, 54,
238-250.
[203]. L. Peng, J. Shen, X. Zheng, R. Xiang, M. Deng, Z. Mao, Z. Feng, L. Zhang, L. Li and Z. Wei,
Rationally design of monometallic NiO-Ni3S2/NF heteronanosheets as bifunctional electrocatalysts for overall
water splitting. J. Catal., 2019, 369, 345-351.
[204]. M. Lee, H.-S. Oh, M. K. Cho, J.-P. Ahn, Y. J. Hwang and B. K. Min, Activation of a Ni
electrocatalyst through spontaneous transformation of nickel sulfide to nickel hydroxide in an oxygen evolution
reaction. Applied Catalysis B: Environmental, 2018, 233, 130-135.
[205]. H. Yang, Z. Chen, W. Hao, H. Xu, Y. Guo and R. Wu, Catalyzing overall water splitting at an
ultralow cell voltage of 1.42 V via coupled Co-doped NiO nanosheets with carbon. Applied Catalysis B:
Environmental, 2019, 252, 214-221.
[206]. G. Ou, P. Fan, H. Zhang, K. Huang, C. Yang, W. Yu, H. Wei, M. Zhong, H. Wu and Y. Li, Large-
scale hierarchical oxide nanostructures for high-performance electrocatalytic water splitting. Nano Energy, 2017,
35, 207-214.
[207]. J. Jiang, M. Wang, W. Yan, X. Liu, J. Liu, J. Yang and L. Sun, Highly active and durable
electrocatalytic water oxidation by a NiB0.45/NiOx core-shell heterostructured nanoparticulate film. Nano Energy,
2017, 38, 175-184.
[208]. A. Wu, Y. Xie, H. Ma, C. Tian, Y. Gu, H. Yan, X. Zhang, G. Yang and H. Fu, Integrating the active
OER and HER components as the heterostructures for the efficient overall water splitting. Nano Energy, 2018, 44,
353-363.
[209]. Y. Li, L. Hu, W. Zheng, X. Peng, M. Liu, P. K. Chu and L. Y. S. Lee, Ni/Co-based nanosheet arrays
for efficient oxygen evolution reaction. Nano Energy, 2018, 52, 360-368.
[210]. A. Nadeema, V. M. Dhavale and S. Kurungot, NiZn double hydroxide nanosheet-anchored
nitrogen-doped graphene enriched with the gamma-NiOOH phase as an activity modulated water oxidation
electrocatalyst. Nanoscale, 2017, 9, 12590-12600.
[211]. J. Chen, Zheng, F., Zhang, S. J., Fisher, A., Zhou, Y., Wang, Z., ... & Sun, S. G., Interfacial
Interaction between FeOOH and Ni-Fe LDH to Modulate the Local Electronic Structure for Enhanced OER
Electrocatalysis. ACS Catalysis, 2018, 8, 11342-11351.
[212]. W. Gao, Z. Xia, F. Cao, J. C. Ho, Z. Jiang and Y. Qu, Comprehensive Understanding of the Spatial
Configurations of CeO2 in NiO for the Electrocatalytic Oxygen Evolution Reaction: Embedded or Surface-Loaded.
Adv. Funct. Mater., 2018, 28.
35
[213]. H. Q. Fu, L. Zhang, C. W. Wang, L. R. Zheng, P. F. Liu and H. G. Yang, 1D/1D Hierarchical Nickel
Sulfide/Phosphide Nanostructures for Electrocatalytic Water Oxidation. ACS Energy Letters, 2018, 3, 2021-2029.
[214]. C. Huang, Y. Zou, Y. Q. Ye, T. Ouyang, K. Xiao and Z. Q. Liu, Unveiling the active sites of Ni-Fe
phosphide/metaphosphate for efficient oxygen evolution under alkaline conditions. Chem. Commun., 2019, 55,
7687-7690.
[215]. J. Huang, Y. Li, Y. Zhang, G. Rao, C. Wu, Y. Hu, X. Wang, R. Lu, Y. Li and J. Xiong, Identification
of Key Reversible Intermediates in Self-Reconstructed Nickel-Based Hybrid Electrocatalysts for Oxygen
Evolution. Angew. Chem. Int. Ed. Engl., 2019, 58, 17458-17464.
[216]. R. Illathvalappil, L. George and S. Kurungot, Coexisting Few-Layer Assemblies of NiO and MoO3
Deposited on Vulcan Carbon as an Efficient and Durable Electrocatalyst for Water Oxidation. ACS Appl. Energy
Mater., 2019, 2, 4987-4998.
[217]. X. Kong, C. Zhang, S. Y. Hwang, Q. Chen and Z. Peng, Free-Standing Holey Ni(OH)2 Nanosheets
with Enhanced Activity for Water Oxidation. Small, 2017, 13.
[218]. Z. Li, W. Niu, L. Zhou and Y. Yang, Phosphorus and Aluminum Codoped Porous NiO Nanosheets
as Highly Efficient Electrocatalysts for Overall Water Splitting. ACS Energy Letters, 2018, 3, 892-898.
[219]. J. Liu, Y. Zheng, Y. Jiao, Z. Wang, Z. Lu, A. Vasileff and S. Z. Qiao, NiO as a Bifunctional Promoter
for RuO2 toward Superior Overall Water Splitting. Small, 2018, 14, e1704073.
[220]. J. Liu, Y. Zheng, Z. Wang, Z. Lu, A. Vasileff and S. Z. Qiao, Free-standing single-crystalline NiFe-
hydroxide nanoflake arrays: a self-activated and robust electrocatalyst for oxygen evolution. Chem. Commun.,
2018, 54, 463-466.
[221]. A. Munir, T. u. Haq, A. Qurashi, H. u. Rehman, A. Ul-Hamid and I. Hussain, Ultrasmall Ni/NiO
Nanoclusters on Thiol-Functionalized and -Exfoliated Graphene Oxide Nanosheets for Durable Oxygen Evolution
Reaction. ACS Appl. Energy Mater., 2018, 2, 363-371.
[222]. H. Sun, Z. Ma, Y. Qiu, H. Liu and G. G. Gao, Ni@NiO Nanowires on Nickel Foam Prepared via
"Acid Hungry" Strategy: High Supercapacitor Performance and Robust Electrocatalysts for Water Splitting
Reaction. Small, 2018, 14, e1800294.
[223]. X. Xu, C. Li, J. G. Lim, Y. Wang, A. Ong, X. Li, E. Peng and J. Ding, Hierarchical Design of
NiOOH@Amorphous Ni-P Bilayer on a 3D Mesh Substrate for High-Efficiency Oxygen Evolution Reaction. ACS
Appl. Mater. Interfaces, 2018, 10, 30273-30282.
[224]. L. Wang, C. Gu, X. Ge, J. Zhang, H. Zhu and J. Tu, Anchoring Ni2P Sheets on NiCo2O4 Nanocone
Arrays as Optimized Bifunctional Electrocatalyst for Water Splitting. Adv. Mater. Interfaces, 2017, 4.
[225]. B. Xia, T. Wang, X. Jiang, J. Li, T. Zhang, P. Xi, D. Gao and D. Xue, N+ ion irradiation engineering
towards the efficient oxygen evolution reaction on NiO nanosheet arrays. J. Mater. Chem. A, 2019, 7, 4729-4733.
[226]. W. Chen, H. Wang, Y. Li, Y. Liu, J. Sun, S. Lee, J. S. Lee and Y. Cui, In Situ Electrochemical
Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation. ACS Cent. Sci., 2015,
1, 244-251.
[227]. R. D. Smith, M. S. Prevot, R. D. Fagan, S. Trudel and C. P. Berlinguette, Water oxidation catalysis:
J. Am. Chem. Soc., 2013, 135, 11580-11586.
[228]. P. W. M. Arindam Indra, Nastaran Ranjbar Sahraie, Arno Bergmann, Chittaranjan Das, Massimo
Tallarida, Dieter Schmeißer, Peter Strasser, and Matthias Driess, Unification of Catalytic Water Oxidation and
Oxygen Reduction Reactions: Amorphous Beat Crystalline Cobalt Iron Oxides. JACS, 2014, 136, 17530-17536.
36
[229]. R. D. Smith, Prévot, M. S., Fagan, R. D., Zhang, Z., Sedach, P. A., Siu, M. K. J., ... & Berlinguette,
C. P., Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis. . Science,
2013, 340, 60-63.
[230]. M. W. Kanan, Nocera, D. G., In situ formation of an oxygen-evolving catalyst in neutral water
containing phosphate and Co2+. Science, 2008, 321, 1072-1075.
[231]. J. B. Gerken, Shaner, S. E., Massé, R. C., Porubsky, N. J., & Stahl, S. S., A survey of diverse earth
abundant oxygen evolution electrocatalysts showing enhanced activity from Ni-Fe oxides containing a third metal.
Energy Environ. Sci., 2014, 7, 2376-2382.
[232]. J. G. McAlpin, Surendranath, Y., Dinca, M., Stich, T. A., Stoian, S. A., Casey, W. H., ... & Britt, R.
D., EPR evidence for Co(IV) species produced during water oxidation at neutral pH. JACS, 2010, 132, 6882-6883.
[233]. Y. Liu, Hua, X., Xiao, C., Zhou, T., Huang, P., Guo, Z. & Xie, Y. , Heterogeneous spin states in
ultrathin nanosheets induce subtle lattice distortion to trigger efficient hydrogen evolution. JACS, 2016, 138, 5087-
5092.
[234]. Y. Jiao, W. Hong, P. Li, L. Wang and G. Chen, Metal-organic framework derived Ni/NiO micro-
particles with subtle lattice distortions for high-performance electrocatalyst and supercapacitor. Appl. Catal. B-
Environmental, 2019, 244, 732-739.
[235]. H. Huang, C. Yu, H. Huang, C. Zhao, B. Qiu, X. Yao, S. Li, X. Han, W. Guo, L. Dai and J. Qiu,
Activation of transition metal oxides by in-situ electro-regulated structure-reconstruction for ultra-efficient oxygen
evolution. Nano Energy, 2019, 58, 778-785.
[236]. P. W. Menezes, C. Walter, J. N. Hausmann, R. Beltran-Suito, C. Schlesiger, S. Praetz, V. Yu
Verchenko, A. V. Shevelkov and M. Driess, Boosting Water Oxidation through In Situ Electroconversion of
Manganese Gallide: An Intermetallic Precursor Approach. Angew. Chem. Int. Ed. Engl., 2019, 58, 16569-16574.
[237]. S. He and H. Lin, In situ growth of layered double hydroxides on boehmite AlOOH for active and
stable oxygen evolution in alkaline media. Nanoscale, 2019, 11, 10348-10357.
[238]. Y. Wang, S. Liu, X. Hao, S. Luan, H. You, J. Zhou, D. Song, D. Wang, H. Li and F. Gao, Surface
reorganization engineering of the N-doped MoS2 heterostructures MoOx@N-doped MoS2-x by in situ
electrochemical oxidation activation for efficient oxygen evolution reaction. J. Mater. Chem. A, 2019, 7, 10572-
10580.
37
38
Chapter II Experimental details
2.1 Synthesis and fabrication approaches
2.1.1 Electrolytic codeposition process

Electrodeposition is a well-known conventional surface modification method to improve the surface
characteristics, decorative and functional, of a wide variety of materials,1 the schematic of which is shown in
Figure 2-1a. Two electrodes, power source and electrolyte form the main components of electrodeposition.
Electrolytic codeposition is an electrodeposition method of incorporation of additive-particles into metallic
coatings obtained from electrolytes containing the particles in a suspended state (as shown in Figure 2-1b),which
is a novel method for preparation of the hybrid electrocatalysts towards water splitting, with the mechanism of two
successive adsorption steps. It was proposed by N. Guglielmi in 1972, and is a versatile and scalable industrial
process that only requires simple equipment.2, 3 For this study, electrolytic codeposition was carried out with a
simple two-electrode system using a field-assisted mechanism consisting of two steps. In the first step, which is
of a physical nature, nanoparticles in the electrolyte were surrounded by a cloud of adsorbed species, mainly metal
ions, which approached the cathode and finally produced a layer of loosely adsorbed particles on the cathodic
surface with a high coverage, driven by fractional irregular Brownian motion. Second, these nanoparticles released
an adsorbed ion cloud and strongly adsorbed on the electrode surface due to the development of a higher electric-
field force under more negative potentials.4
Figure 2-1 Schematics of electrodeposition (a) and electrolytic codeposition (b).
39
2.1.1.1 Materials
Modified Watts Ni baths and electrolytic codeposition process conditions are shown in Table 2-1.
The solutions were prepared from analytic-grade chemicals (procured from Sigma) and double-distilled
water. The pH value of the bath was measured using the the HM-20E pH-meter and was adjusted to
appropriate values with H3BO3. Co3O4 powders with a particle size of 50 nm (Figure 2-1) were also
procured from Sigma. Graphene oxide (GO) nanoplatelets (Figure 2-3) were procured from Suzhou
Tanfeng Graphene Technology Co., Ltd., China. Nickel foam (NF), (Figure 2-4) was used as a substrate,
and a high-purity (99.99%) electrolytic nickel plate or wire mesh were used as the soluble anodes.
Surface area was ca. ten times greater than that of the cathode to ensure that there no problems would
arise from anode polarization, particularly at high current densities. The substrate was chemically
degreased, rinsed with distilled water, and then scrubbed with alcohol and acetone. Next, it was acid
cleaned and activated and rinsed with distilled water, then placed vertically in the electroplating cell
with magnetic stirring, parallel to the anode, with an anode–cathode distance of 5 cm.
Table 2-1 Bath composition and plating conditions for nickel electrolytic codeposition.
Composition and condition (units) Magnitude
NiSO4·6H2O (g/L) 250
NiCl2·6H2O (g/L) 40
H3BO3 (g/L) 40
Lauryl sodium sulfate (g/L) 0.05
Tricobalt tetroxide (g/L) 0.02
Graphene oxide (g/L) 0.01
Temperature (°C) 50
pH 4-5
Time (min) 45
Current density(A/dm2) 0.5-2.5
Stirring rate (rpm) 300
Figure 2-2 SEM image of Co3O4 powders.
40
Figure 2-3 SEM image of GO nanoplatelets.
Figure 2-4 SEM image of NF.
2.1.1.2 Equipment of electrolytic codeposition process

The electrolytic codeposition process was carried out in the simplest two-electrode system (Figure
2-5). The final suspension for electrolytic codeposition was prepared from the Ni bath solution,
containing 0.05g L-1 lauryl sodium sulfate (SDS), 0.02g L-1 Co3O4, and 0.01 g L-1 GO. In order to obtain
a stable nanoparticle suspension, it was essential to sequentially prepare the Ni bath solution, SDS
solution and the two types of suspensions of nanoparticles or nanosheets, and subsequently, to add the
latter three solutions or suspensions to the Ni bath solution, respectively. The hybrid NF@CGO was
obtained with the plating conditions after 45 min. Similarly, NF@N (blank), NF@GO (containing 0.05g
L-1 SDS and 0.01 g L-1 GO) and NF@C (containing 0.05g L-1 SDS and 0.02g L-1 Co3O4) were obtained
with the plating conditions by adding different additives to Ni bath solution.
41
Figure 2-5 Optical photo of the applied two-electrode plating system in electrolytic codeposition process.
2.1.2 High-velocity oxy-fuel spraying process

As an effective process of catalyst deposition, high-velocity oxy-fuel (HVOF) was employed to
obtain a well-bonded precursor coating due to supersonic particle velocity. This technique can not only
obtain well-coated coatings at a lower temperature than other thermal spraying processes, thereby
minimizing the adverse effects of oxidation, but also instantly break up and remove the oxide layer from
the surface of the newly obtained coating.5, 6
2.1.2.1 Materials
Ni–Al alloy (56–44 wt.%, H. C. Starck, Germany) powders with a diameter of 30 μm (Figure 2-6,
Figure 2-7) were prepared to use as the feedstock powders to deposit on the nickel plate (NP). The XRD
patterns of Ni–Al alloy powders confirm the coexistence of Ni2Al3 (JCPDS No. 14-0648) and NiAl
(JCPDS No. 44-1188). The NSs (15 × 10 × 0.5 mm3) with evenly distributed of 2-mm diameter apertures
(Figure 2-8) were ultrasonically cleaned by acetone, deionized water, and absolute ethyl alcohol in
sequence for 25 min, and then dried in the air for 30 min.
42
Figure 2-6 SEM images of Ni-Al alloy powders. (a, b) Top view; (c, d) Cross section view.
Figure 2-7 Particle size distribution and XRD patterns of Ni–Al alloy powders. (a) Particle size distribution;
(b) XRD patterns.
43
Figure 2-8 Images of NP. (a) Optical photo; (b) SEM image.
2.1.2.2 Equipment of high-velocity oxy-fuel spraying

HVOF is a novel means for catalyst deposition, where the particles of the catalyst precursor powder
injected into the flame of HVOF guns are accelerated to high velocities, roughly 650 m/s on average.
An FST- JP5000 HVOF gun (Figure 2-9) was employed for this purpose. For all the experiments, oxygen
and kerosene were used as the oxy-fuel mixture, with flow rates of 1600 and 0.433 SLPM, respectively.
The coatings were deposited at a powder-feeding rate of 5 kg/h and a constant spray distance of 380 mm
(Table 2-2). These spraying parameters were selected to reduce the temperature of the spray particles
for deposition of solid-state particles, to minimize oxidation, and to create rough surfaces and
appropriate micro-voids. Then the porous Ni–Al alloy coatings with a thickness of ca. 50 um were
obtained after 10 passes of depositing on NP. The Ni–Al alloy coating deposited on NP via HVOF is
marked as HNA.
Figure 2-9 HVOF equipment: FST-JP5000. (a) Optical photo; (b) Schematic.
44
Table 2-2 HVOF spraying parameters.

Parameters Value
Torch JP-5000
Oxidizer: Fuel O2 (1600L/min): Kerosene (26 L/h)
Substrate NS
Powder Ni–Al alloy
Powder flow 5 kg/h
Projection distance 380 mm
External cooling Three air jets
2.1.2.3 Chemical activation

In a subsequent chemical activation (CA) process, the as-obtained precursor coatings (the porous
HNA) were chemically activated in 6 M KOH (containing 10 wt.% KNa tartrate-tetrahydrate) at 353 K
for 24 h to form HNA-CA with a hierarchically interlaced 3D network. To avoid a precipitation of
aluminum hydroxide in the mesopores/microchannels of the obtained sponge-like structure, the solution
contained 10 wt.% KNa tartrate-tetrahydrate (Rochelle salt, procured from Sigma) as a complexing
agent. The resulting HNA-CA samples were easily susceptible to oxidation because of extremely high
activity, so they were kept under 6 M KOH solution after activation.
2.1.3 In situ electrochemical activation

The in situ electrochemical activation (ECA) method has mostly been applied for engineering
OEEs, which is a novel electrochemical reconstruction access to enhance catalytic performances in a
facile, mild, green, and controllable manner.7-18 For this study, we set an extremely large current density
(800 mA cm-2), 6 M KOH, and 353K as the conditions of in situ ECA, considering the strict industrial
criteria of AEC that OER process should be energetically catalyzed over a long period at extremely high
current densities (≥ 500 mA cm-2) with overpotentials ≤ 300 mV, which hinders the widespread
implementation of these available electrocatalysts.19-21 We aim to develop cost-effective, highly active,
and durable OEEs and reveal the inherent relationship between the morphological, structural, and
chemical evolution and OER catalytic activity of said OEEs using the in situ ECA approach.
2.2 Physical characterizations

XRD was performed with Bruker AXS D8 focus, equipped with a cobalt anticathode (λ = 1.78897
Å) and operated at 35 kV, 40 mA. SEM were carried out using a JEOL-JSM-7800F system equipped
with an EDS analysis system (BRUCKER SDDX-Flash 6130). Transmission electron microscopy (TEM)
measurements were done using a FEI Tecnai G2 F20 S-TWIN TEM operated at 200 kV in the
TEM/STEM mode. Samples were prepared by ultrasonic dispersion in ethanol and then a droplet of the
45
dispersion allowed to dry on a holey-carbon coated copper grid. Bright-field and high-angle annular
dark field (HAADF) images were recorded. Brunauer-Emmett-Teller (BET, ASAP 2020 V4.00) analysis
was conducted to study the surface area and the porosity distribution of the samples. Raman
spectroscopy tests were performed by using SENTERRA R200-L with the 532 nm line of an 𝐴𝑟 + laser
as the excitation source to validate the structure of CNTs and the formation of Al4C3 phase in the spectral
range from 400 to 2000 cm-1. XPS measurements were carried out by Escalab 250Xi (Thermo Fisher
Ltd), equipped with an Al Kα (λ=1486.6 eV) X-ray source. The spectra were measured with an energy
step of 0.05 eV and normalized to the binding energy of the C1s peak (284.8 eV). Distilled water and
ethanol were used to thoroughly clean all the samples before testing commenced.
2.3 Electrochemical characterizations

All the as-prepared OEEs were activated by CV scanning 50 times, from 1.2 V-1.7 V vs RHE, with
the scan rate of 100 mV s-1 at the conditions of 6 M KOH at 353 K in the three-electrode electrochemical
test system. In order to ensure the effective comparison of data, all the control OEEs would also be
activated under the same condition. All electrochemical measurements were carried out with PGSTAT-
128N (Metrohm Autolab, Switzerland) electrochemical workstation. Hydrogen Reference Electrode
HydroFlex (Gaskatel GmbH, Germany) was used as the reference electrode. The potential measured
using this Hydrogen Reference Electrode (HRE) as the reference electrode didn’t require any complex
conversion to Reversible Hydrogen Electrode (RHE), as in the case allowing any test temperature and
pH of the electrolyte, namely ERHE = EHRE. Furthermore, HRE is suitable for the full pH-range from -2
to 16 and temperature-range from -303 K to 473 K. Even if we tested at temperatures above room
temperature (353 K) and high concentrations (6 M KOH), the data remained stable and reliable. Pt foil
(10 mm×10 mm×0.2 mm) was used as the counter electrode. Bare NS, bare NF, HNA-CA and the HNA-
CA-ECA catalysts were used directly as the working electrode, without further treatments. In order to
better illustrate the catalytic activity of the materials, we tested all the samples under two conditions –1
M KOH at room temperature and 6 M KOH at 353 K (which refer to industrial applications). The
overpotential (η) was calculated by using the formula: η (V) = ERHE-1.23. Polarization and CV curves
were recorded at a scan rate of 2, 5 mV s-1, respectively, and each measurement was repeated at least
three times in order to avoid any incidental error. In order to provide reliable electrochemical data and
avoid the overlap between Ni2+/Ni3+ oxidation and OER, polarization curves were recorded from high
initial potentials to low final potentials. Tafel slopes were derived from OER polarization curves
obtained by plotting overpotential against log(current density) at a scan rate of 1 mV s-1 and iR correction
(EiR=E-i×RS) in all the above test conditions. The resistance of the electrochemical system was estimated
from a simulated equivalent circuit of the electrochemical impedance spectroscopy (EIS), which was
performed over a scanning frequency ranging from 100 kHz to 0.1 Hz with a 10 mV sinusoidal AC
dither under a fixed bias of 1.53 V vs RHE (η = 300 mV). The ECSA was determined by measuring the
46
capacitive current associated with double layer charging from the scan rate CV-dependence. Here, the
CV potential window was 1.07 V-1.17 V vs RHE. The scan rates were 10, 20, 40, 60, 80, 100, and 120
mV s-1. The double-layer capacitance (Cdl) was estimated Δj = (jcharge - joff charge) at 1.12 V vs RHE against
the scan rate. The linear slope is twice of the double-layer capacitance Cdl.
References of Chapter II
[1]. D. Sobha Jayakrishnan, in Corrosion Protection and Control Using Nanomaterials, 2012, DOI:
10.1533/9780857095800.1.86, pp. 86-125.
[2]. G. N., Kinetics of the deposition of inert particles from electrolytic baths. . J. Electrochem. Soc., 1972,
119, 1009-1012.
[3]. R. J. R. Celis J P, Buelens C. , A Mathematical Model for the Electrolytic Codeposition of Particles with
a metallic matrix. J. Electrochem. Soc., 1987, 134, 1402.
[5]. S. Deshpande, S. Sampath and H. Zhang, Mechanisms of oxidation and its role in microstructural
evolution of metallic thermal spray coatings-Case study for Ni-Al. Surf. Coat. Technol., 2006, 200, 5395-5406.
[6]. B. Wielage, A. Wank, H. Pokhmurska, T. Grund, C. Rupprecht, G. Reisel and E. Friesen, Development
and trends in HVOF spraying technology. Surf. Coat. Technol., 2006, 201, 2032-2037.
[7]. W. Chen, H. Wang, Y. Li, Y. Liu, J. Sun, S. Lee, J. S. Lee and Y. Cui, In Situ Electrochemical Oxidation
Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation. ACS Cent. Sci., 2015, 1, 244-251.
10580.
[10]. B. Wang, J. Shang, C. Guo, J. Zhang, F. Zhu, A. Han and J. Liu, A General Method to Ultrathin Bimetal-
MOF Nanosheets Arrays via In Situ Transformation of Layered Double Hydroxides Arrays. Small, 2019, 15.
[11]. N. Todoroki and T. Wadayama, Heterolayered Ni-Fe Hydroxide/Oxide Nanostructures Generated on a
Stainless-Steel Substrate for Efficient Alkaline Water Splitting. ACS Appl. Mater. Interfaces, 2019, 11, 44161-
44169.
[12]. R. D. Smith, M. S. Prevot, R. D. Fagan, S. Trudel and C. P. Berlinguette, Water oxidation catalysis:
J. Am. Chem. Soc., 2013, 135, 11580-11586.
[13]. N. Ortiz Pena, D. Ihiawakrim, M. Han, B. Lassalle-Kaiser, S. Carenco, C. Sanchez, C. Laberty-Robert,
D. Portehault and O. Ersen, Morphological and Structural Evolution of Co 3O4 Nanoparticles Revealed by in Situ
Electrochemical Transmission Electron Microscopy during Electrocatalytic Water Oxidation. ACS Nano, 2019, 13,
11372-11381.
[14]. P. W. Menezes, C. Walter, J. N. Hausmann, R. Beltran-Suito, C. Schlesiger, S. Praetz, V. Yu Verchenko,
A. V. Shevelkov and M. Driess, Boosting Water Oxidation through In Situ Electroconversion of Manganese Gallide:
47
An Intermetallic Precursor Approach. Angew. Chem. Int. Ed. Engl., 2019, 58, 16569-16574.
[15]. J. Li, H. Chen, Y. Liu, R. Gao and X. Zou, In situ structural evolution of a nickel boride catalyst:
synergistic geometric and electronic optimization for the oxygen evolution reaction. J. Mater. Chem. A, 2019, 7,
5288-5294.
[16]. S.-F. Hung, Y. Zhu, G.-Q. Tzeng, H.-C. Chen, C.-S. Hsu, Y.-F. Liao, H. Ishii, N. Hiraoka and H. M.
Chen, In Situ Spatially Coherent Identification of Phosphide-Based Catalysts: Crystallographic Latching for
Highly Efficient Overall Water Electrolysis. ACS Energy Letters, 2019, 12, 2813-2820.
[18]. M. Chatti, J. L. Gardiner, M. Fournier, B. Johannessen, T. Williams, T. R. Gengenbach, N. Pai, C.
Nguyen, D. R. MacFarlane, R. K. Hocking and A. N. Simonov, Intrinsically stable in situ generated electrocatalyst
for long-term oxidation of acidic water at up to 80 °C. Nature Catalysis, 2019, 2, 457-465.
[19]. H. Zhou, F. Yu, Q. Zhu, J. Sun, F. Qin, L. Yu, J. Bao, Y. Yu, S. Chen and Z. Ren, Water splitting by
electrolysis at high current densities under 1.6 volts. Energy Environ. Sci., 2018, 11, 2858-2864.
[20]. X. Zou, Y. Liu, G. D. Li, Y. Wu, D. P. Liu, W. Li, H. W. Li, D. Wang, Y. Zhang and X. Zou, Ultrafast
Formation of Amorphous Bimetallic Hydroxide Films on 3D Conductive Sulfide Nanoarrays for Large-Current-
Density Oxygen Evolution Electrocatalysis. Adv. Mater., 2017, 29.
48
Chapter III Development of OER electrocatalysts by combining electrolytic codeposition and in situ electrochemical
activation
Chapter III Development of OER electrocatalysts by

