Accepted Manuscript

Current progress and challenges in engineering viable artificial leaf for solar water
splitting

Phuc D. Nguyen, Tuan M. Duong, Phong D. Tran

PII: S2468-2179(17)30135-1
DOI: 10.1016/j.jsamd.2017.08.006
Reference: JSAMD 120

To appear in: Journal of Science: Advanced Materials and Devices

Received Date: 31 July 2017

Revised Date: 24 August 2017
Accepted Date: 26 August 2017

Please cite this article as: P.D. Nguyen, T.M. Duong, P.D. Tran, Current progress and challenges in
engineering viable artificial leaf for solar water splitting, Journal of Science: Advanced Materials and
Devices (2017), doi: 10.1016/j.jsamd.2017.08.006.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

Current progress and challenges in engineering viable artificial leaf for solar
water splitting

Phuc D. Nguyen,a,b Tuan M. Duonga and Phong D. Trana*

a
Department of Advanced Materials Science and Nanotechnology, University of
Science and Technology of Hanoi, Vietnam Academy of Science and Technology

PT
18 Hoang Quoc Viet, Hanoi, Vietnam. Email: [email protected]
b
Institute of Materials Science, Vietnam Academy of Science and Technology

RI
18 Hoang Quoc Viet, Hanoi, Vietnam.

U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Tutorial review

Current progress and challenges in engineering viable artificial leaf for solar
water splitting

PT
Abstract

RI
Large scale production of H2, a clean fuel, can be done with just water and solar light
energy by employing a viable energy conversion device called artificial leaf. In this

SC
tutorial review, we dicuss on advances achieved recently and technical challenges
remained toward the creation of such a leaf. Development of key components like

U
catalysts for water electrolysis process and light harvester for harvesting solar energy
AN
as well as strategies being developed for assemling these components to create a
complete artificial leaf will be highlighted.
M

Key words: solar energy, artificial leaf, hydrogen, catalyst, light harvester, device
D
TE
C EP
AC

1
 ACCEPTED MANUSCRIPT
1. Introduction

Our current global energy consumption depends largely on the fossil energies like oil,
natural gas etc. With current development, especially in emerging economies, annual
energy consumption is predicted to be about 30 TW in 2050 which is almost double
compared with consumption of 2015 [1]. It is quite obvious that fossil energy can
continue to offer an energy security in such a huge energy demand situation.

PT
However, burning fossils causes the emission of CO2 and other toxic chemical like
NOx, SOx which are main responsible to the climate change and environmental

RI
disasters. In this context, considerable efforts are being mobilized in order to identify
potential alternatives to fossil energies.

SC
Solar energy represents the most abundant renewable energy source that is available
to the human being. Indeed, one hour of solar flux arriving to our planet is just

U
enough for global consumption over a year. Contemporary challenges are actually to
AN
identify viable technologies for harvesting solar energy and storing it in an efficient
manner. Photovoltaic is such an attractive technology that is already maturated and
available in market, e.g. Si or organic solar cells [2, 3]. In photovoltaic technology,
M

photon energy is harvested and converted into electricity that is readily for use or can
be stored by employing a battery. Alternatively, solar energy can be stored as
D

chemical energy within the molecules of H2 via a solar-driven water splitting process.
TE

The energy stored can be then converted into electricity as per demand through
oxidation of this H2 fuel providing only water molecule as waste (figure 1).
C EP
AC

Figure 1. Solar to electricity conversion employing H2 as a mean for energy storage

2
 ACCEPTED MANUSCRIPT
Indeed, to realize this energy conversion cycle wherein input energy is photon energy
while output energy is electricity and H2 is the energy carrier two appropriate
electrochemical cells are demanded. An artificial leaf is required to conduct the solar
to H2 conversion through solar driven water splitting process. A proton exchange
membrane fuel cell is demanded for converting H2 fuel into electricity.

In this tutorial review, we first describe potential designs and operation of artificial

PT
leaf being developed. We then discuss about material requirements, current progress
as well as engineering challenges for the creation of an efficient artificial leaf for

RI
large scale H2 production.

2. Artificial leaf: designs and operation

SC
2.1 Water splitting in the natural photosynthesis

Water splitting into H2 and O2 is a multiple electron and multiple proton process that

U
consists of two half-redox reactions: the oxygen evolution reaction (OER, eq.1) and
AN
the hydrogen evolution (HER, eq. 2). The thermodynamic potential of the water
splitting process is +1.23 V, corresponding to a Gibbs free energy of +273 KJ/mol
M

(figure 1) [4]. In other words, water splitting is an up-hill process that explains the
need of sufficient energy inputs, e.g. from photon energy. Since solar photon is not
D

absorbed by water molecule itself, it is compulsory to employ a light harvester to

harvest photon energy into potential energy. Subsequently, the resultant energy is
TE

used for splitting water molecule. Because of its multiple electron nature, the HER
and OER are slow kinetic reactions. As a consequence, catalysts are needed to drive
EP

these reactions at acceptable rate.

In the nature, light harvesters within the natural photosynthesis system are two
C

organic dyes absorbing visible light photons, namely Chlorophyll P680 and
AC

Chlorophyll P700 [5]. In the vicinity of these light harvesters locate catalysts that help
to accelerate the OER (namely [CaMn4O5] O2-evolving centre) and HER (namely
hydrogenases). Remarkably, electron communication between the two dyes as well as
between excited dye and catalyst is ensured by an outstanding manner thanks to
presence of electron mediators like quinone and tyrosine (figure 2). Structure and
operation of these components as well as the way they are assembled to offer the best
performance of the natural photosynthesis still remain a great challenge for artificial
photosynthesis systems.

3
 ACCEPTED MANUSCRIPT
2H2O → 4H+ + O2 + 4e- (eq.1)
2H+ + 2e- → H2 (eq.2)
2H2O → 2H2 + O2 (eq.3)

PT
RI
U SC
AN
Figure 2. A simple schematic representation of the natural photosynthesis process
M

2.2 Potential designs for artificial leaf

2.2.1 General considerations

D

Artificial photosynthesis is a photochemical process that converts solar energy into

TE

chemical energy stored within small molecules like H2, CO, HCOOH or CH3OH by
employing a man-made device that mimics the structure and operation of the natural
photosynthesis system. In general, the device employed is a PhotoElectrochemical
EP

Cell, usually denoted as PEC. However, PEC is also used for referring to other energy
conversion devices like Dye-sensitized solar cell. Thus, an exotic theme used for
C

referring to the device wherein the overall water splitting process (equation 3) is
AC

driven by solar light is artificial leaf.

For instance, H2 as fuel or chemical feedstock is generated from natural gas via a
reforming process. In order to make solar H2, generated via the solar water splitting
technology, economically competitive, a road map with several technical
requirements was etabilished by the US Department of Energy [6]. Briefly, artificial
leaf should display solar-to-H2 conversion yield (ηSTH) of 10% or above, operation life
time of over 1000 h and be made of earth abundant elements. The target price for 1 kg
H2 is 2-4 $.

4
 ACCEPTED MANUSCRIPT
Following sections describe several potential designs that can be used to engineer an
artificial leaf.

2.2.2 Artificial leaf made of a single semiconductor having large band gap

Few large band gap semiconductors offers sufficient energy driving force (e.g. Eg >
1.23 eV) as well as appropriate band edge potentials for driving the overall water
splitting process (eq.3). Indeed TiO2 (Eg of 3.2 eV) was the first material being

PT
assayed for water splitting application [7]. Its conduction band edge potential is -
0.17V vs. NHE (Normal Hydrogen Electrode) being sufficient reductive for the HER

RI
while its valence edge potential is +3.03 V vs. NHE being largely sufficient for OER.
The same situation is identified for graphitic carbon nitrile g-C3N4, TaON, CdS, GaN

SC
[8]. Thus, the simplest configuration of artificial leaf uses these large band gap
semiconductors as light harvesters. Onto surface of these light harvesters, two

U
appropriate catalysts for the HER and OER are loaded [9-11]. This configuration was
AN
mainly developed as suspended nanoparticles in solution (figure 3a) but also as
freestanding electrode system. However, it is worth noting these large band gap
semiconductors can only harvest UV and near UV photons that constitute about 5% of
M

the whole solar spectrum. Thus, low solar to H2 conversion yield, being less of 1%, is
usually expected.
D

2.2.3 Artificial leaf made of dual semiconductors having small or narrow band gap
TE

Indeed, the natural photosynthesis system choses chlorophyll P680 and P700 those
display absorption maxima at 680 and 700 nm as the dual light harvesters [5]. These
EP

absorptions correspond to an optical band gap Eg of ca. 1.8 eV. Inspired by this
natural engineering, artificial leaf is also proposed to be composed of two small or
C

narrow band gap semiconductors (figure 3b). Photoanode is made of a n-type

semiconductor while photocathode is made of a p-type semiconductor. These two
AC

electrodes are wired through an Ohmic contact making of high electrical conducting
materials that has appropriate work function level. Ideally, this contact material
should display a high transparency therefore light blocking phenomenon is supressed.
Furthermore, when proton conductivity is concerned, it is highly demanded that the
Ohmic contact material should be embedded within a proton exchange membrane like
Nafion®. Actually, CNTs embedded within Nafion® membrane was developed for
H2 proton exchange membrane fuel cell [12]. Such a membrane could be applied in

5
 ACCEPTED MANUSCRIPT
artificial leaf engineering, in principles. However, integration of a CNTs/ Nafion®
membrane within an artificial leaf has not yet reported, to the best of our knowledge.

Indeed, a complete artificial leaf having design as described this above (figure 3b) is
still to be demonstrated. For instance, photoanode and photocathode are loaded onto
two different conducting substrates, e.g. metal or transparent conducting oxide (TCO)
like fluorine doped tin oxide (FTO) or indium doped tin oxide (ITO). These

PT
electrodes are then wired through another Ohmic contact like metal wire (figure 3c).
Incorporating two photoelectrodes onto a single substrate can be easily made as side-

RI
by-side mode (figure 3d). A back-to-back assemblage, being similar to the design
described in figure 3b, represents a big challenge. To this end, it is needed that these

SC
two electrodes should be grown by a step-wise manner, one after the other. In other
words, photoanode should be grown under experimental conditions those are

U
compatible for stability of the photocathode and vice-versa. In this context,
development of solution roll-roll process for photoelectrode fabrication employing
AN
ambient experimental conditions could be a potential approach. To this end, learning
from fabrication of organic photovoltaics is a possibility. Indeed, with this approach,
M

attractive progresses have been achieved for fabrication of organic material based
photoelectrodes or photoelectrochemical cell [13-15].
D
TE
C EP
AC

Figure 3. Design of artificial leaf made of a single semiconductor having large band
gap (a), a dual photoelectrodes that are assembled with a proton exchange membrane
in back-to-back configuration (b), a dual photoelectrodes wired (c) and a dual
photoelectrodes loaded on a single support in side-by-side configuration (d). The dual

6
 ACCEPTED MANUSCRIPT
photoelectrodes in the three latter cases are made of semiconductors with small or
narrow band gaps.

As it was stated earlier, using catalysts for the HER and OER is needed in order to
achieve a significant water splitting rate. OER catalyst is loaded onto photoanode
while HER catalyst is deposited onto photocathode side. Strategies for incorporating

PT
these catalysts within artificial leafs will be discussed in the section 4.1.

2.2.4 Artificial leaf made of a photovoltaics – electrolyser assemblage

RI
The simplest configuration of an artificial leaf is made via assembling a photovoltaics
and a dual of HER and OER catalysts for water electrolysis. Since stability of solar

SC
cell in water is really a big issue, this configuration allows keeping the photovoltaics
out of contact with water (figure 4a).

U
AN
M
D
TE
EP

Figure 4. Wired (a) and wireless (b) artificial leaf made of photovoltaics – water
C

electrolyser assemblage
AC

Construction of a wireless artificial leaf is more challenging. To this end, HER and
OER catalysts should be incorporated with the photovoltaics creating buried junction
(figure 4b). Because photovoltaics should be immersed into water for operation in
this case, challenges are to identify appropriate strategies to stabilize photovoltaic
materials. Indeed, Si photovoltaic easily gets oxidized in water when soluble O2
concentration is over 15 ppb [16]. Whereas, emerging organic-inorganic perovskite

7
 ACCEPTED MANUSCRIPT
photovoltaics is suffered due to the rapid decomposition in contact with water, even
with humidity in air [17].

2.3 Operation and performance evaluation

2.3.1 Operation

Fundamental operation steps of an artificial leaf made of dual photoelectrodes are

PT
schematically presented in figure 5a. Desired steps (bulk arrows) include light
absorption, charge separation, charge transportation from bulk phase to surface of
light harvester, charge injection to catalyst loaded on its surface and dark catalytic

RI
action of the catalyst. Each of these subsequent steps should be optimized in order to
achieve highest solar energy conversion yield. In very sharp contrast, several

SC
unwanted processes (dash arrows) should be supressed or limited, e.g. light reflection,
light transmission, charge recombination within bulk phase or on surface of the light

U
harvester, dark catalytic process with low reaction rate and high energy
AN
(overpotential) demanded.
M
D
TE
C EP
AC

8
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Figure 5. Schematic presentation of elemental steps occurred within an artificial leaf

made of dual photoelectrodes (a) and absorption of different wavelength photons
within the leaf (b)
EP

Indeed, the optimization of artificial leaf engineering is about identification of a good

C

balance between wanted and un-wanted events. As an example, to improve light

AC

absorption properties of a photoelectrode material, elemental doping can be applied

that helps to tune energy band gap and perhaps absorption co-efficiency [18].
Elemental doping also helps to enhance charge separation and charge mobility within
materials [19, 20]. However, introduction of dopants creates defects within materials,
which can subsequently act as trapping centre for the charge recombination. Thus it
lowers the overall light harvesting yield. Loading of HER and OER catalysts onto
light harvester surface is other demonstration. Indeed, having efficient catalysts is
compulsory to accelerate the electrochemical reactions HER and OER. However,

9
 ACCEPTED MANUSCRIPT
loading these catalysts onto electrode surface in general creates surface defects that
are harmful to the system because of the surface recombination phenomenon [21].
Electrocatalytic performance is decided by number of actual catalytic sites exposed
within the catalyst. However, optimization is needed to achieve high catalytic
performance while limit the volume (thickness) of the catalyst loaded. This is
specially desirable for the case of OER catalyst since light illumination is preferred by

PT
the photoanode side. Works should be done to propose OER catalyst being
catalytically efficient but transparent to remove the unwanted light blocking event.

