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Production of Hydrogen with Solar Energy

Joop Schoonman
Delft University of Technology, Delft, The Netherlands

1 INTRODUCTION
future energy infrastructure will comprise the utilization of
In world history we are at a critical point; in that, we are a mixture of sustainable energy sources taking into account
confronted with the greatest challenge that mankind has ever regional circumstances to determine the optical mix.
faced, and that is climate change. The scientific community Sustainable energy sources that can be used to produce
is certain that the earth’s climate is dramatically affected by electrons, for instance, novel types of small-scale wind
the use of fossil fuels. The impact on the environment is due turbines for the built environment and solar cells can
to the emission of greenhouse gases, in particular CO2 , and be connected to the electricity infrastructure to directly
their contribution to global warming. Current models place contribute to the reduction of carbon dioxide emissions from
us back to the temperature on our planet of three billion the combustion of fossil fuels. The decentralized utilization
years ago during the Pleioscene Era. In order to reduce our of these sustainable energy sources requires storage. Hereto,
present dependence on fossil fuels, a large transition toward materials are being studied for rechargeable batteries.
new, sustainable energy sources is unavoidable. In order to The combination of solar cells and commercial elec-
reduce the greenhouse effect more hydrogen-rich fuels are a trolyzers can split water into oxygen and hydrogen and the
necessity with ultimately the energy carrier hydrogen, that is, electrical energy is stored in the energy carrier hydrogen.
Rifkin’s vision entails the generation of power using renew-
C (coal) → −CH2 – (oil) → CH4 (natural gas) → H2 able technologies, which is stored, distributed, and shared
in the form of the energy carrier hydrogen (Rifkin, 2003,
The global power generating sustainable energy sources 2007). Compared to fuels, hydrogen has a high energy
are wind, hydroelectric, geothermal, tidal and ocean currents, content per unit mass, but a very low energy content per
nuclear, biomass, and solar. The current power consump- unit volume (van de Krol, 2012), which is relevant once
tion of the nearly seven billion inhabitants of our planet storage of hydrogen is required. The following reaction
amounts to 15 TW and is anticipated to increase to 30 TW by shows hydrogen to be an energy carrier,
2050 with an estimated number of inhabitants of 10 billion.
Considering the global power generating capacities of the
2H2 + O2 ↔ 2H2 O + 237 kJ∕mole (1)
sustainable energy sources, solar energy would be the only
source that has the potential to meet all energy needs. The
To date, the industrial processes to produce hydrogen are
total solar power reaching the earth’s surface is 120,000
based on partial oxidation or the steam-reforming reaction
TW and it would require 0.16% of the earth’s surface to be
of hydrocarbons with steam and the subsequent water–gas
covered with 10% efficient solar cells to generate 20 TW of
shift reaction to convert CO as a reaction product in the
power from the sun (Lewis and Nocera, 2006; van de Krol,
steam-reforming reaction with steam to CO2 . In the case
2012). van de Krol and Grätzel (2012) demonstrate that this
of the steam-reforming of natural gas one molecule of CO2
cannot be achieved in the near future and that implicitly a
and four molecules of H2 are formed per CH4 molecule.
Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd. In projects focusing on “Clean Fossil Fuels,” the seques-
This article is © 2015 John Wiley & Sons, Ltd. tration of the formed CO2 is studied, for instance, by using
This article was published in the Handbook of Clean Energy Systems
in 2015 by John Wiley & Sons, Ltd. advanced nanostructured membrane reactors (Tran et al.,
DOI: 10.1002/9781118991978.hces006 2007; Tran, 2011).
2 Solar Energy