combining electrolytic codeposition and in situ
electrochemical activation
3.1 Introduction
Total increase in energy consumption and urgent environmental concern intensively render an
urgent demand for the use of renewable energy sources (such as solar and wind energy) as viable
alternatives to nonrenewable fossil fuels.1-3 However, these sustainable energy sources are usually
intermittent and fluctuant in nature due to regional or seasonal factors, and thus, efficient energy storage
solutions are highly demanded.4, 5 As a carbon-free energy carrier, hydrogen has long been hailed as an
ideal alternative to fossil fuels apart from its high conversion efficiency and gravimetric energy density.5-
7
To date, electrochemical water splitting to produce hydrogen is turning out to be a promising
technology, of which alkaline water electrolysis (AWE) compared with the proton exchange membrane
(PEM) electrolyzers exhibit inherent low-cost characteristic due to possibility of use of non-precious
catalysts rather the noble ones.8-11
Generally, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are two half-
cell reactions of electrochemical water splitting. Compared with HER, OER, with a complex four-
electron transfer process, is recognized as the main bottleneck in water splitting because it is
thermodynamically unfavorable and kinetically sluggish.8-13 In addition, this half-cell reaction induces
structural changes into electrode materials that cause performance degradation and ultimately lead to
electrode breakdown.14 Therefore, developing highly effective and durable electrocatalysts are required
for the OER to afford high current density at low overpotential.11, 15 In general, noble metal-based
electrocatalysts such as IrO2 and RuO2 are recognized as the state-of-the-art catalysts for the OER.2, 11,
16, 17
Despite their superior activity, the large-scale use of these noble-metal based catalysts is hampered
by the high cost, scarcity and the poor stability over long-term operations.12, 18-21 Accordingly, in order
to replace these expensive electrocatalysts, extensive efforts have been devoted to developing alternative
OER electrocatalysts based on the inexpensive and earth-abundant first row transition-metal (e.g. Fe,
Co, Ni, Cu), which are highly active and stable under OER conditions, thus making water splitting more
practically feasible.22-30 Although great progress has been made in designing these type of non-noble
metal based catalysts, the majority of them are in the form of nanostructures including nanoparticles,
nanosheets and nanoribbons, which are required complex preparation methods and also expensive
49
activation
conductive polymers as binder for electrode fabrication, minimizing their potential for practical
applications.5, 21, 31-34
From an industrial perspective, nickel is typically used as the promising electrode material in
commercial electrocatalytic electrolysis units in highly alkaline electrolytes owing to its relatively high
stability and favourable activity.35, 36 Particularly, nickel foam (NF) with a long-range ordered porous
framework, which not only exposes more reaction active sites but also accelerate fast ion and electron
transport, is the most widely used conductive substrate for the construction of three-dimensional (3D)
catalysts.37, 38 Unfortunately, as an oxygen evolution electrode (OEE), Ni metals possess low efficiency
for water splitting. Doping of other transition metal oxides or non-metal elements at Ni site drastically
improves its OER catalytic performance and stability in alkaline solution.39-41 Among various non-
precious metal-based catalysts, nanostructured cobalt tetroxide (Co3O4) has received particular attention
due to its high abundance, low cost, relatively high OER activity and durability in alkaline
electrolytes.42-46 In order to further ameliorate the catalytic activity by enhancing charge transport
capacity and increasing the exposure of active sites, the rational construction and design of an advanced
electrode configuration with active metal or metal oxides, a hybridized nanocarbon material (e.g.
reduced graphene oxide—r-GO or GO) is an appealing strategy.47-50
Currently, OEE needs to meet the most stringent requirements in industrial applications such as
delivery of very high current density (≥ 500 mA cm-2) at low overpotentials (≤ 300 mV), and certain
mechanical robustness and prolonged durability during harsh oxidizing conditions and the complicated
mechanism of the OER.51, 52 On the other hand, for large-scale industrial applications, AWEs also
require the commodious scale production of large areal type electrodes (e.g. where the geometric surface
area of the electrode can reach several square meters). At the same time, since the developed OEE needs
to be stable in strong alkaline media (pH >14) and at an intermediate temperature (> 353K), a practical
solution to ensure greater efficiency of operations during the hard anodic condition53 cannot be avoided,
especially for a metal element. Electrolytic codeposition is a process largely used for the reinforcement
of submicron and nanosized metallic particles, polymer additives or nonmetallic compounds in the metal
matrix. The co-deposition process is an auspicious alternative to deposit layers with appropriate
microstructure and properties preventing the rise of residual stress. This cost-effective process not only
involves a simple and controllable setup, but it also can be performed at approximately room temperature.
This process also is a widely used and effective methodology to apply coatings in a large scale and to
create a layer uniformly covering the surface of components even with complex and irregular shapes.
Here, we report a co-doped 3D NF by Ni crystals, Co3O4 nanoparticles, GO nanosheets and in situ

generated Ni(OH)2/NiOOH nanoflakes via electrolytic codeposition in combination with in situ
electrochemical activation as a promising electrocatalyst (the activated NF@CGO) for OER in AWE.
50
activation
The 3D interconnected bi-continuous macroscopic porous structure across the whole NF substrate offers
a very high specific surface area, electrical conductivity and integrity.52 The Ni crystals in the activated
NF@CGO not only possesses the properties of good electrical conductivity, high specific surface area,
but also the close contact of Co3O4 nanoparticles and GO nanosheets on the Ni foam, which waives the
need for adding auxiliary conducting material or binders, allows for efficiently deliver large current
densities at low OER over potential.
Interestingly, Ni(OH)2/NiOOH nanoflakes with ultra-high OER activity, which are formed by
oxidative etching of fine micron-sized nickel grains in the subsequent electrochemical activation, will
grow in situ and cover the surface of the electrode. Therefore, a catalytic layer with an arbitrary thickness,
excellent electrical conductivity and high-efficient catalytic activity for OER can be obtained. While
maintaining the sufficiently high performance, this uniform catalytic layer also allows maintain long-
term durability of OEE without significant deterioration during harsh and oxidative OER operation
condition, which is one of the drastic requirements necessary for industrial application. The development
of such hierarchical nanostructures is an important step in advanced nanotechnology to
effectively perceive better OER performance by intelligent combination of Multiplex components.
3.2 Effect of additives in electrolytic codeposition on OER
performance
In order to reasonably reveal the synergistic effect of all active species on OER, polarization curves
for NF, NF@N (blank), NF@GO (containing 0.05g L-1 SDS and 0.01 g L-1 GO), NF@C (containing
0.05g L-1 SDS and 0.02g L-1 Co3O4) and NF@CGO (containing 0.05g L-1 SDS, 0.01 g L-1 GO and 0.02g
L-1 Co3O4) catalysts in 1 M KOH at RT with a scan rate of 1 mV s-1 are obtained. As shown in Figure 3-
1a, NF@CGO generates the OER current density of 10 mA cm-2 at the lowest potential and the smallest
overpotential of 140 mV and 1.37 V vs. RHE, respectively, as compared with other counterparts, NF
(349 mV and 1.579 V vs. RHE), NF@N (339 mV and 1.569 V vs. RHE.), NF@GO (301 mV and 1.531
V vs. RHE) and NF@C (272 mV and 1.502 V vs. RHE). By comparing the overpotentials of different
catalysts, obviously, Ni crystals, Co3O4 or GO alone also has contributions to OER, which is not more
impressive. However, when all active species are reasonably combined to form NF@CGO, the most
promising catalytic activity is produced, which eloquently clarifies their synergistic effect on OER.
Furthermore, as can be concluded from Nyquist plots (Figure 3-1b), the smallest interfacial Rct of the
hybrid NF@CGO than the other catalysts clearly indicate its better electronic transport capability and
better reactant diffusivity towards electrode surface, which clearly justify the superior OER performance
of the hybrid NF@CGO and synergistic effect of all active species.
51
activation
Figure 3-1 Electrochemical characterizations of NF, NF@N, NF@GO, NF@C and NF@CGO in 1 M
KOH at RT. (a) Polarization curves with the scan rate of 1 mV s-1 ; (b) Nyquist plots.
3.3 Effect of current density in electrolytic codeposition on OER
performance
The current density of electrolytic codeposition may have effect on the OER catalytic performance
of NF@CGO, because the current density may not only affect the deposition efficiency, but also
determine the maximum particle diameter of the active additive that can be deposited on the NF surface.
Figure 3-2 showed OER performance of NF@CGO with different current densities in electrolytic
codeposition (NF@CGO-0.5, NF@CGO-1.5 and NF@CGO-2.5 stands for electrolytic codeposition
current density of 0.5, 1.5 and 2.5 A dm-2). Figure 3-2a showed the CVs appeared for the three kinds of
NF@CGO electrodes. The area enclosed by the CV positively related the ECSA of the electrode, so the
ECSA became larger along with the increase of the current density of electrolytic codeposition.
Meanwhile, the large slope (like Tafel slope from Polarisation curve) of the linear part of CV curve
predicted more favorable and fast-catalytic OER kinetics, suggesting worsened OER kinetics with
increasing current density of electrolytic codeposition. Hence, the NF@CGO-1.5 had better OER
performance owning its larger ECSA and faster OER kinetics. Furthermore, as could be concluded from
Nyquist plots (Figure 3-2b), the smallest interfacial Rct of the NF@CGO-1.5 than the other catalysts
clearly indicated its better electronic transport capability and better reactant diffusivity towards electrode
surface, which clearly justify the superior OER performance of the NF@CGO-1.5.
52
activation
Figure 3-2 The effect of different current densities of electrolytic codeposition on the OER performance of
NF@CGO. (a) CVs with the scan rate of 3 mV s-1 ; (b) Nyquist plots.
3.4 In situ electrochemical activation of a codoped heterogeneous
system as a highly efficient OER electrocatalyst
3.4.1 Synthesis strategy of the NF@CGO

The hybrid NF@CGO electrode was prepared by co-doping the catalyst nanoparticles onto the 3D
NF (see Experimental details). Figure 3-3 shows the schematic illustration of electrolytic codeposition,
which is currently one of the most widely used electrochemical synthesis methods to fabricate the most
active composite materials.54 NF@CGO matrix composite coatings were electrodeposited in a modified
Watt's bath by using electrolytic codeposition techniques. Electrolytic codeposition, with the mechanism
of two successive adsorption steps, which was proposed by N. Guglielmi in 1972, is a versatile and
scalable industrial process that only requires simple equipment.55, 56 A two-step electrolytic codeposition
was carried using a two-electrode system through a field-assisted mechanism consisting of two steps. In
the first step, which is of a physical nature, nanoparticles in the electrolyte were surrounded by a cloud
of adsorbed species mainly metal ions approach the cathode and finally produce a layer of loosely
adsorbed particles on the cathodic surface with a high coverage driven by fractional irregular Brownian
motion (indicated by the random red arrows in Figure 3-3). Secondly, these nanoparticles released an
adsorbed ion clouds and strongly adsorb on the electrode surface (indicated by the red arrows in the
direction of the vertical electrode in Figure 3-3) due to the development of a higher electric field force
under more negative potentials.59 Finally this self-assembly 3D electrode (NF@CGO) has been
fabricated using NF as the skeleton and also Ni crystals, Co3O4 nanoparticles and GO nanosheets as
OER composite catalysts.
53
activation
Figure 3-3 Schematic illustration of the synthesis of the hybrid NF@CGO electrode.
The electrolytic codeposition process led to a certain thickness of the catalytic layer, with the larger
roughness of the surface deposited on the NF substrate (Figure 3-4a and b). A physical cross-section of
the NF@CGO electrode (Figure 3-4c) shows that the Co3O4 nanoparticles surrounded by ions have
partially agglomerated in the electrolyte. These agglomerated particles evenly distributed on the
deposited layer along the deposition direction. Different variety of multiple dispersants and particles
agglomerated into several hundred nanometres and even some without agglomeration were assessed due
to various factors such as dispersant viscosity and electrolyte agitation, which is necessary to maintain
the particles in suspension and to transport the particles to the electrode surface. As can be seen in inset
illustration of Figure 3-4c, high-resolution SEM image shows that this electrolytic codeposition
methodology yields the Co3O4 particles that are ca. 30 nm. Meanwhile, GO nanosheets surrounding the
ion cloud exhibited different angles when deposited into the cathode. Nanosheets GOs, which were
parallel and perpendicular to the surface of the electrode, represent a complete sheet and a very thin rib
in the deposition layer and the remaining parts appeared between face and rib.
54
activation
Figure 3-4 (a) SEM image of bare NF; (b) SEM image of hybrid NF@CGO electrode; (c) Cross-
section of the hybrid NF@CGO electrode, inset illustration: high magnification morphology.
3.4.2 Physical characterization of the activated NF@CGO

Physical characterizations of the activated NF@CGO catalysts would be showed as below. It is
found that, the deposition is uniform on the macroscopic 3D skeleton of NF resulting in high catalyst
loadings and large amounts of accessible active sites (Figure 3-5a and Figure 3-4b). Figure 3-5b displays
a high-resolution SEM (HR-SEM) of the hybrid NF@CGO marked in Figure 3-5a. The 3D NF surface
was completely covered by nanoflowers made of Co3O4 , GO, and clusters of Ni species. Each cluster
shows highly rippled nanosheet structures, which are significantly different from the morphologies of
activated bare NF and bare NP (Nickel plate with the size of 15×10×0.3 mm, Figure 3-6 and Figure
3-7). The lateral extension of the nanosheets ranged from dozens of nanometers to 100 nm and the
thickness is generally ca. 10 nm and the rippled nanosheets are interconnected, forming mesoporous and
microporous nanostructures with the pore size from ca. 30 nm to ca. 100 nm (Figure 3-8). These
microporous or mesoporous in the activated NF@CGO are exposed to the electrolyte for the access of
ions to form electrochemical double layers. Elemental mapping analysis of Figure 3-5c shows that Co,
O and C are homogeneously distributed in the nanoflower nanostructures with Ni surrounding them.
The above results suggest that mesoporous nanostructures with Co, O and C elements were formed on
the macro-porous NF, forming a hierarchically structured electrode.
Figure 3-5 (a) SEM image of the activated NF@CGO; (b) HR-SEM image of the nanoflowers in Figure 3-
5a; (c) Corresponding elemental mappings of the single nanoflower in Figure 3-5b.
55
activation
Figure 3-6 (a) SEM image of the activated bare NP; (b) High resolution SEM image of the area squared in
Figure 3-6a.
Figure 3-7 (a) SEM image of the activated bare NF; (b) High resolution SEM image of the area squared
in Figure 3-7a; (c) High resolution SEM image of the area squared in Figure 3-7b.
Figure 3-8 High resolution SEM image of Ni cluster.
Transmission electron microscopy (TEM) of the activated NF@CGO (Figure 3-9a and Figure 3-
10) further reveals that Co-based nanocrystals (ca. 30 nm), typical morphology of Ni-based
polycrystalline (oxy)hydroxides and GO nanosheets are present in the activated NF@CGO. The
corresponding selected area electron diffraction (SAED) pattern (Figure 3-9b) and high-resolution TEM
56
activation
(HR-TEM) image (Figure 3-9c) confirm the Co-based nanocrystals to be crystalline spinel structured
Co3O4. With d-spacing values of 0.243 and 0.285 nm, the lattice matches well with the (311) and the
(220) planes of Co3O4 (ICSD no. 28158), respectively.42 The large surface area as well as the mesoporous
structure greatly increases the amount of exposed electroactive sites and promotes mass transfer, which
is expected to improve the electrocatalytic performance. In addition, Figure 3-9d reveals that
nanocrystalline is possibly present in the activated hybrid NF@CGO, which was further confirmed by
the polycrystalline diffraction ring appearing in the SAED (Figure 3-9b). The Ni-based polycrystalline
(oxy)hydroxides are possibly ascribable to the newly formed Ni(OH)2/NiOOH phases upon in situ
electrochemical activation. XRD (Figure 3-11) indicates no apparent patterns other than metallic Ni,
spinel Co3O4 and GO nanosheets, suggesting that these Ni-based polycrystalline (oxy)hydroxides are
likely embedded in the nanoflowers of the activated hybrid NF@CGO. 57 Meanwhile, Figure 3-9a and
Figure 3-10 show that nanosheets GO are successfully doped into the catalytic layer to further ameliorate
the catalytic activity by enhancing charge transport capacity and increasing the exposure of active sites.3
Figure 3-9 (a) TEM image of the hybrid nanoflakes scratched off from the hybrid activated NF@CGO; (b)
Corresponding SAED pattern of Co3O4 and Ni(OH)2/NiOOH, respectively; (c) Corresponding HR-TEM image
of Co3O4; (d) Corresponding HR-TEM image of Ni(OH)2/NiOOH.
Figure 3-10 TEM images of the hybrid nanoflakes scratched off from the hybrid activated NF@CGO.
57
activation
Figure 3-11 The typical XRD of commercial GO, bare NF and the hybrid activated NF@CGO.
This is further evidenced by XRD (Figure 3-11) and Raman spectra (Figure 3-14) and HR-XPS
spectra of C 1s in Figure 3-16. As the active site of OER, these Co-based spinel nanostructures and Ni-
based nanocrystal (oxy)hydroxides like petals, are uniformly embedded in a mixed matrix of metallic
nickel and GO nanosheets, which undoubtedly increases the active surface area. A large number of
mesoporous structures are naturally formed between the petals, as shown in HR-SEM (Figure 3-5b).
The mesoporous feature of the activated hybrid nanosheets observed by SEM and TEM was confirmed
by Brunauer-Emmett-Teller (BET) measurement. The N2 adsorption/desorption isotherm curve (Figure
3-12a) possesses the typical feature of mesoporous materials, with a BET surface area of 150.6 m2 g-1,
the total pore volume of 0.04 cm3 g-1and the average size of the mesopores is estimated to be about 4.8
nm (Figure 3-12a, inset). The large active surface area as well as the mesoporous structure, not only
greatly increases the amount of exposed electroactive sites, but also promotes mass transfer and OH-
diffusion, which is expected to improve the electrocatalytic performance.42, 58 The hybrid matrix of
metallic nickel and GO nanosheets like a torus closely links the petals (Figure 3-5b), so that electrons
can be transmitted to each petal as quickly as possible while exciting each active site for OER reaction.
The introduction of the heterogeneous catalytic phases in electrolytic codeposition changes the nickel
nucleation mechanism, from homogeneous nucleation to heterogeneous nucleation, and refine nickel
crystals which promote the oxidative etching of nickel in the process of in situ electrochemical activation
58
activation
due to the larger surface energy. This causes Co3O4 nanoparticles and GO nanoflakes originally covered
by the nickel layer to be exposed to the electrolyte, with more active sites appearing. Moreover, nickel
crystals with mesoporous caused by oxidation etching mentioned above are in situ conversion of nickel
into Ni(OH)2/NiOOH nanoflakes with ultra-high OER activity. They form a complete catalytic system,
which will eventually lead to a highly active and stable OEE.
Figure 3-12 N2 adsorption-desorption isotherms of the hybrid NF@CGO, Inset: Pore size distribution. (a)
after activated; (b) before activated. Base on the N2 adsorption-desorption isotherms, the BET surface of
NF@CGO before and after activation were measured to be 40.5 and 150.6 m2 g-1, respectively.
As physical parameters have a huge effect on the catalytic properties of OER catalysts, various
analyses have been carried out on the activated hybrid NF@CGO. As shown in Figure 3-11 and Figure
3-13, the XRD patterns of the NF@CGO show sharp and well-defined peaks at 2θ = 36.5⁰, 43.1⁰, 45.1⁰,
70.2⁰ and 77.5⁰, which correspond to Co3O4 (ICSD no. 28158), which is in agreement with SEM and
TEM results.3, 59 Figure 3-14 shows the comparative Raman spectra of commercial Co3O4, GO and the
hybrid NF@CGO. Four distinct peaks in the range of 450-750 cm-1 for the hybrid NF@CGO are
observed corresponding to E1g, F2g2, F2g1, and A1g vibrational modes of spinel Co3O4. Noticeably, these
peaks are in a same position compared to those for the commercial Co3O4.42 Additionally, hybrid
NF@CGO also shows a pair of peaks at 475 and 554 cm-1 ascribable to the Ni-O vibration in NiOOH,
and a broad peak at 800-1100 cm-1, characteristic of “active oxygen” on the NiOOH surface, which is
in agreement with TEM results.57, 60, 61 On the other hand, peaks at 1350 cm-1, 1600 cm-1, 2700 cm-1 and
2900 cm-1 are identified for the hybrid NF@CGO corresponding to the D, G, 2D, and (D+G) bands of
carbonaceous material, which is comparable with those in the GO Raman spectrum, further
demonstrating the coexistence of GO in the hybrid NF@CGO illustrated by the elemental mapping
images of SEM and TEM nanosheets (Figure 3-5b, Figure 3-5c, Figure 3-9a) and Figure 3-10 ).42, 62
59
activation
Figure 3-13 The typical XRD spectra of the hybrid NF@CGO and bare NF.
Figure 3-14 Raman spectra of commercial Co3O4 nanoparticles, commercial GO nanosheets and the hybrid
NF@CGO.
To gain further information on surface composition and chemical state of the hybrid NF@CGO,
X-ray photoelectron spectroscopy (XPS) is performed. Their XPS survey spectra unambiguously
indicate the presence of Co, O, Ni, and C (Figure 3-15), suggesting that Ni crystals, Co3O4 and GO have
been successfully deposited on to the NF framework. In the high-resolution XPS spectra of Co 2p, three
pairs of spin-orbit doublets around 779.7/794.8, 780.8/796 and 782.6/797.6 eV can be deconvoluted,
60
activation
along with their weak shake-up satellites at high binding energy side (Figure 3-16a), suggesting
coexistence of Co2+ and Co3+ in the hybrid activated NF@CGO. The Co 2p peaks of hybrid activated
NF@CGO match well with those of commercial Co3O4 except slight shift to higher binding energy side,
which is probably ascribed to the fact that the species of Ni and C near Co3O4 in hybrid activated
NF@CGO change coordination environments of Co ions.63 The application of mixed metal oxides
containing Co ions of different valence states usually results in the decrement of OER overpotential.5
As illustrated in Figure 3-16b, the characteristic peaks of Ni from the hybrid activated NF@CGO
is detected. In the Ni 2p region, the fitting peaks at 874.7 and 857.1 eV represent Ni 3+ from NiOOH,
whereas the fitting peaks at 873.1 and 855.2 eV correspond to the small amount of Ni 2+ from Ni(OH)2
and the fitting peaks at 870.1 and 852.7 eV correspond to a minimum amount of metallic Ni present in
the hybrid activated NF@CGO. It is clear that the main nickel-based species on the surface of the hybrid
activated NF@CGO can be confirmed as NiOOH, with a minority of Ni(OH)2 and metallic Ni. The C1s
XPS spectra of the hybrid activated NF@CGO indicated the presence of three types of carbon bonds:
C=C-C (284.7 eV), C-O (286.8 eV), C=O (288.3 eV) (Figure 3-16c). There are two kinds of distinct
peaks with varying detection points in the hybrid activated NF@CGO. In the spectra of some sites, the
peek still retained the characteristics of GO, but the peak intensities associated with oxygenated groups
are much weaker than those in the spectrum of GO for other sites. Small amount of oxygen-containing
functional groups of GO nanosheets in the hybrid activated NF@CGO was probably reduced to
electrochemically reduce graphene oxide (ERGO) by gaining electrons from the cathode during the
electrolytic codeposition process, eventually formed GO/ERGO, which further strengthens the OER
electrocatalytic activity of the hybrid activated NF@CGO.62, 64-67 These results further confirmed the
formation of hierarchically structured activated NF@CGO, which are composed of the deposited Co3O4,
GO/ERGO and in situ generated Ni(OH)2/NiOOH, onto the 3D NF.
Figure 3-15 XPS survey spectra of the activated hybrid activated NF@CGO electrode.
61
activation
Figure 3-16 (a) High-resolution Co 2p XPS spectra of commercial Co3O4 and the hybrid activated
NF@CGO; (b) High-resolution Ni 2p XPS spectra of the hybrid activated NF@CGO; (c) High-resolution C 1s
XPS spectra of the hybrid activated NF@CGO.
3.4.3 Electrocatalytic oxygen evolution at the activated NF@CGO