RI
Regarding operation, for an artificial leaf made of a single large band gap
semiconductor or a photovoltaics-electrolyser assemblage, the question of photon

SC
illumination direction is not critical. However, in the case of an artificial leaf made of
a dual photoelectrodes, illumination from the front-photoanode or from the back-
photocathode offers different performances. Indeed, short wavelength photons usually

U
display short absorption depth. Thus, to better harvest the whole solar spectrum, it
AN
would be better to avoid driving short wavelength photons through a long distance
within the artificial leaf. In other words, it is preferable to drive illumination first
M

through front-photoanode where shorter wavelength photons are harvested while

longer wavelength photons are transmitted and driven to back-photocathode where
D

these photons are harvested (figure 5b).

It is worth noting that, because of this operation principle a larger band gap
TE

semiconductor is preferred for engineering the front-photoanode while a narrowed

band gap semiconductor is used for the back-photocathode. By that way these two
EP

electrodes harvest photons of two complementary regions. In contrast, if two

electrode materials have comparable or similar band gap energy, they absorb same
C

photons. In that case, absorption of the back-photocathode is hinted by the front-

photoanode, especially for photons having short wavelength.
AC

To the best of our knowledge, only few artificial leaves made of dual photoelectrodes
have been demonstrated to date. Such operating artificial leaf is composed of large
band gap n-type semiconductor like BiVO4 or GaN as photoanode and narrow band
gap p-type semiconductor like Cu2O, CdS/CuGa3Se5/(Ag,Cu)GaSe2, or InGaN as
photocathode [22-24].

10
 ACCEPTED MANUSCRIPT
2.3.2 Performance assay

Artificial leaf performance is determined by the solar-to-H2 conversion yield,

abbreviated as ηSTH. In this section, we draw on principles to theoretically calculate
ηSTH value for different operating systems.

For suspended nanoparticle photocatalyst

PT
For the case of suspended nanoparticle photocatalyst acting as artificial leaf for solar
H2 generation, e.g. a single semiconductor having large band gap, a theoretical

RI
calculation of its solar-to-H2 conversion yield is not available. The only possible
method to assay its performance is following what usually employed for

SC
homogeneous photocatalytic system e.g. photosensitizer-catalyst dyas [25]. In brief,
generated amout of H2 should be experimentally quantified after a given period of
time and with a given input photon energy Pin [9-11, 26].

U
We note that above discussion deals only with the solar-to-H2 conversion yield under
AN
illumination of the whole solar spectrum. Indeed, this performance together with the
robustness of artificial leaf, that can be easily determined by assaying the performance
M

over long operation time, are the two most important descriptors. However, as a
photocatalyst other descriptors are of interests such as quantum yield, turnover
D

number (TON), turnover frequency (TOFs). TON and TOFs are also two fundamental
characteristics of HER and OER catalysts. Indeed, by conducting above described
TE

assay with monochromic light source, quantum yield of artificial leaf or photocatalyst
can be easily determined. Determination of actual TON, TOFs is challenging for
EP

heterogeneous photocatalysts or catalysts because it is difficult to quantify the actual

number of catalytic active sites. In such a case, lower limit TON and TOFs, that are
C

deduced by assuming bulk phase and surface of the material under investigation are
AC

equally active, are discussed. We will discuss more in details about this issue in the
next sections dealing with materials aspects for the artificial leaf engineering.

For artificial leaf made of a dual photoelectrodes

From photogenerated I-V curve of each independent photoelectrode, namely

photoanode and photocathode, operation point can be deduced (figure 6). The
operating current density jop is actually theoretical photocurrent that flows through
these two photoelectrodes under light illumination. Since this current flow is resulted
due to the water splitting process occurring on these two photoelectrodes, we deduce

11
 ACCEPTED MANUSCRIPT
amount of energy stored within molecules of H2 by multiple this jop with theoretical
thermodynamic potential of the water splitting process 1.23 V. In this case, ηSTH is
calculated by dividing output energy 1.23 x jop (mW/cm2) to input photon energy (Pin
mW/cm2) [27].

PT
RI
U SC
AN
M

Figure 6. Overlaid I-V curves of a p-type photocathode and an n-type photoanode

those constitute an artificial leaf for driving solar water splitting. The shaded area
represents the net solar energy stored within the molecules of H2.
D
TE

Indeed, this theoretical (maximum) ηSTH is calculated assuming (i) two

photoelectrodes are wired without any Ohmic drop and any issue regarding the work
EP

function of the wire employed and (ii) illuminated photocathode generates the same
driving force or electrical field compared with the external bias applied to the
C

photoanode when assaying its photocatalytic performance by employing a

AC

conventional three electrode setup. Therefore, in order to quantify the actual ηSTH
value, it is compulsory to construct a real artificial leaf from these two
photoelectrodes. The leaf then gets operated over an appropriate period, being suitable
for quantification of H2 amount generated. For example, it is possible that
photogenerated current in figure 6 is not relevant to the photo-driven OER or HER
chemical process but an unwanted self-corrosion event of photoelectrode materials.
Indeed, non-negligible photocorrosion was recorded for electrode materials like
CdS(Se) [28, 29], Cu2O [30, 31]. We found that a Cu2O based photocathode offered

12
 ACCEPTED MANUSCRIPT
only ca. 30% photocurrent to H2 conversion yield while 70% of photocurrent caused
Cu2O-to-Cu reduction [32]. For instance, operating BiVO4-Cu2O artificial leaf can
last for only few minutes making this actual performance determination impossible
[22].

Because it is relevant to the performance calculation of the final artificial leaf, the
operation of each individual photoelectrode should be assayed by a right manner. In

PT
this context, employment of electron or hole scavenger together with water should be
avoided. Indeed, hole scavenger like Na2S, ascorbic acid or even H2O2 is usually

RI
employed when assaying photocatalytic performance of photoanode material,
especially those facing the photocorrosion issue like CdS(Se) [33, 34]. This assay

SC
provides the best light harvesting performance that can be expected for the light
harvester under investigation. However, the performance is just relevant to the photo-

U
induced oxidation of hole scavenger but not water. In other words, the performance
recorded is not relevant to the solar-driven water splitting process of interests.
AN
For artificial leaf made of photovoltaics – water electrolyser assemblage

In this simple design, photovoltaics is used to power the electrolyser that splits water
M

molecule into H2 and O2 through the water electrolysis process. From the operation
curve of the photovoltaics (figure 7, bulk blue trace) and that of water electrolyser
D

(figure 7, dots black trace) we can assume the ideal operation point where the
TE

photovoltage created by photovoltaics induces the water splitting process with a rate
of jop [27, 35]. This gives idea of the water electrolysis yield driven by the system
EP

(1.23 V/ Eop). Multiplication this electrolysis yield with the solar-to-electric power
conversion efficiency of the photovoltaic gives the theoretical solar-to-H2 conversion
yield of the artificial leaf. Taking into account of the series resistance, lower ηSTH
C

value is expected for the actual operation (figure 7, bulk black trace). Therefore, it is
AC

critical to construct a real artificial leaf and get it operated over an appropriate of time
that generates sufficient amount of H2 for quantification experimentally e.g. by gas
chromatography. Such an operating device is a must to valid the actual ηSTH
performance.

13
 ACCEPTED MANUSCRIPT

PT
RI
SC
Figure 7. Overlaid current density-potential behaviour for a photovoltaics and a
water electrolyser.
U
AN
In practice, operation of photovoltaics and electrolyser are separately characterized.
The water electrolysis I-V curve is constructed by combining I-V curves of two half
M

reactions HER and OER determined through identical potential polarization rate.
From the operation principles, we note that improvement of ηSTH is feasible either by
D

enhancing the water electrolysis performance, e.g. via using a dual HER and OER
TE

catalysts functioning with low overpotential requirement (figure 7, bulk red trace), or
by enhancing power conversion efficiency of photovoltaics (figure 7, dash blue
trace).
EP

3. Materials aspects
C

In following sections we discuss on current trenches in development of materials

toward creation of a viable artificial leaf. Development of each component will be
AC

discussed with perspectives of its incorporation within different artificial leaf designs.

3.1 Light harvesting materials

3.1.1 For artificial leaf constituted of a large band gap semiconductor

As stated earlier (section 2.2.2), to be used within a single semiconductor based

artificial leaf, a semiconductor should fulfil following technical requirements:

14
 ACCEPTED MANUSCRIPT
(i) Display appropriate conduction band and valence band edge potentials for
driving the HER and OER.
(ii) Display band gap energy of at least 1.23 V that requires for the water
splitting process (eq. 3). Actually, overpotentials are required for driving
the HER (ηHER of ca. 100 mV) and the OER (ηOER of ca. 300 mV) at a
significant rate. Therefore, a band gap energy value larger than 1.6 eV is

PT
expected.
(iii) Display reasonable (photo)chemical stability

RI
To date, several large band gap semiconductors were investigated for the solar water
splitting like TiO2 [36], SrTiO3 [37], g-C3N4 [11, 38]. TiO2 displays a band gap

SC
energy Eg of 3.2 eV and suitable band edge potentials for driving force to drive the
overall solar water splitting. However, because of its large band gap, TiO2 absorbs

U
only in the UV region of the solar spectrum. To shift its absorption toward the visible
region, dopants being non-metal like N [18, 39, 40], P [41], S [41, 42] or metal like
AN
Cu [43], Fe [44] were introduced. In fact, elemental dopant either tunes the band
position or creates novel sub-band within the band gap causing the shifting of
M

absorption. As a consequence, visible light driven water splitting performance was

found to be significantly enhanced by doping strategy [18]. The same element doping
D

strategy was adopted to improve performance of graphitic carbon nitride g-C3N4,

TE

SrTiO3 [45, 46].

However, the ultimate goal is harvesting the whole solar spectrum for large-scale
solar H2 production. To this end, employing small or narrow band gap
EP

semiconductors is demanded. For instance, using semiconductor with small band gap
energy of ca. 2.0 eV for driving the solar water splitting process is challenging. Only
C

recently, Domen et al. successfully demonstrated the use of LaMg1/3Ta2/3O2N (Eg of

AC

2.08 eV) nanoparticles based artificial leaf under orange light (600 nm) [10]. This
represents an important progress toward harvesting the whole solar spectrum.
Otherwise, semiconductors with band gap energy of 2.0 eV or smaller are usually
suitable for only the HER or OER but not the overall water splitting process due to its
inappropriate band edge potentials (figure 8). Thus, they should be used in tandem.

15
 ACCEPTED MANUSCRIPT

PT
RI
Figure 8. Band edge potentials of some selected semiconductors (interfaced with a

SC
pH 0 electrolyte solution

3.1.2 For artificial leaf made of dual photoelectrodes

U
Photoanode carries the water oxidation process. Thus, n-type semiconductor is
AN
appropriate for this application. Moreover, it is compulsory that photo-generated
holes display sufficient oxidative driving force for driving the OER process.
Immersed in a pH 0 electrolyte solution, photoanode material should display a
M

valence band edge potential of + 1.23V vs. NHE or larger. Taking into account
overpotential requirement for the OER process on photoanode surface, e.g. about 300
D

mV for an efficient catalyst like IrO2, the valence band edge potential should be
TE

higher, e.g. at +1.53V vs. NHE. Indeed, several materials can fulfil this requirement
like large band gap semiconductor TiO2, WO3, BiVO4, or narrower band gap like
EP

CdS, Fe2O3, etc (figure 8). In contrast, p-type semiconductor having conduction band
edge potential of more reductive than 0V vs. NHE like Cu2O, Si is desired for
photocathode construction.
C

Chemical and or photochemical stability is also an important criteria for selection of

AC

semiconductor for artificial leaf engineering. Indeed, the material of choice should be
stable at least under operating conditions, namely under light illumination, being
immersed in corrosive electrolyte and with presence of generated H2 and O2 gases.
While several large band gap semiconductors like Ti2O, BiVO4, WO3, SrTiO3 etc are
chemical and photochemically stable, most of small or narrow band gap
semiconductors suffer from chemical and or photochemical corrosion issue. Indeed,
Si (Eg of 1.1 eV) is being largely exploited for both photoanode and photocathode
construction [16, 47-49]. However, it is suffered due to the chemical oxidation even

16
 ACCEPTED MANUSCRIPT
with an extremely low concentration of O2 in the operating medium. Whereas, Cu2O
(Eg of 2.1 eV) a promising photocathode material is suffered due to the
photocorrosion process [30]. Under light illumination Cu2O is rapidly reduced into
inactive Cu (Cu2O + 2e- + 2H+ → 2Cu + H2O) because of the photogenerated
electrons. Dealing with this issue, strategies are being proposed to protect Si, Cu2O as
well as other corrosive semiconductors, e.g. by employing smart protective materials

PT
like graphene sheets [50, 51], TiO2/ZnO based multiple layers [30] or catalyst layers
[16, 32, 48].

RI
Other figure of merits that need to be considered when selecting semiconductor for
solar water splitting application are mobility of carriers (electron and hole) and

SC
absorption depth of photon within semiconductor. As described in figure 5, high
mobility of carriers is desired for efficiently conducting the photogenerated carriers to

U
semiconductor surface where chemical processes (HER and OER) are expected. In
this context, emerging organic–inorganic hybrid perovskite that displays outstanding
AN
carrier diffusion length up to 1 µm [52, 53] is an ideal candidate if its instability issue
in contact with water is solved [17]. Other semiconductor usually displays nanoscale
M

carrier diffusion length. α-Fe2O3, a photoanode material being largely investigated,

displays very short diffusion length of 2-20 nm [54]. Elemental dopant helps to
D

promote the mobility of carriers but also creates defects for carriers trapping and
TE

recombination. Another potential approach to deal with the short diffusion length
issue is by creating nanostructure semiconductor like nanopillars, nanowires,
nanorods etc [55-58]. This nanoengineering approach is also valuable for dealing with
EP

the short diffusion depth of photon within semiconductor. In an ideal case, creation of
a nanowires semiconductor photoelectrode with wire width being equal to the
C

diffusion length of carriers allow maximizing the collection of carriers for driving
AC

HER and/ or OER process. At the same time, the nanowires forest trap solar light
limiting the unwanted light transmission and reflection (figure 9). Technical
challenge is to create such a perfect nanostructure in a well control manner, e.g.
avoiding the collapse of nanowires, especially when the length-to-width ratio of
nanowires is important.

17
 ACCEPTED MANUSCRIPT

PT
RI
Figure 9. A nanoengineering approach to maximize solar light harvesting
performance of semiconductor by dealing with short diffusion length of carriers and

SC
short absorption depth of photon within semiconductor

3.2 Catalyst
U
AN
Catalysts plays important role in accelerating multiple-electron and multiple-proton
chemical reactions, namely the Hydrogen Evolution Reaction (HER) and Oxygen
M

Evolution Reaction (OER) occurred on the surface of the light harvesters. In

following sections we describe current progress in development of novel OER and
D

HER catalysts as alternatives to noble metal based ones that had been known and used
TE

in water electrolysis. Our discussion highlights on biomimetic features of catalyst

design since remarkable advances were achieved by learning natural metalloenzymes.
EP

3.2.1 OER catalyst

Oxide of noble metals like IrO2, RuO2 were known to be efficient and robust catalysts
C

for the OER. IrO2 requires moderate overpotential of ca. 300 mV for operation. Ir and
AC

Ru are however among the elements being rarest on the earth`s crust. As a result,
abundant alternatives to these catalysts are hugely demanded in perspectives to scale
up renewable energy production via water electrolysis or solar water splitting.