One of the main requirements for a hydrogen economy 2 PHOTOELECTROCHEMICAL CELLS


is the availability of a clean and efficient technology for
producing hydrogen using sustainable energy sources. In The principle of operation of a PEC cell for the splitting of
particular, the production of hydrogen from water and solar water in oxygen and hydrogen is presented in Figure 1. The
energy via direct photoelectrolysis is one of the few methods PEC cell comprises a semiconducting electrode, an aqueous
for both renewable and sustainable hydrogen production. electrolyte, and a metallic counter electrode. The chemical
Fujishima and Tryk (1968) published the first report in reactions are written for an alkaline solution. In this case,
English on photochemical and photoelectrochemical water an n-type semiconductor is chosen as a photoanode and an
splitting, followed by the landmark paper of Fujishima and electric field is formed at the surface of the semiconductor in
Honda presenting a photoelectrochemical (PEC) cell, based contact with the aqueous electrolyte, because free electrons
on a TiO2 photoanode (Fujishima & Honda, 1972). While from the bulk of the semiconductor are trapped into surface
indeed water splitting can be carried out with coupled solar states. The electric field causes a bending of the valence band
cells – water electrolysis systems, the direct photoelectrol- and the conduction band and hence a space charge region
ysis with a semiconductor photoelectrode is a more elegant is present. The negative surface charge is compensated by
and cheaper approach (Grätzel, 2001; van de Krol and the remaining positive charges in the space charge region,
Schoonman, 2008). Here, the photoactive semiconductor which are ionized shallow donors. In case of an n-type semi-
is immersed in water and the photogenerated electrons conducting metal oxide these are oxide ion vacancies, which
and holes are directly used to reduce and oxidize water, have an effective positive charge 2q, or aliovalent impurities
respectively. The direct photoelectrolysis is the Holy Grail with an effective positive charge. The concentration of elec-
of electrochemistry, using the power of light. The average
trons in the space charge region is negligible and often this
energy of an electron is 0.025 eV at room temperature
region is referred to as the depletion layer.
and, for instance, one green photon has an energy of 2.5
When the photoanode is irradiated with photons having
eV at room temperature. It should be mentioned that to
an energy equal to or larger than the band gap energy, elec-
date also many research efforts on solar water splitting are
trons are excited from the valence band into the conduc-
directed toward systems based on a photocatalyst powder
tion band leaving electron holes in the valence band. If the
suspended in an aqueous solution. Incident light penetrates
charge carriers are generated in the bulk of the semiconductor
the suspension and generates electron–hole pairs in the
recombination will occur. If excited in the depletion layer
photocatalytic particles. Subsequently, the electrons and
the electric field is the driving force for the transport of the
the electron holes will reduce and oxidize water at different
photogenerated electrons and electron holes toward the bulk
surface sites of the particles (Maeda and Domen, 2010;
Mukherji et al., 2011; Teoh et al., 2012; Wang et al., 2012a; and the surface, respectively, and recombination is avoided.
Kamat and Bisquert, 2013). An important advantage of the The schematic energy band diagram as presented in
PEC cell is that the evolving hydrogen and oxygen gases Figure 1 holds for the PEC cell under irradiation. Compared
can be collected in separate volumes. to the energy band diagram of the PEC cell in equilibrium
In this article the principle of the PEC cell for water in the dark, irradiation decreases the band bending, and
splitting will be presented, along with photoelectrode mate- near the semiconductor–electrolyte interface the Fermi
rials and their requirements for application in a PEC cell. level EF splits into quasi-Fermi levels for the electrons and
Also attention will be focused on photocatalyst particles the electron holes (van de Krol, 2012). In Figure 1, only
in suspension. To date, the decreasing length scale to the the quasi-Fermi level of the electrons is included. A bias
nanoscale of the functional materials for photoelectrochem- potential will be required to aid the reduction reaction if
ical and photocatalytic applications attracts widespread the conduction band edge is positioned below the reduction
attention and a variety of synthesis routes has been potential of water.
designed to manufacture, for instance, nanotubes, nanoflake For the storage of hydrogen metal hydrides are being
surface structures, and fractal surface morphologies of studied (Slapbach and Züttel, 2001; Froudakis, 2011; Pivak,
photoelectrodes and photocatalysts. 2012). It has been shown that the metal hydride concept
It is common practice to use aqueous solutions as elec- can be integrated into a PEC cell (Schoonman, 1982a,b).
trolyte in PEC cells. Besides water, aqueous hydrogen sulfide The photoelectrochemical conversion and storage (PECCS)
solutions have also been used to produce hydrogen. While cell combines the advantages of a two-electrode system
sufficient water is present on our planet, an example will with simultaneous storage of hydrogen in the form of a
be discussed; how large-scale photoelectrolysis of hydrogen metal hydride. The PECCS cell is schematically presented
sulfide can contribute to reduce an environmental problem in in Figure 2 and in an acidic aqueous electrolyte the oxidation
and by the world’s largest anoxic basin – the Black Sea. reaction at the semiconducting photoanode is given by