To better characterize electrochemical performance, besides the evaluation of OER performance of
electrode in 1M KOH at room temperature (RT), electrochemical tests is also conducted on half-cell in
6 M KOH solution and 353 K in three electrode system to meet rigorous industry requirements.
Electrochemical characterizations of NP, NF and the hybrid activated NF@CGO in 1 M KOH at RT are
shown in Figure 3-17. Figure 3-18 showed the CVs appeared for the Ni-based electrodes. A couple of
oxidation-reduction peaks marked as pa1 and pc1 appeared at the potentials 1.48 V vs. RHE and 1.24 V
vs. RHE. The part of the voltammogram having these peaks is analogous to that observed for the NP
and NF electrode and the peak potential values coincided with the reported values.68, 69
62
activation
Figure 3-17 Electrochemical characterizations of the activated NP, NF and hybrid activated NF@CGO in 1
M KOH at RT. (a) Polarization curves with the scan rate of 1 mV s-1 ; (b) Corresponding Tafel plots; (c) Cdl
curves; (d) Nyquist plots.
Figure 3-18 CV curves of bare NP, bare NF and hybrid activated NF@CGO in 1M KOH at RT.
In order to quantitatively compare the performance of all Ni-based catalysts, polarization curves
for NP, NF and the hybrid activated NF@CGO catalysts in 1 M KOH at RT with a scan rate of 1 mVs-1
are also obtained as shown in Figure 3-17a. The potential required for water oxidation to obtain the
current density of 10 mA cm-2 is commonly used to judge the OER activity.70 As can be concluded from
63
activation
Figure 3-17a, interestingly, the activated NF@CGO generates the OER current density of 10 mA cm-2
at a much lower potential and smaller overpotential of 212 mV and 1.422V vs. RHE, respectively, as
compared with other counterparts, NF (349 mV and 1.579 V vs. RHE) and NP (434 mV and 1.664 V vs.
RHE.), which is considerably much closer or even more superior than the earlier reports (as shown in
Table 3-1). Therefore, as based on the above observation, the activated NF@CGO showed an excellent
OER activity with a very low overpotential, whereas bare NP and NF show hardly any OER activity.
Table 3-1 Comparison of the OER performance of hybrid activated NF@CGO with the recently reported
state-of-the-art catalysts.
Materials (substrate) Electrolyte I/mA cm-2 η/mV Tafel slope mV dec-1 Year
NF@CGO (NF)-This work 1 M KOH 10 212 43 2019

71
CoxFe1-xN0.5 (Glass carbon) 1 M KOH 10 266 30 2019
72
Ni QD@NC@rGO (Glass carbon) 1 M KOH 10 265 65 2019
73
CoZn-Se (Glass carbon) 1 M KOH 10 320 66 2019
74
CoOx-NeC/TiO2C (Glass carbon) 1 M KOH 10 220 75 2019
S|NiNx-PC/EG (Glass carbon)75 1 M KOH 10 280 45 2019
76
NiFeMo IOS@ (NF) 1 M KOH 10 198 36 2019
77
Ni-Co3O4 nanosheets (NF) 1 M KOH 10 170 76.9 2018
78
OESSC (Stainless Steel) 1 M KOH 10 290 38 2019
79
Co3O4/MoS2 (NF) 1 M KOH 10 205 45 2019
80
Co3-xAlxO4 (Glass carbon) 1 M KOH 10 248 80.6 2019
Ni-BDC/Ni(OH)2 (Glass carbon)81 1 M KOH 10 320 41 2019
Ni-Co-hydroxide/Ni2P2O7 (NF)82 1 M KOH 10 197 63 2019
83
Fe-Co3O4 H-NSs (NF) 1 M KOH 10 204 38 2018
84
Ni3S2 (NF) 1 M KOH 10 312 111 2018
85
NF@Ni/C (NF) 1 M KOH 10 256 62 2018
86
Fe(II)-MOF-74 (NF) 1 M KOH 10 207 41.1 2019
IP/NP (NF)87 1 M KOH 10 185 47 2019
NiCoSe2@NiO@CoNi2S4@CoS2(NF)88 1 M KOH 10 353 159.1 2018
89
Ni3(S1-xSex)2@NiOOH (NF) 1 M KOH 10 320 48 2018
Moreover, as shown in Figure 3-17b, the hybrid activated NF@CGO catalyst exhibits much smaller
Tafel slope (43 mV dec-1) as compared with that of NP (126 mV dec-1) and NF (98 mV dec-1) catalysts
suggesting more favorable and fast-catalytic OER kinetics (OER intermediate adsorption and desorption)
for the activated NF@CGO hybrid catalyst in an alkaline environment compared with other counterparts.
Moreover, the electrochemical double-layer capacitance (Cdl), which is assumed to be directly
proportional to the electrochemical active surface area (ECSA), is ascertained from CV in a potential
scan range of 1.07-1.17 V vs RHE where the Faradic current is negligible (Figure 3-19). The improved
Cdl of the activated NF@CGO hybrid catalyst (12.39 mF cm-2) compared to NP (0.44 mF cm-2) and NF
64
activation
(0.96 mF cm-2) suggests a higher ECSA of the activated NF@CGO. The much superior ECSA of the
activated NF@CGO compared with other catalysts would be likely a key role for its high OER
performance. As can be seen in Figure 3-17c, the much superior Cdl and consequently, ECSA of the
activated NF@CGO along with hierarchal structure and more catalytically active sites compared with
other catalysts would be likely key factors make the activated NF@CGO a catalyst shows the much
higher overall OER performance in terms of lower overpotential and higher current density, than other
Ni-based catalysts. The smaller Cdl value of NP compared with that of NF possessing a 3D porous
morphology with a large surface area can be attributed to the its two-dimensional-planar morphology
with low surface area. Figure 3-17d shows the Nyquist plots based on EIS analysis. The Nyquist plots
fitted well with the equivalent circuit model presented in the inset image, where Rs represents the
solution resistance (i.e. the crossover point at high frequency with the real axis) and Rct is ascribed to
the interfacial charge transfer resistance at the catalyst/electrolyte interface, which is directly related to
the catalytic kinetics.21, 90, 91 The smaller interfacial charge transfer resistance of the hybrid activated
NF@CGO than the NP and NF catalysts clearly indicates its better electronic transport capability and
better reactant diffusivity towards electrode surface, which clearly justify the superior OER performance
of the hybrid activated NF@CGO.
Figure 3-19 CV curves of bare NP (a), bare NF (b) and hybrid activated NF@CGO (c) at various scan rates
(10 mV s-1, 20 mV s-1, 40 mV s-1, 60 mV s-1, 80 mV s-1, 100 mV s-1 and 120 mV s-1) in the potential range
of 1.07-1.17 V vs RHE and the current measured at 1.12 V vs RHE plotted as a function of scan rate.
Furthermore, we tested the catalytic performances of the hybrid activated NF@CGO electrode
under extreme conditions in concentrated KOH solution, intermediate temperature and very high current,
which are quite often encountered in commercial alkaline water electrolyzers. As shown in Figure 3-
20a, long-term durability OER performance of the hybrid activated NF@CGO was investigated using a
chrono potentiometric method by applying a current density of 800 mA cm-2 in 6 M KOH at 353 K. The
hybrid electrode exhibited exceptional stability, with almost constant overpotential of 350 mV (230 mV
with iR correction) over 100 h, indicating that the hybrid activated NF@CGO electrode was catalytically
stable and mechanically robust during the harsh anodic condition. The polarization curve of the activated
NF@CGO hybrid after 100 h shows no deterioration compared with the original one, suggesting that
the fast-catalytic kinetic is still maintained after the 100 h operation (Figure 3-20b). In addition, the
activated NF@CGO hybrid maintained its morphologies after long term electrocatalytic performance
65
activation
indicative of its stable and good structural properties (Figure 3-21). The hybrid activated NF@CGO has
the potential to meet the long-term stability of catalytic performance for future commercial AWE at
higher current densities with the lowest overpotential. The water electrolyzer with H 2 and O2 bubbles
generated show in Figure 3-20c.
Figure 3-20 The long-term durability of the activated hybrid NF@CGO electrode in 6 M KOH at 353K. (a)
Chronopotentiometry curve; (b) Comparison of polarization curves before and after CA-100 h; (c) An optical
photo showing the water electrolyzer with H2 and O2 bubbles generated. Scale bare in (c) is 10 mm.
Figure 3-21 (a) SEM image of hybrid activated NF@CGO after CA-100 h; (b) High magnification of a
66
activation
single nanoflower in Figure 3-21a.
3.4.4 Discussion
The nickel nanolayer covering on the surface of the hybrid activated NF@CGO during electrolytic
codeposition would be slowly transformed to Ni(OH)2/NiOOH nanoflakes upon in situ electrochemical
activation.57 Etching will inevitably occur under harsh conditions (1.2-1.7 V, 6 M KOH at 353 K) until
Co3O4 and GO/ERGO are encountered and exposed to the electrolyte. The above conclusions would
be confirmed by comparing surface morphology (Figure 3-22) and Raman spectra (Figure 3-23) of the
NF@CGO before and after in situ ECA. More interestingly, the BET surface area of the activated
NF@CGO increased from 40.5 to 150.6 m2 g-1, an increase of nearly 4 times (Figure 3-12). This would
greatly increase the catalytic active sites since most of the electrode surface would be covered by
Ni(OH)2/NiOOH nanoflakes, Co3O4 nanorods and GO/ERGO nanosheets, referring to the Pourbaix
diagrams of Ni and Co under 353 K (Figure 3-24).40 In addition, the Co3O4 nanoparticles used in the
electrolytic codeposition were mostly agglomerated into microporous spheres with different sizes. The
pore sizes were found to be about 30 nm (Figure 3-25). These pores would be filled with nickel
nucleation and growth during electrolytic codeposition (Figure 3-4c inset illustration), which are be
slowly oxidized and finally etched out during in situ electrochemical activation. This process led to the
formation of Co3O4 with porous spherical shape coated with GO nanosheets on NF skeleton (Figure 3-
5b, Figure 3-5c and Figure 3-9a)).
Figure 3-22 SEM image of the hybrid NF@CGO. (a) before activated; (b) after activated.
67
activation
Figure 3-23 Raman spectra of the before activated NF@CGO and after activated NF@CGO.
Figure 3-24 The Pourbaix diagrams for Ni (a), and Co (b) in water under 353 K.
68
activation
Figure 3-25 (a) SEM image of commercial Co3O4; (b) High resolution SEM image of the area squared in
Figure 3-25a; (c) High resolution SEM image of the area squared in Figure 3-25b.
The aforementioned results reveal the high catalytic activity and excellent stability of the hybrid
activated NF@CGO when used as an electrocatalyst for OER. Such an excellent OER performance
could be explained as follows. Firstly, compared to the bare NP and NF, the hybrid activated NF@CGO
possessed more exposed active sites, which were favourable for the proton-coupled electron transfer
process during the water oxidation reaction. Secondly, the unique structural features of the activated
hybrid NF@CGO (i.e. a large surface area and hierarchical structures and interconnected electrically
conductive networks) facilitated the access of the electrolytes to the catalysts. Thirdly, the electrolytic
codeposition process with self-assembly was an effective method for the formation of uniform catalysts’
layer on 3D NF, resulting from the intact interaction between them without any binders. This could
facilitate the rapid electron/charge transfer in the OER, accelerate the reaction kinetics of electrocatalysis
and guarantee prolonged durability.
3.5 Summary
In summary, a highly efficient, freestanding hybrid activated NF@CGO with hierarchical
structures was prepared by the self-assembly of Ni crystals, Co3O4 nanorods, GO/ERGO nanoflakes and
in situ generated Ni(OH)2/NiOOH nanoflakes onto 3D NF via electrolytic codeposition process followed
by in situ electrochemical activation process. Based on our experiment, the obtained hybrid NF@CGO
exhibits excellent catalytic activity and stability for OER in both medium and harsh alkaline solution,
which is comparable or even better than the state-of-the-art related OER electrocatalysts, making the
hybrid activated NF@CGO a promising candidate for a next-generation OER electrocatalyst.
Remarkably, the synergistic effects of the hierarchical structure with uniform distribution of the
interconnected active species, which offer a large active surface area, fast mass transport and fast
electron transport in the electrode led to the promising catalytic performance. Furthermore, the activated
NF@CGO showed pronounced long-term operational stability (in 6 M KOH at 353 K) with a very lower
overpotential (350 mV) at the constant current density of 800 mA cm-2 over 100 h with no deterioration.
We ensured excellent and durable performance for industrial applications in the harsh oxidative
anodic condition by the design of a thick enough catalyst layer with a uniform distribution over the 3D
69
activation
NF. It is anticipated that the electrolytic codeposition approach can be easily adapted in industry for
large-scale production. This work might provide a strategy to design highly active, stable and universally
available 3D porous electrocatalysts for water splitting and inspire the development of next-generation
electrocatalysts for renewable energy applications.
References of Chapter III

[1]. S. Anantharaj, S. R. Ede, K. Sakthikumar, K. Karthick, S. Mishra and S. Kundu, Recent trends and
perspectives in electrochemical water splitting with an emphasis on sulfide, selenide, and phosphide catalysts of
Fe, Co, and Ni: a review. ACS Catalysis, 2016, 6, 8069-8097.
[2]. M. Gong, Y. Li, H. Wang, Y. Liang, J. Z. Wu, J. Zhou, J. Wang, T. Regier, F. Wei and H. Dai, An advanced
Ni-Fe layered double hydroxide electrocatalyst for water oxidation. JACS, 2013, 135, 8452-8455.
[3]. Y. Liang, Y. Li, H. Wang, J. Zhou, J. Wang, T. Regier and H. Dai, Co 3O4 nanocrystals on graphene as a
synergistic catalyst for oxygen reduction reaction. Nat. Mater., 2011, 10, 780-786.
[4]. Y. Li, L. Zhang, X. Xiang, D. Yan and F. Li, Engineering of ZnCo-layered double hydroxide nanowalls
toward high-efficiency electrochemical water oxidation. J. Mater. Chem. A, 2014, 2.
[5]. L. Zhang, T. Mi, M. A. Ziaee, L. Liang and R. Wang, Hollow POM@MOF hybrid-derived porous
Co3O4/CoMoO4 nanocages for enhanced electrocatalytic water oxidation. J. Mater. Chem. A, 2018, 6, 1639-1647.
[6]. Z. Jiang, T. Xiao, V. á. Kuznetsov and P. Edwards, Turning carbon dioxide into fuel. Philosophical
Transactions of the Royal Society of London A: Mathematical, Physical Engineering Sciences, 2010, 368, 3343-
3364.
[7]. M. Dresselhaus and I. Thomas, Alternative energy technologie. Nature, 2001, 414, 332.
[8]. P. Li and H. C. Zeng, Bimetallic Ni-Fe phosphide nanocomposites with a controlled architecture and
composition enabling highly efficient electrochemical water oxidation. J. Mater. Chem. A, 2018, 6, 2231-2238.
[9]. S. Wan, J. Qi, W. Zhang, W. Wang, S. Zhang, K. Liu, H. Zheng, J. Sun, S. Wang and R. Cao, Hierarchical
Co(OH)F Superstructure Built by Low-Dimensional Substructures for Electrocatalytic Water Oxidation. Adv.
Mater., 2017, 29.
[10]. Y. Wu, M. Chen, Y. Han, H. Luo, X. Su, M. T. Zhang, X. Lin, J. Sun, L. Wang and L. Deng, Fast and
Simple Preparation of Iron ‐ Based Thin Films as Highly Efficient Water ‐ Oxidation Catalysts in Neutral
Aqueous Solution. Angew. Chem. Int. Ed., 2015, 54, 4870-4875.
[11]. C. C. McCrory, S. Jung, J. C. Peters and T. Jaramillo, Benchmarking heterogeneous electrocatalysts for
the oxygen evolution reaction. JACS, 2013, 135, 16977-16987.
[12]. J. Suntivich, K. J. May, H. A. Gasteiger, J. B. Goodenough and Y. Shao-Horn, A perovskite oxide
optimized for oxygen evolution catalysis from molecular orbital principles. Science, 2011, 334, 1383-1385.
[13]. Y. Zhao, R. Nakamura, K. Kamiya, S. Nakanishi and K. Hashimoto, Nitrogen-doped carbon
nanomaterials as non-metal electrocatalysts for water oxidation. Nat. Commun., 2013, 4, 2390.
[14]. J. O. M. Bockris, Kinetics of activation controlled consecutive electrochemical reactions: anodic
evolution of oxygen. J Chem. Phys., 1956, 24, 817-827.
[15]. M. Tahir, L. Pan, F. Idrees, X. Zhang, L. Wang, J.-J. Zou and Z. L. Wang, Electrocatalytic oxygen
evolution reaction for energy conversion and storage: A comprehensive review. Nano Energy, 2017, 37, 136-157.
[16]. Y. Lee, J. Suntivich, K. J. May, E. E. Perry and Y. Shao-Horn, Synthesis and activities of rutile IrO2 and
70
activation
RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett., 2012, 3, 399-404.
[17]. Y. Tong, P. Chen, T. Zhou, K. Xu, W. Chu, C. Wu and Y. Xie, A Bifunctional Hybrid Electrocatalyst for
Oxygen Reduction and Evolution: Cobalt Oxide Nanoparticles Strongly Coupled to B, N‐Decorated Graphene.
Angew. Chem., 2017, 129, 7227-7231.
[18]. A. Minguzzi, F.-R. F. Fan, A. Vertova, S. Rondinini and A. J. Bard, Dynamic potential-pH diagrams
application to electrocatalysts for water oxidation. Chemical Science, 2012, 3, 217-229.
[19]. Z. Xiao, Y. Wang, Y.-C. Huang, Z. Wei, C.-L. Dong, J. Ma, S. Shen, Y. Li and S. Wang, Filling the
oxygen vacancies in Co3O4 with phosphorus: an ultra-efficient electrocatalyst for overall water splitting. Energy
Environ. Sci., 2017, 10, 2563-2569.
[20]. C. C. McCrory, S. Jung, J. C. Peters and T. F. Jaramillo, Benchmarking heterogeneous electrocatalysts
for the oxygen evolution reaction. JACS, 2013, 135, 16977-16987.
[21]. Y. Teng, X.-D. Wang, J.-F. Liao, W.-G. Li, H.-Y. Chen, Y.-J. Dong and D.-B. Kuang, Atomically Thin
Defect-Rich Fe-Mn-O Hybrid Nanosheets as High Efficient Electrocatalyst for Water Oxidation. Adv. Funct.
Mater., 2018, 28, 1802463.
[23]. Y. Li, P. Hasin and Y. Wu, NixCo3−xO4 nanowire arrays for electrocatalytic oxygen evolution. Adv. Mater.,
2010, 22, 1926-1929.
[24]. P. Du and R. Eisenberg, Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting:
recent progress and future challenges. Energy Environ. Sci., 2012, 5, 6012-6021.
[25]. X. Deng and H. Tüysüz, Cobalt-Oxide-Based Materials as Water Oxidation Catalyst: Recent Progress
Challenges. ACS Catal., 2014, 4, 3701-3714.
[26]. A. R. Parent and K. Sakai, Progress in Base‐Metal Water Oxidation Catalysis. ChemSusChem, 2014,
7, 2070-2080.
[27]. S. Chen and S.-Z. Qiao, Hierarchically porous nitrogen-doped graphene-NiCo2O4 hybrid paper as an
advanced electrocatalytic water-splitting material. ACS Nano, 2013, 7, 10190-10196.
[28]. S. Mao, Z. Wen, T. Huang, Y. Hou and J. Chen, High-performance bi-functional electrocatalysts of 3D
crumpled graphene-cobalt oxide nanohybrids for oxygen reduction and evolution reactions. Energy Environ. Sci.,
2014, 7, 609-616.
[29]. H. Liang, F. Meng, M. Cabán-Acevedo, L. Li, A. Forticaux, L. Xiu, Z. Wang and S. Jin, Hydrothermal
continuous flow synthesis and exfoliation of NiCo layered double hydroxide nanosheets for enhanced oxygen
evolution catalysis. Nano Lett., 2015, 15, 1421-1427.
[30]. L. Han, S. Dong and E. Wang, Transition-Metal (Co, Ni, and Fe)-Based Electrocatalysts for the Water
Oxidation Reaction. Adv. Mater., 2016, 28, 9266-9291.
[31]. H. A. Younus, N. Ahmad, A. H. Chughtai, M. Vandichel, M. Busch, K. Van Hecke, M. Yusubov, S. Song
and F. Verpoort, A Robust Molecular Catalyst Generated In Situ for Photo- and Electrochemical Water Oxidation.
ChemSusChem, 2017, 10, 862-875.
[32]. J. Wang, K. Li, H. X. Zhong, D. Xu, Z. L. Wang, Z. Jiang, Z. J. Wu and X. B. Zhang, Synergistic Effect
between Metal-Nitrogen-Carbon Sheets and NiO Nanoparticles for Enhanced Electrochemical Water-Oxidation
Performance. Angew. Chem. Int. Ed. Engl., 2015, 54, 10530-10534.
[33]. S. W. Sheehan, J. M. Thomsen, U. Hintermair, R. H. Crabtree, G. W. Brudvig and C. A. Schmuttenmaer,
A molecular catalyst for water oxidation that binds to metal oxide surfaces. Nat. Commun., 2015, 6, 6469.
71
activation
[34]. K. Fan, H. Chen, Y. Ji, H. Huang, P. M. Claesson, Q. Daniel, B. Philippe, H. Rensmo, F. Li, Y. Luo and
L. Sun, Nickel-vanadium monolayer double hydroxide for efficient electrochemical water oxidation. Nat.
Commun., 2016, 7, 11981.
[35]. K. Zeng and D. Zhang, Recent progress in alkaline water electrolysis for hydrogen production and
applications. Prog. Energy Combust. Sci., 2010, 36, 307-326.
[36]. K. C. K., Development of Hydrogen Electrodes for Alkaline Water Electrolysis. DTU Mechanical
Engineering, 2014.
[38]. Y. Yan, B. Y. Xia, B. Zhao and X. Wang, A review on noble-metal-free bifunctional heterogeneous
catalysts for overall electrochemical water splitting. J. Mater. Chem. A, 2016, 4, 17587-17603.
[39]. X. Zhu, C. Tang, H.-F. Wang, B.-Q. Li, Q. Zhang, C. Li, C. Yang and F. Wei, Monolithic-structured
ternary hydroxides as freestanding bifunctional electrocatalysts for overall water splittin. J. Mater. Chem. A, 2016,
4, 7245-7250.
[40]. X. Liu, X. Wang, X. Yuan, W. Dong and F. Huang, Rational composition and structural design of in situ
grown nickel-based electrocatalysts for efficient water electrolysis. J. Mater. Chem. A, 2016, 4, 167-172.
[41]. X. Wang, W. Li, D. Xiong and L. Liu, Fast fabrication of self-supported porous nickel phosphide foam
for efficient, durable oxygen evolution and overall water splitting. J. Mater. Chem. A, 2016, 4, 5639-5646.
[42]. Y. Li, C. Zhong, J. Liu, X. Zeng, S. Qu, X. Han, Y. Deng, W. Hu and J. Lu, Atomically Thin Mesoporous
Co3O4 Layers Strongly Coupled with N-rGO Nanosheets as High-Performance Bifunctional Catalysts for 1D
Knittable Zinc-Air Batteries. Adv. Mater., 2018, 30.
[43]. J. Fu, D. U. Lee, F. M. Hassan, L. Yang, Z. Bai, M. G. Park and Z. Chen, Flexible High‐Energy
Polymer‐Electrolyte‐Based Rechargeable Zinc–Air Batteries. Adv. Mater., 2015, 27, 5617-5622.
[44]. Y. Sun, S. Gao, F. Lei, J. Liu, L. Liang and Y. Xie, Atomically-thin non-layered cobalt oxide porous
sheets for highly efficient oxygen-evolving electrocatalysts. Chemical Science, 2014, 5, 3976-3982.
[45]. M. G. Park, D. U. Lee, M. H. Seo, Z. P. Cano and Z. Chen, 3D Ordered Mesoporous Bifunctional
Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries. Small, 2016, 12, 2707-2714.
[46]. J. Fu, F. M. Hassan, J. Li, D. U. Lee, A. R. Ghannoum, G. Lui, M. A. Hoque and Z. Chen, Flexible
Rechargeable Zinc‐Air Batteries through Morphological Emulation of Human Hair Array. Adv. Mater., 2016, 28,
6421-6428.
[47]. Y. Tong, P. Chen, T. Zhou, K. Xu, W. Chu, C. Wu and Y. Xie, A Bifunctional Hybrid Electrocatalyst for
Oxygen Reduction and Evolution: Cobalt Oxide Nanoparticles Strongly Coupled to B,N-Decorated Graphene.
Angew. Chem. Int. Ed. Engl., 2017, 56, 7121-7125.
[48]. Y. Liang, H. Wang, P. Diao, W. Chang, G. Hong, Y. Li, M. Gong, L. Xie, J. Zhou and J. Wang, Oxygen
reduction electrocatalyst based on strongly coupled cobalt oxide nanocrystals and carbon nanotubes. JACS, 2012,
134, 15849-15857.
[49]. H. Jin, J. Wang, D. Su, Z. Wei, Z. Pang and Y. Wang, In situ cobalt-cobalt oxide/N-doped carbon hybrids
as superior bifunctional electrocatalysts for hydrogen and oxygen evolution. JACS, 2015, 137, 2688-2694.
[50]. J. Wang, F. Xu, H. Jin, Y. Chen and Y. Wang, Non-Noble Metal-based Carbon Composites in Hydrogen
Evolution Reaction: Fundamentals to Applications. Adv. Mater., 2017, 29, 1605838.
[51]. R. D. Smith, M. S. Prévot, R. D. Fagan, Z. Zhang, P. A. Sedach, M. K. J. Siu, S. Trudel and C.
Berlinguette, Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.
72
activation
Science, 2013, 340, 60-63.