Remarkably, OER catalytic centre within the photosystem II (PS II) of the natural
photosynthesis system was revealed to be an asymmetric cubane [CaMn4O5] (figure
10a) [59]. Mechanistic operation of this catalyst was discussed in details [60].
Because this catalyst operates in an efficient manner within the PSII, it quickly
became a source of inspiration for creation of novel OER catalyst. Indeed, several

18
 ACCEPTED MANUSCRIPT
mononuclear, binuclear, trinuclear and tetranuclear complexes of Mn were
synthesized [61, 62]. These synthetic compounds showed O2-evolving catalytic
activities that are still very far from the actual performance of the PSII, unfortunately.
One of possible reasons is due to the high symmetry of the synthetic compounds
making their conformation less flexible and thus they are less active for creation of O-
O bond. Even an identical [Mn4CaO4]6+ cubane designed by Agapie et al. [63] that

PT
displayed almost identical structural and spectroscopic features to those of the
[CaMn4O5] OER centre within PSII, showed much lower catalytic properties. Other

RI
than Mn, coordination compounds of other transition metals like Fe, Co, Ni, Ru were
investigated as OER catalysts [62]. Of all the catalysts, a Ru complex designed by

SC
Sun group displayed outstanding O2-evolving catalytic activities. It can speed up to a
record catalytic rate (turnover frequency TOFs) of over 300 s-1 being comparable with
the O2-evolving rate of 100-400 s-1 recorded for the [CaMn4O5] catalyst within PSII

U
[64]. However, the coordination complexes suffer from the oxidative decomposition
AN
during the operation, generating metal oxides small nanoparticles in some cases [65].
The [Mn4O4L6]+ cubane (where L is an organic ligand, namely diaryl phosphinate)
M

embedded within a Nafion membrane decomposed once high oxidation potential was
applied (e.g. +1.0V vs. Ag/AgCl) providing manganese-oxide nanoparticles which act
D

subsequently as the actual OER catalyst [65].

TE
C EP
AC

19
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Figure 10. Some selected OER catalyst. O2-evolving centre within the Natural
EP

photosynthesis (a) [59], Birnessite wherein an alkaline earth metal M is intercalated

between MnO2 layers (b) [66], amorphous cobalt oxide based, named as CoPi (c)
C

[67, 68], (Ni,Fe)OOH layered double hydroxide (d) [69] and absorption spectra
showing high transparency of a Fe doped NiOx catalyst (e) [70]
AC

As an alternative to the molecular approach described this above, designing of

nanomaterials based catalysts also offers great advances. Manganese oxide displaying
layered structure was found to display attractive OER catalytic activities [66, 71].
Interestingly, catalytic performance of this material can be tuned by incorporating
different alkaline and calcium column ions that act likely as Lewis acid site to
promote the O-O bond formation and or to accelerate the release of O2 molecule

20
 ACCEPTED MANUSCRIPT
(figure 10b) [66, 72]. It is worth noting that Ca2+ ion within the [CaMn4O5] cubane
also plays a key role during the O2-evolving cycle rather than just the role of a
spectator [60]. The catalytic performance of manganese oxides as well as of other
layered oxide materials was found to be tunable by changing the space distance
between layers. Thus, outstanding OER catalysts were achieved recently by using
single layer, few layers, nanosheets or thin nanoplates of metal oxides or metal

PT
hydroxides [73-76].

It is now a quite general observation that amorphous solid material displays higher

RI
catalytic activities compared with a crystalline equivalence. Within the disordered
structure of amorphous material, chemical bonding is more flexible compared with

SC
that within crystallized material. As a result, amorphous material offers better
activities for O-O or H-H chemical bond formation or cleavage. Indeed, Co3O4 is

U
significantly less active than an amorphous cobalt-oxide based material that was
referred to as CoPi by Nocera et al. (figure 10c) [67, 77, 78]. Furthermore, while
AN
generation of crystalline structure requires hard conditions like high temperature, high
pressure or vacuum, the amorphous material can be prepared employing relatively
M

soft conditions and thus it is scalable. The preparation of this CoPi can be accessed by
different methods like wet chemical solution, electrodeposition [67], photo-induced
D

deposition [49, 79, 80], etc. Remarkably, the CoPi displays several structural and
spectroscopic similarities to those of [CaMn4O5] cubane of the PSII [68, 81]. Perhaps
TE

because of this similarity, CoPi operates in a quite comparable mechanism compared

with [CaMn4O5] cubane [68, 82]. Most remarkably, CoPi displays self-healing
EP

capability that somehow the unique property of natural systems making this catalyst
an attractive catalyst for engineering long-term operation devices [83].
C

Other amorphous transition metal oxides like nickel-oxide-borate [84, 85], FeOOH
AC

[86, 87], were also developed. For instance, these catalysts are less active compared
with CoPi catalyst. However, it is important to note that crystalline iron oxide like
Fe2O3, Fe3O4 were known to be inactive while 10 nm thick film of amorphous
FeOOH catalyses the OER in 1M Na2CO3 solution with rather small onset
overpotential of ca. 350mV and reaction rate of 10 mA/cm2 is achieved at an applied
overpotential of 550 mV [86]. This performance is thus comparable to that obtained
for the amorphous cobalt-oxide-borate catalyst.

21
 ACCEPTED MANUSCRIPT
When the incorporation within artificial leaf is concerned, the transition metal oxides
are confronted with two limitations namely low electrical conductivity and light
absorption blocking properties. Transition metal oxides are semiconductors having
large band gaps, e.g. 3.7 eV for NiO. Thus, to overcome the electrical conductivity
issue, designing catalyst in form of thin film represents a potential approach.
Furthermore, thin film also offers better light transparency. We recall that for the

PT
artificial leaf engineering (figures 3b-d, 4b), light illumination is preferred from the
front photoanode side. Thus, light absorption and blocking properties of OER catalyst

RI
loaded onto photoanode is critical. In the visible light region, the transparency of up
to 90% is desired. A promising approach recently emerged is to dope the transition

SC
metal oxide catalysts with another transition metal or to develop novel bimetal oxide
catalysts (figures 10d,e) [70, 88]. That allows both enhancement of catalytic
performance and light transparency. Fe-doped NiO thin film was found to display

U
much higher catalytic performance compared with pristine NiO [88]. The same
AN
phenomenon was observed for CoOOH catalyst where Fe doping improved OER
activities up to 100 fold higher [89]. Details on operation mechanism of these doped
M

oxides as well as those of bimetal oxides like (NiFe)OOH are still under investigation
[69, 90, 91]. However, it is very likely that co-operation of two transition metal
D

centres results in enhanced catalytic performance.

To sum up, several OER catalysts both at molecular scale and nanoscale have been
TE

developed. Among them, amorphous oxides of transition metal and of bimetals appear
to be the most promising candidates. Indeed, they are readily for incorporation within
EP

artificial leaf engineering.

3.2.2 HER catalyst

C

Similar to the case of OER catalysts, noble metal based catalysts remain as the most
AC

effective and robust ones for the HER application. Pt catalyses the HER with almost
zero overpotential requirement. It offers high catalytic rate TOFs of 0.9 s-1 in pH 0
electrolyte solution [92]. However, due to its extremely low concentration in the earth
crust as well as its important uses in other applications like cancer treatment drug,
scaling up a hydrogen energy technology with Pt catalyst maybe questionable [93]. Pt
catalyst is being used in current H2 fuel cell technology [94, 95]. Searching for new
alternatives to Pt catalyst for both fuel cell technology and solar H2 generation
technology is urgently demanded.

22
 ACCEPTED MANUSCRIPT
Innovative alternatives can be created by inspiring structure and operation of natural
metalloenzymes like hydrogenases [96], CO-dehydrogenases [97] or nitrogenases
[98]. Remarkably, Armstrong and coll. demonstrated that a [NiFe] hydrogenases
expresses comparable catalytic activities for both HER and HOR (the Hydrogen
Oxidation Reaction) to those achieved with Pt nanoparticles catalyst [99]. To date,
few hundreds synthetic compounds mimicking the active centre of hydrogenases have

PT
been prepared and investigated for the HER. Progress of this research field has been
reviewed elsewhere [100-103]. Among the synthetic compounds, families of nickel

RI
bisdiphosphine and cobaloxime complexes gain great attentions. HER catalytic
activities of these complexes can be tuned by introducing a structural modification,

SC
e.g. via ligand design [100]. These catalysts can be also adapted for a post grafting
onto electrode surface (see section 4.1). Nickel bisdiphosphine complexes grafted
onto surface of CNTs electrodes displayed outstanding catalytic activities for both

U
HER and HOR processes with almost zero overpotential requirement [104-106].
AN
M
D
TE
EP

Figure 11. Layered structure of Cu2MoS4 made of [CuI4S4MoVI] building block unit
C

(a) and its H2-evolving catalytic activities assayed in different pH solution (b) [107].
AC

Other than hydrogenases, Mo-containing CO-deshydrogenases also display

hydrogenase activities under certain conditions [108]. By mimicking the active site of
this enzyme, we were successfully synthesized a solid crystalline material, namely
Cu2MoS4 (figure 11a) [107]. This material structure revealed by XRD powder
analysis showed a layer structure with [CuI4MoVIS4] building block. Thus, it has some
similarities to the structure of CO-hydrogenase active centre. We demonstrated that

23
 ACCEPTED MANUSCRIPT
Cu2MoS4 is an efficient HER and robust catalyst in water over a wide range of pH
solution (figure 11b). Therefore, this catalyst can be considered for incorporation
with both acidic and alkaline tolerant light harvester like Si or Cu2O. We found that
the H2-evolving catalytic activities are relied on the MoVI site while the CuI site just
plays as a Lewis centre. As a consequence, Cu2WS4 displayed significant weaker
performance while Ag2MoS4 showed similar activities compared with Cu2MoS4

PT
analogous.

RI
U SC
AN
M
D
TE
C EP
AC

Figure 12. Schematic representation of the MoS2 crystal structure with different
number of exposed edge site in function of platelet size (a)[109] and evolution of HER
catalytic activities in function of MoS2 area coverage and edge length (b) [92].

Among solid HER catalysts developed, molybdenum sulfide based materials (and its
tungsten, selenide analogous) were largely exploited and found to be among the most
promising alternatives to Pt catalyst [110-112]. Molybdenum sulfides refer to so-

24
 ACCEPTED MANUSCRIPT
called amorphous non-stoichiometric MoSx and layered crystalline MoS2. The
preparation of these materials can be easily accessed by different methods like wet
chemistry, electrodeposition, chemical vapour deposition, or just by a simple
exfoliation process using bulk MoS2 material [111-113]. For the case of MoS2, a rich
variety of morphology is accessible like nanoparticles, nanosheets, few-to-single layer
nanosheets. Remarkably, preparation of MoS2 quantum dots was recently

PT
demonstrated [114, 115]. By tuning the size of MoS2 platelets, number of exposed
Mo-edge sites is varied (figure 12a) [109]. This represents a valuable approach to

RI
tune the HER performance of this material. Indeed, it was evidenced that HER
catalytic activity was decided by the Mo-edge plane. A perfect linear dependence

SC
between H2-evolving reaction rate and MoS2 edge length was experimentally
evidenced by Chorkendorff et al. (figure 12b) [92]. In the sharp contrast, MoS2 basal
plane is essentially inactive. However, the basal plane can be activated by an

U
appropriate manner like chemical functionalization using a surfactant to tune the
AN
surface energy or creation of S-vacant sites via a thermal treatment process with H2
reagent [116] or a O2-plasma treatment [117]. Improvement of MoS2 catalytic
M

activities can be achieved by making nanosheets or nanoparticles in smaller size, thus

displaying higher specific surface area. Alternatively, high catalytic activities are
D

obtained by preparing MoS2 with few or single layers. HER performance depends
linearly to the number of layers [118]. HER performance also depends on the phase of
TE

MoS2. As such metastable phase 1T-MoS2 was found to be more active than the stable
2H-MoS2 phase [119]. Thus, strategies like using S-covalent chemical
EP

functionalization [120] or surfactant [121] were proposed to “stabilize” the active 1T-
MoS2 phase by lowing down its phase transformation to the 2H-MoS2.
C
AC

25
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Figure 13. Coordination polymer structure of amorphous molybdenum sulfide MoSx
M

constituted of [Mo3S13] 2- cluster and Mo=O defects (a) [122]. The cluster [123] and
defect species can be isolated from MoSx by treating this material with a KOH or
D

concentrated HCl solution (b)

TE

The structure of amorphous molybdenum sulfide MoSx is fundamentally different to

EP

that of MoS2. Recently we evidenced that MoSx is a coordination polymer made of

[Mo3S13]2- clusters as building blocks (figure 13a) [122]. In the perfect structure,
these clusters share two of their three terminal disulfide ligands making polymeric
C

chain. However, during growing, several defects sites being MoV-vacant or MoV=O
AC

(oxo) are incorporated within the structure. Most recently we successfully isolated a
[MoV=OCl4]- species from the MoSx polymer by treating this material with
concentrated HCl solution at 70°C (figure 13b). It is worth noting that the a-MoSx
material is relatively soft and its crystallization to MoS2 is readily induced by thermal
annealing [124], by an electron beam during TEM analysis or by a laser beam during
the Raman spectroscopic analysis [125]. Perhaps, this could be an explanation to the
fact that MoSx had been proposed having similar layered structure to MoS2 but with
more defect sites within its structure [126-128].

26
 ACCEPTED MANUSCRIPT
Even though, important progresses have been achieved for the molybdenum sulfide
based catalysts, several critical questions are still under debate. It was experimentally
evidenced that incorporation of a transition metal like Co, Ni within MoSx or MoS2
materials promoted its HER performance by a significant manner [128, 129]. The so-
called promoters were proposed to be located on the S-edge plane of MoS2, allowing
activate these planes [129]. Co promoter lowers down the free energy of the hydrogen

PT
adsorption ∆GH on the S-edge within MoS2 from +0.18 eV to 0.10 eV [129]. In other
words, adding Co promoter creates novel active sites for the H2 evolution. Indeed,

RI
Co(S2)Mo bimetal complexes were readily visualized on the S-edge plane of Co-
promoted MoS2 [130]. Structure of Co-promoted MoSx was also discussed recently

SC
[131]. Co promoter was proposed to present as CoS which bonds with MoS clusters
via S-S bond. This structure needs to be further elucidated in parallel with the
revealing of actual roles of Co sites onto the catalytic operation of CoMoSx materials.