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
Production of Hydrogen with Solar Energy 3

Vbias

4H2O + 4e− → 4OH− + 2H2


EF,metal


EF 1.23 eV

4OH− + 4h+ → 2H2O + O2

Semiconductor Electrolyte Metal electrode

Figure 1. The energy diagram of a PEC cell for the photoelectrolysis of water. The cell diagram is based on an n-type semiconducting
photoanode under irradiation. Source: Reproduced with permission from Krol and Schoonman, 2008. © Springer.

In order to measure the activity of hydrogen in the metal


O2 hydride, a Nernst-type sensor is incorporated as illustrated
in Figure 2. The sensor comprises the metal hydride, a
hν second PCM, and a reference metal hydride MHx (ref) with a
fixed hydrogen activity. The open-circuit voltage across both
H+ MHx
V metal hydrides is given by the Nernst equation (Schoonman
et al., 1982).
H2O/H+ The transport of protons in solid-state PCMs can be
described by a vehicle mechanism, which is based on
PCM MHx (ref) an assembly that carries the protons, that is, OH− , H2 O
(Schoonman, 1982a, 1982b), H3 O+ , and NH4 + , or by
Figure 2. Schematics of a PECCS cell. The semiconducting the Grotthus mechanism, which describes free proton
photoanode oxidizes water when light is absorbed. The protons conduction between relatively stationary host ions. To
diffuse to the proton conducting membrane and are reduced at
the PCM–MHx interface. By measuring the potential between the ensure maximum compatibility with a large variety of metal
active metal hydride and a reference metal hydride, the hydrogen hydrides, water-free proton conductors are being preferred.
content can be determined. Source: Reproduced from Schoonman, As an example, the lithium titanium oxide spinel Li4 Ti5 O12
1982a (© Elsevier) and Schoonman, 1982b (© John Wiley & Sons). reveals proton-exchange properties, and H1.1 Li2.9 Ti5 O12
does not show lithium-ion conduction, but proton conduc-
tion instead (Simon, 2007). A review of proton conductors
2H2 O → O2 (g) + 4H+ + 4e− (2) for PCMs is beyond the scope of this article.

The protons diffuse to the aqueous electrolyte–proton-


conducting membrane interface, diffuse through the proton-
conducting membrane (PCM), and are discharged at the 3 PHOTOELECTRODE MATERIALS AND
PCM–MHx interface. PHOTOCATALYSTS
MHx + y H+ + y e− → MHx+y (3) 3.1 Materials requirements

Once the metal hydride is fully loaded with hydrogen, The performance of a PEC cell for water splitting is critically
it can be replaced with the metal M, and the hydrogen can dependent on a suitable semiconductor that will be used as a
be released by heating and can be used to generate power. photoanode and/or a photocathode. Suitable photoelectrode