[53]. L. Liu, M. Wang, Z. Wang and Y. Zhang, The corrosion resistance of Ni anode and Ga electrowinning
in alkaline sulfide solutions. J. Appl. Electrochem., 2015, 45, 1255-1263.
[54]. G. Yasin, M. Arif, M. N. Nizam, M. Shakeel, M. A. Khan, W. Q. Khan, T. M. Hassan, Z. Abbas, I.
Farahbakhsh and Y. Zuo, Effect of surfactant concentration in electrolyte on the fabrication and properties of
nickel-graphene nanocomposite coating synthesized by electrochemical co-deposition. RSC Advances, 2018, 8,
20039-20047.
[55]. G. N., Kinetics of the deposition of inert particles from electrolytic baths. . J. Electrochem. Soc., 1972,
119, 1009-1012.
[56]. R. J. R. Celis J P, Buelens C. , A Mathematical Model for the Electrolytic Codeposition of Particles with
a metallic matrix. J. Electrochem. Soc., 1987, 134, 1402.
[58]. O. Diaz-Morales, I. Ledezma-Yanez, M. T. M. Koper and F. Calle-Vallejo, Guidelines for the Rational
Design of Ni-Based Double Hydroxide Electrocatalysts for the Oxygen Evolution Reaction. ACS Catalysis, 2015,
5, 5380-5387.
[59]. H. Y. Wang, S. F. Hung, H. Y. Chen, T. S. Chan, H. M. Chen and B. Liu, In Operando Identification of
Geometrical-Site-Dependent Water Oxidation Activity of Spinel Co3O4. J. Am. Chem. Soc., 2016, 138, 36-39.
[61]. B. J. Trzesniewski, O. Diaz-Morales, D. A. Vermaas, A. Longo, W. Bras, M. T. Koper and W. A. Smith,
In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect
of pH on Electrochemical Activity. J. Am. Chem. Soc., 2015, 137, 15112-15121.
[62]. J. Chen, K. Sheng, P. Luo, C. Li and G. Shi, Graphene hydrogels deposited in nickel foams for high-
rate electrochemical capacitors. Adv. Mater., 2012, 24, 4569-4573.
[63]. X. Yan, L. Tian, M. He and X. Chen, Three-Dimensional Crystalline/Amorphous Co/Co3O4 Core/Shell
Nanosheets as Efficient Electrocatalysts for the Hydrogen Evolution Reaction. Nano. Lett., 2015, 15, 6015-6021.
[64]. M. R. Mahmoudian, Y. Alias and W. J. Basirun, The electrical properties of a sandwich of
electrodeposited polypyrrole nanofibers between two layers of reduced graphene oxide nanosheets. Electrochim.
Acta, 2012, 72, 53-60.
[65]. L. Chen, Y. Tang, K. Wang, C. Liu and S. Luo, Direct electrodeposition of reduced graphene oxide on
glassy carbon electrode and its electrochemical application. Electrochem. Commun., 2011, 13, 133-137.
[66]. W. J. Basirun, M. Sookhakian, S. Baradaran, Z. Endut, M. R. Mahmoudian, M. Ebadi, R. Yousefi, H.
Ghadimi and S. Ahmed, Graphene oxide electrocatalyst on MnO 2 air cathode as an efficient electron pump for
enhanced oxygen reduction in alkaline solution. Sci. Rep., 2015, 5, 9108.
[67]. W. J. Basirun, Sookhakian, M., Baradaran, S., Mahmoudian, M. R., & Ebadi, M., Solid-phase
electrochemical reduction of graphene oxide films in alkaline solution. Nanoscale Research Letters 2013, 8, 397.
[68]. K. Xu, H. Ding, H. Lv, S. Tao, P. Chen, X. Wu, W. Chu, C. Wu and Y. Xie, Understanding Structure-
Dependent Catalytic Performance of Nickel Selenides for Electrochemical Water Oxidation. ACS Catalysis, 2016,
7, 310-315.
73
activation
[69]. K. Xu, P. Chen, X. Li, Y. Tong, H. Ding, X. Wu, W. Chu, Z. Peng, C. Wu and Y. Xie, Metallic nickel
nitride nanosheets realizing enhanced electrochemical water oxidation. J. Am. Chem. Soc., 2015, 137, 4119-4125.
[70]. F. Razmjooei, K. P. Singh, D.-S. Yang, W. Cui, Y. H. Jang and J.-S. Yu, Fe-Treated Heteroatom
(S/N/B/P)-Doped Graphene Electrocatalysts for Water Oxidation. ACS Catalysis, 2017, 7, 2381-2391.
[71]. L. An, J. Feng, Y. Zhang, Y.-Q. Zhao, R. Si, G.-C. Wang, F. Cheng, P. Xi and S. Sun, Controllable tuning
of Fe-N nanosheets by Co substitution for enhanced oxygen evolution reaction. Nano Energy, 2019, 57, 644-652.
[72]. Z. Chen, H. Xu, Y. Ha, X. Li, M. Liu and R. Wu, Two-dimensional dual carbon-coupled defective nickel
quantum dots towards highly efficient overall water splitting. Applied Catalysis B: Environmental, 2019, 250, 213-
223.
[73]. G. Fang, Q. Wang, J. Zhou, Y. Lei, Z. Chen, Z. Wang, A. Pan and S. Liang, Metal Organic Framework-
Templated Synthesis of Bimetallic Selenides with Rich Phase Boundaries for Sodium-Ion Storage and Oxygen
Evolution Reaction. ACS Nano, 2019, 13, 5635-5645.
[74]. L. He, J. Liu, B. Hu, Y. Liu, B. Cui, D. Peng, Z. Zhang, S. Wu and B. Liu, Cobalt oxide doped with
titanium dioxide and embedded with carbon nanotubes and graphene-like nanosheets for efficient trifunctional
electrocatalyst of hydrogen evolution, oxygen reduction, and oxygen evolution reaction. J. Power Sources, 2019,
414, 333-344.
[75]. Y. Hou, M. Qiu, M. G. Kim, P. Liu, G. Nam, T. Zhang, X. Zhuang, B. Yang, J. Cho, M. Chen, C. Yuan,
L. Lei and X. Feng, Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets
for efficient water oxidation. Nat. Commun., 2019, 10, 1392.
[76]. C.-T. Hsieh, C.-L. Huang, Y.-A. Chen and S.-Y. Lu, NiFeMo alloy inverse-opals on Ni foam as
outstanding bifunctional catalysts for electrolytic water splitting of ultra-low cell voltages at high current densities.
Applied Catalysis B: Environmental, 2020, 267, 118376.
[77]. L. Zeng, K. Zhou, L. Yang, G. Du, L. Liu and W. Zhou, General Approach of in Situ Etching and Doping
To Synthesize a Nickel-Doped MxOy (M=Co, Mn, Fe) Nanosheets Array on Nickel Foam as Large-Sized
Electrodes for Overall Water Splitting. ACS Appl. Energy Mater., 2018, 1, 6279-6287.
[78]. Y. Lyu, R. Wang, L. Tao, Y. Zou, H. Zhou, T. Liu, Y. Zhou, J. Huo, S. P. Jiang, J. Zheng and S. Wang,
In-situ evolution of active layers on commercial stainless steel for stable water splitting. Applied Catalysis B:
Environmental, 2019, 248, 277-285.
[79]. A. Muthurasu, V. Maruthapandian and H. Y. Kim, Metal-organic framework derived Co3O4/MoS2
heterostructure for efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution
[80]. X. Wang, P. Sun, H. Lu, K. Tang, Q. Li, C. Wang, Z. Mao, T. Ali and C. Yan, Aluminum-Tailored Energy
Level and Morphology of Co3-xAlxO4 Porous Nanosheets toward Highly Efficient Electrocatalysts for Water
Oxidation. Small, 2019, 15, e1804886.
[81]. D. Zhu, J. Liu, L. Wang, Y. Du, Y. Zheng, K. Davey and S. Z. Qiao, A 2D metal-organic
framework/Ni(OH)2 heterostructure for an enhanced oxygen evolution reaction. Nanoscale, 2019, 11, 3599-3605.
[82]. N. R. Chodankar, I. V. Bagal, S. W. Ryu, Y. K. Han and D. H. Kim, Nano-Micro-Structured Nickel-
Cobalt Hydroxide/Ni2P2O7 Assembly on Nickel Foam: An Outstanding Electrocatalyst for Alkaline Oxygen
Evolution Reaction. ChemCatChem, 2019, 11, 4256-4261.
238-250.
74
activation
[84]. G. Ren, Q. Hao, J. Mao, L. Liang, H. Liu, C. Liu and J. Zhang, Ultrafast fabrication of nickel sulfide
film on Ni foam for efficient overall water splitting. Nanoscale, 2018, 10, 17347-17353.
[85]. H. Sun, Y. Lian, C. Yang, L. Xiong, P. Qi, Q. Mu, X. Zhao, J. Guo, Z. Deng and Y. Peng, A hierarchical
nickel-carbon structure templated by metal-organic frameworks for efficient overall water splitting. Energy
Environ. Sci., 2018, 11, 2363-2371.
[86]. Q. Wang, F. Wei, D. Manoj, Z. Zhang, J. Xiao, X. Zhao, F. Xiao, H. Wang and S. Wang, In situ growth
of Fe(ii)-MOF-74 nanoarrays on nickel foam as an efficient electrocatalytic electrode for water oxidation: a
mechanistic study on valence engineering. Chem. Commun., 2019, 55, 11307-11310.
[87]. X. Xu, X. Tian, Z. Zhong, L. Kang and J. Yao, In-situ growth of iron/nickel phosphides hybrid on nickel
foam as bifunctional electrocatalyst for overall water splitting. J. Power Sources, 2019, 424, 42-51.
[89]. X. Zheng, Y. Zhang, H. Liu, D. Fu, J. Chen, J. Wang, C. Zhong, Y. Deng, X. Han and W. Hu, In Situ
Fabrication of Heterostructure on Nickel Foam with Tuned Composition for Enhancing Water-Splitting
[90]. P. Chakthranont, J. Kibsgaard, A. Gallo, J. Park, M. Mitani, D. Sokaras, T. Kroll, R. Sinclair, M. B.
Mogensen and T. Jaramillo, Effects of Gold Substrates on the Intrinsic and Extrinsic Activity of High-Loading
Nickel-Based Oxyhydroxide Oxygen Evolution Catalysts. ACS Catalysis, 2017, 7, 5399-5409.
[91]. C. Zhang, C. P. Berlinguette and S. Trudel, Water oxidation catalysis: an amorphous quaternary Ba-Sr-
Co-Fe oxide as a promising electrocatalyst for the oxygen-evolution reaction. Chem. Commun., 2016, 52, 1513-
1516.
75
activation
76
Chapter IV Development of OER electrocatalysts by combining high-velocity oxy-fuel spraying and in situ electrochemical
activation
Chapter IV Development of OER electrocatalysts by

combining high-velocity oxy-fuel spraying and in situ
4.1 Introduction
As mentioned before, OER is more energy-consuming due to the high thermodynamic potential
required for water oxidation (1.23 V vs NHE at pH 0) and the sluggish kinetic hindrance of the multi-
electron evolving charge-transfer reactions.1, 2 Recently, earth-abundant transition metal-based oxides,
(oxy) hydroxides, and their derivatives have been extensively used as catalysts for OER due to their
tunability, abundance, and potential stability in alkaline electrolyte.3-5 Nevertheless, the suboptimal
intrinsic activity, the limited active sites exposure and the inherently poor electronic conductivity are
key problem to hamper further catalytic performance enhancement of these catalysts.6-8
Focusing on these issues, several rational strategies were employed to further develop OER
catalysts with abundant active sites exposure, fast charge transfer ability and super electronic
conductivity. Han et. al increased the density of the crystalline-amorphous phase boundary to enhance
the intrinsic activity and electronic conductivity of the catalyst.1 Shinagawa et.al induced “active oxygen”
to improve the intrinsic activity of the NiOOH nanosheets.5 Chen et. al systematically demonstrated
transition metal chalcogenides derived nano porous oxides as excellent water oxidation catalysts by
increasing active sites exposure.2 Meanwhile, induced lattice distortion for efficiently triggering
hydrogen evolution by enhancing intrinsic activity were explored extensively by researchers. 9, 10 These
mysterious structure defects, which can greatly increase the catalytic activity, still need to be further
explored and utilized.
Moreover, OER is a process involved electrocatalytic reactions at the boundary of gas-liquid-solid
phases. Catalytic reactions take place at the interface of the catalyst and the electrolyte, catalytic activity
can also be restricted due to the lack of bubble transport channels.11, 12 In practice, rational design of
the OER catalyst architecture can dramatically promote activity in electrocatalytic water splitting.13, 14
Therefore, ingenious designing the morphology, structure, and composition of the electrocatalysts is
pivotal for achieving high catalytic activity towards OER. To achieve effective ways of further
promoting OER performance at the three-phase boundary, the design of 3D supports with facile
charge/electrolyte/bubble migration and higher catalysts loading contributions to the catalytic OER
activity has to be further explored. Recently, it has been recognized that the catalytic performance of
electrocatalysts would be extremely optimized due to the improvement of intrinsic activity or active
sites exposure upon in situ electrochemical oxidation tuning process, in which the electrocatalysts
experienced morphology, structural or compositional changes with nanopore and nanostructure defects,
77
Chapter IV Development of OER electrocatalysts by combining high-velocity oxy-fuel spraying and in situ
emerging amorphous phase, oxygen vacancy and lattice distortion.15-19

Thermal spraying processes which are cost-effective and rapid manufacturing, have shown their
capability to deposit electrocatalytically active electrode coatings for water splitting mainly by
increasing large surface areas.20-26 Among different thermal spraying techniques, high velocity oxy-fuel
(HVOF) is expected to be a promising method for producing active electrode coatings for water splitting
for the reason that HVOF characterized by high particle velocity and relatively low temperatures allows
deposition of surface coatings with low-oxide contents.24 However, it is far from satisfying industrial
needs to obtain excellent catalytic electrodes for water splitting simply by increasing the active surface
area. Therefore, it is urgent to use coatings obtained by thermal spraying process as precatalysts,
combined with some post-treatment methods to greatly improve the intrinsic activity of the catalytic
electrodes.
Enlightened by the above discussion, herein, we report an effective approach for phase, surface,
and morphology of elaborated 3D hierarchically porous architecture with lattice-dislocated nickel (oxy)
hydroxide nanosheets in situ growth, namely HNA-CA-ECA, for OER electrocatalyst application. The
3D hierarchically porous architecture is properly designed by chemical dealloying activation (CA) of
the high-velocity oxy-fuel (HVOF) sprayed Ni-Al alloy coating (HNA) with micro-voids randomly
distributed. In the CA process of HNA, the aluminum element in the coating is selectively etched away,
leaving a large number of nanopores and capillary channels, which constitute a hierarchically interlaced
3D network (HNA-CA) together with micro-voids remaining in precursor HNA. The HAN-CA not only
structurally prepares for the formation of the lattice-dislocated nickel (oxy) hydroxide nanosheets
carrying optimal intrinsic activity, which are subsequently in situ generated by electrochemical
activation (ECA), but also delicately provides a huge surface for in situ growth of these highly active
nanosheets and a typical 3D hierarchical porous network ensuring efficient and rapid
charge/electrolyte/bubble migration.
4.2 HNA-CA-ECA as a highly efficient OER electrocatalyst
4.2.1 Synthesis of the HNA-CA-ECA

Firstly, the precursor HNA coating was prepared by depositing Ni-Al alloy powders on the nickel
plate (NP) via HVOF. The porous structure was designed by leaving some micro-voids in the coating
with specific HVOF parameters (Figure 4-1a). As a novel process of catalyst deposition, HVOF was
employed to obtain a well-bonded precursor coating to meet the long-term catalytic stability used as a
catalyst because the supersonic Ni-Al alloy particles ejected from the HVOF gun can instantly break up
and remove the oxide layer from the surface of the newly obtained coating.27 The crystal structures of
the obtained HNA coating were maintained compared with those of the feedstock powders, both of
78
activation
which were composed of nickel-rich phase (NiAl phase) and aluminum-rich phase (Ni2Al3 phase) by an
examination of the X-ray diffraction (XRD, Figure 4-2). Subsequently, the 3D hierarchically porous
architecture, HNA-CA, was elaborated by CA of the HNA in the 6 M KOH aqueous solution (contained
10 wt.% KNa tartrate-tetrahydrate) at 353 K for 24 h. As shown in Figure 4-2b, a large number of
microchannels/microcracks appeared resulting from the leaching of aluminum atoms out of the
aluminum-rich phase. Moreover, the zone near the micro-voids left in the precursor HNA coating was
more severely etched. To avoid precipitation of aluminum hydroxide in the microchannels/microcracks
of the obtained sponge-like structure — HNA-CA, KNa tartrate-tetrahydrate (Rochelle salt) as a
complexing agent was added into the strong alkali aqueous solution to formation of water-soluble
complexes by complexation of aluminum hydroxide.28 Together with micro-voids left in the precursor
HNA coating, a hierarchically interlaced 3D architecture was constituted, giving rise to the strikingly
enhanced active surface area, accelerated electron/ion transport, and further promoted reaction kinetics
of OER. The morphology of the 3D architecture could be inherited into the as de-alloyed products, and
it was called as DIE or corrosion inheritance effect.29 Notably, these microchannels/microcracks
emerged by etching under the alkali aqueous solution, resulting that all fresh surface would be
completely wetted by the almost identical alkali electrolyte and entirely participated in the OER process.
Finally, the nickel (oxy) hydroxide-Jamborite (Ni(OH)2/NiOOH hybrid) nanosheets are formed upon in
situ electrochemical oxidation of the HNA-CA with 3D hierarchically porous architecture (Figure 4-1c
and Figure 4-3c). In a summary, the synthesis was very effective and could be easily scaled up for
practical use.
Figure 4-1 Cross-section views of typical SEM images. (a) HNA; (b) HNA-CA; (c) HNA-CA-ECA.
79
Figure 4-2 The typical XRD spectra of Ni-Al alloy powder and the HNA coating.
Figure 4-3 Top views of typical SEM images. (a) HNA; (b) HNA-CA; (c) HNA-CA-ECA.
4.2.2 Physical characterization of the HNA-CA-ECA

Physical characterizations of the HNA-CA-ECA catalysts would be showed as below. The crystal
structures of the HNA, HNA-CA, and HNA-CA-ECA samples were studied by the X-ray diffraction
(XRD) spectra, as shown in Figure 4-4. The XRD patterns of HNA sample confirmed the coexistence
of Ni2Al3 (JCPDS No. 14-0648) and NiAl (JCPDS No. 44-1188). Obviously, the peaks of the Ni2Al3
(JCPDS No. 14-0648) in the HNA sample disappeared in that of the HNA-CA sample, while the new
peaks located at 51.99°, 60.81°, and 91.70° could be indexed as crystal planes (111), (200), and (220)
of metallic Ni (JCPDS No. 89-7128), respectively. More interestingly, the (111) peak located at 51.99°
80
activation
of metallic Ni was asymmetrical, with a bulge on its left side, suggesting a superposition of the peak
from another new phase. It could be assigned to the (012) peak located at 50.72° of NiO (JCPDS No.
44-1159), together with other weak broad peaks located at 43.54°, 74.60°, 90.50°, and 95.73°, which
might be attributed to nanosized or low crystallinity.
Figure 4-4 XRD patterns of the as-achieved HNA, HNA-CA and HNA-CA-ECA catalysts
Further high-resolution transmission electron microscopy (HR-TEM) analysis of flakes scratched

off HNA-CA (Figure 4-5) indicated that the lattice fringes with spacings of 0.241 and 0.203 nm are
indexed to the (101) face of NiO shell and the (111) face of Ni crystallites core, respectively.
Simultaneously, a large number of mesopores were mainly distributed at the boundary of the core-shell
nanostructure. It could be concluded that aluminum was selectively removed during CA, and the retained
mesoporous Ni crystallites was spontaneously oxidized, which was an ideal way to grow NiO outside
the Ni crystallites core.29 Benefiting from the unique architecture of mesoporous Ni/NiO-core/shell
nanostructures, the OER performance of HNA-CA catalysts would be promoted significantly.
81
Figure 4-5 HR-TEM image of the unique architecture of mesoporous Ni/NiO-core/shell in the HNA-CA.
After ECA treatment, all the NiO phase peaks in the HNA-CA-ECA sample increased with respect
to that of HNA-CA. Moreover, the HNA-CA-ECA sample was well characterized with new peaks at
13.28°, 26.75°, 40.37°, 45.62°, 54.30°, and 72.87°, which can be assigned to the nickel (oxy) hydroxide-
Jamborite (Ni(OH)2/NiOOH hybrid, JCPDS No. 89-7111)3, which was obtained by further oxidation of
the Ni/NiO-core/shell nanostructures upon ECA.2, 3, 15, 18, 30-33 More importantly, the peaks of NiAl
phase (JCPDS No. 44-1188) were stably presented in all samples, confirming that this nickel-rich phase
prevent further leaching of the Ni-Al alloy, consequently, NiAl phase would act as a skeleton of in situ
generating Jamborite nanosheets, the active substance of OER, and simultaneously maintain the stability
of the 3D architecture.34
Interestingly, XRD detection further investigated the relationship between the structure of the
HNA-CA-ECA catalysts and the time of ECA (Figure 4-6). Samples with different activation times were
82
activation
marked HNA-CA-ECA0h (refer to HNA-CA), HNA-CA-ECA1h, HNA-CA-ECA2h (refer to HNA-