U
These fundamental findings are critical food for thoughts in order to further improve
AN
catalytic performance of these sulfide materials as well as to design novel materials
being alternative to Pt catalyst.
M

4. Device engineering challenges

4.1 Creation of hybrid photoelectrode

D

Indeed, in all designs of artificial leaf (figures 3,4), catalysts are required to
TE

accelerate the slow kinetic of multiple electron reactions on light harvester surface. To
achieve this goal, light harvester - catalyst assemblage needs to fill several technical
EP

requirements: (i) electron communication in an efficient manner, (ii) robust linker,

(iii) limit surface defects (or surface passivation) to limit or supress the charges
surface recombination and (iv) give a protective layer to surface. In this section, we
C

discuss on different strategies already developed to create light harvester - catalyst

AC

assemblage with highlights on above technical requirements.

4.1.1 Assemblage via physical adsorption

Catalyst can be easily loaded onto surface or embedded within mesopores of light
harvester via physical interaction. Dropping a solution of [Mo3S4]4+ HER catalyst
onto Si pillars electrode resulted in generation of an efficient hybrid photocathode for
solar H2 generation [56]. In this electrode, [Mo3S4]4+ cluster is expected to be
physically adsorbed onto Si nanopilar surface. Not only molecular (or cluster based)

27
 ACCEPTED MANUSCRIPT
catalyst can be loaded onto electrode by this approach but also nanoparticle catalyst.
A suppension of Cu2MoS4 nanoparticle HER catalyst was applied via drop-casting
onto surface of Cu2O thin film electrode resulted in generation of Cu2O/Cu2MoS4
photocathode being interesting for the solar H2 generation in aqueous solution under
visible light illumination [32]. By this approach, thickness (also molar amount) of
catalyst loaded can be varied. Furthermore, this catalyst layer can act also as a

PT
protective layer for Cu2O against photocorrosion issue. However, in practice,
employing dip-coasting, drop-casting or spin-coating technics results in production of

RI
catalyst or photoelectrode with low mechanical stability where loaded catalyst weakly
binds to light harvester surface. As a consequence, higher performance is lower

SC
stability is since the catalyst progressively detaches from light harvester together with
H2 or O2 bubbles. A thermal treatment helps to improve mechanical properties as well
as the communication between light harvester and catalyst, thus improve both

U
performance and robustness of hybrid photoelectrodes.
AN
4.1.2 Assemblage via non-covalent chemical grafting

In order to achieve a robust photoelectrode, chemical interaction between catalyst

M

loaded and light harvester is hugely demanded. Indeed, chemical interaction is usually
stronger than a physical adsorption. Moreover, under some circumstance when the
D

chemical interaction is finely designed it can help to promote or even direct the
TE

electron transfer between the light harvester and the catalyst grafted.

Chemical interaction is classified into weak non-covalent grafting and stronger

EP

covalent grafting. Non-covalent grafting can be achieved through a π-π stacking

interaction between two appropriate conjugated aromatic systems. This approach has
been widely developed for functionalization of carbon nanotubes (CNTs) and
C

graphene sheets [105, 132]. For example, a pyrene group being a building block of
AC

CNTs or graphene is introduced into nickel bisdiphosphine HER catalyst.

Subsequently, this nickel-pyrene catalyst can be easily loaded onto CNTs or graphene
surface via π-π stacking (figure 14a) [105]. Thus, this strategy is applicable for
pyrene-based light harvester like carbon quantum dots or CNTs, graphene sensitized
with light harvester by quantum dots, nanoparticles or molecular dyes [133, 134]. It is
worth noting that graphene and carbon nanotubes were found to be effective
protective materials for Si [50, 135], Cu2O [136] light harvesters. In such a case,
loading catalyst onto graphene/light harvester surface is feasible.

28
 ACCEPTED MANUSCRIPT

PT
Figure 14. Schematic representation of some selected strategies for preparing

RI
electrode assemblage: via π-π stacking (a)[105], via embedding active agents within

SC
a conducting polymer (b)[137], and via covalent grafting (c)[138]

U
For other light harvesters where pyrene function or building block is not available, a
direct π-π stacking with catalyst molecule is unlikely to occur. However, non-
AN
covalent grafting can be achieved by employing a polymer as binder for light
harvester and catalyst assembling. Taking into account the HER and OER are
M

multiple-electron and multiple-proton process, polymer additive chosen should

display (i) a good electrophilic properties, (ii) good proton conductivity and (iii) good
D

electrical conductivity. Indeed, identification of a polymer filling all these

TE

requirements is challenging. Conducting polymers like PEDOT, polypyrrole display

good electrical conductivities (good hole transporter) but they resist to proton
transport. Even though, outstanding MoSx/polypyrrole HER catalyst was achieved by
EP

embedding MoSx catalyst within the polymer matrix of polypyrrole [139, 140].
Incorporating MoSx HER catalyst within a Ru-based polypyrrole light harvester
C

results in formation of an attractive photocathode for solar H2 evolution (figure 14b)

AC

[137]. Thus, it would be interesting to apply these catalyst/ conducting polymer

composites both as catalytic and protective layer for other light harvesters like Si,
Cu2O, etc.

For instance, other than conjugated conducting polymers, Nafion® that is a

hydrophilic and proton conductive polymer is usually employed as additive to
enhance light harvester - catalyst binding. Noting that Nafion® is privileged as proton
conducting membrane for construction of complete dual photoelectrodes artificial leaf
(figure 3b). Because Nafion® is an anionic mesoporous polymer [141], cationic

29
 ACCEPTED MANUSCRIPT
catalyst like [Mn4O4L6]+ can be easily incorporated via ion exchange process [142]. In
any case, the quantity of Nafion® added should be carefully optimized since Nafion®
is not electrical conductive. Thus, large amount of Nafion® additive may lower down
or even suppress the electron transfer between light harvester and catalyst embedded
within Nafion® matrix. Furthermore, Nafion® displays strong acidity that can be
harmful for several light harvesters like Cu2O and catalyst.

PT
To conclude, non-covalent grafting is relatively easy to access. However, to achieve a
robust photoelectrode, employment of covalent grafting is preferred.

RI
4.1.3 Assemblage via covalent chemical grafting

SC
Indeed, covalent grafting has been well developed for molecular dyas where
molecular dye (light sensitizer) is coupled with a catalyst via linker [143]. However,
less progress was achieved for semiconductor based light sensitizers, either in form of

U
nanoparticles or thin film electrodes. GaP electrode surface was first functionalized
AN
with a polyvinylpyridine polymer layer, created via the oxidative polymerization of
process. This polymer then offered a covalent bond with cobaloxime HER catalyst
since pyridine acted as an axial ligand (figure 14c) [138]. For oxide-based
M

semiconducting photoelectrodes, chemical functionalization can be made via

phosphate linker [144]. A versatile method to functionalize semiconducting electrode
D

surface (also for conducting electrode and dielectric material) is via reduction of
TE

appropriate diazonium salt [104, 145, 146]. Thus, electrode surface is first decorated
with desired chemical functions like amine, ester, thiol, etc. Subsequently, catalyst is
EP

loaded by creating strong chemical bond with readily available chemical functions on
the semiconductor surface.
C

4.1.4 Interfacing light harvester - catalyst via photo-assisted deposition

AC

In this section, we discuss on a strategy to create efficient and robust light harvester -
catalyst assemblage. Idea is to benefit photogenerated electron that is migrated within
semiconductor conduction band or photogenerated hole that is migrated within
semiconductor valence band as reducing and oxidizing driving force to convert
appropriate precursor into HER and OER catalyst. By this way, HER and OER
catalysts are located at the active sites on the surface of light harvester, where carriers
(electron and hole) are transferred. Thus, we can consider HER and OER catalysts are
positioned at the best position for their subsequent operation, namely H2-evolution

30
 ACCEPTED MANUSCRIPT
and O2-evolution reactions. Such a well positioned situation could be difficult to
achieve for other assemblage methods described this above.

PT
RI
U SC
AN
Figure 15. Photoassisted deposition of cobalt oxide based OER catalyst on ZnO
nanorods (a)[79] and molybdenum sulfide based HER catalyst on B-doped Si wafer
M

(b)[48]
D

CoPi OER catalyst which is an amorphous cobalt oxide based material was
TE

successfully decorated onto surface of ZnO nanorods (figure 15a) [79], Fe2O3 thin
film [80] when these light harvesters are illuminated by visible light while immersed
EP

in a deposition bath consisted of Co(NO3)2 precursor and phosphate electrolyte. Other

OER catalyst like amorphous FeO(OH) was also successfully deposited onto light
C

harvester surface by employing the same method [87, 147]. Resultant photoanode
displayed significant enhancement of solar-driven water splitting performance
AC

compared with pristine light harvester without OER catalyst decoration.

Adopting the same strategy, we successfully created MoSx based hybrid

photocathodes being efficient for solar H2 generation. Amorphous MoSx, CoMoSx
thin layer was deposited on p-type B-doped Si electrode immersed in a deposition
bath consisted of [MoS4]2- or [Co(MoS4)2]2- precursor when this electrode is
illuminated by visible light (figure 15b) [48]. With this method, we were able to
finely control thickness (amount) of deposits in order to offer the best catalytic

31
 ACCEPTED MANUSCRIPT
performance as well as the best protective effect to Si light harvester. Indeed,
Si/CoMoSx with a catalyst layer of 92 nm in thickness offers the best H2-evolution
performance under 1 Sun standard light source illumination: photovoltage of +0.25 V
vs. RHE (Reversible Hydrogene Electrode) and photocurrent of 17.5 mA/cm2 at
applied voltage of 0V vs. RHE. This behaviour belongs to the best performances
achieved to date for a noble metal free photocathodes. Applying the same method,

PT
MoSx HER catalyst was loaded onto surface of semiconductor nanoparticles like
CdZnS [148], TiO2 [149] and CdS sensitized graphene oxide [150]. In these cases

RI
with nanoparticle semiconductors, a hole scavenger like methanol is demanded that
helps to suppress photogenerated hole and therefore drive photogenerated electron to

SC
semiconductor surface for creating HER catalysts.

It was noted that photoelectrodes prepared by this method offered not only high

U
photocatalytic performance but also attractive robustness. Si/CoMoSx can last for
hours of operation: small degradation of 10% of the initial performance was observed
AN
after 3h [48]. It indicates a strong electron communication between light harvester and
catalyst as well as robustness of the assemblage. Nocera and coll. used the term of
M

buried junction to describe this light harvester - catalyst structure. Indeed, we notice
that light harvester - catalyst binding nature in these electrodes can be just physical
D

adsorption, like in the case of Si/CoMoSx photocathode [48]. However, strong

covalent grafting can be also expected as for the cases ZnCdS/MoSx (e.g. via thiolate
TE

linker) or ZnO/CoPi (e.g. via oxo/ hydroxo linker) [79, 148].

4.2 Creation of bias free artificial leaf

EP

This above discussion points out difficulties in creation of an effective

photoelectrode, both photocathode and photoanode side. Actually, some methods
C

described this above can be easily applied for creation of complete artificial leaf.
AC

However, other methods seem to be complicated with costly efforts need to be

invested if we want to adopt.

4.2.1 Creation of photovoltaics - electrolyser assemblage

This simple configuration is achieved by wiring a solar cell generating sufficient

photovoltage and an electrolyser made of two appropriate HER and OER catalysts.
Once solar cell stands out of water and only two HER and OER electrodes are
immersed in water, the technical challenge is minimized. Keeping a CH3NH3PbI3

32
 ACCEPTED MANUSCRIPT
pervoskite solar cell, having solar-to-electric power conversion efficiency of 17.3%,
out of contact with water and employing NiFe layered double hydroxide deposited on
Ni foam electrode as catalyst for both the HER and OER, Gratzel and coll.
demonstrated an artificial leaf that offers solar-to-H2 conversion yield of 12.3% [151].
The word record of 30% was recently reported by Jaramillo and coll. by using a triple
junction InGaP/GaAs/GaInNAs solar cell to power a dual of proton exchange

PT
membrane electrolyser constituted of Pt HER catalyst and Ir OER catalyst [152].

Enormous challenges are confronted when a wireless artificial leaf is desired. To this

RI
end, HER and OER catalysts should be loaded onto two sides of the solar cell. In
principles, all assemblage methods described this above can be applied. However,

SC
non-covalent and covalent methods are not used because intensive synthetic works are
demanded like chemical functionalization of solar cell surface as well as of HER,

U
OER catalysts prior to assembled. Nocera et al. proposed a successful approach by
employing electrodeposition and photo-assisted deposition methods [49]. As such,
AN
negative side of a triple junction amorphous Si solar cell was coated with NiMoZn
alloy acting as efficient HER catalyst. CoPi OER catalyst layer was coated onto the Si
M

side, the positive side of Si solar cell, by employing the light assisted
electrodeposition. To protect Si against the chemical corrosion, a conducting and
D

transparent protective layer made of ITO was applied. The resultant CoPi/Si/NiMoZn
artificial leaf displayed solar-to-H2 conversion yield of 4.7% under standard 1 Sun
TE

light illumination and in pH 9.2 electrolyte solution. Slight alkaline condition is

applied in order to avoid the chemical corrosion of the catalyst layers. With identical
EP

Si triple junction solar cell but with NiFeOx used as both HER, OER catalysts,
Rocheleau and Miller reported engineering of an artificial leaf with better conversion
C

yield of 7% [153]. Indeed, these achievements represent significant progress in the

AC

field. However, robustness of these devices remains as a big challenge. For instance,
these devices can last for hours under operation conditions. After 24h, Nocera`s leaf
lost ca. 20% of its initial performance. Since HER and OER catalysts employed are
robust, it is likely that instability of Si solar cell, even it is protected, causes
degradation of the leaf.