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
4 Solar Energy

materials for efficient hydrogen generation have to fulfill the are able to oxidize and not reduce water and most non-oxide
following requirements: semiconductors are able to reduce and not oxidize water. For
some materials, for example Fe2 O3 and WO3 , an externally
• Sufficiently high (visible) light absorption applied voltage or a separate electrode compartment with a
• High chemical stability in the dark and under illumina- different pH is required for the reduction reaction (Fujishima
tion (no photocorrosion) and Honda, 1972). A few semiconducting metal oxides have
• Suitable band edge positions been demonstrated to be able to evolve both oxygen and
• Efficient charge transport in the semiconductor hydrogen. SrTiO3 has been shown to be the only metal oxide,
• Low overpotentials for the reduction–oxidation reaction which in a two-electrode system, could split water without
(high catalytic activity) any assistance (Maivroides et al., 1976). The bandgap of this
• Low cost titanate is 3.2 eV and owing to this large bandgap the effi-
ciency is less than 1%. In order to improve the efficiency
These requirements have been discussed recently in detail Tinnemans and Mackor (1981) studied the spectral sensi-
along with examples (van de Krol, 2012; van de Krol and tization of SrTiO3 photoanodes with several ruthenium (II)
Schoonman, 2008; van de Krol et al., 2008) and will be complexes.
summarized here. In addition, requirements for photoactive In insulators and intrinsic semiconductors the bandgap
materials for use as photocatalysts will be reviewed in the separates a completely filled valence band from a completely
next section, along with recent research. empty conduction band at 0 K. Disorder in the electronic
The Gibbs free energy change for water splitting is 237
structure at finite temperatures of an intrinsic semiconductor
kJ/mole; hence the potential for water splitting is 1.23 eV.
is the result of thermal or optical excitation of electrons
However, the minimum band gap to split water requires to
across the bandgap to occupy the conduction band. Usually
include the thermodynamic losses, that is, ∼0.4 eV (Weber
the electrons in the conduction band and the holes in the
and Dignam, 1984) and the overpotentials which are required
valence band have high mobilities (Sze, 1981; Chiang et al.,
to ensure sufficiently fast reaction kinetics, that is, ∼0.3–0.4
1997), which is a precondition for the fourth requirement,
eV in the system (Murphy et al., 2006; Bolton et al., 1985).
that is, efficient charge transport. In 3d-transition metal
Therefore, the band gap should be at least ∼1.9 eV and this
oxides the overlap of the 3d orbitals leads to high electron
corresponds to a wavelength of ∼650 nm. Below ∼400 nm
mobilities and the overlap between the O-2p orbitals deter-
the intensity of solar radiation (AM 1.5 conditions) drops
mines the hole mobility. However, bandgaps of interesting
rapidly, imposing an upper limit of ∼3.1 eV to the band gap.
The optical band gap should, therefore, be between 1.9 and 3d-transition metal oxides allow absorption of the near ultra-
3.1 eV, which is in the range of the visible solar spectrum. violet (UV) solar spectrum and, therefore, doping of these
Murphy et al. (2006), Bolton et al. (1985), and Weber and oxides with aliovalent impurities is studied in order to absorb
Dignam (1986) have reported predictions of the maximum more the visible part of the solar spectrum. These aliovalent
attainable efficiency based mainly on the band gap and esti- impurities may influence both the electronic and ionic defect
mated values for thermodynamic losses, overpotentials, and disorder in the metal oxide. In addition, deviations from stoi-
optical reflection losses. For a hypothetically ideal material chiometry are also creating extrinsic electronic and ionic
with a band gap of 2.03 eV a maximum efficiency of 16.8% defects. Because the doping levels or the deviations from
was predicted (Murphy et al., 2006). stoichiometry do not lead to impurity bands in the bandgap,
Corrosion limits the usefulness of many semiconducting electronic charge carriers move via a hopping mechanism
photoactive materials and especially nonoxide semiconduc- over the donor and/or acceptor levels, which will lead to
tors, such as Si, GaAs, CdS, either dissolve or form a thin increased recombination.
oxide film at the semiconductor–electrolyte interface that The photoelectrode–electrolyte interface in Figure 1 is
will passivate the surface of the material and thus prevents used to illustrate the fifth requirement. Here the hole transfer
charge transfer across the interface. With regard to the across the interface should be fast in order to compete
stability of metal oxide semiconductors, the general trend is with a potential anodic decomposition reaction. In case of
that wide-band gap oxide semiconductors are stable against a p-type semiconductor photoelectrode, the transfer of elec-
corrosion, whereas small-band gap oxide semiconductors trons should be sufficiently fast. In addition to competing
are not. with photoelectrode decomposition reactions, accumulation
The third requirement implies that the conduction band of holes in the space charge of an n-type conductor or elec-
minimum (EC ) should be above the reduction potential Ered trons in the space charge of a p-type conductor will decrease
(H2 /H+ ) and the valence band maximum below the oxidation the electric field and hence also increase electron–hole
potential Eox (OH− /O2 ) of water. Most oxide semiconductors recombination.