CA-ECA), and HNA-CA-ECA168h, respectively. Obviously, the peaks of NiO and Jamborite-
(Ni(OH)2/NiOOH hybrid) gradually increased and turned sharper as the activation time from 0 to 2 h,
suggesting that the Ni crystallites obtained upon CA was rapidly oxidized to NiO during ECA and further
oxidized to Jamborite-(Ni(OH)2/NiOOH hybrid). While the corresponding peaks never changed too
much during the activation time from 2 to 168 h, indicating that the above transformations were
completed within the first two hours of the in situ electrochemical oxidation. Notably, the robust nature
of the in situ electrochemical tuning Jamborite-(Ni(OH)2/NiOOH hybrid) could be maintained under
commercial alkaline water electrolysis due to the same harsh environment — (6 M KOH, 353 K).
Figure 4-6 XRD patterns of the as-achieved HNA, HNA-CA and HNA-CA-ECA with different ECA time.
Scanning electron microscopy (SEM) images of the HNA-CA-ECA catalysts revealed that the
wrinkled Jamborite-(Ni(OH)2/NiOOH hybrid) nanosheets with typical morphology of (oxy)hydroxides
were in situ generated on the surface of the nickel-rich microspheres (Figure 4-7 and Figure 4-3c), which
were converted by the mesoporous Ni/NiO-core/shell nanostructures (Figure 4-5) on the surface of the
NiAl skeleton in HNA-CA, which was consistent with the XRD measurements. Impressively, the film
exhibited a highly porous cross-linked structure with pore diameter ranging from ca. 100 to ca. 300 nm
(Figure 4-7b). The interconnecting network was made up of wrinkled nanosheets with thicknesses of
83
about ca. 10 nm, and no coalescence between neighboring nanosheets or obstruction of the pores was
observed, indicating the strong mechanical strength of the Jamborite-(Ni(OH)2/NiOOH hybrid)
nanosheets. Such a unique hierarchical network structure led to the exposure a large number of
electroactive sites to electrolyte ions for OER, while the coexistence of mesopores (between inter-
nanosheets) and macropores (between inter-microspheres and micro-voids) effectively shortened ions
transport paths and efficiently promoted ions diffusion of the electrolyte. By virtue of its large specific
surface area and hierarchical porous structure, the HNA-CA-ECA would be the promising catalysts
toward OER.
Figure 4-7 (a) Typical SEM image of the HNA-CA-ECA; (b) HR-SEM image of the wrinkled nanosheets.
Transmission electron microscopy (TEM) was used to analyze the detailed crystal structure of
Jamborite-(Ni(OH)2/NiOOH hybrid) nanosheets as shown in Figures below. As was seen in Figure 4-
8, the mesoporous nanosheets exhibited ribbon-like morphology with different degrees of twist,
indicating their severe lattice distortion. Elemental mapping and the energy-dispersive X-ray spectra
(EDS) was conducted to examine the change of composition after the in situ ECA. The corresponding
elemental mapping showed that HNA-CA-ECA was mainly composed of Ni and O elements and
contained very few Al and K elements, of which Al and K ions probably derived from the Al-doped
Jamborite nanosheets because of the maternal inheritance (Ni2Al3 is the precursor phase of Jamborite)
and electrolyte (Figure 4-9), respectively. Based on the EDS of the HNA-CA-ECA and the HNA-CA
samples (Figure 4-8 insert and Figure 4-10), the Al content decreased from 28.75 to 2.30 at.%, but the
O content increased from 33.82 to 65.53 at.% upon ECA, indicating that Jamborite-(Ni(OH)2/NiOOH
hybrid) nanosheets, acting as the active substance of the OER catalyst, in situ transformed and covered
on the almost entire surface of the NiAl skeleton.
84
activation
Figure 4-8 TEM image of the ribbon-like nanosheets scratched off from the HNA-CA-ECA catalysts (insert:
corresponding EDS).
85
Figure 4-9 (a) Elemental mappings in Figure 4-8 purple square area; (b) Colours in elemental mapping images:
blue for Ni, purple for O, green for Al, and red for K; K is due to the residual electrolyte (6 M KOH).
Figure 4-10 (a) TEM image of the nanoparticle scratched off from the HNA-CA sample; (b) Corresponding
EDS.
Notably, the Jamborite-(Ni(OH)2/NiOOH hybrid) nanosheets had huger active specific surface
areas due to the genetic structure of the porous precursor HNA-CA, and more importantly, ECA also
triggered more mesoporous defects, which were assessed by N2 adsorption-desorption measurements.
In addition to the HNA sample, the N2 adsorption-desorption isotherms of the HNA-CA and HNA-CA-
ECA samples (Figure 4-11a) could be classified as type IV with a hysteresis loop, indicating that the
obtained samples were mesoporous materials. The Brunauer-Emmett-Teller (BET) surface areas were
calculated to be 9.1, 33.0, and 77.7 m2 g-1 for HNA, HNA-CA, and HNA-CA-ECA, respectively.
Additionally, the mesoporous feature of the samples was confirmed by the pore size distribution (Figure
4-11b). The average pore diameters are in the mesoporous region. To further reveal structural defects at
lower latitudes, high-resolution transmission electron microscopy (HR-TEM) was employed.
86
activation
Figure 4-11 (a) N2 adsorption-desorption isotherms of the samples; (b) Pore size distributions of HNA, HNA-CA
and HNA-CA-ECA. Base on the N2 adsorption-desorption isotherms, the BET surface of the samples were
measured to be 9.1, 33.0, and 77.7 m2 g-1, respectively.
HR-TEM analysis (Figure 4-12a) indicated that the lattice fringes with spacings of 0.259 and 0.151
nm are indexed to the (012) and (113) faces of Jamborite-(Ni(OH)2/NiOOH hybrid), respectively. The
selected area electron diffraction (SAED) rings (Figure 4-12b) further proved the existence of (012) and
(113) lattice planes in the nanocrystalline Jamborite-(Ni(OH)2/NiOOH hybrid), which was consistent
with XRD analysis. Impressively, we could clearly observe the tiny lattice distortions in some parts of
the HR-TEM image; the angle of the twisted and regular atomic arrangement was ca. 10°. These subtle
lattice distortions might be conductive to the formation of the high conductivity and the additional
electrochemical reaction active sites, resulting in ultra-high intrinsic activity.8-10, 35-37
Figure 4-12 (a) HR-TEM image of the lattice-dislocated Jamborite nanosheet in Figure 4-8 yellow square area;
(b) SAED pattern of the HNA-CA-ECA catalysts in Figure 4-8 whole area.
To eliminate the interference of intermetallic compounds in XRD detection of nickel oxides, (oxy)
87
hydroxides during the CA and ECA, Raman spectroscopy was further utilized to investigate the oxide
phases in the samples, as shown in Figure 4-14As expected, no apparent peaks were observed on HNA,
consistent with its metallic nature. Meanwhile, the Raman peaks in the HNA-CA sample cantered at 450
and 560 cm-1 can be assigned to the first-order transverse optical mode (TO) and one-phonon
longitudinal optical mode (LO) of NiO, respectively.18, 38-40 However, the broadening of Raman peaks
suggested the high degree of disorder29 due to the large amount of amorphous boundaries contained in
the Ni/NiO-core/shell structure (Figure 4-5). It is noteworthy that the HNA-CA-ECA sample showed a
pair of sharp peaks at 475 and 554 cm-1 ascribable to well-crystallized Jamborite-(Ni(OH)2/NiOOH
hybrid) and a broad peak at 800-1100 cm-1, a characteristic of “active oxygen” on the Jamborite-
(Ni(OH)2/NiOOH hybrid) surface.31, 41-43
Figure 4-13 Raman spectra of the as-achieved HNA, HNA-CA and HNA-CA-ECA catalysts.
Furthermore, detailed valence and oxidation states of the samples were investigated by X-ray
photoelectron spectroscopy (XPS). Their XPS survey spectra unambiguously indicate the presence of
O, Ni, C, K and Al (Figure 4-14).
Figure 4-14 XPS survey spectra. (a) HNA; (b) HNA-CA; (c) HNA-CA-ECA.
The Ni 2p high-resolution XPS spectra of the samples were shown in Figure 4-15a. In the Ni 2p
region from HNA sample, the binding energies (BEs) at 852.9 and 870.3 eV could be assigned to metallic
88
activation
Ni (Ni 2p1/2 and Ni 2p3/2, respectively, identified as “Ni0”) from the Ni-Al alloy coating, while the BE at
855.8 eV was corresponded to shakeup satellite (identified as “Sat.”) of Ni0. Notably, after the CA
process, the Ni0 peaks weakened, and two new pairs of peaks (873.2 and 855.6 eV) appeared, which
corresponded to Ni2+ from NiO present in the HNA-CA sample, indicating that spontaneous oxidation
occurs during CA.17, 18 Impressively, a comparison of the spectra of the HNA-CA-ECA sample with that
of HNA-CA clearly showed that the Ni3+ (the BEs at 875.6 and 857.9 eV) appeared with the Ni0 peaks
vanishing and the Ni2+ weakening, manifesting the acceleration of Ni0 being oxidized to NiO and
Ni(OH)2 (identified as “Ni2+”) and further oxidized NiOOH (identified as “Ni3+”) due to the large amount
of oxygen released during the ECA process in the HNA-CA-ECA catalysts.31, 33, 44
Note that the
incorporation of Ni3+ into the primitive lattice of Ni/NiO nanoparticles upon ECA, generating a local
lopsided Coulomb force, would cause a subtle atomic rearrangement, providing a large number of
electrochemical reaction active sites.10 The HR-TEM image from Figure 4-12a advantageously
demonstrated this phenomenon. In the O 1s region from the HNA-CA-ECA sample (Figure 4-15b), the
BEs at 531.8 and 530.7 eV can be indexed to oxygen-hydrogen and nickel-oxygen bonds, respectively.
The peak at 533.8 eV can be attributed to adsorbed water or possibly adsorbed O2.44 As indicated in
Figure 4-15c, the aluminum species (metal and oxide) in the aluminum-rich phase on the surface of the
HNA sample was gradually etched, while the Ni crystallites were gradually exposed to the electrolyte
and spontaneously oxidized into Ni/NiO core/shell nanostructures.45-47
Figure 4-15 The high-resolution XPS spectra of the as-achieved HNA, HNA-CA and HNA-CA-ECA catalysts.
(a) Ni 2p; (b) O 1s; (c) Al 2p and Ni 3p.
Furthermore, the ribbon-like Jamborite (Ni(OH)2/NiOOH hybrid) was obtained by further

oxidation of the mesoporous Ni/NiO-core/shell nanostructures upon ECA. The final residual aluminum
species came from the tiny exposed NiAl phase skeleton, where was not covered by the Jamborite-
(Ni(OH)2/NiOOH hybrid) nanosheets. All these XPS observations were consistent with the XRD and
TEM results and supported the successful synthesis of the nickel (oxy) hydroxide on the surface of the
HNA-CA-ECA catalysts.
In summary, the HNA-CA-ECA catalysts were fabricated by a three-step method derived from the
Ni-Al alloy (Figure 4-16, for details see the Experimental Section).
89
Figure 4-16 Schematic illustration of the synthesis procedure of HNA-CA-ECA catalysts.
4.2.3 Electrocatalytic oxygen evolution at the HNA-CA-ECA

To better characterize electrochemical performance, in addition to the evaluation of the OER
performance of the electrode in 1M KOH at RT, electrochemical tests were also conducted on a half-
cell in 6 M KOH solution and 353 K in a three-electrode configuration to meet rigorous industry
requirements. Electrochemical characterizations of NP, NF, HNA-CA, and the HNA-CA-ECA catalysts
in 1 M KOH at RT were shown in Figure 4-17.
90
activation
Figure 4-17 Electrochemical characterizations of the activated NP, NF and the as-achieved HNA-CA and HNA-
CA-ECA catalysts in 1 M KOH at RT. (a) Polarization curves with the scan rate of 1 mV s-1 ; (b) Corresponding
Tafel plots; (c) Nyquist plots; (d) Cdl curves; (e) A Chronopotentiometry test carried out at a constant current
density of 10 mA cm-2 in 1 m KOH solution.
A commercial IrO2 catalyst loaded on NF (marked as IrO2/NF) and bare NP, bare NF and HNA-
CA samples were also measured as controls. To prepare the IrO2/NF electrodes, 100 mg IrO2 (Alfa Aesar),
200 μL Nafion (Alfa Aesar), 1 mL ethanol and 1 mL deionized water were ultrasonicated for 60 min to obtain
a homogeneous dispersion. Then, three pieces of clean NFs were dipped into the dispersion, which were then
dried in air at 333 K for 6 h. The mass loading of IrO2 catalyst on nickel foam was controlled to be ca. 3 mg
91
cm-2. In order to quantitatively compare the performance of all Ni-based catalysts, polarization curves
for NP, NF, HNA-CA and the HNA-CA-ECA catalysts in 1 M KOH at RT with a scan rate of 1 mV s-1
are also obtained, as shown in Figure 4-17a. The potential required for water oxidation to obtain the
current density of 10 mA cm-2 was used to judge the OER activity. As can be concluded from Figure 4-
17a, interestingly, HNA-CA-ECA catalysts generated the OER current density of 10 mA cm-2 at a
smaller overpotential of 193 mV (with the potential of 1.423 V vs. RHE), compared to other counterparts
– NP (433 mV and 1.663 V vs. RHE.), NF (348 mV and 1.578 V vs. RHE), IrO2/NF (216 mV and 1.446
V vs. RHE) and HNA-CA (226 mV and 1.456 V vs. RHE). Therefore, based on the above observation,
the HNA-CA, especially the HAN-CA-ECA catalysts, showed an excellent OER activity with the lowest
overpotential, whereas bare NP and NF show hardly any OER activity.
Accordingly, as shown in Figure 4-17b, the HAN-CA-ECA catalysts exhibited a much smaller
Tafel slope (39 mV dec-1) compared to that of NP (128 mV dec-1), NF (95 mV dec-1), IrO2/NF (65 mV
dec-1) and HNA-CA (58 mV dec-1) catalysts, suggesting more favorable and fast-catalytic OER
kinetics (OER intermediate adsorption and desorption) for HNA-CA-ECA catalysts in an alkaline
environment compared to other counterparts due to in situ generation of well-crystallized Jamborite-
(Ni(OH)2/NiOOH hybrid) with subtle lattice distortions (Figure 4-8, Figure 4-9 and Figure 4-12a).
Figure 4-17c showed the Nyquist plots based on EIS analysis. The Nyquist plots fit well with the
equivalent circuit model presented in the inset image, where RS represented the solution resistance (i.e.
the crossover point at a high frequency with the real axis) and Rct was ascribed to the interfacial charge
transfer resistance at the catalyst/electrolyte interface, which was directly related to the catalytic kinetics.
The smaller interfacial charge transfer resistance of the HNA-CA-ECA compared to the HNA-CA
clearly indicated its better electronic transport capability and better reactant diffusivity towards the
electrode surface, which clearly justified the superior OER performance of the HNA-CA-ECA catalysts.
The unfavorable catalytic OER kinetics and electronic transport capability of HNA-CA might be
restricted by the intrinsically poor electronic conductivity of the amorphous phase (Figure 4-5)
commonly discovered between Ni and NiO in HNA-CA.1
Additionally, the electrochemical double-layer capacitance (Cdl, as shown in Figure 4-17d), which
was assumed to be directly proportional to the electrochemical active surface area (ECSA, Figure 4-18),
was ascertained from CV in a potential scan range of 1.07-1.17 V vs. RHE where the Faradic current
was negligible. The improved Cdl of HNA-CA-ECA catalysts (71.7 mF cm-2) compared to NP (0.3 mF
cm-2), NF (1.4 mF cm-2), and HNA-CA (56.3 mF cm-2) suggested a higher ECSA of HNA-CA-ECA
catalysts. The much superior ECSA of HNA-CA and HNA-CA-ECA catalysts compared to other
catalysts would likely be one of key reasons for their high OER performance. Consequently, the
hierarchically interlaced 3D network HNA-CA-ECA led to the exposure of a large number of
electroactive sites to electrolyte ions for OER, while the coexistence of mesopores (2-50 nm, between
inter-nanosheets) and macropores (> 50 nm, between inter-microspheres and micro-voids) effectively
92
activation
shortened ions transports paths and efficiently promoted ions diffusion of the electrolyte. By virtue of
its large specific surface area and hierarchical porous structure, a much superior C dl was obtained,
resulting in a promising OER performance in terms of lower overpotential and higher current density
than other Ni-based catalysts. Despite being a 3D structure, the Cdl value of HNA-CA was nearly 50
times larger than NF because of the unique hierarchically interlaced 3D mesoporous network upon CA.
The smallest Cdl value of NP compared to that of NF possessing a 3D porous morphology with a large
surface area could be attributed to its two-dimensional-planar morphology with low surface area (Figure
4-19). These results were considerably much closer to or even more superior than the earlier reports
(Table 4-1).
Figure 4-18 CV curves of bare NP (a), bare NF (b), HNA-CA (c), HNA-CA-ECA catalysts at various scan rates
(10 mV s-1, 20 mV s-1, 40 mV s-1, 60 mV s-1, 80 mV s-1, 100 mV s-1 and 120 mV s-1) in the potential range of
1.07-1.17 V vs RHE and the anodic charging current measured at 1.12 V vs RHE plotted as a function of scan
rate.
Table 4-1 Comparison of the OER performance of HNA-CA-ECA catalysts with the recently reported state-of-
the-art catalysts.
Materials (substrate) Electrolyte I/mA cm-2 η/mV Tafel slope mV dec-1 Year
HNA-CA-ECA (NP)-This work 1 M KOH 10 212 43 2020

IrO2(NF)- This work 1 M KOH 10 236 65 2020
93
CoxFe1-xN0.5 (Glass carbon)48 1 M KOH 10 266 30 2019