33
 ACCEPTED MANUSCRIPT

Table 1. Selected operating bias-free artificial leaf

STH
Light HER OER Robustnes Operating
Entry Leaf design efficiency Refs.
harvester catalyst catalyst s condition
(%)
Mo:BiVO4
(anode)
1 Colloidal Ru RuOx 1.1 NA pH 6.8 [154]
La,Rh:SrTiO3

PT
(Cathode)

RI
CoO neutral
2 Colloidal CoO CoO ~5 ~1 hour [155]
nanoparticles water

SC
3 PV-electrolyser CuInGaS Pt Pt 10.5 NA 3M H2SO4 [156]

InGaP/GaAs/

U
AN
GaInAsSb neutral
4 PV-electrolyser Pt Ir 30 >48 hrs [152]
triple junction water
solar cell
a-Si:H/a-
Si:H/ µc-Si:H 0.1 M
M

5 PV-electrolyser Pt RuO2 9.5 > 4 hrs [157]

triple junction KOH
solar cell
0.5 M KBi
D

3 junction a-Si 2.5 and 1.5 M

6 PV-Electrolyser CoPi NiMoZn KNO3 [49]
solar cell
1.75 ~10 hours 1M KBi
TE

lost 7%
perovskite
7 PV-electrolyser NiCo2O4 NiCo2O4 6.2 after 0.1M KOH [158]
solar cell
30min
EP

Neutral
Mo:BiVO4
Dual NiOOH/ phosphate
8 and Pt 0.67 > 2 hrs [24]
photoelectrodes FeOOH buffer
(Ag,Cu)GaSe2
solution
C

no decay phosphate
Dual α-Fe2O3 and
9 Pt NiFeOx 0.91 after first buffer pH [159]
photoelectrodes Si/TiO2
AC

10h 11.8
19.3
Ga0.41In0.59P
Dual (acidic); acidic or
10 and Ru RuOx 20h [160]
photoelectrodes 18.5 neutral pH
Ga0.89In0.11As
(neutral)
Dual GaN/InGaN
11 Pt Pt 2 NA 1M HBr [23]
photoelectrodes and Si/InGaN

34
 ACCEPTED MANUSCRIPT
4.2.2 Creation of artificial leaf constituted of a dual photoelectrodes

In a simple way, two photoelectrodes are wired in series. Sivula et al. demonstrated an
operating artificial leaf constituted of a BiVO4 photoanode and a Cu2O photocathode
[22]. Cobalt oxide (CoPi) and RuOx were used as OER and HER catalysts,
respectively. The solar-to-H2 conversion yield was estimated to be moderate, ca.
0.5%, based on the photoelectrode operation I-V curves. However, the actual

PT
performance determined based on the H2 quantification was not available due to the
instability of the leaf, e.g. it is stable for only for few minutes. The degradation was

RI
attributed to the detachment of CoPi catalyst from photoanode during the O2-
evolution. For instance, an efficient artificial leaf by this dual photoelectrodes design

SC
is still to be demonstrated. We note that, with this configuration, a Nafion membrane
can be used to separate the anode and cathode compartments. In such an ideal

U
situation a separate collection of H2 and O2 generated will be feasible (figure 3c).
AN
Alternatively, these two electrodes can be packed via back-to-back manner employing
a transparent conducting oxide (TCO) layer like ITO, FTO or CNTs as Ohmic contact
as described in figure 3b. Recently, Krauss et al. demonstrated an effective proton
M

and electron transport through a membrane made of vertically aligned single wall
carbon nanotube (SWCNTs) being free of Nafion® [161]. This SWCNTs membrane
D

can be thus used for assembling with dual photoelectrodes. However, technical
TE

challenges are remained for assembling these CNTs based membranes with light
harvesters. For instance, applying a CNTs based membrane onto surface of a
photoelectrode seems to be feasible [135] but growing a photoelectrode material on
EP

these membranes is challenging. To the best of our knowledge, a complete bias free
artificial leaf constructed following the design in figure 3b still lacks in the open
C

literature.
AC

35
 ACCEPTED MANUSCRIPT

PT
RI
Figure 16. Ink made of La,Ru-codoped SrTiO3 photocathode nanoparticles and Mo-

SC
doped BiVO4 photoanode nanoparticles (a) used for fabrication of artificial leaf by
screen printing onto an Au substrate (b) [154]

U
Alternative to above described design, a rather simple way to construct dual
AN
photoelectrodes artificial leaf is via assembling the dual electrodes onto the same
conducting substrate by a side-to-side manner. Any conducting substrate, either TCO
or metal, can be used. Screen printing an ink constituted of La,Ru-codoped SrTiO3
M

photocathode nanoparticles and Mo-doped BiVO4 photoanode nanoparticles (figure

16a) onto an Au substrate resulted in generation of an artificial leaf that displayed
D

solar-to-H2 conversion yield of over 1% and an outstanding apparent quantum yield of

TE

over 30% at short wavelength of 419 nm (figure 16b) [154]. Indeed, this remarkable
technology proposed by Domen et al. could open up the large-scale production of
EP

artificial leaf. A drawback, if any, of this technology is the difficulty to collect H2 and
O2 gases separately. That is because photoanode and photocathode materials are co-
deposited on the same surface location for instance. We note that a separate collection
C

of H2 and O2 gases produced is an essential safety requirement in regard of large-scale

AC

production of H2 fuel. To this end, the design described in figure 3d could be a

solution if the photocathode and photocathode inks are deposited selectively on two
locations of an Au substrate surface.

4.3 Stability issue

Few operating artificial leaves were developed by adopting different designs

described this above. For the reported leaves, robustness remains as the biggest
challenge. The best leaf can operate for hours [153]. But it is still too far from the

36
 ACCEPTED MANUSCRIPT
target of 1000 h demanded by the US Department of Energy. Several reasons behind
this limited stability can be pointed out. Serious issue comes from light harvesting
materials. Excluding few cases like α-Fe2O3, almost all small or narrow band gap
semiconductors are not chemically or photochemically stable. They are subjected to
chemical corrosion (like Si, CH3NH3PbX3 perovskite) or photoelectrochemical
corrosion (like Cu2O, CdS, CdSe, etc). Thus, a challenge remained now is to identify

PT
appropriate strategy to protect these light harvesters while still keep or even improve
its light harvesting performance [30, 50, 162].

RI
Instability of artificial leaf can also potentially come from the degradation of HER
and OER catalysts employed. It is now a precaution that detail verification and

SC
characterization should be done on catalyst just after being incorporated within
photoelectrode or artificial leaf as well as after operation of these devices. It was

U
demonstrated that in some cases, molecular catalysts decomposed right after being
incorporated or during catalytic operation. [Mn4O4L6]+ cubane, embedded within
AN
Nafion® membrane, decomposed generating small manganese oxide nanoparticle that
subsequently acted as actual OER catalyst [65]. Cobalt-based molecular catalysts
M

decomposition giving cobalt oxide based nanoparticles acting as HER catalyst was
also evidenced [163, 164]. We observed recently the phase transformation from
D

amorphous molybdenum sulfide MoSx to crystalline MoS2 induced by light

TE

illumination [125]. Since MoSx is more catalytic active than MoS2, this phase
transformation can cause a degradation of photoelectrode performance.

Another important consideration is the stability of the HER and OER catalysts under
EP

redox stress conditions. This issue is critical for single nanoparticle based artificial
leaf (figure 3a). Indeed, HER catalyst is expected to work with photogenerated
C

electrons, meaning under reducing conditions. However, if the carrier transport is not
AC

directional selective, the HER catalyst can be exposed to a strong oxidative potential
caused by the photogenerated holes. It was demonstrated that oxidation stress causes a
destructive oxidation of MoSx and MoS2 HER catalyst generating un-reactive MoO3
[125, 129]. A destructive reduction can be also happened for OER catalyst loaded.
Fortunately this phenomenon is suppressed in the photovoltaic-electrolyser or dual
photoelectrodes artificial leaf configurations because HER and OER catalysts are
located onto photocathode and photoanode sides, respectively. Concerning the case of

37
 ACCEPTED MANUSCRIPT
the single nanoparticle-based artificial leaf, to limit or avoid these unwanted
decomposition events following strategies can be considered:

(i) employment of robust HER and OER catalysts those resist to any
destructive oxidation and reduction. Noble metal based catalysts like Pt,
IrO2, RuO2 full fill this requirement. Indeed, Domen et al. have developed
several attractive systems based on this concept [165].

PT
(ii) employment of bifunctional or Janus catalyst [11, 166-168]. Cobalt oxide
based material is efficient for the OER under oxidative condition [67,

RI
166]. Once it is conditioned in reductive potential, it is converted into
cobalt oxo/hydroxo based material which is efficient for the HER [166].

SC
We have demonstrated that cobalt oxide acts as both HER and OER
catalyst for activating the graphitic carbon nitride (g-C3N4) light harvester

U
thus generating an robust g-C3N4/Cobalt oxide nanoparticle based artificial
leaf [11].
AN
Lastly, stability issue of the artificial leaf is caused by weak binding between
M

components, e.g. between light harvester and catalyst. Covalent binding (see section
4.1.3) could be a solution if the linker deployed can drive the electron transfer
D

between light harvester and catalyst.

TE

To sum up, in order to achieve 1000 h of operation, artificial leaf should be made of
components whose robustness last for at least 1000 h. Furthermore, these components
EP

should be assembled via a perfect manner. Alternatively, artificial leaf can be made of
components displaying low stability but they can be self-healed once they
C

decomposed under operation conditions. Indeed, natural photosysnthesis is

engineered by adopting this strategy [5]. Depending on light intensity, natural
AC

photosynthesis system can be last only for a short period of 30-60 min [5]. However,
natural leaf operates for years thanks to the remarkable self-healing properties of the
natural photosynthesis system. Engineering an artificial leaf displaying this self-
healing property could be a strategy to be exploited in order to achieve the enormous
1000 h operation target. For instance, Nocera et al. demonstrated the self-healing
properties of cobalt oxide based OER catalyst [83]. At open circuit voltage, cobalt
oxide film dissolved into phosphate buffer solution. However, applying an oxidative

38
 ACCEPTED MANUSCRIPT
potential quickly results in the re-deposition of this cobalt oxide thin film onto
electrode surface.

5. Conclusions and remarks

To conclude, important progresses have been achieved in development of components

those are essential for creation of an artificial leaf. Chemistry of the natural
photosynthesis offers a great source of inspiration for designing novel catalyst for the

PT
water electrolysis process. Indeed, efficient and robust HER and OER catalysts made
of earth abundant elements, just being attractive alternatives to noble metal based

RI
catalyst like Pt, IrO2, are now available. On the other hand, thanks to the evolution of
photovoltaics community, several families of semiconductors are identified as

SC
promising light harvesters for solar water splitting applications like nanostructured
and doped Si, Cu2O, Fe2O3, solution processing organic based light harvester, etc.

U
From these components, few examples of complete artificial leaf that operate with
AN
just water and solar energy input were demonstrated. However, their performances
and robustness still need to be significantly improved. To this end, improving
performance and robustness of each component separately prior to get the device
M

assembled could be a strategy. However, experiences gained from the photovoltaics

community shows that device performance could be better and faster progressed by
D

getting the device assembled and operated under the technological relevant
TE

conditions. Therefore, with readily available artificial leaves we could expect for
more significant advances in coming years in order to make possible the large scale
H2 production by solar water splitting technology.
EP

Acknowledgment
C

This work was supported by the National Foundation for Science and Technology
AC

Development (NAFOSTED, project code 103.99-2015.46).

References and Notes

[1] N.S. Lewis, D.G. Nocera, Powering the planet: Chemical challenges in solar
energy utilization, Proc. Natl. Acad. Sci. U.S.A 103 (2006) 15729-15735.
[2] K.A. Mazzio, C.K. Luscombe, The future of organic photovoltaics, Chem. Soc.
Rev. 44 (2015) 78-90.
[3] C. Battaglia, A. Cuevas, S. De Wolf, High-efficiency crystalline silicon solar
cells: status and perspectives, Energy Environ. Sci. 9 (2016) 1552-1576.

39
 ACCEPTED MANUSCRIPT
[4] A. Kudo, Y. Miseki, Heterogeneous photocatalyst materials for water splitting,
Chem. Soc. Rev. 38 (2009) 253-278.
[5] J. Barber, Photosynthetic energy conversion: natural and artificial, Chem. Soc.
Rev. 38 (2009) 185-196.
[6] https://energy.gov/eere/fuelcells/doe-technical-targets-hydrogen-
production-photoelectrochemical-water-splitting.
[7] A. FUJISHIMA, K. HONDA, Electrochemical Photolysis of Water at a
Semiconductor Electrode, Nature, 238 (1972) 37-38.
[8] T. Hisatomi, J. Kubota, K. Domen, Recent advances in semiconductors for

PT
photocatalytic and photoelectrochemical water splitting, Chem. Soc. Rew. 43
(2014) 7520-7535.
[9] K. Maeda, K. Teramura, D. Lu, N. Saito, Y. Inoue, K. Domen, Noble-

RI
Metal/Cr2O3 Core/Shell Nanoparticles as a Cocatalyst for Photocatalytic Overall
Water Splitting, Angew. Chem. Int. Ed., 45 (2006) 7806-7809.
[10] C. Pan, T. Takata, M. Nakabayashi, T. Matsumoto, N. Shibata, Y. Ikuhara, K.

SC
Domen, A Complex Perovskite-Type Oxynitride: The First Photocatalyst for
Water Splitting Operable at up to 600 nm, Angew. Chem. Int. Ed., 54 (2015)
2955-2959.
[11] R.-L. Lee, P.D. Tran, S.S. Pramana, S.Y. Chiam, Y. Ren, S. Meng, L.H. Wong, J.

U
Barber, Assembling graphitic-carbon-nitride with cobalt-oxide-phosphate to
AN
construct an efficient hybrid photocatalyst for water splitting application, Catal.
Sci. Tech. 3 (2013) 1694-1698.
[12] Y.-H. Liu, B. Yi, Z.-G. Shao, D. Xing, H. Zhang, Carbon Nanotubes Reinforced
Nafion Composite Membrane for Fuel Cell Applications, Electrochem. Solid State
M

Lett. 9 (2006) A356-A359.

[13] M. Haro, C. Solis, G. Molina, L. Otero, J. Bisquert, S. Gimenez, A. Guerrero,
Toward Stable Solar Hydrogen Generation Using Organic Photoelectrochemical
D

Cells, J. Phys. Chem. C, 119 (2015) 6488-6494.

[14] T. Bourgeteau, D. Tondelier, B. Geffroy, R. Brisse, C. Laberty-Robert, S.
TE

Campidelli, R. de Bettignies, V. Artero, S. Palacin, B. Jousselme, A H2-evolving

photocathode based on direct sensitization of MoS3 with an organic photovoltaic
cell, Energy Environ. Sci. 6 (2013) 2706-2713.
EP

[15] H.C. Rojas, S. Bellani, F. Fumagalli, G. Tullii, S. Leonardi, M.T. Mayer, M.

Schreier, M. Gratzel, G. Lanzani, F. Di Fonzo, M.R. Antognazza, Polymer-based
photocathodes with a solution-processable cuprous iodide anode layer and a
polyethyleneimine protective coating, Energy Environ. Sci. 9 (2016) 3710-3723.
C

[16] B. Seger, A.B. Laursen, P.C.K. Vesborg, T. Pedersen, O. Hansen, S. Dahl, I.