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
Production of Hydrogen with Solar Energy 5

For large-scale application low-cost materials are a prereq- Many photocatalysts are only able to evolve either oxygen
uisite. or hydrogen and do not lead to the stoichiometric splitting
of water. If only oxygen (hydrogen) evolves, a sacrificial
electron acceptor (electron donor) needs to be present to
3.2 Photocatalyst materials ensure the stoichiometric splitting of water in an H2 :O2 ratio
of 2 : 1. The examples given earlier do not need any sacrificial
From the discussion of the requirements for photoelectrodes substance.
for water splitting, it is obvious that the worldwide search It is obvious that the modification of a photocatalyst with
for the optimal material is still going on. As an alterna- a cocatalyst is an important physical and materials chem-
tive, materials for tandem cells are being studied. Also the istry challenge with focus on composition, interfaces, nano-
dispersion of a photocatalyst powder in water is an important size, and defect chemistry. The interfaces are solid–aqueous
alternative and the materials research focused on efficient solution and solid–solid. The solid–solid interfaces are
photocatalysts also attracts widespread attention. van de Krol formed by a photocatalyst and a cocatalyst and can be a
et al. (2008) recently presented an overview of particle-based metallic cocatalyst on an inorganic photocatalyst, an inor-
photocatalyst systems that are able to split water in stoi- ganic cocatalyst on an inorganic photocatalyst, and between
chiometric ratios. It is interesting to see that several photo- two inorganic photocatalysts. The photocatalyst can be an
catalysts are also being studied as photoelectrodes and for ionic non-semiconducting material (stoichiometric TiO2 ), or
designing advanced tandem cells. a semiconductor (n-type CdS). In the composite particles,
Before addressing recent developments in photoelectrode for example, a p-n, n-n, or a p-p junction can be formed,
materials for PEC cells, it is worthwhile to consider develop- depending on the type of semiconductivity of the comprising
ments in the research of photocatalytic materials. In general, photocatalysts. The same holds for the contact between the
these particle-based photocatalyst systems comprise single photocatalyst and the cocatalyst in case the cocatalyst is
particles such as BaIn0.5 Nb0.5 O3 , In0.9 Ni0.1 TaO4 ; layered a nonmetallic inorganic material. In a mixture of photo-
materials such as Ba:La2 TiO7 ; composite particles such as catalytic particle systems the oxidation and the reduction
Cr:Ba2 In2 O5 : In2 O3 ; and particle mixtures such as WO3 / of water take place on two different particles which need
(Ca,Ta):SrTiO3 (van de Krol and Schoonman, 2008; van de not come in direct contact with each other. Here, an I− /I3 −
Krol et al., 2008). Here the oxidation and the reduction reac- redox mediator is used to transport electrons from the oxygen
tions take place at the same surface of a single particle and evolving particles to the hydrogen evolving counterparts. In
in order to avoid recombination of oxygen and hydrogen and addition, the downsizing of the photocatalyst and/or cocata-
electrons and holes usually small amounts of cocatalysts are lyst to the nanoscale is widely studied.
deposited on the surface of the photocatalyst, that is, Pt, NiO, Maeda and Domen (2010) and Kamat and Bisquert (2013)
NiOx , or RuO2 , in order to ensure that oxygen and hydrogen have presented recent progress and future challenges in the
evolve at spatially separate surface sites (Figure 3). photocatalytic splitting of water. In addition, here, several
recent studies will be presented briefly.
Hydrogen Zong et al. (2010) have studied the photocatalytic
Potential evolution site hydrogen production on MoS2 /CdS photocatalysts in the
(V vs. NHE)
pH 7 presence of different sacrificial reagents under visible light
hν > Eg e− (𝜆 > 420 nm). Here the junction formed between the catalyst
(H+/H2) H2 and the cocatalyst is of the n–n type and this junction plays
CB
−0.41 an important role in enhancing the photocatalytic activity
Eg H+ of the MoS2 /CdS; in that, the photoelectrons created in
H2O CdS can easily cross the junction and form hydrogen at the
+0.82
VB cocatalyst surface. In the case of lactic acid as the sacrificial
(O2/H2O)
O2 h+ agent, the photoholes created in CdS react to form protons
Photocatalyst and CO2 . The 0.2 wt% MoS2 /CdS photocatalyst calcined at
Oxygen 573 K achieves the highest overall activity for H2 evolution
evolution site
and demonstrates even higher activity than a 0.2 wt% Pt/CdS
photocatalyst, irrespective of different sacrificial reagents
Figure 3. Energy diagram for a particle-based photocatalyst for
water splitting (see third requirement). CB, conduction band; VB, used. In addition, electrochemical measurements reveal that
valence band; NHE, normal hydrogen electrode. Source: Repro- MoS2 is an excellent H2 evolution catalyst, which is another
duced with permission from Maeda and Domen, 2010. © American important factor responsible for the enhancement of the
Chemical Society. photocatalytic activity of the MoS2 /CdS photocatalysts.