Ni QD@NC@rGO (Glass carbon)49 1 M KOH 10 265 65 2019
CoZn-Se (Glass carbon)50 1 M KOH 10 320 66 2019
51
CoOx-NeC/TiO2C (Glass carbon) 1 M KOH 10 220 75 2019
52
S|NiNx-PC/EG (Glass carbon) 1 M KOH 10 280 45 2019
53
NiFeMo IOS@ (NF) 1 M KOH 10 198 36 2019
54
Ni-Co3O4 nanosheets (NF) 1 M KOH 10 170 76.9 2018
55
OESSC (Stainless Steel) 1 M KOH 10 290 38 2019
Co3O4/MoS2 (NF)56 1 M KOH 10 205 45 2019
57
Co3-xAlxO4 (Glass carbon) 1 M KOH 10 248 80.6 2019
58
Ni-BDC/Ni(OH)2 (Glass carbon) 1 M KOH 10 320 41 2019
59
Ni-Co-hydroxide/Ni2P2O7 (NF) 1 M KOH 10 197 63 2019
60
Fe-Co3O4 H-NSs (NF) 1 M KOH 10 204 38 2018
61
Ni3S2 (NF) 1 M KOH 10 312 111 2018
NF@Ni/C (NF)62 1 M KOH 10 256 62 2018
63
Fe(II)-MOF-74 (NF) 1 M KOH 10 207 41.1 2019
64
IP/NP (NF) 1 M KOH 10 185 47 2019
65
NiCoSe2@NiO@CoNi2S4@CoS2(NF) 1 M KOH 10 353 159.1 2018
66
Ni3(S1-xSex)2@NiOOH (NF) 1 M KOH 10 320 48 2018
Figure 4-19 SEM images. (a and b) the bare NP; (c and d) the bare NF.
94
activation
The stability of the catalyst is another important indicator in practical devices. Hence, A
Chronopotentiometry test (Figure 4-17e) was carried out at a constant current density of 10 mA cm-2 in
1 m KOH solution to compare the operational stability of HNA-CA-ECA catalyst and that of the state-
of-the-art commercial IrO2/NF. As can be seen, the HNA-CA-ECA catalyst exhibits a remarkable
stability and completely maintains its high catalytic activity over 40 h continuous operation whereas the
IrO2/NF appears obvious attenuation (overpotential decay to 68.8%) after the stability test for 10 h.
Notably, we need to realize that HNA-CA-ECA catalyst is mainly obtained upon effective in situ ECA,
while the IrO2/NF is assembled by using traditional conductive adhesives. The sharp contrasts confirm
the outstanding durability of HNA-CA-ECA catalyst, and further demonstrate that this kind of self-
supporting electrode based on in situ ECA is an effective development to improve the stability of
catalysts, due to in situ growth of active substance—lattice-dislocated Jamborite nanosheets on the
surface of the NiAl phase framework, thus, avoiding the disadvantages of using traditional conductive
adhesives.
Furthermore, we tested the catalytic performances of HNA-CA-ECA catalysts under extreme
conditions in a concentrated KOH solution with an intermediate temperature and a very high current,
which were quite often encountered in commercial alkaline water electrolyzers. As shown in Figure 4-
20a, the long-term durability OER performance of the HNA-CA-ECA catalysts was investigated using
a chrono potentiometric method by applying a current density of 800 mA cm-2 in 6 M KOH at 353 K.
The HNA-CA-ECA catalysts exhibited exceptional stability, with almost constant overpotential of 229
mV over 168 h, indicating that the HNA-CA-ECA catalysts were catalytically stable and mechanically
robust during the harsh anodic condition. In addition, HNA-CA-ECA catalysts maintained their
morphologies after long-term electrocatalytic performance, which is indicative of its stable and good
structural properties (Figure 4-21 and Figure 4-6). The HNA-CA-ECA catalysts had the potential to
meet the long-term stability of catalytic performance for future commercial AWE at higher current
densities with the lowest overpotential. The water electrolyzer with H2 and O2 bubbles generated is
shown in Figure 4-20b.
95
Figure 4-20 The long-term durability of the HNA-CA-ECA catalysts in 6 M KOH at 353 K. (a)
Chronopotentiometry curve; (b) An optical photo showing the water electrolyzer with H2 and O2 bubbles
generated.
Figure 4-21 HR-SEM image of the HNA-CA-ECA catalysts after chronoamperometric method 168 h by
applying a current density of 800 mA cm-2 in 6 M KOH at 353 K.
4.2.4 Discussion
The above data confirmed that the promising OER catalyst, HNA-CA-ECA, was obtained upon
CA and ECA, which simply and effectively tuned the active specific surface area and intrinsic activity
of the Ni-Al alloy coating, respectively. Notably, the in situ growth of the lattice-distorted Jamborite-
(Ni(OH)2/NiOOH hybrid) upon ECA played a more critical role in improving the OER electrocatalytic
performance of the HNA-CA-ECA catalyst, therefore it deserved to be systematically explored.
The electrochemical performance of the as-prepared catalysts with different ECA times in 6 M
KOH at 353 K were shown in Figure 4-22. CV curves of HNA-CA-ECA0h, HNA-CA-ECA1h, HNA-
CA-ECA2h, and HNA-CA-ECA168h at a scan rate 5 mV s-1 were shown for comparison in Figure 4-
22a. For all the catalysts, a pair of well-defined redox peaks within 1.1-1.5 V were observable, indicating
typical pseudocapacitive behavior. The specific capacitances were correlated to the average area of a
96
activation
CV curve, which followed the order of HNA-CA-ECA0h < HNA-CA-ECA1h < HNA-CA-ECA2h <
HNA-CA-ECA168h. It was further confirmed by the Cdl of the catalysts (Figure 4-22b, Figure 4-23 and
Figure 4-24), which were 192.7, 227.1, 228.2, and 233.1 mF cm-2. The results demonstrated that the Cdl
of the catalyst only by CA (HNA-CA-ECA0h) was very ultra-huge, revealing that the process of CA
could effectively tune the active specific surface area of the catalysts due to the 3D hierarchically porous
architecture. Moreover, with the extension of ECA time, the active specific surface area gradually
increased, but not significantly, manifesting that the architecture was not destroyed during the harsh
ECA; therefore, the HNA-CA-ECA catalyst showed excellent long-lasting performance.
Figure 4-22 Electrochemical performance of the as-prepared catalysts with different ECA times in 6 M KOH at
353 K. (a) CV curves; (b) Tafel plots and Cdl.
97
Figure 4-23 CV curves of the as-prepared catalysts with different ECA time in 6 M KOH at 353K. (a) HNA-CA-
ECA0h; (b) HNA-CA-ECA1h; (c) HNA-CA-ECA2h; (d) HNA-CA-ECA168h. At various scan rates (10 mV s-1,
20 mV s-1, 40 mV s-1, 60 mV s-1, 80 mV s-1, 100 mV s-1 and 120 mV s-1) in the potential range of 1.07-1.17 V vs
RHE and the anodic charging current measured at 1.12 V vs RHE plotted as a function of scan rate.
Figure 4-24 Cdl curves of the as-prepared catalysts with different ECA time in 6 M KOH at 353K.
Furthermore, the Tafel slopes of the HNA-CA-ECA catalysts (Figure 4-25b) were calculated from
their polarization curves (Figure 4-25) to precisely describe OER catalytic kinetics, which were 39.2,
18.8, 16.4, and 16.1 mV dec-1, respectively, indicating the longer the ECA time, the more favorable
98
activation
and fast-catalytic OER catalytic kinetics. Impressively, Tafel slope of HNA-CA-ECA0h (refer to HNA-
CA) decreased by half than that of HNA-CA-ECA2h, but the Tafel slope of HNA-CA-ECA2h was
undoubtedly very close to that of HNA-CA-ECA2h, which was determined by the microstructure
transformations upon ECA. As XRD detection displayed (Figure 4-6), the peaks of NiO and Jamborite-
(Ni(OH)2/NiOOH hybrid) gradually increased and turned sharper as the ECA time increased from 0 to
2 h, suggesting that the Ni crystallites obtained by CA was rapidly oxidized to NiO during ECA and
further oxidized to the Jamborite-(Ni(OH)2/NiOOH hybrid). However, the corresponding peaks changed
slightly during the ECA time from 2 to 168 h, indicating that the above transformations were almost
completed within the first 2 h. This was particularly consistent with the OER performance from Figure
4-22b. Additionally, when a certain current density was reached, the required overpotential of the HNA-
CA-ECA catalysts gradually decreased as the ECA time increased (Figure 4-25a). For example, when
the current density of 800 mA cm-2 was applied, the overpotentials were 280, 246, 238 and 233 mV,
respectively.
Figure 4-25 (a) Polarization curves of the as-prepared catalysts with different ECA time in 6 M KOH at 353K;
(b) Corresponding Tafel plots.
Finally, although HNA-CA did not obtain a bad OER performance mainly because of the
appearance of the Ni/NiO-core/shell nanostructures and a large amount of amorphous boundaries
between them, which unfortunately ineluctably attached the obstacle of poor interparticle electron
migration during the OER process, resulting in lower OER catalytic kinetics.9 In this regard, the
concept that introducing subtle distortion of atomic arrangement into the ultrathin nanosheets was
emerged in response to the above-mentioned drawback, the benefits of which could maintain the original
electron conjugated system along the two-dimensional plane and be conducive to quick electron transfer
between the domain boundaries.
Fortunately, by in situ electrochemical transition simply upon ECA, we obtained lattice-distorted
Jamborite-(Ni(OH)2/NiOOH hybrid) nanosheets, which made HNA-CA-ECA become a promising
electrocatalyst towards OER. Regarding the causes of lattice distortion, on the one hand, as
previously-mentioned, changes in the valence state of nickel would cause local lopsided Coulomb force,
99
and the emergent micro-mechanic filed derivate disturbance would consequentially induce subtle
distortion of the atomic arrangement. On the other hand, the mechanical stress generated by the
formation and release of a large number of oxygen molecules in OER, together with the thermal stress
induced by the circumstance temperature (353 K), advantageously caused strain of the nanosheets,
thereby contributing to the formation of lattice distortions, thus finally engineering additional exposed
active sites of the HAN-CA-ECA catalysts for the OER. This conclusion could be fully verified by the
curved ribbon-like Jamborite-(Ni(OH)2/NiOOH hybrid) nanosheets appearing in the TEM image
(Figure 4-7a) of the HNA-CA-ECA catalysts.
4.3 Summary
In conclusion, an effective strategy has been developed to induce defects in the HNA-CA-ECA
catalysts, including nanostructure defects (lattice distortions) for enhancing intrinsic catalytic activity
and morphology defects (micro-voids, microchannels/microcracks, and mesopores) for increasing
active surface area and accelerating electron/ion transport, which finally, resulted in an active and stable
OER electrocatalyst. The factors of inducing lattice distortion in HNA-CA-ECA catalysts mainly
involved two aspects: one was due to the change of the valence state of nickel, causing local lopsided
Coulomb force and the emergent micro-mechanic filed derivate disturbance; the other was thanks to the
severe strain of nanosheets from the mechanical stress generated by the formation and release of a large
number of oxygen molecules in OER and the thermal stress induced by the circumstance temperature
(353 K).
Notably, the novel methodology of combining conventional thermal spray process and two-
consecutive-activation has the potential to produce large-size-electrode for AWE, which can broaden
our horizons and provide new dimensions in design of highly active and stable self-supporting OEEs.
Meanwhile, it is anticipated that a series of self-supporting electrodes can be developed using this
effective and environmentally friendly strategy.
References of Chapter IV
[1]. H. Han, H. Choi, S. Mhin, Y.-R. Hong, K. M. Kim, J. Kwon, G. Ali, K. Y. Chung, M. Je, H. N. Umh,
D.-H. Lim, K. Davey, S.-Z. Qiao, U. Paik and T. Song, Advantageous crystalline-amorphous phase boundary for
enhanced electrochemical water oxidation. Energy Environ. Sci., 2019, 12, 2443-2454.
2016, 16, 7588-7596.
[3]. T. Wang, G. Nam, Y. Jin, X. Wang, P. Ren, M. G. Kim, J. Liang, X. Wen, H. Jang, J. Han, Y. Huang, Q.
Li and J. Cho, NiFe (Oxy) Hydroxides Derived from NiFe Disulfides as an Efficient Oxygen Evolution Catalyst
for Rechargeable Zn-Air Batteries: The Effect of Surface S Residues. Adv. Mater., 2018, 30, 1800757.
[4]. B. Kim, A. Oh, M. K. Kabiraz, Y. Hong, J. Joo, H. Baik, S. I. Choi and K. Lee, NiOOH Exfoliation-
100
activation
Free Nickel Octahedra as Highly Active and Durable Electrocatalysts Toward the Oxygen Evolution Reaction in
an Alkaline Electrolyte. ACS Appl. Mater. Interfaces, 2018, 10, 10115-10122.
[6]. T. Zhang, M.-Y. Wu, D.-Y. Yan, J. Mao, H. Liu, W.-B. Hu, X.-W. Du, T. Ling and S.-Z. Qiao,
Engineering oxygen vacancy on NiO nanorod arrays for alkaline hydrogen evolution. Nano Energy, 2018, 43, 103-
109.
[7]. S. H. Chang, N. Danilovic, K. C. Chang, R. Subbaraman, A. P. Paulikas, D. D. Fong, M. J. Highland, P.
M. Baldo, V. R. Stamenkovic, J. W. Freeland, J. A. Eastman and N. M. Markovic, Functional links between stability
and reactivity of strontium ruthenate single crystals during oxygen evolution. Nat. Commun., 2014, 5, 4191.
[8]. Y. Zhao, X. Jia, G. Chen, L. Shang, G. I. Waterhouse, L. Z. Wu, C. H. Tung, D. O'Hare and T. Zhang,
Ultrafine NiO Nanosheets Stabilized by TiO2 from Monolayer NiTi-LDH Precursors: An Active Water Oxidation
Electrocatalyst. JACS, 2016, 138, 6517-6524.
[9]. Y. Liu, Hua, X., Xiao, C., Zhou, T., Huang, P., Guo, Z. & Xie, Y. , Heterogeneous spin states in ultrathin
nanosheets induce subtle lattice distortion to trigger efficient hydrogen evolution. JACS, 2016, 138, 5087-5092.
[10]. Y. Jiao, W. Hong, P. Li, L. Wang and G. Chen, Metal-organic framework derived Ni/NiO micro-particles
with subtle lattice distortions for high-performance electrocatalyst and supercapacitor. Appl. Catal. B-
Environmental, 2019, 244, 732-739.
[11]. A. E. Dorfi, A. C. West and D. V. Esposito, Quantifying Losses in Photoelectrode Performance Due to
Single Hydrogen Bubbles. J. Phys. Chem. C, 2017, 121, 26587-26597.
[12]. Z. Lu, W. Zhu, X. Yu, H. Zhang, Y. Li, X. Sun, X. Wang, H. Wang, J. Wang, J. Luo, X. Lei and L. Jiang,
Ultrahigh hydrogen evolution performance of under-water "superaerophobic" MoS2 nanostructured electrodes.
Adv. Mater., 2014, 26, 2683-2687.
[13]. X. Huang, S. Chang, W. S. V. Lee, J. Ding and J. M. Xue, Three-dimensional printed cellular stainless
steel as a high-activity catalytic electrode for oxygen evolution. J. Mater. Chem. A, 2017, 5, 18176-18182.
[14]. S. Chang, Huang, X., Ong, C. Y. A., Zhao, L., Li, L., Wang, X., & Ding, J. , High loading accessible
active sites via designable 3D-printed metal architecture towards promoting electrocatalytic performance. J. Mater.
Chem. A, 2019, 7, 18338-18347.
3, 122-133.
Commun., 2016, 7, 12324.
1900113.
[18]. M. Zhang, Z. Huang, Z. Shen, Y. Gong, B. Chi, J. Pu and J. Li, High-Performance Aqueous
Rechargeable Li-Ni Battery Based on Ni(OH)2/NiOOH Redox Couple with High Voltage. Adv. Energy Mater.,
2017, 7, 1700155.
[19]. T. Jiang, S.-A. Ansar, X. Yan, C. Chen, X. Fan, F. Razmjooei, R. Reisser, G. Montavon and H. Liao, In
Situ Electrochemical Activation of a Codoped Heterogeneous System as High Efficient Catalyst for Oxygen
Evolution Reaction in Alkaline Water Electrolysis. ACS Appl. Energy Mater., 2019, 2, 8809-8817.
101
[20]. G. Schiller, Henne, R., & Borck, V., Vacuum plasma spraying of high-performance electrodes for
alkaline water electrolysis. J. Therm. Spray Technol., 1995, 4, 185-194.
[21]. M. Aghasibeig, A. Dolatabadi, R. Wuthrich and C. Moreau, Three-dimensional electrode coatings for
hydrogen production manufactured by combined atmospheric and suspension plasma spray. Surf. Coat. Technol.,
2016, 291, 348-355.
[22]. M. Aghasibeig, H. Monajatizadeh, P. Bocher, A. Dolatabadi, R. Wuthrich and C. Moreau, Cold spray as
a novel method for development of nickel electrode coatings for hydrogen production. Int. J. Hydrogen Energy,
2016, 41, 227-238.
[23]. M. Aghasibeig, C. Moreau, A. Dolatabadi and R. Wuthrich, Fabrication of nickel electrode coatings by
combination of atmospheric and suspension plasma spray processes. Surf. Coat. Technol., 2016, 285, 68-76.
[24]. M. Aghasibeig, C. Moreau, A. Dolatabadi and R. Wuthrich, Engineered Three-Dimensional Electrodes
by HVOF Process for Hydrogen Production. J. Therm. Spray Technol., 2016, 25, 1561-1569.
[25]. M. Aghasibeig, M. Mousavi, F. Ben Ettouill, C. Moreau, R. Wuthrich and A. Dolatabadi,
Electrocatalytically Active Nickel-Based Electrode Coatings Formed by Atmospheric and Suspension Plasma
Spraying. J. Therm. Spray Technol., 2013, 23, 220-226.
[26]. M. Robotti, S. Dosta, M. Gardon, I. G. Cano, J. M. Guilemany, M. Kourasi, B. Mellor and R. Wills,
Enhancing the performance of common electrode materials by means of atmospheric plasma spray coatings.
Journal of Energy Storage, 2016, 5, 127-133.
[27]. A. Vardelle, C. Moreau, J. Akedo, H. Ashrafizadeh, C. C. Berndt, J. O. Berghaus, M. Boulos, J. Brogan,
A. C. Bourtsalas and A. Dolatabadi, The 2016 thermal spray roadmap. J. Therm. Spray Technol., 2016, 25, 1376-
1440.
[28]. A. H. White, The volumetric estimation of alumina, and free and combined sulphuric acid in alums.
JACS, 1902, 24, 457-466.
[30]. C. Tang, N. Cheng, Z. Pu, W. Xing and X. Sun, NiSe Nanowire Film Supported on Nickel Foam: An
Efficient and Stable 3D Bifunctional Electrode for Full Water Splitting. Angew. Chem. Int. Ed. Engl., 2015, 54,
9351-9355.
[31]. X. Xiong, D. Ding, D. Chen, G. Waller, Y. Bu, Z. Wang and M. Liu, Three-dimensional ultrathin
Ni(OH)2 nanosheets grown on nickel foam for high-performance supercapacitors. Nano Energy, 2015, 11, 154-
161.
2676.
2018, 54, 4987-4990.
[34]. R. Wang, Zhilong Lu, and Tsun Ko, The structural transitions during leaching of Ni 2Al3 phase in a Raney
Ni-Al alloy. Journal of materials science, 2001, 36, 5649-5657.
[35]. C. Xia, H. Liang, J. Zhu, U. Schwingenschlögl and H. N. Alshareef, Active Edge Sites Engineering in
Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution. Adv. Energy Mater., 2017, 7,
1602089.
102
activation
[36]. Y. Teng, X.-D. Wang, J.-F. Liao, W.-G. Li, H.-Y. Chen, Y.-J. Dong and D.-B. Kuang, Atomically Thin
Defect-Rich Fe-Mn-O Hybrid Nanosheets as High Efficient Electrocatalyst for Water Oxidation. Adv. Funct.
Mater., 2018, 28, 1802463.
[37]. X. Zhang, X. Sun, S.-X. Guo, A. M. Bond and J. Zhang, Formation of lattice-dislocated bismuth
nanowires on copper foam for enhanced electrocatalytic CO2 reduction at low overpotential. Energy Environ. Sci.,
2019, 12, 1334-1340.
[38]. Y. Zhong, H. Huang, K. Wang, Z. He, S. Zhu, L. Chang, H. Shao, J. Wang and C.-n. Cao, NiO@MnO2
core-shell composite microtube arrays for high-performance lithium ion batteries. RSC ADV, 2017, 7, 4840-4847.
[39]. H. Wu, G. Wu, Q. Wu and L. Wang, Facile synthesis and microwave absorbability of C@Ni-NiO core-
shell hybrid solid sphere and multi-shelled NiO hollow sphere. Mater. Charact., 2014, 97, 18-26.
[40]. Y. Shen, X. Yan, Z. Bai, X. Zheng, Y. Sun, Y. Liu, P. Lin, X. Chen and Y. Zhang, A self-powered
ultraviolet photodetector based on solution-processed p-NiO/n-ZnO nanorod array heterojunction. RSC ADV, 2015,
5, 5976-5981.
[42]. B. J. Trzesniewski, O. Diaz-Morales, D. A. Vermaas, A. Longo, W. Bras, M. T. Koper and W. A. Smith,
In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect
of pH on Electrochemical Activity. J. Am. Chem. Soc., 2015, 137, 15112-15121.
[43]. S. H. Yanshuo Jin, Xin Yue, Hongyu Du, and Pei Kang Shen, Mo-and Fe-modified Ni(OH)2/NiOOH
nanosheets as highly active and stable electrocatalysts for oxygen evolution reaction. ACS Catal., 2018, 8, 2359-
2363.
[45]. F. Devred, A. H. Gieske, N. Adkins, U. Dahlborg, C. M. Bao, M. Calvo-Dahlborg, J. W. Bakker and B.
E. Nieuwenhuys, Influence of phase composition and particle size of atomised Ni-Al alloy samples on the catalytic
performance of Raney-type nickel catalysts. Appl. Catal. A-Gen., 2009, 356, 154-161.
[46]. H. Lei, Song, Z., Tan, D., Bao, X., Mu, X., Zong, B., & Min, E. , Preparation of novel Raney-Ni catalysts
and characterization by XPS. Appl. Catal. A-Gen., 2001, 214, 69-76.
[47]. H. Hu, Qiao, M., Xie, F., Fan, K., Lei, H., Tan, D., ... & Zhang, X., Comparative X-ray Photoelectron
Spectroscopic Study on the Desulfurization of Thiophene. J. Phys. Chem. B, 2005, 109, 5186-5192.
[48]. L. An, J. Feng, Y. Zhang, Y.-Q. Zhao, R. Si, G.-C. Wang, F. Cheng, P. Xi and S. Sun, Controllable tuning
of Fe-N nanosheets by Co substitution for enhanced oxygen evolution reaction. Nano Energy, 2019, 57, 644-652.
223.
[50]. G. Fang, Q. Wang, J. Zhou, Y. Lei, Z. Chen, Z. Wang, A. Pan and S. Liang, Metal Organic Framework-
Templated Synthesis of Bimetallic Selenides with Rich Phase Boundaries for Sodium-Ion Storage and Oxygen
Evolution Reaction. ACS Nano, 2019, 13, 5635-5645.
[51]. L. He, J. Liu, B. Hu, Y. Liu, B. Cui, D. Peng, Z. Zhang, S. Wu and B. Liu, Cobalt oxide doped with
titanium dioxide and embedded with carbon nanotubes and graphene-like nanosheets for efficient trifunctional
electrocatalyst of hydrogen evolution, oxygen reduction, and oxygen evolution reaction. J. Power Sources, 2019,
103
414, 333-344.
[52]. Y. Hou, M. Qiu, M. G. Kim, P. Liu, G. Nam, T. Zhang, X. Zhuang, B. Yang, J. Cho, M. Chen, C. Yuan,
L. Lei and X. Feng, Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets
for efficient water oxidation. Nat. Commun., 2019, 10, 1392.
[54]. L. Zeng, K. Zhou, L. Yang, G. Du, L. Liu and W. Zhou, General Approach of in Situ Etching and Doping
To Synthesize a Nickel-Doped MxOy (M=Co, Mn, Fe) Nanosheets Array on Nickel Foam as Large-Sized
Electrodes for Overall Water Splitting. ACS Appl. Energy Mater., 2018, 1, 6279-6287.
Environmental, 2019, 248, 277-285.
[56]. A. Muthurasu, V. Maruthapandian and H. Y. Kim, Metal-organic framework derived Co3O4/MoS2
heterostructure for efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution
[57]. X. Wang, P. Sun, H. Lu, K. Tang, Q. Li, C. Wang, Z. Mao, T. Ali and C. Yan, Aluminum-Tailored Energy
Level and Morphology of Co3-xAlxO4 Porous Nanosheets toward Highly Efficient Electrocatalysts for Water
Oxidation. Small, 2019, 15, e1804886.
[58]. D. Zhu, J. Liu, L. Wang, Y. Du, Y. Zheng, K. Davey and S. Z. Qiao, A 2D metal-organic
framework/Ni(OH)2 heterostructure for an enhanced oxygen evolution reaction. Nanoscale, 2019, 11, 3599-3605.
[59]. N. R. Chodankar, I. V. Bagal, S. W. Ryu, Y. K. Han and D. H. Kim, Nano-Micro-Structured Nickel-
Cobalt Hydroxide/Ni2P2O7 Assembly on Nickel Foam: An Outstanding Electrocatalyst for Alkaline Oxygen
Evolution Reaction. ChemCatChem, 2019, 11, 4256-4261.
238-250.
[61]. G. Ren, Q. Hao, J. Mao, L. Liang, H. Liu, C. Liu and J. Zhang, Ultrafast fabrication of nickel sulfide
film on Ni foam for efficient overall water splitting. Nanoscale, 2018, 10, 17347-17353.
[62]. H. Sun, Y. Lian, C. Yang, L. Xiong, P. Qi, Q. Mu, X. Zhao, J. Guo, Z. Deng and Y. Peng, A hierarchical
nickel-carbon structure templated by metal-organic frameworks for efficient overall water splitting. Energy
Environ. Sci., 2018, 11, 2363-2371.
[63]. Q. Wang, F. Wei, D. Manoj, Z. Zhang, J. Xiao, X. Zhao, F. Xiao, H. Wang and S. Wang, In situ growth
of Fe(ii)-MOF-74 nanoarrays on nickel foam as an efficient electrocatalytic electrode for water oxidation: a
mechanistic study on valence engineering. Chem. Commun., 2019, 55, 11307-11310.
[64]. X. Xu, X. Tian, Z. Zhong, L. Kang and J. Yao, In-situ growth of iron/nickel phosphides hybrid on nickel
foam as bifunctional electrocatalyst for overall water splitting. J. Power Sources, 2019, 424, 42-51.
104
activation
105
106
Chapter V Electrochemical characterizations of dynamic self-optimized catalysts in hydrogen evolution reaction and
overall water splitting
Chapter V Electrochemical characterizations of dynamic

self-optimized catalysts in hydrogen evolution reaction and
5.1 Introduction
Efficient development of low-cost bifunctional electrocatalysts with superior activity for both the
sluggish anodic OER and the fairly facile cathodic hydrogen evolution reaction (HER) is of great
importance for the widespread application of the water-splitting technique.1-6 Unfortunately, active OER
catalysts generally work well in a neutral or basic medium, whereas most HER catalysts perform better
in an acidic medium, which complicates the water-splitting system due to requirements for different
accessories and preparation and optimization procedures.7-12 Thus, the search for cost-efficient
bifunctional catalysts with high activity for a full water-splitting cell in the same electrolyte is of key
importance.13-16 The evolution of bifunctional electrocatalysts has diminished the complexity of catalytic
setup and further reduced the overall cost because a single electrolyte, single electrocatalyst, and single
container are utilized in this system, which could greatly facilitate the advancement of hydrogen
technologies.1, 17-20
In situ ECA, as a new pretreating technique for enhanced catalytic performance for water splitting,
mainly comprises electrochemical processes such as OER17, 21-46 and HER17, 23-25, 27, 47-49. The in situ ECA
strategy utilizes as-prepared materials as precatalysts to create active species on surfaces in situ, which
yields a stronger binding force between scaffolds and active films. Such a unique hybrid structure may
be beneficial for faster electron transportation and structural stability. Additionally, during in situ ECA
treatments, the catalyst surfaces are modified from the bulk phase, which can allow for tuning local
electronic structures, creating more active species, increasing surface area and thus improving catalytic
performance. This technique can also couple atomic, electronic structures with electrocatalysis
mechanisms for water splitting. Therefore, in situ ECA techniques show advantages over traditional
optimization treatments, such as facile operation, variable control, high efficiency, flexibility, and being
eco-friendly.50
Notably, in situ ECA is a dynamically self-optimizing (DSO) mechanism. It has gradually come to
be used as a strategy for developing bifunctional electrocatalysts17, 23-27, 51 for efficient and durable
overall water splitting because these special precatalysts can be dynamically self-optimized under both
the anodic and cathodic environments, inducing high-active substance catalyzing water splitting grown
in situ on the surface of the precatalysts.
In the work presented in this chapter, we developed HEEs (marked as H-NF@CGO, H-HNA-CA)
by DSO of the precatalysts (NF@CGO and HNA-CA), and coupled them with previously discussed
107
OEEs (marked as O-NF@CGO and O-HNA-CA, respectively) to form two-electrode configurations (O-
NF@CGO(+)||H-NF@CGO(-), O-HNA-CA(+)||H-HNA-CA(-)). These two-electrode configurations were
both compared with the integrated state-of-the-art IrO2/NF(+)||Pt foil(-) electrode by electrochemical
characterizations in alkaline overall water splitting.
5.2 Electrochemical characterization of the activated NF@CGO
electrocatalyst in HER and overall water splitting
5.2.1 Electrocatalytic hydrogen evolution of the H-NF@CGO

The HER electrocatalytic performance of the H-NF@CGO was investigated using a typical three-
electrode configuration with Hydrogen Reference Electrode HydroFlex (Gaskatel GmbH, Germany)
and with the commercial NF as reference electrode and counter electrode, respectively. The H-
NF@CGO was activated by a one-hour Chronopotentiometry test at a current density of −800 mA cm-2
with the conditions of 6 M KOH at 353 K in the three-electrode electrochemical test system. In order to
ensure the effective comparison of data, H-NF, H-NF@N, H-NF@GO and Pt foil were also activated
under the same conditions. H-NF@CGO was performed in 1 M KOH by polarization curve with H-NF,
H-NF@N, H-NF@GO, and Pt foil as comparisons. The corresponding iR-corrected polarization curves
for the five samples are shown in Figure 5-1a. As expected, the NF exhibits fairly poor activity toward
HER with −100 mA cm-2 current response up to ca. −365 mV vs. RHE, while H-NF@CGO shows high-
performance HER activity with a low potential of −265 mV vs. RHE, which is much more positive than
H-NF@N (−339 mV vs. RHE) and H-NF@GO (−306 mV vs. RHE). In particular, Pt foil reached a very
high potential −354 mV vs. RHE, yielding a current density of −100 mA cm-2. Taking the catalytic
current density of 10 mA cm-2 for direct comparison, H-NF@CGO requires only −138 mV overpotential,
while H-NF, H-NF@N, H-NF@GO and Pt foil require overpotential (ƞ) of −237, −210, −181, and −170
mV, respectively, suggesting the superior electrocatalytic H2-evolving activity of H-NF@CGO. This
overpotential contrasts favorably with that of the commercial Pt and those previously reported for non-
precious metal-based HER catalysts in alkaline media.48, 52-65 Accordingly, H-NF@CGO exhibits a small
Tafel slope of 42.6 mV dec-1 (Figure 5-1b), which is much lower than those for H-NF (216.2 mV dec-
1
), H-NF@N (75.8 mV dec-1), H-NF@GO (51.9 mV dec-1) and state-of-the-art Pt foil (82.1 mV dec-1),
demonstrating the faster HER kinetics of H-NF@GO.
108
Figure 5-1 (a) Polarization curves for NF, NF@N, NF@GO, Pt foil and H-NF@CGO at a scan rate of 2 mV s-1
(iR-corrected). (b) The corresponding Tafel slope plots derived from (a).
Additionally, the electrode kinetics for HER were further measured by electrochemical impedance
spectroscopy (EIS), as shown in Figure 5-2. The H-NF@CGO exhibits much lower charge transfer
resistance than H-NF@GO, state-of-the-art Pt foil, H-NF@N, and H-NF confirming the more favorable
HER kinetics of the H-NF@CGO. The incorporation of GO and Co3O4 into Ni crystals possibly induces
significantly enhanced HER activity in comparison to the individual H-NF@N, suggesting the
synergistic effect of Ni, GO, and Co3O4 for HER. Moreover, the synergy between the restructuring
NF@CGO skeletons and their supported newly constructed active phases may also promote the catalytic
activity of the H-NF@CGO.
109
Figure 5-2 Nyquist plots of NF, NF@N, NF@GO, Pt foil and H-NF@CGO in1 M KOH at an overpotential of
−150 mV.
To further understand the superior HER catalytic activity of H-NF@CGO, the electrochemically
active surface areas (ECSAs) of the prepared catalysts were measured, as shown in Figure 5-3(a−c).
Briefly, the ECSAs were determined through capacitance measurements using a simple cyclic
voltammetry (CV) method in the non-Faradaic region of 0−0.10 V vs RHE. Based on the measured
capacitances (1/2 slope, Figure 5-3d), which are proportional to the effective active surface areas, the
Cdl value of H-NF@CGO (18.09 mF cm-2) is significantly higher than that of H-NF (1.36 mF cm-2) and
Pt foil (4.82 mF cm-2), suggesting that H-NF@CGO has a much larger ECSA. This result demonstrates
that the large ECSA resulting from the constructional features of the H-NF@CGO contributes to its high
catalytic activity.
110
Figure 5-3 CV curves of H-NF (a); Pt foil (b); H-NF@CGO (c); Corresponding Cdl curves. CV curves at various
scan rates (10 mV s-1, 20 mV s-1, 40 mV s-1, 60 mV s-1, 80 mV s-1, 100 mV s-1 and 120 mV s-1) in the potential
range of 0−0.10 V vs RHE and the anodic charging current measured at 0.05 V vs RHE plotted as a function of
scan rate.
The stability of the catalyst is another important indicator in practical devices. Hence, a
Chronoamperometry test (Figure 5-4) was carried out at a constant current density of −100 mA cm-2 in
1 M KOH solution to compare the operational stability of the H-NF@CGO catalyst with that of the
state-of-the-art commercial Pt foil. As can be seen, the H-NF@CGO catalyst exhibited a remarkable
stability and completely maintained its high catalytic activity at 8 hours of continuous operation,
whereas the Pt foil displayed obvious attenuation (overpotential decay to 16.1%) after the stability test
for 8 hours. Notably, the self-supported H-NF@CGO catalyst is mainly obtained upon simple and
effective in situ ECA based on HER. The sharp contrasts confirm the outstanding durability of H-
NF@CGO catalyst, and further demonstrate that this kind of self-supporting electrode based on in situ
ECA is an effective development for improving the stability of catalysts. This is due to in situ growth of
active substances on the surface of the 3D porous NF@CGO framework, which avoids the
disadvantages of using traditional conductive adhesives.
111
Figure 5-4 A Chronopotentiometry test of H-NF@CGO and Pt foil carried out at a constant current density of
−100 mA cm-2 in 1 m KOH solution.
All of the above results reveal the highly efficient and robust stability of the self-supported H-
NF@CGO cathode. Such an enhanced HER catalytic performance compared with unmodified materials
(bare NF) could be rationalized as follows. (1) The self-supported design with good substrate adhesion
removes the extra electrical resistance raised by binders, leads to a better electrical connection and
promotes electron transport. (2) A mild evolution of H2 gas bubbles drives in situ structural
rearrangement and results in a highly porous structure with exposed active edges possessing sites with
fairly high activity. (3) The interconnected hierarchical architectures of 3D NF@CGO facilitate fast
mass transport and electrolyte penetration and allow efficient accessibility of more surface area as well
as active sites for electrocatalytic reaction. (4) The synergy between Ni, GO, and Co3O4, and the
promoting effect of the restructuring NF@CGO skeletons also contributes to the enhanced HER
catalytic activity and high durability of the porous H-NF@CGO electrode.
5.2.2 O-NF@CGO(+)||H-NF@CGO(-) electrocatalytic overall water
splitting
Encouraged by the exceptional activity and stability of the DSO NF@CGO for OER and HER, an
112
alkaline water electrolyzer was constructed by applying O-NF@CGO and H-NF@CGO as anode and
cathode materials. Notably, an overall water splitting current density of 10 mA cm-2 was attained at only
1.68 V vs. RHE cell potential (polarization curve) in the two-electrode configuration, while NP
(NP(+)||NP(-)), NF (NF(+)||NF(-)), and state-of-the-art commercial (IrO2/NF(+)||Pt(-)) required cell potentials
of 1.88 V vs. RHE, 1.82 V vs. RHE, and 1.72 V vs. RHE, respectively, suggesting the superior
electrocatalytic O2−H2-evolving activity of the DSO NF@CGO (Figure 5-5 a). To the best of our
knowledge, DSO NF@CGO is comparable with other noble−free metal-based bifunctional catalysts
reported to date.24, 25, 27
Additionally, the two-electrode configuration kinetics for overall water splitting were further
measured by EIS, as shown in Figure 5-5 b. The DSO NF@CGO (O-NF@CGO (+)||H-NF@CGO(-))
exhibits much lower charge transfer resistance than NP (NP(+)||NP(-)) and NF (NF(+)||NF(-)), and is
comparable with state-of-the-art commercial (IrO2/NF(+)||Pt(-)), confirming the favorable overall water
splitting kinetics of the DSO NF@CGO (O-NF@CGO (+)||H-NF@CGO(-)). The synergy between the
restructuring NF@CGO skeletons and their supported newly constructed active phases upon DSO may
promote the catalytic activity of the DSO NF@CGO (O-NF@CGO (+)||H-NF@CGO(-)).
Figure 5-5 Overall water splitting bifunctional activities of the DSO NF@CGO (O-NF@CGO (+)||H-
NF@CGO(-)) in a two-electrode configuration in1 M KOH. (a) Polarization curves at a scan rate of 2 mV s-1; (b)
Nyquist plots at an overpotential of 300 mV. NP (NP(+)||NP(-)), NF (NF(+)||NF(-)) and state-of-the-art commercial
(IrO2/NF(+)||Pt(-)) for comparison.
Moreover, when a constant current density of 10 mA cm-2 was applied across the anode and cathode
to monitor the durability of the DSO NF@CGO (O-NF@CGO (+)||H-NF@CGO(-)), almost no activity
loss was observed over a period of 26 hours with a lower overpotential ca. 460 mV (Figure 5-6), which
indicates the excellent catalytic activity and exceptional robustness of the DSO NF@CGO electrodes in
comparison with state-of-the-art commercial (IrO2/NF(+)||Pt(-)) (with overpotential ca. 610 mV only over
a period of 12 hours), and NF(+)||NF(-) (with overpotential ca. 700 mV over a period of 6 hours).
113
Figure 5-6 A Chronopotentiometry test of the DSO NF@CGO (O-NF@CGO (+)||H-NF@CGO(-)) carried out at a
constant current density of 10 mA cm-2 in 1 M KOH solution. NF (NF(+)||NF(-)) and state-of-the-art commercial
In summary, H-NF@CGO was prepared by dynamic self-optimization of the fresh NF@CGO to