Chorkendorff, Hydrogen Production Using a Molybdenum Sulfide Catalyst on a
AC

Titanium-Protected n+p-Silicon Photocathode, Angew. Chem. Int. Ed., 51 (2012)

9128-9131.
[17] S.N. Habisreutinger, T. Leijtens, G.E. Eperon, S.D. Stranks, R.J. Nicholas, H.J.
Snaith, Carbon Nanotube/Polymer Composites as a Highly Stable Hole Collection
Layer in Perovskite Solar Cells, Nano Lett. 14 (2014) 5561-5568.
[18] S. Hoang, S. Guo, N.T. Hahn, A.J. Bard, C.B. Mullins, Visible Light Driven
Photoelectrochemical Water Oxidation on Nitrogen-Modified TiO2 Nanowires,
Nano Lett. 12 (2012) 26-32.
[19] H.S. Park, K.E. Kweon, H. Ye, E. Paek, G.S. Hwang, A.J. Bard, Factors in the
Metal Doping of BiVO4 for Improved Photoelectrocatalytic Activity as Studied by

40
 ACCEPTED MANUSCRIPT
Scanning Electrochemical Microscopy and First-Principles Density-Functional
Calculation, J. Phys. Chem. C, 115 (2011) 17870-17879.
[20] D. Shan, Y. Ji, D. Li, J. Xu, M. Qian, L. Xu, K. Chen, Enhanced carrier mobility in
Si nano-crystals via nanoscale phosphorus doping, Appl. Surf. Sci., 425 (2017)
492-496.
[21] Y. Ma, S.R. Pendlebury, A. Reynal, F. Le Formal, J.R. Durrant, Dynamics of
photogenerated holes in undoped BiVO4 photoanodes for solar water oxidation,
Chem. Sci. 5 (2014) 2964-2973.
[22] P. Bornoz, F.F. Abdi, S.D. Tilley, B. Dam, R. van de Krol, M. Graetzel, K. Sivula,

PT
A Bismuth Vanadate–Cuprous Oxide Tandem Cell for Overall Solar Water
Splitting, J. Phys. Chem. C, 118 (2014) 16959-16966.
[23] B. AlOtaibi, S. Fan, S. Vanka, M.G. Kibria, Z. Mi, A Metal-Nitride Nanowire

RI
Dual-Photoelectrode Device for Unassisted Solar-to-Hydrogen Conversion under
Parallel Illumination, Nano Lett. 15 (2015) 6821-6828.
[24] J.H. Kim, H. Kaneko, T. Minegishi, J. Kubota, K. Domen, J.S. Lee, Overall

SC
Photoelectrochemical Water Splitting using Tandem Cell under Simulated
Sunlight, ChemSusChem, 9 (2016) 61-66.
[25] A. Fihri, V. Artero, M. Razavet, C. Baffert, W. Leibl, M. Fontecave, Cobaloxime-
Based Photocatalytic Devices for Hydrogen Production, Angew. Chim. Int. Ed.,

U
120 (2008) 574-577.
AN
[26] K. Maeda, K. Teramura, D. Lu, T. Takata, N. Saito, Y. Inoue, K. Domen,
Photocatalyst releasing hydrogen from water, Nature, 440 (2006) 295-295.
[27] M.G. Walter, E.L. Warren, J.R. McKone, S.W. Boettcher, Q. Mi, E.A. Santori, N.S.
Lewis, Solar Water Splitting Cells, Chem. Rev. 110 (2010) 6446-6473.
M

[28] D.J. Fermín, E.A. Ponomarev, L.M. Peter, A kinetic study of CdS
photocorrosion by intensity modulated photocurrent and photoelectrochemical
impedance spectroscopy, J. Electroanal. Chem. 473 (1999) 192-203.
D

[29] Y. Tang, X. Hu, C. Liu, Perfect inhibition of CdS photocorrosion by graphene

sheltering engineering on TiO2 nanotube array for highly stable photocatalytic
TE

activity, Phys. Chem. Chem. Phys. 16 (2014) 25321-25329.

[30] A. Paracchino, V. Laporte, K. Sivula, M. Grätzel, E. Thimsen, Highly active
oxide photocathode for photoelectrochemical water reduction, Nat. Mater. 10
EP

(2011) 456-461.
[31] M.-B. Ignacio, C. Marc, F. Hong Jin, F. Denis, Conformal Cu 2 S-coated Cu 2 O
nanostructures grown by ion exchange reaction and their photoelectrochemical
properties, Nanotechnology, 26 (2015) 185401.
C

[32] C. Yang, P.D. Tran, P.P. Boix, P.S. Bassi, N. Yantara, L.H. Wong, J. Barber,
Engineering a Cu2O/NiO/Cu2MoS4 hybrid photocathode for H2 generation in
AC

water, Nanoscale, 6 (2014) 6506-6510.

[33] Z. Bai, X. Yan, Y. Li, Z. Kang, S. Cao, Y. Zhang, 3D-Branched ZnO/CdS
Nanowire Arrays for Solar Water Splitting and the Service Safety Research, Adv.
Energy Mater., 6 (2016) 1501459.
[34] J. Luo, L. Ma, T. He, C.F. Ng, S. Wang, H. Sun, H.J. Fan, TiO2/(CdS, CdSe, CdSeS)
Nanorod Heterostructures and Photoelectrochemical Properties, J. Phys. Chem.
C, 116 (2012) 11956-11963.
[35] D.G. Nocera, The Artificial Leaf, Acc. Chem. Res. 45 (2012) 767-776.
[36] R. Li, Y. Weng, X. Zhou, X. Wang, Y. Mi, R. Chong, H. Han, C. Li, Achieving
overall water splitting using titanium dioxide-based photocatalysts of different
phases, Energy Environ. Sci. 8 (2015) 2377-2382.

41
 ACCEPTED MANUSCRIPT
[37] K. Han, T. Kreuger, B. Mei, G. Mul, Transient Behavior of Ni@NiOx
Functionalized SrTiO3 in Overall Water Splitting, ACS Catal. 7 (2017) 1610-1614.
[38] G. Zhang, Z.-A. Lan, X. Wang, Surface engineering of graphitic carbon nitride
polymers with cocatalysts for photocatalytic overall water splitting, Chem. Sci. 8
(2017) 5261-5274.
[39] P.V.R.K. Ramacharyulu, D.B. Nimbalkar, J.P. Kumar, G.K. Prasad, S.-C. Ke, N-
doped, S-doped TiO2 nanocatalysts: synthesis, characterization and
photocatalytic activity in the presence of sunlight, RSC Adv. 5 (2015) 37096-
37101.

PT
[40] Y. Cong, J. Zhang, F. Chen, M. Anpo, Synthesis and Characterization of
Nitrogen-Doped TiO2 Nanophotocatalyst with High Visible Light Activity, The J.
Phys. Chem. C, 111 (2007) 6976-6982.

RI
[41] K. Yang, Y. Dai, B. Huang, Understanding Photocatalytic Activity of S- and P-
Doped TiO2 under Visible Light from First-Principles, J. Phys. Chem. C, 111
(2007) 18985-18994.

SC
[42] T. Ohno, M. Akiyoshi, T. Umebayashi, K. Asai, T. Mitsui, M. Matsumura,
Preparation of S-doped TiO2 photocatalysts and their photocatalytic activities
under visible light, Appl. Catal. A: General, 265 (2004) 115-121.
[43] H.M. Yadav, S.V. Otari, V.B. Koli, S.S. Mali, C.K. Hong, S.H. Pawar, S.D. Delekar,

U
Preparation and characterization of copper-doped anatase TiO2 nanoparticles
AN
with visible light photocatalytic antibacterial activity, J. Photochem. Photobiol. A:
Chemistry, 280 (2014) 32-38.
[44] S. Piskunov, O. Lisovski, J. Begens, D. Bocharov, Y.F. Zhukovskii, M. Wessel, E.
Spohr, C-, N-, S-, and Fe-Doped TiO2 and SrTiO3 Nanotubes for Visible-Light-
M

Driven Photocatalytic Water Splitting: Prediction from First Principles, J. Phys.

Chem. C, 119 (2015) 18686-18696.
[45] C. Wang, H. Qiu, T. Inoue, Q. Yao, Band gap engineering of SrTiO3 for water
D

splitting under visible light irradiation, Int. J. Hydrogen Energy, 39 (2014)

12507-12514.
TE

[46] Y. Yang, S. Wang, Y. Li, J. Wang, L. Wang, Strategies for Efficient Solar Water
Splitting Using Carbon Nitride, Chem. Asian J., 12 (2017) 1421-1434.
[47] A.C. Nielander, M.J. Bierman, N. Petrone, N.C. Strandwitz, S. Ardo, F. Yang, J.
EP

Hone, N.S. Lewis, Photoelectrochemical Behavior of n-Type Si(111) Electrodes

Coated With a Single Layer of Graphene, J. Am. Chem. Soc. 135 (2013) 17246-
17249.
[48] Y. Chen, P.D. Tran, P. Boix, Y. Ren, S.Y. Chiam, Z. Li, K. Fu, L.H. Wong, J.
C

Barber, Silicon Decorated with Amorphous Cobalt Molybdenum Sulfide Catalyst

as an Efficient Photocathode for Solar Hydrogen Generation, ACS Nano, 9 (2015)
AC

3829-3836.
[49] S.Y. Reece, J.A. Hamel, K. Sung, T.D. Jarvi, A.J. Esswein, J.J.H. Pijpers, D.G.
Nocera, Wireless Solar Water Splitting Using Silicon-Based Semiconductors and
Earth-Abundant Catalysts, Science, 334 (2011) 645-648.
[50] A.C. Nielander, A.C. Thompson, C.W. Roske, J.A. Maslyn, Y. Hao, N.T. Plymale,
J. Hone, N.S. Lewis, Lightly Fluorinated Graphene as a Protective Layer for n-Type
Si(111) Photoanodes in Aqueous Electrolytes, Nano Lett. 16 (2016) 4082-4086.
[51] F. Yang, A.C. Nielander, R.L. Grimm, N.S. Lewis, Photoelectrochemical
Behavior of n-Type GaAs(100) Electrodes Coated by a Single Layer of Graphene,
J. Phys. Chem. C, 120 (2016) 6989-6995.

42
 ACCEPTED MANUSCRIPT
[52] S.D. Stranks, G.E. Eperon, G. Grancini, C. Menelaou, M.J.P. Alcocer, T. Leijtens,
L.M. Herz, A. Petrozza, H.J. Snaith, Electron-Hole Diffusion Lengths Exceeding 1
Micrometer in an Organometal Trihalide Perovskite Absorber, Science, 342
(2013) 341-344.
[53] G. XING, N. MATHEWS, S. SUN, S.S. LIM, Y.M. LAM, M. GRÄTZEL, S.
MHAISALKAR, T.C. SUM, Long-Range Balanced Electron- and Hole-Transport
Lengths in Organic-Inorganic CH3NH3PbI3, Science, 342 (2013) 344-347.
[54] M. Barroso, S.R. Pendlebury, A.J. Cowan, J.R. Durrant, Charge carrier
trapping, recombination and transfer in hematite ([small alpha]-Fe2O3) water

PT
splitting photoanodes, Chem. Sci. 4 (2013) 2724-2734.
[55] C. Liu, N.P. Dasgupta, P. Yang, Semiconductor Nanowires for Artificial
Photosynthesis, Chem. Mater. 26 (2014) 415-422.

RI
[56] Y. Hou, B.L. Abrams, P.C.K. Vesborg, M.E. Björketun, K. Herbst, L. Bech, A.M.
Setti, C.D. Damsgaard, T. Pedersen, O. Hansen, J. Rossmeisl, S. Dahl, J.K. Nørskov, I.
Chorkendorff, Bioinspired molecular co-catalysts bonded to a silicon

SC
photocathode for solar hydrogen evolution, Nat. Mater., 10 (2011) 434-438.
[57] J.R. Maiolo, B.M. Kayes, M.A. Filler, M.C. Putnam, M.D. Kelzenberg, H.A.
Atwater, N.S. Lewis, High Aspect Ratio Silicon Wire Array Photoelectrochemical
Cells, J. Am. Chem. Soc. 129 (2007) 12346-12347.

U
[58] P.D. Tran, S.S. Pramana, V.S. Kale, M. Nguyen, S.Y. Chiam, S.K. Batabyal, L.H.
AN
Wong, J. Barber, J. Loo, Novel Assembly of an MoS2 Electrocatalyst onto a Silicon
Nanowire Array Electrode to Construct a Photocathode Composed of Elements
Abundant on the Earth for Hydrogen Generation, Chem. Eur. J., 18 (2012) 13994-
13999.
M

[59] Y. Umena, K. Kawakami, J.-R. Shen, N. Kamiya, Crystal structure of oxygen-

evolving photosystem II at a resolution of 1.9 A°, Nature, 473 (2011) 55-60.
[60] J. Barber, A mechanism for water splitting and oxygen production in
D

photosynthesis, Nat. Plants, 3 (2017) 17041.

[61] W. Rüttinger, G.C. Dismukes, Synthetic Water-Oxidation Catalysts for
TE

Artificial Photosynthetic Water Oxidation, Chem. Rev. 97 (1997) 1-24.

[62] J.D. Blakemore, R.H. Crabtree, G.W. Brudvig, Molecular Catalysts for Water
Oxidation, Chem. Rev. 115 (2015) 12974-13005.
EP

[63] J.S. Kanady, E.Y. Tsui, M.W. Day, T. Agapie, A Synthetic Model of the Mn3Ca
Subsite of the Oxygen-Evolving Complex in Photosystem II, Science, 333 (2011)
733-736.
[64] L. Duan, F. Bozoglian, S. Mandal, B. Stewart, T. Privalov, A. Llobet, L. Sun, A
C

molecular ruthenium catalyst with water-oxidation activity comparable to that

of photosystem II, Nat. Chem. 4 (2012) 418-423.
AC

[65] R.K. Hocking, R. Brimblecombe, L.-Y. Chang, A. Singh, M.H. Cheah, C. Glover,
W.H. Casey, L. Spiccia, Water-oxidation catalysis by manganese in a geochemical-
like cycle, Nat. Chem. 3 (2011) 461-466.
[66] M. Wiechen, I. Zaharieva, H. Dau, P. Kurz, Layered manganese oxides for
water-oxidation: alkaline earth cations influence catalytic activity in a
photosystem II-like fashion, Chem. Sci. 3 (2012) 2330-2339.
[67] M.W. Kanan, D.G. Nocera, In Situ Formation of an Oxygen-Evolving Catalyst
in Neutral Water Containing Phosphate and Co2+, Science, 321 (2008) 1072-
1075.
[68] M.W. Kanan, J. Yano, Y. Surendranath, M. Dincă, V.K. Yachandra, D.G. Nocera,
Structure and Valency of a Cobalt−Phosphate Water Oxidation Catalyst

43
 ACCEPTED MANUSCRIPT
Determined by in Situ X-ray Spectroscopy, J. Am. Chem. Soc. 132 (2010) 13692-
13701.
[69] D. Friebel, M.W. Louie, M. Bajdich, K.E. Sanwald, Y. Cai, A.M. Wise, M.-J.
Cheng, D. Sokaras, T.-C. Weng, R. Alonso-Mori, R.C. Davis, J.R. Bargar, J.K.
Nørskov, A. Nilsson, A.T. Bell, Identification of Highly Active Fe Sites in
(Ni,Fe)OOH for Electrocatalytic Water Splitting, J. Am. Chem. Soc. 137 (2015)
1305-1313.
[70] C.G. Morales-Guio, M.T. Mayer, A. Yella, S.D. Tilley, M. Grätzel, X. Hu, An
Optically Transparent Iron Nickel Oxide Catalyst for Solar Water Splitting, J. Am.