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
6 Solar Energy

Wang et al. (2012) have prepared and studied the photo- performance in converting solar energy into chemical
catalytic properties of graphene-like Cu2 ZnSnS4 (CZTS), a energy. Graphene enhances the efficiency of photocata-
direct-transition-type semiconductor with a bandgap of ∼1.5 lysts because of its unique 2D conjugated structure and
eV and a large absorption coefficient (>104 /cm). CZTS is an electronic properties. Xiang and Jiaguo (Xiang and Jiaguo,
excellent light-harvesting material for solar cells and photo- 2013) summarized significant advances on the design and
catalysis (Winkler et al., 2014; Jimbo et al., 2007). CZTS applications of graphene-based photocatalytic compos-
was prepared for the first time by a modified sol–gel method, ites and described rational designs for high performance
which involves the conversion of the sol–gel precursors into photocatalysts using graphene-based materials.
powder precursors, leading to the slow volatilization of the Not only 2D graphene-like and graphene nanostruc-
solvent and the formation of a 2D structure. The structure tured photocatalysts and cocatalysts are being studied,
comprises uniform nanosheets with a thickness of only 2–3 but also carbon quantum dots as cocatalyst are receiving
nm and lateral sizes of several hundreds of nanometers, being attention. Huijun et al. (Huijun et al., 2014) have prepared
intercrossed by self-assembly (Wang, 2012). Owing to the carbon quantum dots-modified P25 TiO2 composites
self-assembly of the as-prepared CZTS the structure is highly (CQDs/P25) with a “dyade”-like structure via a facile
porous. The H2 evolution of this structure from an aqueous one-step hydrothermal reaction. CQDs-P25 exhibited
solution containing SO3 2− and S2− was examined using an improved photocatalytic H2 evolution under UV–visible
Xe lamp radiation (Figure 4). The rate of hydrogen evolution (𝜆 > 420 nm) irradiation without any noble metal cocatalyst,
during successive runs was ∼30 μmol/h 20 mg/cat without compared to pure P25. Detailed measurements of the
using a cocatalyst, which is much higher than that of CdS transient photocurrent response, surface photovoltage, and
and N-doped TiO2 under the same conditions (Wang, 2012). of hydroxyl radicals were used to propose a mechanism of
The photocatalyst exhibits about 95% activity after 50 the photocatalytic hydrogen production activity over the
h of irradiation without additional sacrificial reagents. This composite photocatalyst CQDs-P25. In the mechanism the
special structure of graphene-like CZTS represents a good carbon quantum dots play a dual role; in that, under UV
candidate for further application in the fields of photocatal- irradiation they act as an electron reservoir to improve an
ysis and photovoltaics (Jimbo et al., 2007). The prepara- efficient separation of the photoexcited electron–hole pairs
tion of simple and effective methods to achieve high quality in P25, whereas under visible-light irradiation the carbon
CZTS thin films with enhanced phase and composition quantum dots act as a photosensitizer to sensitize P25 into
controllability is, therefore, studied in detail (Zhou et al., a visible-light response “dyade” structure for H2 evolution
2014). (Huijun et al., 2014).
Graphene-based photocatalysts are gaining increasing Commercial Degussa P25 comprises a mixture of 20%
interest as they improve the photocatalytic H2 production rutile and 80% anatase TiO2 and time-resolved microwave