effectively catalyze HER. The resultant H-NF@CGO catalyst exhibited exceptional HER performance.
(+)
In addition, the DSO NF@CGO (O-NF@CGO ||H-NF@CGO(-)) delivered excellent activity and
stability when applied as the cathode and anode for HER and OER, and the attained activity levels
surpass those of well-known state-of-the-art noble metal-based catalysts.
5.3 Electrochemical characterization of the activated HNA-CA
electrocatalyst in HER and overall water splitting
5.3.1 Electrocatalytic hydrogen evolution of the H-HNA-CA

The HER electrocatalytic performance of the H-HNA-CA was investigated using a typical three-
electrode configuration with Hydrogen Reference Electrode HydroFlex (Gaskatel GmbH, Germany)
and commercial IrO2/NF used as reference electrode and counter electrode, respectively. The H-HNA-
CA was activated by a one-hour Chronopotentiometry test at a current density of −800 mA cm-2 with
the conditions of 6 M KOH at 353 K in the three-electrode electrochemical test system. In order to
ensure effective comparison of data, NP, NF, HNA-CA and Pt foil also were activated under the same
condition. H-HNA-CA was performed in 1 M KOH by polarization curve with NP, NF, HNA-CA, and
Pt foil as a comparison. The corresponding iR-corrected polarization curves on the five surfaces are
shown in Figure 5-7a. As expected, the NP and NF both exhibit fairly poor activity toward HER with -
100 mA cm-2 current response up to ca. −302 mV and −290 mV vs. RHE, respectively, while H-HNA-
CA shows high-performance HER activity with a low potential of −87 mV vs. RHE, which is much
more positive than HNA-CA (−106 mV vs. RHE). Notably, the potential required for H-HNA-CA is
114
less than that of Pt foil (−94 mV vs. RHE), to deliver current density of −100 mA cm-2. Taking the
catalytic current density of 10 mA cm-2 for direct comparison, HNA-CA and H-HNA-CA both require
an ultralow overpotential of ca. −20 mV, while NP and NF require very high overpotentials of −195 mV
and −168 mV, respectively, and that of Pt foil is 51.9 mV, suggesting the superior electrocatalytic H2-
evolving activity of H-HNA-CA. This overpotential contrasts favorably with the commercial Pt and
most values previously reported for HER catalysts.66-73 Accordingly, HNA-CA and H-HNA-CA exhibit
very small Tafel slopes of 25.7 mV dec-1 and 28.2 mV dec-1 (Figure 5-7b), which are much lower than
those of NP (251.2 mV dec-1), NF (194.3 mV dec-1), and state-of-the-art Pt foil (57.5 mV dec-1),
demonstrating the faster HER kinetics of HNA-CA, especially for H-HNA-CA.
Figure 5-7 (a) Polarization curves for NP, NF, HNA-CA, Pt foil and H-HNA-CA at a scan rate of 2 mV s-1 (iR-
corrected). (b) The corresponding Tafel slope plots derived from (a).
Additionally, the electrode kinetics for HER was further measured by EIS, as shown in Figure 5-8.
Obviously, the H-HNA-CA exhibits much lower charge transfer resistance than HNA-CA, NF, and NP.
Moreover, the charge transfer resistance of H-HNA-CA rivals the state-of-the-art Pt foil, confirming the
favorable HER kinetics of the H-NF@CGO. The 3D hierarchical porous NiAl framework and the active
substance induced by DSO upon HER possibly ensure significantly enhanced HER activity in
comparison to the individual HNA-CA. Moreover, the synergy between the restructuring HNA-CA
skeletons and their supported newly constructed active phases may also promote the catalytic activity
of the H-HNA-CA.
115
Figure 5-8 Nyquist plots of NP, NF, HNA-CA, Pt foil and H-HNA-CA in1 M KOH at an overpotential of −150
mV.
To further understand the superior HER catalytic activity of H-HNA-CA, the ECSAs of the
prepared catalysts were measured, as shown in Figure 5-9. Briefly, the ECSA was determined through
capacitance measurements using the CV method in the non-Faradaic region of −0.09-0.03 V vs RHE.
Based on the measured capacitances (1/2 slope, Figure 5-10), which are proportional to the effective
ECSA, the Cdl value of H-HNA-CA (30.88 mF cm-2) is significantly higher than that of HNA-CA (8.18
mF cm-2), suggesting that H-HNA-CA has a much larger ECSA. This result demonstrates that the large
ECSA resulting from the constructional features of the H-HNA-CA contributes to its high catalytic
activity.
116
Figure 5-9 CV curves (a) HNA-CA; (b) H-HNA-CA. CV curves at various scan rates (10 mV s-1, 20 mV s-1, 40
mV s-1, 60 mV s-1, 80 mV s-1, 100 mV s-1 and 120 mV s-1) in the potential range of −0.09-0.03 V vs RHE and the
anodic charging current measured at −0.05 V vs RHE plotted as a function of scan rate.
Figure 5-10 The corresponding Cdl curves derived from Figure 5-9.
The stability of the catalyst is another important indicator in practical devices. Hence, a
Chronopotentiometry test (Figure 5-11) was carried out at a constant current density of −10 mA cm-2 in
1 M KOH solution to compare the operational stability of the H-HNA-CA catalyst and that of state-of-
the-art commercial Pt foil. As can be seen, the H-HNA-CA catalyst exhibited a remarkable stability and
117
completely maintained its high catalytic activity over 24 hours of continuous operation whereas the Pt
foil displayed obvious attenuation after the stability test for 12 h. Notably, the self-supported H-HNA-
CA catalyst is mainly obtained upon simple and effective in situ ECA based on HER. The sharp contrasts
confirm the outstanding durability of the H-HNA-CA catalyst, and further demonstrate that this kind of
self-supporting electrode based on in situ ECA is an effective development toward improve the stability
of catalysts, due to in situ growth of the active substance on the surface of the 3D hierarchical porous
NiAl framework, which avoids the disadvantages of using traditional conductive adhesives.
Figure 5-11 A Chronopotentiometry test of H-HNA-CA and Pt foil carried out at a constant current density of
−10 mA cm-2 in 1 m KOH solution.
All of the above results reveal the highly efficient and robust stability of the self-supported H-
HNA-CA cathode. Such an enhanced HER catalytic performance compared with unmodified materials
(bare NP) could be rationalized as follows. (1) The self-supported design with good substrate adhesion
removes the extra electrical resistance raised by binders, leads to a better electrical connection, and
promotes electron transport. (2) A mild evolution of H2 gas bubbles upon DSO based on HER drives in
situ structural rearrangement and results in a highly porous structure with exposed active edges
possessing sites with fairly high activity. (3) The 3D hierarchical H-HNA-CA facilitates fast mass
transport and electrolyte penetration and allows efficient accessibility of more surface area as well as
active sites for electrocatalytic reactions. (4) The active substance generated in situ over the restructuring
118
NiAl skeletons also contributes to the enhanced HER catalytic activity and high durability of the 3D
self-supported H-HNA-CA electrode.
5.3.2 O-HNA-CA(+)||H-HNA-CA(-) electrocatalytic overall water
splitting
Encouraged by the exceptional activity and stability of the DSO HNA-CA for OER and HER, we
attempted to construct an alkaline water electrolyzer by applying the O-HNA-CA and H-HNA-CA as
anode and cathode materials. Surprisingly, an overall water splitting current density of 10 mA cm-2 was
attained at an extremely low cell potential of 1.49 V vs. RHE (polarization curve) in the two-electrode
configuration, while NP (NP(+)||NP(-)), NF (NF(+)||NF(-)), and state-of-the-art commercial (IrO2/NF(+)||Pt(-))
required cell potential of 1.88 V vs. RHE, 1.82 V vs. RHE, and 1.72 V vs. RHE, respectively, suggesting
the superior electrocatalytic O2-H2-evolving activity of the DSO HNA-CA (Figure 5-12a). To the best
of our knowledge, DSO HNA-CA is comparable with other noble-free metal based bifunctional catalysts
reported to date.24, 25, 27
Additionally, the two-electrode configuration kinetics for overall water splitting were further
measured by EIS, as shown in Figure 5-12b. The DSO HNA-CA (O-HNA-CA(+)||H-HNA-CA(-))
exhibits much lower charge transfer resistance than NP (NP(+)||NP(-)) and NF (NF(+)||NF(-)), and is
comparable with state-of-the-art commercial (IrO2/NF(+)||Pt(-)), confirming the favorable overall water
splitting kinetics of the DSO HNA-CA (O-HNA-CA(+)||H-HNA-CA(-)). The synergy between the
restructuring NiAl skeletons and their supported newly constructed active phases upon DSO may
promote the catalytic activity of the DSO HNA-CA (O-HNA-CA(+)||H-HNA-CA(-)).
Figure 5-12 Overall water splitting bifunctional activities of the DSO HNA-CA (O-HNA-CA (+)||H-HNA-CA (-))
in a two-electrode configuration in1 M KOH. (a) Polarization curves at a scan rate of 2 mV s-1; (b) Nyquist plots
at an overpotential of 300 mV. NP (NP(+)||NP(-)), NF (NF(+)||NF(-)) and state-of-the-art commercial
In addition, when a constant current density of 10 mA cm-2 was applied across the anode and
119
cathode to monitor the durability of the DSO HNA-CA (O-HNA-CA(+)||H-HNA-CA(-)), almost no

activity loss was observed over a period of 69 hours with a lower overpotential ca. 350 mV (Figure 5-
6), which renders the excellent catalytic activity and exceptional robustness of the DSO HNA-CA
electrodes in comparison to state-of-the-art commercial (IrO2/NF(+)||Pt(-)) (with a overpotential ca. 610
mV only over a period of 12 hours), and NF(+)||NF(-) (with a overpotential ca. 700 mV over a period of
6 hours).
Figure 5-13 A Chronopotentiometry test of the DSO HNA-CA (O-HNA-CA (+)||H-HNA-CA (-)) carried out at a
constant current density of 10 mA cm-2 in 1 m KOH solution. NF (NF(+)||NF(-)) and state-of-the-art commercial
In summary, H- HNA-CA was prepared by DSO of the fresh HNA-CA to effectively catalyze HER.
The resultant H-HNA-CA catalyst exhibited exceptional performance towards HER. In addition, the
DSO HNA-CA (O-HNA-CA(+)||H-HNA-CA(-)) delivered excellent activity and stability when applied
as the cathode and anode for HER and OER, and the attained activity levels surpass those of well-known
state-of-the-art noble metal-based catalysts.
References of Chapter V
[1]. E. Hu, Y. Feng, J. Nai, D. Zhao, Y. Hu and X. W. Lou, Construction of hierarchical Ni-Co-P hollow
nanobricks with oriented nanosheets for efficient overall water splitting. Energy Environ. Sci., 2018, 11, 872-880.
[2]. I. Amorim, J. Xu, N. Zhang, D. Xiong, S. M. Thalluri, R. Thomas, J. P. S. Sousa, A. Araújo, H. Li and
L. Liu, Bi-metallic cobalt-nickel phosphide nanowires for electrocatalysis of the oxygen and hydrogen evolution
reactions. Catal. Today, 2019, DOI: 10.1016/j.cattod.2019.05.037.
223.
[4]. G. Cheng, T. Kou, J. Zhang, C. Si, H. Gao and Z. Zhang, O22-/O- functionalized oxygen-deficient Co3O4
nanorods as high performance supercapacitor electrodes and electrocatalysts towards water splitting. Nano Energy,
2017, 38, 155-166.
120
[6]. J. Du, R. Wang, Y. R. Lv, Y. L. Wei and S. Q. Zang, One-step MOF-derived Co/Co9S8 nanoparticles
embedded in nitrogen, sulfur and oxygen ternary-doped porous carbon: an efficient electrocatalyst for overall water
splitting. Chem. Commun., 2019, 55, 3203-3206.
[7]. C. Guan, W. Xiao, H. Wu, X. Liu, W. Zang, H. Zhang, J. Ding, Y. P. Feng, S. J. Pennycook and J. Wang,
Hollow Mo-doped CoP nanoarrays for efficient overall water splitting. Nano Energy, 2018, 48, 73-80.
[8]. X. Wang, W. Li, D. Xiong, D. Y. Petrovykh and L. Liu, Bifunctional nickel phosphide nanocatalysts
supported on carbon fiber paper for highly efficient and stable overall water splitting. Adv. Funct. Mater., 2016,
26, 4067-4077.
[9]. Y. Wu, G. D. Li, Y. Liu, L. Yang, X. Lian, T. Asefa and X. Zou, Overall Water Splitting Catalyzed
Efficiently by an Ultrathin Nanosheet‐Built, Hollow Ni3S2‐Based Electrocatalyst. Adv. Funct. Mater., 2016,
26, 4839-4847.
[10]. F. Yu, H. Zhou, Y. Huang, J. Sun, F. Qin, J. Bao, W. A. Goddard, S. Chen and Z. Ren, High-performance
bifunctional porous non-noble metal phosphide catalyst for overall water splitting. Nat. Commun., 2018, 9, 1-9.
[11]. Z. Zhou, N. Mahmood, Y. Zhang, L. Pan, L. Wang, X. Zhang and J.-J. Zou, CoP nanoparticles embedded
in P and N co-doped carbon as efficient bifunctional electrocatalyst for water splitting. Journal of energy chemistry,
2017, 26, 1223-1230.
[12]. I. Roger, M. A. Shipman and M. D. Symes, Earth-abundant catalysts for electrochemical and
photoelectrochemical water splitting. Nature Reviews Chemistry, 2017, 1, 1-13.
[13]. J. Duan, S. Chen and C. Zhao, Ultrathin metal-organic framework array for efficient electrocatalytic
water splitting. Nat. Commun., 2017, 8, 15341.
[14]. S. Hao, L. Yang, D. Liu, R. Kong, G. Du, A. M. Asiri, Y. Yang and X. Sun, Integrating natural biomass
electro-oxidation and hydrogen evolution: using a porous Fe-doped CoP nanosheet array as a bifunctional catalyst.
Chem. Commun., 2017, 53, 5710-5713.
[15]. W. Hao, R. Wu, H. Huang, X. Ou, L. Wang, D. Sun, X. Ma and Y. Guo, Fabrication of practical catalytic
electrodes using insulating and eco-friendly substrates for overall water splitting. Energy Environ. Sci., 2020, 13,
102-110.
[17]. S.-F. Hung, Y. Zhu, G.-Q. Tzeng, H.-C. Chen, C.-S. Hsu, Y.-F. Liao, H. Ishii, N. Hiraoka and H. M.
Chen, In Situ Spatially Coherent Identification of Phosphide-Based Catalysts: Crystallographic Latching for
Highly Efficient Overall Water Electrolysis. ACS Energy Letters, 2019, 12, 2813-2820.
[18]. Y. Li, S. Guo, T. Jin, Y. Wang, F. Cheng and L. Jiao, Promoted synergy in core-branch CoP@NiFe-OH
nanohybrids for efficient electrochemical-/photovoltage-driven overall water splitting. Nano Energy, 2019, 63.
[19]. Z. Li, W. Niu, L. Zhou and Y. Yang, Phosphorus and Aluminum Codoped Porous NiO Nanosheets as
Highly Efficient Electrocatalysts for Overall Water Splitting. ACS Energy Letters, 2018, 3, 892-898.
[20]. J. Liu, J. Wang, B. Zhang, Y. Ruan, H. Wan, X. Ji, K. Xu, D. Zha, L. Miao and J. Jiang, Mutually
beneficial Co3O4@MoS2 heterostructures as a highly efficient bifunctional catalyst for electrochemical overall
water splitting. J. Mater. Chem. A, 2018, 6, 2067-2072.
121