PT
Chem. Soc. 137 (2015) 9927-9936.
[71] I. Zaharieva, P. Chernev, M. Risch, K. Klingan, M. Kohlhoff, A. Fischer, H. Dau,
Electrosynthesis, functional, and structural characterization of a water-oxidizing

RI
manganese oxide, Energy Environ. Sci. 5 (2012) 7081-7089.
[72] S. Bang, Y.-M. Lee, S. Hong, K.-B. Cho, Y. Nishida, M.S. Seo, R. Sarangi, S.
Fukuzumi, W. Nam, Redox-inactive metal ions modulate the reactivity and

SC
oxygen release of mononuclear non-haem iron(III)–peroxo complexes, Nat.
Chem. 6 (2014) 934-940.
[73] M. Gong, Y. Li, H. Wang, Y. Liang, J.Z. Wu, J. Zhou, J. Wang, T. Regier, F. Wei, H.
Dai, An Advanced Ni–Fe Layered Double Hydroxide Electrocatalyst for Water

U
Oxidation, J. Am. Chem. Soc. 135 (2013) 8452-8455.
AN
[74] K. Fan, H. Chen, Y. Ji, H. Huang, P.M. Claesson, Q. Daniel, B. Philippe, H.
Rensmo, F. Li, Y. Luo, L. Sun, Nickel–vanadium monolayer double hydroxide for
efficient electrochemical water oxidation, Nat. Commun. 7 (2016) 11981.
[75] X. Long, Z. Wang, S. Xiao, Y. An, S. Yang, Transition metal based layered
M

double hydroxides tailored for energy conversion and storage, Mater. Today, 19
(2016) 213-226.
[76] F. Song, X. Hu, Exfoliation of layered double hydroxides for enhanced oxygen
D

evolution catalysis, Nat. Commun. 5 (2014) 4477.

[77] X. Deng, H. Tüysüz, Cobalt-Oxide-Based Materials as Water Oxidation
TE

Catalyst: Recent Progress and Challenges, ACS Catal. 4 (2014) 3701-3714.

[78] J.D. Blakemore, H.B. Gray, J.R. Winkler, A.M. Müller, Co3O4 Nanoparticle
Water-Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids, ACS Catal.,
EP

3 (2013) 2497-2500.
[79] E.M.P. Steinmiller, K.-S. Choi, Photochemical deposition of cobalt-based
oxygen evolving catalyst on a semiconductor photoanode for solar oxygen
production, Pro. Natl. Acad. Sci. U.S.A, 106 (2009) 20633-20636.
C

[80] D.K. Zhong, M. Cornuz, K. Sivula, M. Gratzel, D.R. Gamelin, Photo-assisted

electrodeposition of cobalt-phosphate (Co-Pi) catalyst on hematite photoanodes
AC

for solar water oxidation, Energy Environ. Sci., 4 (2011) 1759-1764.

[81] M. Risch, V. Khare, I. Zaharieva, L. Gerencser, P. Chernev, H. Dau, Cobalt−Oxo
Core of a Water-Oxidizing Catalyst Film, J. Am. Chem. Soc., 131 (2009) 6936-
6937.
[82] M. Risch, F. Ringleb, M. Kohlhoff, P. Bogdanoff, P. Chernev, I. Zaharieva, H.
Dau, Water oxidation by amorphous cobalt-based oxides: in situ tracking of
redox transitions and mode of catalysis, Energy Environ. Sci., 8 (2015) 661-674.
[83] D.A. Lutterman, Y. Surendranath, D.G. Nocera, A Self-Healing Oxygen-
Evolving Catalyst, J. Am. Chem. Soc., 131 (2009) 3838-3839.

44
 ACCEPTED MANUSCRIPT
[84] M. Dincă, Y. Surendranath, D.G. Nocera, Nickel-borate oxygen-evolving
catalyst that functions under benign conditions, Proc. Natl. Acad. Sci. U.S.A, 107
(2010) 10337-10341.
[85] D.K. Bediako, B. Lassalle-Kaiser, Y. Surendranath, J. Yano, V.K. Yachandra,
D.G. Nocera, Structure–Activity Correlations in a Nickel–Borate Oxygen Evolution
Catalyst, J. Am. Chem. Soc., 134 (2012) 6801-6809.
[86] W.D. Chemelewski, H.-C. Lee, J.-F. Lin, A.J. Bard, C.B. Mullins, Amorphous
FeOOH Oxygen Evolution Reaction Catalyst for Photoelectrochemical Water
Splitting, J. Am. Chem. Soc., 136 (2014) 2843-2850.

PT
[87] J.A. Kurzman, K.E. Dettelbach, A.J. Martinolich, C.P. Berlinguette, J.R. Neilson,
Structural Characteristics and Eutaxy in the Photo-Deposited Amorphous Iron
Oxide Oxygen Evolution Catalyst, Chem. Mater., 27 (2015) 3462-3470.

RI
[88] B. Mei, A.A. Permyakova, R. Frydendal, D. Bae, T. Pedersen, P. Malacrida, O.
Hansen, I.E.L. Stephens, P.C.K. Vesborg, B. Seger, I. Chorkendorff, Iron-Treated
NiO as a Highly Transparent p-Type Protection Layer for Efficient Si-Based

SC
Photoanodes, J. Phys. Chem. Lett., 5 (2014) 3456-3461.
[89] M.S. Burke, M.G. Kast, L. Trotochaud, A.M. Smith, S.W. Boettcher, Cobalt–Iron
(Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and
Composition on Activity, Stability, and Mechanism, J. Am. Chem. Soc., 137 (2015)

U
3638-3648.
AN
[90] H.S. Ahn, A.J. Bard, Surface Interrogation Scanning Electrochemical
Microscopy of Ni1–xFexOOH (0 < x < 0.27) Oxygen Evolving Catalyst: Kinetics of
the “fast” Iron Sites, J. Am. Chem. Soc., 138 (2016) 313-318.
[91] B.J. Trześniewski, O. Diaz-Morales, D.A. Vermaas, A. Longo, W. Bras, M.T.M.
M

Koper, 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., 137 (2015) 15112-15121.
D

[92] T.F. Jaramillo, K.P. Jørgensen, J. Bonde, J.H. Nielsen, S. Horch, I. Chorkendorff,
Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2
TE

Nanocatalysts, Science, 317 (2007) 100-102.

[93] R.B. Gordon, M. Bertram, T.E. Graedel, Metal stocks and sustainability, Pro.
Natl. Acad. Sci. U.S.A, 103 (2006) 1209-1214.
EP

[94] S. Sui, X. Wang, X. Zhou, Y. Su, S. Riffat, C.-j. Liu, A comprehensive review of
Pt electrocatalysts for the oxygen reduction reaction: Nanostructure, activity,
mechanism and carbon support in PEM fuel cells, J. Mater. Chem. A, 5 (2017)
1808-1825.
C

[95] A. Kongkanand, N.P. Subramanian, Y. Yu, Z. Liu, H. Igarashi, D.A. Muller,

Achieving High-Power PEM Fuel Cell Performance with an Ultralow-Pt-Content
AC

Core–Shell Catalyst, ACS Catal., 6 (2016) 1578-1583.

[96] J.C. Fontecilla-Camps, A. Volbeda, C. Cavazza, Y. Nicolet, Structure/Function
Relationships of [NiFe]- and [FeFe]-Hydrogenases, Chem. Rev., 107 (2007) 4273-
4303.
[97] M. Can, F.A. Armstrong, S.W. Ragsdale, Structure, Function, and Mechanism
of the Nickel Metalloenzymes, CO Dehydrogenase, and Acetyl-CoA Synthase,
Chem. Rev., 114 (2014) 4149-4174.
[98] B.M. Hoffman, D. Lukoyanov, Z.-Y. Yang, D.R. Dean, L.C. Seefeldt, Mechanism
of Nitrogen Fixation by Nitrogenase: The Next Stage, Chem. Rev., 114 (2014)
4041-4062.

45
 ACCEPTED MANUSCRIPT
[99] A.K. Jones, E. Sillery, S.P.J. Albracht, F.A. Armstrong, Direct comparison of the
electrocatalytic oxidation of hydrogen by an enzyme and a platinum catalyst,
Chem. Commun., (2002) 866-867.
[100] D.L. DuBois, Development of Molecular Electrocatalysts for Energy Storage,
Inorg. Chem., 53 (2014) 3935-3960.
[101] V. Artero, M. Chavarot-Kerlidou, M. Fontecave, Splitting Water with Cobalt,
Angew. Chem. Int. Ed., 50 (2011) 7238-7266.
[102] V.S. Thoi, Y. Sun, J.R. Long, C.J. Chang, Complexes of earth-abundant metals
for catalytic electrochemical hydrogen generation under aqueous conditions,

PT
Chem. Soc. Rev., 42 (2013) 2388-2400.
[103] J.R. McKone, S.C. Marinescu, B.S. Brunschwig, J.R. Winkler, H.B. Gray, Earth-
abundant hydrogen evolution electrocatalysts, Chem. Sci., 5 (2014) 865-878.

RI
[104] A.L. Goff, V. Artero, B. Jousselme, P.D. Tran, N. Guillet, R. Métayé, A. Fihri, S.
Palacin, M. Fontecave, From hydrogenases to noble metal–free catalytic
nanomaterials for H2 production and uptake, Science, 326 (2009) 1384-1387.

SC
[105] P.D. Tran, A.L. Goff, J. Heidkamp, B. Jousselme, N. Guillet, S. Palacin, H. Dau,
M. Fontecave, V. Artero, Noncovalent Modification of Carbon Nanotubes with
Pyrene-Functionalized Nickel Complexes: Carbon Monoxide Tolerant Catalysts
for Hydrogen Evolution and Uptake, Angew. Chim. Int. Ed., 123 (2011) 1407-

U
1410.
AN
[106] T.N. Huan, R.T. Jane, A. Benayad, L. Guetaz, P.D. Tran, V. Artero, Bio-
inspired noble metal-free nanomaterials approaching platinum performances for
H2 evolution and uptake, Energy Environ. Sci., 9 (2016) 940-947.
[107] P.D. Tran, M. Nguyen, S.S. Pramana, A. Bhattacharjee, S.Y. Chiam, J. Fize, M.J.
M

Field, V. Artero, L.H. Wong, J. Loo, J. Barber, Copper molybdenum sulfide: a new
efficient electrocatalyst for hydrogen production from water, Energy Environ.
Sci., 5 (2012) 8912-8916.
D

[108] B. Santiago, O. Meyer, Characterization of hydrogenase activities associated

with the molybdenum CO dehydrogenase from Oligotropha carboxidovorans,
TE

FEMS Microbio. Lett., 136 (1996) 157-162.

[109] J.V. Lauritsen, J. Kibsgaard, S. Helveg, H. Topsoe, B.S. Clausen, E.
Laegsgaard, F. Besenbacher, Size-dependent structure of MoS2 nanocrystals, Nat.
EP

Nanotechnol., 2 (2007) 53-58.

[110] P.C.K. Vesborg, B. Seger, I. Chorkendorff, Recent Development in Hydrogen
Evolution Reaction Catalysts and Their Practical Implementation, J. Phys. Chem.
Lett., 6 (2015) 951-957.
C

[111] C.G. Morales-Guio, X. Hu, Amorphous Molybdenum Sulfides as Hydrogen

Evolution Catalysts, Acc. Chem. Res., 47 (2014) 2671-2681.
AC

[112] J.D. Benck, T.R. Hellstern, J. Kibsgaard, P. Chakthranont, T.F. Jaramillo,

Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide
Nanomaterials, ACS Catal., 4 (2014) 3957-3971.
[113] M. Chhowalla, H.S. Shin, G. Eda, L.-J. Li, K.P. Loh, H. Zhang, The chemistry of
two-dimensional layered transition metal dichalcogenide nanosheets, Nat.
Chem., 5 (2013) 263-275.
[114] S. Xu, D. Li, P. Wu, One-Pot, Facile, and Versatile Synthesis of Monolayer
MoS2/WS2 Quantum Dots as Bioimaging Probes and Efficient Electrocatalysts
for Hydrogen Evolution Reaction, Adv. Funct. Mater., 25 (2015) 1127-1136.

46
 ACCEPTED MANUSCRIPT
[115] W. Qiao, S. Yan, X. Song, X. Zhang, Y. Sun, X. Chen, W. Zhong, Y. Du,
Monolayer MoS2 quantum dots as catalysts for efficient hydrogen evolution, RSC
Adv., 5 (2015) 97696-97701.
[116] D. Kiriya, P. Lobaccaro, H.Y.Y. Nyein, P. Taheri, M. Hettick, H. Shiraki, C.M.
Sutter-Fella, P. Zhao, W. Gao, R. Maboudian, J.W. Ager, A. Javey, General Thermal
Texturization Process of MoS2 for Efficient Electrocatalytic Hydrogen Evolution
Reaction, Nano Lett., 16 (2016) 4047-4053.
[117] L. Tao, X. Duan, C. Wang, X. Duan, S. Wang, Plasma-engineered MoS2 thin-
film as an efficient electrocatalyst for hydrogen evolution reaction, Chem.

PT
Commun., 51 (2015) 7470-7473.
[118] K. Chang, M. Li, T. Wang, S. Ouyang, P. Li, L. Liu, J. Ye, Drastic Layer-
Number-Dependent Activity Enhancement in Photocatalytic H2 Evolution over

RI
nMoS2/CdS (n ≥ 1) Under Visible Light, Adv. Energy Mater., 5 (2015) 1402279.
[119] H. Wang, Z. Lu, S. Xu, D. Kong, J.J. Cha, G. Zheng, P.-C. Hsu, K. Yan, D.
Bradshaw, F.B. Prinz, Y. Cui, Electrochemical tuning of vertically aligned MoS2

SC
nanofilms and its application in improving hydrogen evolution reaction, Pro.
Natl. Acad. Sci. U.S.A, 110 (2013) 19701-19706.
[120] Q. Tang, D.-e. Jiang, Stabilization and Band-Gap Tuning of the 1T-MoS2
Monolayer by Covalent Functionalization, Chem. Mater., 27 (2015) 3743-3748.