160

140
H2 evolution (μmol/20 mg)

120

100

80

60

40

20

0 10 20 30 40 50
Time (h)

Figure 4. Photocatalytic hydrogen evolution in 10 consecutive cycles under irradiation with an Xe lamp. Source: Reproduced with
permission from Wang et al., 2012. © Royal Society of Chemistry.

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
Production of Hydrogen with Solar Energy 7

conductivity (TRMC) measurements reveal that P25 has is the result of the surface-phase junctions, as confirmed
higher conductivity and longer electron lifetimes (Carneiro, by high resolution transmission electron microscopy
2010; Kroeze et al., 2004) than other commercial TiO2 (HRTEM), UV Raman spectroscopy, transient absorption
samples such as Hombikat UV pure anatase (Emilio et al., with picosecond resolution, and photocurrent measure-
2006). The role of the rutile–anatase interface has been ments. The photocurrents reveal that the photoexcited
presented by Carneiro (2010), considering that there are electrons transfer from the 𝛽 to the 𝛼 phase. A fast relaxation
well-defined domains between rutile and anatase within the (2–6 ps) is associated with charge carrier redistribution
same agglomerates of particles. The intimate contacts are between the two phases of the surface junctions. Because
proposed to enhance the separation of photoexcited elec- of the efficient separation of the photoexcited electrons
trons and holes. A mechanistic model is given in Figure 5 and holes recombination is suppressed and as a result the
(Carneiro, 2010; Sun and Smirniotis, 2003; Emeline and photocatalytic water splitting is substantially improved
Serpone, 2002). (Wang et al., 2012c). The authors conclude that surface-
The optically excited holes in anatase can be injected into phase junctions comprising different crystalline phases of a
the rutile phase, resulting in higher lifetimes of the excited semiconductor may provide a new strategy to design high
electrons in the anatase phase. It is generally assumed that performance photocatalysts for the stoichiometric splitting
in this type of model the charge separation induced by the of water.
presence of the rutile phase leads to a more efficient photo- Besides this type of junctions, in a mixture of photo-
catalytic process, as the holes can oxidize surface OH of catalytic particle systems the oxidation and reduction of
the rutile particle and the electrons can reduce species at water take place on two different particles which need not
the surface of the anatase phase. However, as indicated in be in direct contact to each other. Overall water splitting
Figure 5, the number of surface OH of the anatase particle is through two-step photoexcitation (Z-scheme) was reported
far beyond that of the surface OH of the rutile particle. While by Maeda et al. (2011a). The valence band potential of
the presence of the rutile phase increases the separation effi- TaON (bandgap 2.5 eV) can be shifted negatively due to the
ciency of the optically excited charge carriers, this separation hybridization of the O-2p and N-2p orbitals and as a result