[22]. X. Liu, K. Ni, B. Wen, R. Guo, C. Niu, J. Meng, Q. Li, P. Wu, Y. Zhu, X. Wu and L. Mai, Deep
Reconstruction of Nickel-Based Precatalysts for Water Oxidation Catalysis. ACS Energy Letters, 2019, 4, 2585-
2592.
Environmental, 2019, 248, 277-285.
[24]. C. Panda, P. W. Menezes, M. Zheng, S. Orthmann and M. Driess, In Situ Formation of Nanostructured
Core-Shell Cu3N-CuO to Promote Alkaline Water Electrolysis. ACS Energy Letters, 2019, 4, 747-754.
[25]. Z. Qiu, C.-W. Tai, G. A. Niklasson and T. Edvinsson, Direct observation of active catalyst surface phases
and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting. Energy
Environ. Sci., 2019, 12, 572-581.
[27]. X. Zou, Y. Wu, Y. Liu, D. Liu, W. Li, L. Gu, H. Liu, P. Wang, L. Sun and Y. Zhang, In Situ Generation
of Bifunctional, Efficient Fe-Based Catalysts from Mackinawite Iron Sulfide for Water Splitting. Chem, 2018, 4,
1139-1152.
[28]. M. Chatti, J. L. Gardiner, M. Fournier, B. Johannessen, T. Williams, T. R. Gengenbach, N. Pai, C.
Nguyen, D. R. MacFarlane, R. K. Hocking and A. N. Simonov, Intrinsically stable in situ generated electrocatalyst
for long-term oxidation of acidic water at up to 80 °C. Nature Catalysis, 2019, 2, 457-465.
[29]. W. Chen, H. Wang, Y. Li, Y. Liu, J. Sun, S. Lee, J. S. Lee and Y. Cui, In Situ Electrochemical Oxidation
Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation. ACS Cent. Sci., 2015, 1, 244-251.
[30]. S. He and H. Lin, In situ growth of layered double hydroxides on boehmite AlOOH for active and stable
oxygen evolution in alkaline media. Nanoscale, 2019, 11, 10348-10357.
[32]. J. Li, H. Chen, Y. Liu, R. Gao and X. Zou, In situ structural evolution of a nickel boride catalyst:
synergistic geometric and electronic optimization for the oxygen evolution reaction. J. Mater. Chem. A, 2019, 7,
5288-5294.
[33]. P. W. Menezes, C. Walter, J. N. Hausmann, R. Beltran-Suito, C. Schlesiger, S. Praetz, V. Yu Verchenko,
A. V. Shevelkov and M. Driess, Boosting Water Oxidation through In Situ Electroconversion of Manganese Gallide:
An Intermetallic Precursor Approach. Angew. Chem. Int. Ed. Engl., 2019, 58, 16569-16574.
[34]. N. Ortiz Pena, D. Ihiawakrim, M. Han, B. Lassalle-Kaiser, S. Carenco, C. Sanchez, C. Laberty-Robert,
D. Portehault and O. Ersen, Morphological and Structural Evolution of Co 3O4 Nanoparticles Revealed by in Situ
Electrochemical Transmission Electron Microscopy during Electrocatalytic Water Oxidation. ACS Nano, 2019, 13,
11372-11381.
[35]. N. Todoroki and T. Wadayama, Heterolayered Ni-Fe Hydroxide/Oxide Nanostructures Generated on a
Stainless-Steel Substrate for Efficient Alkaline Water Splitting. ACS Appl. Mater. Interfaces, 2019, 11, 44161-
44169.
[36]. B. Wang, J. Shang, C. Guo, J. Zhang, F. Zhu, A. Han and J. Liu, A General Method to Ultrathin Bimetal-
MOF Nanosheets Arrays via In Situ Transformation of Layered Double Hydroxides Arrays. Small, 2019, 15.
122
10580.
[38]. Z. Xia, H. Sun, X. He, Z. Sun, C. Lu, J. Li, Y. Peng, S. Dou, J. Sun and Z. Liu, In situ construction of
CoSe2@vertical-oriented graphene arrays as self-supporting electrodes for sodium-ion capacitors and
electrocatalytic oxygen evolution. Nano Energy, 2019, 60, 385-393.
2016, 16, 7588-7596.
[40]. J. Han, S. Hao, Z. Liu, A. M. Asiri, X. Sun and Y. Xu, In situ development of amorphous Mn-Co-P shell
on MnCo2O4 nanowire array for superior oxygen evolution electrocatalysis in alkaline media. Chem. Commun.,
2018, 54, 1077-1080.
[42]. J. Ryu, N. Jung, J. H. Jang, H.-J. Kim and S. J. Yoo, In Situ Transformation of Hydrogen-Evolving CoP
Nanoparticles: Toward Efficient Oxygen Evolution Catalysts Bearing Dispersed Morphologies with Co-
oxo/hydroxo Molecular Units. ACS Catalysis, 2015, 5, 4066-4074.
Commun., 2016, 7, 12324.
2676.
2018, 54, 4987-4990.
3, 122-133.
[48]. C. Yang, M. Y. Gao, Q. B. Zhang, J. R. Zeng, X. T. Li and A. P. Abbott, In-situ activation of self-
supported 3D hierarchically porous Ni3S2 films grown on nanoporous copper as excellent pH-universal
electrocatalysts for hydrogen evolution reaction. Nano Energy, 2017, 36, 85-94.
[49]. T. Zhang, M.-Y. Wu, D.-Y. Yan, J. Mao, H. Liu, W.-B. Hu, X.-W. Du, T. Ling and S.-Z. Qiao,
Engineering oxygen vacancy on NiO nanorod arrays for alkaline hydrogen evolution. Nano Energy, 2018, 43, 103-
109.
[50]. X. Shang, B. Dong, Y.-M. Chai and C.-G. Liu, In-situ electrochemical activation designed hybrid
electrocatalysts for water electrolysis. Science Bulletin, 2018, 63, 853-876.
123
1900113.
[52]. M. Gong, W. Zhou, M. C. Tsai, J. Zhou, M. Guan, M. C. Lin, B. Zhang, Y. Hu, D. Y. Wang, J. Yang, S.
J. Pennycook, B. J. Hwang and H. Dai, Nanoscale nickel oxide/nickel heterostructures for active hydrogen
evolution electrocatalysis. Nat. Commun., 2014, 5, 4695.
[53]. H. Zhang, An, P., Zhou, W., Guan, B. Y., Zhang, P., Dong, J., & Lou, X. W. D. , Dynamic traction of
lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction. Sci. adv., 2018,
4, 6657.
[54]. J. Chen, J. Liu, J.-Q. Xie, H. Ye, X.-Z. Fu, R. Sun and C.-P. Wong, Co-Fe-P nanotubes electrocatalysts
derived from metal-organic frameworks for efficient hydrogen evolution reaction under wide pH range. Nano
Energy, 2019, 56, 225-233.
[55]. Z. Chen, R. Wu, Y. Liu, Y. Ha, Y. Guo, D. Sun, M. Liu and F. Fang, Ultrafine Co Nanoparticles
Encapsulated in Carbon-Nanotubes-Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen
Evolution Reaction. Adv. Mater., 2018, 30, e1802011.
[56]. X. Dong, H. Yan, Y. Jiao, D. Guo, A. Wu, G. Yang, X. Shi, C. Tian and H. Fu, 3D hierarchical V-Ni-
based nitride heterostructure as a highly efficient pH-universal electrocatalyst for the hydrogen evolution reaction.
J. Mater. Chem. A, 2019, 7, 15823-15830.
[57]. Y. Hou, H. Pang, L. Zhang, B. Li, J. Xin, K. Li, H. Ma, X. Wang and L. Tan, Highly dispersive bimetallic
sulfides afforded by crystalline polyoxometalate-based coordination polymer precursors for efficient hydrogen
evolution reaction. J. Power Sources, 2020, 446.
[58]. C. Hu, H. Liu, Y. Liu, J.-F. Chen, Y. Li and L. Dai, Graphdiyne with tunable activity towards hydrogen
evolution reaction. Nano Energy, 2019, 63.
[59]. K. Jiang, B. Liu, M. Luo, S. Ning, M. Peng, Y. Zhao, Y. R. Lu, T. S. Chan, F. M. F. de Groot and Y. Tan,
Single platinum atoms embedded in nanoporous cobalt selenide as electrocatalyst for accelerating hydrogen
evolution reaction. Nat. Commun., 2019, 10, 1743.
[60]. H. Jin, X. Liu, S. Chen, A. Vasileff, L. Li, Y. Jiao, L. Song, Y. Zheng and S.-Z. Qiao, Heteroatom-Doped
Transition Metal Electrocatalysts for Hydrogen Evolution Reaction. ACS Energy Letters, 2019, 4, 805-810.
[61]. S. Jing, L. Zhang, L. Luo, J. Lu, S. Yin, P. K. Shen and P. Tsiakaras, N-Doped Porous Molybdenum
Carbide Nanobelts as Efficient Catalysts for Hydrogen Evolution Reaction. Applied Catalysis B: Environmental,
2018, 224, 533-540.
[62]. M. Kim, M. A. R. Anjum, M. Lee, B. J. Lee and J. S. Lee, Activating MoS 2 Basal Plane with NiP
Nanoparticles for Pt-Like Hydrogen Evolution Reaction in Acidic Media. Adv. Funct. Mater., 2019, 29.
[63]. T. Kou, S. Wang, J. L. Hauser, M. Chen, S. R. J. Oliver, Y. Ye, J. Guo and Y. Li, Ni Foam-Supported Fe-
Doped β-Ni(OH)2 Nanosheets Show Ultralow Overpotential for Oxygen Evolution Reaction. ACS Energy Letters,
2019, 4, 622-628.
[64]. T. Liu, P. Li, N. Yao, G. Cheng, S. Chen, W. Luo and Y. Yin, CoP-Doped MOF-Based Electrocatalyst
for pH-Universal Hydrogen Evolution Reaction. Angew. Chem. Int. Ed. Engl., 2019, 58, 4679-4684.
[65]. X. F. Lu, L. Yu, J. Zhang and X. W. D. Lou, Ultrafine Dual-Phased Carbide Nanocrystals Confined in
Porous Nitrogen-Doped Carbon Dodecahedrons for Efficient Hydrogen Evolution Reaction. Adv. Mater., 2019, 31,
e1900699.
[66]. Z. Pu, J. Zhao, I. S. Amiinu, W. Li, M. Wang, D. He and S. Mu, A universal synthesis strategy for P-rich
noble metal diphosphide-based electrocatalysts for the hydrogen evolution reaction. Energy Environ. Sci., 2019,
12, 952-957.
124
[67]. X. Meng, L. Yu, C. Ma, B. Nan, R. Si, Y. Tu, J. Deng, D. Deng and X. Bao, Three-dimensionally
hierarchical MoS2/graphene architecture for high-performance hydrogen evolution reaction. Nano Energy, 2019,
61, 611-616.
[68]. L. Peng, X. Zheng, L. Li, L. Zhang, N. Yang, K. Xiong, H. Chen, J. Li and Z. Wei, Chimney effect of
the interface in metal oxide/metal composite catalysts on the hydrogen evolution reaction. Applied Catalysis B:
Environmental, 2019, 245, 122-129.
[69]. C. N. R. Rao and M. Chhetri, Borocarbonitrides as Metal-Free Catalysts for the Hydrogen Evolution
Reaction. Adv. Mater., 2019, 31, e1803668.
[70]. L. Wu, N. Y. Dzade, M. Yu, B. Mezari, A. J. F. van Hoof, H. Friedrich, N. H. de Leeuw, E. J. M. Hensen
and J. P. Hofmann, Unraveling the Role of Lithium in Enhancing the Hydrogen Evolution Activity of MoS 2:
Intercalation versus Adsorption. ACS Energy Lett., 2019, 4, 1733-1740.
[71]. Z. Yuan, S.-M. Bak, P. Li, Y. Jia, L. Zheng, Y. Zhou, L. Bai, E. Hu, X.-Q. Yang, Z. Cai, Y. Sun and X.
Sun, Activating Layered Double Hydroxide with Multivacancies by Memory Effect for Energy-Efficient Hydrogen
Production at Neutral pH. ACS Energy Lett., 2019, 4, 1412-1418.
[72]. J. Zhu, Z. C. Wang, H. Dai, Q. Wang, R. Yang, H. Yu, M. Liao, J. Zhang, W. Chen, Z. Wei, N. Li, L. Du,
D. Shi, W. Wang, L. Zhang, Y. Jiang and G. Zhang, Boundary activated hydrogen evolution reaction on monolayer
MoS2. Nat. Commun., 2019, 10, 1348.
[73]. Y. Zhu, H.-C. Chen, C.-S. Hsu, T.-S. Lin, C.-J. Chang, S.-C. Chang, L.-D. Tsai and H. M. Chen,
Operando Unraveling of the Structural and Chemical Stability of P-Substituted CoSe2 Electrocatalysts toward
Hydrogen and Oxygen Evolution Reactions in Alkaline Electrolyte. ACS Energy Lett., 2019, 4, 987-994.
125
126
Chapter VI Conclusions and perspectives
6.1 Conclusions
Two kinds of high performance OER electrocatalysts were fabricated through two conventional
coating processes combined with in situ ECA, guided by the present PhD study objective of development
of highly active and stable earth-abundant OER electrocatalysts with 3D hierarchical porous architecture
via facile, effective and potentially commercial means.
For the first OER electrocatalyst, a codoped 3D NF by Ni crystals, Co3O4 nanoparticles, GO
nanosheets, and in situ-generated Ni(OH)2/NiOOH nanoflakes via electrolytic codeposition, in
combination with in situ ECA based on OER, was reported as a promising OER electrocatalyst in
alkaline electrolyzer. Notably, this hybrid catalyst shows good electrocatalytic performance of OER in
1.0 M KOH with 212 mV overpotentials to achieve a catalytic current density of 10 mA cm-2, which is
comparable with the state-of-the-art noble catalysts. The hybrid catalyst, as an electrocatalytically active
and robust OEE, also exhibits strong long-term electrochemical durability, releasing a large current
density of 800 mA cm-2 at 350 mV without degradation after a 100-hour test. Such a remarkable
performance can be benefiting from the introduced OER catalyst materials deposited on NF, in situ-
generated Ni(OH)2/NiOOH nanoflakes and their synergistic effects. Collectively, so far, the hybrid
catalyst developed in this work is one of the most efficient OEEs in alkaline electrolytes, and could
potentially be implemented in large-scale water electrolysis systems.
For the second OER electrocatalyst, an efficient method of combining high-velocity oxy-fuel
(HVOF) spraying followed by chemical activation (CA), and in situ ECA based on OER, was developed
to obtain a promising self-supported OER electrocatalyst with lattice-distorted Jamborite
(Ni(OH)2/NiOOH hybrid) nanosheets generated in situ on the elaborated 3D hierarchically porous NiAl
framework. The catalyst developed in this work exhibits not only exceptionally low overpotential (10
mA cm-2 at an overpotential of 193 mV) and a low Tafel slope (39 mV dec-1) toward oxygen evolution
reaction (OER), but also remarkable stability, completely maintaining its high catalytic activity over 40
hours of continuous operation in 1 M KOH, both of which surpass the state-of-the-art noble commercial
catalysts. Moreover, it also exhibits strong long-term electrochemical durability, releasing a large current
density of 800 mA cm-2 at an overpotential of 229 mV without degradation after a 168-hour test in 6 M
KOH at 353 K. The remarkable features of this catalyst lie in the synergistic effect of the high intrinsic
activity arising from the in situ growth of lattice-dislocated Jamborite (Ni(OH)2/NiOOH hybrid)
nanosheets as the highly active substance of OER, the extremely high specific surface, and the
accelerated electron/ion transport associated with the elaborated 3D hierarchically porous architecture.
Notably, the novel methodology has the potential to produce large-sized electrodes for AWE, which can
127
broaden the horizons of the field and provide new dimensions in the design of highly active and stable
self-supported OER electrocatalysts.
Furthermore, we have also explored initial development of effective HEEs upon in situ ECA based
on HER, coupled with the obtained superior OEEs forming two-electrode configurations, respectively,
both of which rival the integrated state-of-the-art IrO2(+)/Pt(-) electrode in alkaline overall water splitting.
In summary, a methodology of fabricating easy-to-commercialize, high-performance catalytic
electrodes by combining electrolytic codeposition or HVOF followed by CA, with in situ ECA,
respectively, has been realized and well developed. The in situ ECA based on OER or HER mentioned
above exhibits DSO behavior, which is facile, flexible, effective, and eco-friendly as a strategy of
activating self-supported electrodes for efficient and durable overall water splitting. We hope our work
can promote advanced development toward large-scale H2 production using excess electrical power
whenever and wherever available.
128
6.2 Perspectives
In order to further develop our work on hydrogen production by water splitting, we hope to continue
investigating on the following aspects in the future.
For the catalytic mechanism, we will further improve the physical and electrocatalytic
characterizations to fully reveal the essential connections between catalytic performance and the
evolution of phase, surface, and morphology on the surface of the electrocatalysts, especially for HER
electrocatalysts. If possible, we will work with researchers in the density functional theory field to better
explain the catalytic mechanisms of the resultant electrocatalysts.
For the preparation process, we will further optimize the fabrication processes which have been
employed, with the aim of improving catalytic activity and durable performance. In addition, we will
try to prepare more large electrodes close to the needs of industry and assemble them into a full cell, to
directly serve the industrial production of electrolyzed water.
In addition, we will put forward new exploration directions for future fabrication of bifunctional
electrocatalysts for overall water splitting, such as 3D-printing or melting processes, in combination
with in situ ECA. Based on the characteristics of these processes, they could be used to design self-
supported catalytic electrode materials.
After initial exploration, we find that electrocatalytic reactions relevant for water splitting can be
improved by employing magnetic heating of the prepared nickel-based catalysts. The combination of
the conventional manufacturing process and the magnetic field to produce highly active electrocatalysts
is also in its infancy and achieving remarkable results. Hence, developing the effective use of magnetic
fields in electrode fabrication and applications will represent another interesting attempt to obtain
promising electrocatalysts.
129
130
Abstract
Abstract
Splitting water into hydrogen and oxygen by electrolysis using electricity from intermittent ocean
current, wind, or solar energies is one of the easiest and cleanest routes for high-purity hydrogen
production and an effective way to store the excess electrical power without leaving any carbon
footprints. The key dilemma for efficient large-scale production of hydrogen by splitting of water via
the hydrogen and oxygen evolution reactions is the high overpotential required, especially for the
oxygen evolution reaction. Hence, engineering highly active and stable earth-abundant oxygen evolution
electrocatalysts with three-dimensional hierarchical porous architecture via facile, effective and
commercial means is the main objective of the present PhD study. Finally, we developed two kinds of
good performance oxygen evolution electrocatalysts through two different way combined with in situ
electrochemical activation.
For the first oxygen evolution electrocatalyst, we report a codoped nickel foam by nickel crystals,
tricobalt tetroxide nanoparticles, graphene oxide nanosheets, and in situ generated nickel hydroxide and
nickel oxyhydroxide nanoflakes via electrolytic codeposition in combination with in situ
electrochemical activation as a promising electrocatalyst for oxygen evolution reaction. Notably, this
hybrid catalyst shows good electrocatalytic performance, which is comparable to the state-of-the-art
noble catalysts. The hybrid catalyst as an electrocatalytically-active and robust oxygen evolution
electrocatalyst also exhibits strong long-term electrochemical durability. Such a remarkable
performance can be benefiting from the introduced active materials deposited on nickel foam, in situ
generated nickel oxyhydroxide nanoflakes and their synergistic effects. It could potentially be
implemented in large-scale water electrolysis systems.
For the second oxygen evolution electrocatalyst, an efficient means of combining high-velocity
oxy-fuel spraying followed by chemical activation, and in situ electrochemical activation based on
oxygen evolution reaction has been developed to obtain a promising self-supported oxygen evolution
electrocatalyst with lattice-distorted Jamborite nanosheets in situ generated on the three-dimensional
hierarchical porous framework. The catalyst developed in this work exhibits not only exceptionally low
overpotential and Tafel slope, but also remarkable stability. Such a remarkable feature of this catalyst
lies in the synergistic effect of the high intrinsic activity arising from the lattice-dislocated Jamborite
nanosheets as the highly active substance, and the accelerated electron/ion transport associated with the
hierarchical porous architecture. Notably, this novel methodology has the potential to produce large-
size-electrode for alkaline water electrolyzer, which can provide new dimensions in design of highly
active and stable self-supported electrocatalysts.
Furthermore, we have also initially developed good hydrogen evolution electrocatalysts upon in
situ electrochemical activation, coupled with the obtained superior oxygen evolution electrocatalysts
forming two-electrode configurations, respectively, both of which rivalled the integrated state-of-the-art
ruthenium dioxide-platinum electrode in alkaline overall water splitting.
In summary, a methodology of fabricating easy-to-commercial, high performance catalytic
electrodes by combining traditional coating processes with in situ electrochemical activation has been
realized and well developed. The in situ electrochemical activation mentioned above is a dynamic self-
131
Abstract
optimization behavior which is facile, flexible, effective and eco-friendly, as a strategy of fabricating
self-supported electrodes for efficient and durable overall water splitting. We hope our work can promote
advanced development toward large-scale hydrogen production using excess electrical power whenever
and wherever available.
Keyword: Hydrogen production; Electrolysis; Oxygen evolution electrocatalyst
132
Résumé
Résumé
La décomposition électrolytique de l’eau en hydrogène et oxygène à l’aide d’électricité

renouvelable générée par les courants marins ou à partir d’énergie éolienne ou solaire, constitue l’une
des voies les plus propres et directes pour produire de l’hydrogène. Toutefois, la production de grands
volumes d’hydrogène par décomposition électrolytique de l’eau comporte un verrou technologique qui
réside dans la forte surtension à vaincre à l’anode où de l’oxygène est dégagé. Ce travail de thèse s’est
attaché donc à mettre au point des matériaux d’électrodes capables de catalyser de l’eau en oxygène de
façon efficace et stable, en utilisant des éléments chimiques suffisamment abondants sur terre. Pour cela
nous avons exploré des composés présentant des porosités à structures hiérarchiques et des procédés de
préparation efficaces, aisées à mettre en œuvre et susceptibles d’un usage à l’échelle industrielle. Nous
avons développé deux types d’électrocatalyseurs d’oxydation de l’eau en oxygène en mettant au point
deux voies de préparation impliquant chacune une phase d’activation in situ. Le premier type est une
mousse de nickel dopée à la fois avec des cristaux de nickel, des nanoparticules de tétroxyde de tricobalt
et des nanofeuilles d’oxyde de graphène via nickelage électrolytique, suivi d’une activation
électrochimique in situ pour former de l’hydroxyde de nickel et des nano-plaques d’oxy-hydroxyde du
même métal. Ce catalyseur hybride s’est avéré avoir des performances électrocatalytiques de bon niveau,
comparables à celles des électrodes à base de métaux nobles qui sont disponibles dans l’état actuel de
la technique ; il a en outre fait preuve d’une excellente stabilité en fonctionnement. Ces propriétés
remarquables semblent liées à la fois aux dépôts formés sur la mousse de nickel par les différentes phases
actives citées, aux nanoparticules d’oxy-hydroxyde de nickel, ainsi qu’aux effets de synergie qu’elles y
induisent. Le second type d’électrocatalyseurs a été obtenu en combinant la projection thermique
(HVOF) et un processus d’activation chimique puis électrochimique. Le matériau résultant possède de
nanocouches du type jamborite formée in situ, sur la matrice poreuse à structure hiérarchique. Le
catalyseur développé dans ce travail présente non seulement une surtension et une pente de Tafel
exceptionnellement faibles, mais également une stabilité remarquable. Ces performances sont dues à un
puissant effet de synergie dans laquelle interviennent la grande activité intrinsèque des nanofeuilles de
jamborite et la grande rapidité des transports d’électrons et d’ions assurée par l'architecture poreuse
hiérarchique. Il convient de noter que cette nouvelle méthodologie a le potentiel de produire des
électrodes de grandes tailles apte à l’électrolyse alcaline de l'eau et crée ainsi de nouvelles perspectives
dans le cadre de la conception d'électrocatalyseurs à la fois très actifs et stables. Nous avons également
développé, initialement, des électrocatalyseurs destinés à la réduction de l’eau en hydrogène, qui
impliquent également une activation électrochimique in situ. Ces électrodes peuvent être ainsi couplées
aux électrodes précitées d’oxydation de l’eau en oxygène pour former des cellules électrochimiques
complètes à deux électrodes, dont les performances rivalisent avec celles développées par le couple
dioxyde de ruthénium/platine qui représente le meilleur état de la technique dans le cadre de la
production d’hydrogène et d’oxygène par électrolyse de l’eau. En résumé, en combinant des techniques
conventionnelles de revêtement et d’activation électrochimique in situ, ce travail a permis de développer
une méthodologie de préparation d'électrodes catalytiques offrant de hautes performances et susceptibles
de commercialisation. La technique d’activation électrochimique in situ exploite un comportement
133
Résumé
d'auto-optimisation dynamique qui est aisé à mettre en œuvre, facilement adaptable, efficace et
respectueux de l'environnement.
Mots clés: Production d'hydrogène; Électrolyse; Électrocatalyseur à évolution d'oxygène
134
List of participation activities and peer-reviewed publications
List of participation activities
I. Engineered Thermal Sprayed Oxygen Electrode for Hydrogen Production by Alkaline Water
Electrolysis. 2019 International Thermal Spray Conference and Exposition (ITSC),
Yokohama Japan, May 27, 2019.
II. Dynamic self-optimization of hierarchical Ni-based compounds as efficient catalysts for overall
water splitting. 237th Electrochemical Society (ECS) Meeting with IMCS 2020 in Montreal
Canada, May 10, 2020.
List of peer-reviewed publications
I. Tao Jiang*, Syed-asif Ansar, Ghislain Montavon, Hanlin Liao, et al. Dynamic self-optimization
of Ni-based precatalysts as self-supported electrodes for efficient overall water splitting.
Manuscript in preparation
II. Tao Jiang*, Syed-asif Ansar, Ghislain Montavon, Hanlin Liao, et al. Electrochemical tuning of
lattice-dislocated nanosheets in situ growing over NiAl core to promote oxygen evolution
reaction. Under review in Science Advances
III. Tao Jiang*, Syed-asif Ansar, Ghislain Montavon, Hanlin Liao, et al. In situ electrochemical
activation of a codoped heterogeneous system as a highly efficient catalyst for the oxygen
evolution reaction in alkaline water electrolysis. ACS Applied Energy Materials 2019, 2, 8809-
8817.
135

Development of Alkaline Electrolyzer Electrodes and Their Characterization

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Development of Alkaline Electrolyzer Electrodes and Their Characterization

Uploaded by

Copyright:

Available Formats

Development of Alkaline Electrolyzer Electrodes and

Their Characterization in Overall Water Splitting

Université de Technologie de Belfort-Montbéliard

Development of Alkaline Electrolyzer Electrodes and Their

Defense expected 20 May 2020

With the jury composed of

General introduction ................................................................................................................................. I

2.1.2.2 Equipment of high-velocity oxy-fuel spraying ...................................................................... 44

6.1 Conclusions .......................................................................................................................... 127

O-HNA-CA(+)||H-HNA-CA(-) Two-electrode configuration

Chapter I Introduction of water electrolysis

1.2 Fundamentals of water electrolysis

1.2.1 The principle

Figure 1-2 Conceptual set-up of an AEC.14

1.2.2 Reaction mechanism of OER catalysts in alkaline medium

1.2.3 Performance parameters of OER catalysts in alkaline medium

1.2.3.1 Electrode and electrolyte

1.2.3.2 Onset overpotential and overpotential

1.2.3.3 Electrochemical impedance spectrum analysis

1.2.3.4 Tafel slope and exchange current density

η = blog j + a (Tafel equation) (1-17)

1.2.3.5 Electrochemical active surface area

1.2.3.7 Turnover frequency

1.2.3.8 Faradic efficiency

1.3 Water electrolysis technologies

Figure 1-4 Conceptual set-up of PEMEC and SOEC.14

Table 1-1 Main characteristics of AEC, PEMEC and SOEC systems.14

40 wt.% KOH) 5 Nafion) 47 (YSZ) 48

Cathode Ni, Ni-Mo alloys 5 Pt, Pt-Pd 47 Ni/YSZ 48

Anode Ni, Ni-Co alloys 5 RuO2, IrO2 47 LSMb/YSZ 48

Current density (A cm-2) 0.2-0.4 47 0.6-2.0 47 0.3-2.0 48

Cell voltage (V) 1.8-2.4 47 1.8-2.2 47 0.7-1.5 48

Cell area (m2) <4 14 <0.3 14 <0.01 14

Operating Temp. (℃) 60-80 47 50-80 47 650-1000 48

Operating Pressure (bar) <30 14 <200 14 <25 14

Production RateC (m3H2h-1) <760 14 <40 14 <40 14

Gas purity (%) >99.5 5 99.99 5 99.9 a

Stack Lifetime (h) 60,000-90,000 5 20,000-60,000 5 <10,000 a

Maturity Mature Commercial Demonstration a

Capital Cost (€ kWel -1) 1000-1200 5 1860-2320 5 >2000 5

Power (kW) 2-6000 49 1.8-2000 49 N.A.d

1.3.1 Alkaline electrolysis cell technology

Figure 1-5 Layout of AEC system.51

1.3.2 Other methods of hydrogen production

1.3.3 Industrial application parameters in alkaline electrolysis cell

Table 1-2 Water electrolyzer developers and cell operating conditions.5

Corp. Ltd. systems

Cell type B-FP B-FP M-T B-FP B-FP

Anode Expanded Ni-plated Activated Ni- Ni-coated Steel Ni screen PTFE-bonded

Mild steel coated Steel Noble metal

Cathode Activated Ni-plated Activated Ni- Steel Ni screen PTFE-bonded

Steel coated Steel Noble metal

Pressure (MPa) Ambient Ambient Ambient 0.2 0.4

Electrolyte 29 % KOH 25 % KOH 28 % KOH 35 % KOH Nafion

Current density (A m-2) 1500 1750 1340 2000 5000

Cell voltage (V) 1.85 1.75 1.9 1.9 1.7

Current efficiency (%) 98.5 98.5 >99 NR NR

Oxygen purity (%) 99.6 99.3-99.7 99.3-99.7 >98.0 >98.0

Hydrogen purity (%) 99.9 98.9-99.9 99.9 99.99 >99.0

1.4 Synthetic strategies of OER catalysts for alkaline medium

1.4.1 Noble metals and their oxides as OER catalysts

importantly with the significant improvement of the stability.30

1.4.2 First-row transition metal compounds as OER catalysts