U
[121] A.S. Goloveshkin, I.S. Bushmarinov, A.A. Korlyukov, M.I. Buzin, V.I.
AN
Zaikovskii, N.D. Lenenko, A.S. Golub, Stabilization of 1T-MoS2 Sheets by
Imidazolium Molecules in Self-Assembling Hetero-layered Nanocrystals,
Langmuir, 31 (2015) 8953-8960.
[122] P.D. Tran, T.V. Tran, M. Orio, S. Torelli, Q.D. Truong, K. Nayuki, Y. Sasaki, S.Y.
M

Chiam, R. Yi, I. Honma, J. Barber, V. Artero, Coordination polymer structure and

revisited hydrogen evolution catalytic mechanism for amorphous molybdenum
sulfide, Nat. Mater., 15 (2016) 640-646.
D

[123] J. Kibsgaard, T.F. Jaramillo, F. Besenbacher, Building an appropriate active-

site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2−
TE

clusters, Nat. Chem., 6 (2014) 248-253.

[124] Under an Ar inert atmosphere, the a-MoSx to MoS2 crystallization is
readily happened at 350C.
EP

[125] D.N. Nguyen, L.N. Nguyen, P.D. Nguyen, T.V. Thu, A.D. Nguyen, P.D. Tran,
Crystallization of Amorphous Molybdenum Sulfide Induced by Electron or Laser
Beam and Its Effect on H2-Evolving Activities, J. Phys. Chem. C, 120 (2016)
28789-28794.
C

[126] E.A. Ponomarev, M. Neumann-Spallart, G. Hodes, C. Lévy-Clément,

Electrochemical deposition of MoS2 thin films by reduction of
AC

tetrathiomolybdate, Thin Solid Films, 280 (1996) 86-89.

[127] D. Merki, S. Fierro, H. Vrubel, X. Hu, Amorphous molybdenum sulfide films
as catalysts for electrochemical hydrogen production in water, Chem. Sci., 2
(2011) 1262-1267.
[128] D. Merki, H. Vrubel, L. Rovelli, S. Fierro, X. Hu, Fe, Co, and Ni ions promote
the catalytic activity of amorphous molybdenum sulfide films for hydrogen
evolution, Chem. Sci., 3 (2012) 2515-2525.
[129] J. Bonde, P.G. Moses, T.F. Jaramillo, J.K. Norskov, I. Chorkendorff, Hydrogen
evolution on nano-particulate transition metal sulfides, Farad. Discuss., 140
(2009) 219-231.

47
 ACCEPTED MANUSCRIPT
[130] Y. Zhu, Q.M. Ramasse, M. Brorson, P.G. Moses, L.P. Hansen, C.F. Kisielowski,
S. Helveg, Visualizing the Stoichiometry of Industrial-Style Co-Mo-S Catalysts
with Single-Atom Sensitivity, Angew. Chem. Int. Ed., 53 (2014) 10723-10727.
[131] J. Staszak-Jirkovsky, C.D. Malliakas, P.P. Lopes, N. Danilovic, S.S. Kota, K.-C.
Chang, B. Genorio, D. Strmcnik, V.R. Stamenkovic, M.G. Kanatzidis, N.M. Markovic,
Design of active and stable Co-Mo-Sx chalcogels as pH-universal catalysts for the
hydrogen evolution reaction, Nat. Mater., 15 (2016) 197-203.
[132] V. Georgakilas, M. Otyepka, A.B. Bourlinos, V. Chandra, N. Kim, K.C. Kemp,
P. Hobza, R. Zboril, K.S. Kim, Functionalization of Graphene: Covalent and Non-

PT
Covalent Approaches, Derivatives and Applications, Chem. Rev., 112 (2012)
6156-6214.
[133] K.A.S. Fernando, S. Sahu, Y. Liu, W.K. Lewis, E.A. Guliants, A. Jafariyan, P.

RI
Wang, C.E. Bunker, Y.-P. Sun, Carbon Quantum Dots and Applications in
Photocatalytic Energy Conversion, ACS Appl. Mater. Interfaces, 7 (2015) 8363-
8376.

SC
[134] R. Wang, K.-Q. Lu, Z.-R. Tang, Y.-J. Xu, Recent progress in carbon quantum
dots: synthesis, properties and applications in photocatalysis, J. Mater. Chem. A, 5
(2017) 3717-3734.
[135] K. Yoon, J.-H. Lee, J. Kang, J. Kang, M.J. Moody, M.C. Hersam, L.J. Lauhon,

U
Metal-Free Carbon-Based Nanomaterial Coatings Protect Silicon Photoanodes in
AN
Solar Water-Splitting, Nano Lett., 16 (2016) 7370-7375.
[136] P.D. Tran, S.K. Batabyal, S.S. Pramana, J. Barber, L.H. Wong, S.C.J. Loo, A
cuprous oxide-reduced graphene oxide (Cu2O-rGO) composite photocatalyst for
hydrogen generation: employing rGO as an electron acceptor to enhance the
M

photocatalytic activity and stability of Cu2O, Nanoscale, 4 (2012) 3875-3878.

[137] Y. Lattach, J. Fortage, A. Deronzier, J.-C. Moutet, Polypyrrole-Ru(2,2′-
bipyridine)32+/MoSx Structured Composite Film As a Photocathode for the
D

Hydrogen Evolution Reaction, ACS Appl. Mater. Interfaces, 7 (2015) 4476-4480.

[138] A. Krawicz, J. Yang, E. Anzenberg, J. Yano, I.D. Sharp, G.F. Moore,
TE

Photofunctional Construct That Interfaces Molecular Cobalt-Based Catalysts for

H2 Production to a Visible-Light-Absorbing Semiconductor, J. Am. Chem. Soc.,
135 (2013) 11861-11868.
EP

[139] Y. Lattach, A. Deronzier, J.-C. Moutet, Electrocatalytic Hydrogen Evolution

from Molybdenum Sulfide–Polymer Composite Films on Carbon Electrodes, ACS
Appl. Mater. Interfaces, 7 (2015) 15866-15875.
[140] T. Wang, J. Zhuo, K. Du, B. Chen, Z. Zhu, Y. Shao, M. Li, Electrochemically
C

Fabricated Polypyrrole and MoSx Copolymer Films as a Highly Active Hydrogen

Evolution Electrocatalyst, Adv. Mater., 26 (2014) 3761-3766.
AC

[141] K.A. Mauritz, R.B. Moore, State of Understanding of Nafion, Chem. Rev., 104
(2004) 4535-4586.
[142] R. Brimblecombe, A. Koo, G.C. Dismukes, G.F. Swiegers, L. Spiccia, Solar
Driven Water Oxidation by a Bioinspired Manganese Molecular Catalyst, J. Am.
Chem. Soc., 132 (2010) 2892-2894.
[143] A. Fihri, V. Artero, M. Razavet, C. Baffert, W. Leibl, M. Fontecave,
Cobaloxime-Based Photocatalytic Devices for Hydrogen Production, Angew.
Chem. Int. Ed., 47 (2008) 564-567.
[144] F. Lakadamyali, E. Reisner, Photocatalytic H2 evolution from neutral water
with a molecular cobalt catalyst on a dye-sensitised TiO2 nanoparticle, Chem.
Commun., 47 (2011) 1695-1697.

48
 ACCEPTED MANUSCRIPT
[145] D. Belanger, J. Pinson, Electrografting: a powerful method for surface
modification, Chem. Soc. Rev., 40 (2011) 3995-4048.
[146] R. Matheu, L. Francàs, P. Chernev, M.Z. Ertem, V. Batista, M. Haumann, X.
Sala, A. Llobet, Behavior of the Ru-bda Water Oxidation Catalyst Covalently
Anchored on Glassy Carbon Electrodes, ACS Catal., 5 (2015) 3422-3429.
[147] J.A. Seabold, K.-S. Choi, Efficient and Stable Photo-Oxidation of Water by a
Bismuth Vanadate Photoanode Coupled with an Iron Oxyhydroxide Oxygen
Evolution Catalyst, J. Am. Chem. Soc., 134 (2012) 2186-2192.
[148] M. Nguyen, P.D. Tran, S.S. Pramana, R.L. Lee, S.K. Batabyal, N. Mathews, L.H.

PT
Wong, M. Graetzel, In situ photo-assisted deposition of MoS2 electrocatalyst onto
zinc cadmium sulphide nanoparticle surfaces to construct an efficient
photocatalyst for hydrogen generation, Nanoscale, 5 (2013) 1479-1482.

RI
[149] S. Kanda, T. Akita, M. Fujishima, H. Tada, Facile synthesis and catalytic
activity of MoS2/TiO2 by a photodeposition-based technique and its oxidized
derivative MoO3/TiO2 with a unique photochromism, J. Colloid Interface Sci.,

SC
354 (2011) 607-610.
[150] Y. Li, H. Wang, S. Peng, Tunable Photodeposition of MoS2 onto a Composite
of Reduced Graphene Oxide and CdS for Synergic Photocatalytic Hydrogen
Generation, J. Phys. Chem. C, 118 (2014) 19842-19848.

U
[151] J. Luo, J. Im, M. Mayer, M. Schreier, M. Nazeeruddin, N. Park, S. Tilley, H.
AN
Fan, M. Grätzel, Water photolysis at 12.3% efficiency via perovskite
photovoltaics and Earth-abundant catalysts, Science, 345 (2014) 1593-1596.
[152] J. Jia, L.C. Seitz, J.D. Benck, Y. Huo, Y. Chen, J.W.D. Ng, T. Bilir, J.S. Harris, T.F.
Jaramillo, Solar water splitting by photovoltaic-electrolysis with a solar-to-
M

hydrogen efficiency over 30%, Nat. Commun., 7 (2016) 13237.

[153] R.E. Rocheleau, E.L. Miller, A. Misra, High-Efficiency Photoelectrochemical
Hydrogen Production Using Multijunction Amorphous Silicon Photoelectrodes,
D

Energy Fuels, 12 (1998) 3-10.

[154] Q. Wang, T. Hisatomi, Q. Jia, H. Tokudome, M. Zhong, C. Wang, Z. Pan, T.
TE

Takata, M. Nakabayashi, N. Shibata, Y. Li, I.D. Sharp, A. Kudo, T. Yamada, K.

Domen, Scalable water splitting on particulate photocatalyst sheets with a solar-
to-hydrogen energy conversion efficiency exceeding 1%, Nat. Mater., 15 (2016)
EP

611-615.
[155] L. Liao, Q. Zhang, Z. Su, Z. Zhao, Y. Wang, Y. Li, X. Lu, D. Wei, G. Feng, Q. Yu,
X. Cai, J. Zhao, Z. Ren, H. Fang, F. Robles-Hernandez, S. Baldelli, J. Bao, Efficient
solar water-splitting using a nanocrystalline CoO photocatalyst, Nat. Nanotech., 9
C

(2014) 69-73.
[156] T.J. Jacobsson, V. Fjallstrom, M. Sahlberg, M. Edoff, T. Edvinsson, A
AC

monolithic device for solar water splitting based on series interconnected thin
film absorbers reaching over 10% solar-to-hydrogen efficiency, Energy Environ.
Sci., 6 (2013) 3676-3683.
[157] F. Urbain, V. Smirnov, J.-P. Becker, A. Lambertz, F. Yang, J. Ziegler, B. Kaiser,
W. Jaegermann, U. Rau, F. Finger, Multijunction Si photocathodes with tunable
photovoltages from 2.0 V to 2.8 V for light induced water splitting, Energy
Environ. Sci., 9 (2016) 145-154.
[158] T. Sharifi, C. Larsen, J. Wang, W.L. Kwong, E. Gracia-Espino, G. Mercier, J.
Messinger, T. Wågberg, L. Edman, Toward a Low-Cost Artificial Leaf: Driving
Carbon-Based and Bifunctional Catalyst Electrodes with Solution-Processed
Perovskite Photovoltaics, Adv. Energy Mater., 6 (2016) 1600738.

49
 ACCEPTED MANUSCRIPT
[159] J.-W. Jang, C. Du, Y. Ye, Y. Lin, X. Yao, J. Thorne, E. Liu, G. McMahon, J. Zhu, A.
Javey, J. Guo, D. Wang, Enabling unassisted solar water splitting by iron oxide and
silicon, Nat. Commun., 6 (2015) 7447.
[160] W.-H. Cheng, M.H. Richter, M.M. May, J. Ohlmann, D. Lackner, F. Dimroth, T.
Hannappel, H.A. Atwater, H.-J. Lewerenz, Monolithic Photoelectrochemical
Device for 19% Direct Water Splitting, Condensed Matter Materials Science,
https://arxiv.org/abs/1706.01493 (2017) arXiv:1706.01493.
[161] G.A. Pilgrim, A.R. Amori, Z. Hou, F. Qiu, S. Lampa-Pastirk, T.D. Krauss,
Carbon Nanotube-Based Membrane for Light-Driven, Simultaneous Proton and

PT
Electron Transport, ACS Energy Lett., 2 (2017) 129-133.
[162] J. Gu, Y. Yan, J.L. Young, K.X. Steirer, N.R. Neale, J.A. Turner, Water reduction
by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a

RI
molecular cobalt catalyst, Nat. Mater., 15 (2016) 456-460.
[163] S.E. Ghachtouli, R. Guillot, F. Brisset, A. Aukauloo, Cobalt-Based Particles
Formed upon Electrocatalytic Hydrogen Production by a Cobalt Pyridine Oxime

SC
Complex, ChemsusChem, 6 (2013) 2226-2230.
[164] E. Anxolabéhère-Mallart, C. Costentin, M. Fournier, S. Nowak, M. Robert, J.-
M. Savéant, Boron-Capped Tris(glyoximato) Cobalt Clathrochelate as a Precursor
for the Electrodeposition of Nanoparticles Catalyzing H2 Evolution in Water, J.

U
Am. Chem. Soc., 134 (2012) 6104-6107.
AN
[165] D. Wang, T. Hisatomi, T. Takata, C. Pan, M. Katayama, J. Kubota, K. Domen,
Core/Shell Photocatalyst with Spatially Separated Co-Catalysts for Efficient
Reduction and Oxidation of Water, Angew. Chem. Int. Ed., 52 (2013) 11252-
11256.
M

[166] S. Cobo, J. Heidkamp, P.-A. Jacques, J. Fize, V. Fourmond, L. Guetaz, B.

Jousselme, V. Ivanova, H. Dau, S. Palacin, M. Fontecave, V. Artero, A Janus cobalt-
based catalytic material for electro-splitting of water, Nat. Mater., 11 (2012) 802-
D

807.
[167] A. Han, H. Zhang, R. Yuan, H. Ji, P. Du, Crystalline Copper Phosphide
TE

Nanosheets as an Efficient Janus Catalyst for Overall Water Splitting, ACS Appl.
Mater. Interfaces, 9 (2017) 2240-2248.
[168] L.-A. Stern, L. Feng, F. Song, X. Hu, Ni2P as a Janus catalyst for water
EP

splitting: the oxygen evolution activity of Ni2P nanoparticles, Energy Environ.

Sci., 8 (2015) 2347-2351.
C
AC

50