is shown not to be favorable for photocatalytic reactions in TaON powders exhibit good photocatalytic activity for not
an aqueous environment (Carneiro, 2010). only oxygen evolution but also hydrogen evolution (Chun
In a different approach Wang et al. (2012c) reported et al., 2003; Sayama, 2012). TaON particles with nanopartic-
that the n-type semiconductor Ga2 O3 with tuneable 𝛼-𝛽 ulate RuO2 were prepared by an impregnation method using
surface-phase junctions can significantly improve photocat- (NH4 )3 RuCl6 as precursor followed by calcination in air at
alytic overall water splitting in H2 and O2 over individual different temperatures. Impregnation of TaON with 0.5 wt%
α- and β-Ga2 O3 surface phases. They have prepared n–n of Ru precursor and followed by calcination for 1 h revealed
junctions of 𝛼-Ga2 O3 covered with different numbers of the highest photocatalytic activity for oxygen evolution from
𝛽-Ga2 O3 nanoparticles. The rates of hydrogen and oxygen an aqueous NaIO3 solution under visible-light irradiation
evolution increase with increasing calcination temperature (𝜆 > 420 nm). The activity of this photocatalyst is strongly
to a maximum activity at 863 K, that is, ∼140 μmol/h/m2 dependent on the generation of optimally dispersed RuO2
for hydrogen and ∼70 μmol/h/m2 for oxygen. The improved nanoparticles, which simultaneously promote both the oxida-
performance of the catalyst in photocatalytic water splitting tion of water and the reduction of IO3 − (Maeda et al., 2011a).
For the Z-scheme the optimized RuO2 -TaON photocatalyst
was used in combination with a Pt-loaded ZrO2 -TaON photo-
OH hν > Ebg catalyst for hydrogen evolution from an aqueous NaI solu-
OH OH tion. The Z-scheme is schematically presented in Figure 6.
OH CB
HO
CB The experimental results indicate that the efficiency of this
HO e− e− system is limited by the competitive oxidation of I− with the
OH
valence band holes in RuO2 -TaON and the photoreduction
HO VB of oxygen that can occur on the RuO2 -TaON surface (Maeda
VB
HO OH et al., 2011a).
HO OH Rutile The potential of the conduction band bottom is close
OH
to the potential of H+ /H2 and, therefore, TaON is with
Anatase
an external bias a promising semiconductor for a photo-
Figure 5. Schematic model for the photoexcited mixed-phase electrode. A porous TaON photoelectrode exhibited under
system. Source: Reproduced with permission from Carneiro, 2010. visible-light irradiation (300 W-Xe, >420 nm) a photocur-
© J. Carneiro. rent of 20 μA/cm2 (Sayama, 2012; Abe et al., 2005).

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DOI: 10.1002/9781118991978.hces006
8 Solar Energy

RuO2 Pt
λ < 500 nm λ < 500 nm
e− e− e−
e− H2
I−
H+
H2O e−
IO3−
O2 e−
h+ h+

RuO2/TaON Pt/ZrO2/TaON
(O2 evolution system) (H2 evolution system)

Figure 6. The overall water splitting through two-step photoexcitation of an O2 evolution photocatalyst and a H2 evolution photocatalyst.
Source: Reproduced with permission from Maeda et al., 2011a. © American Chemical Society.

Maeda et al. (2011b) have reported recent research heterojunction structure. Moreover, these authors found
progress in the development of visible-light-driven photo- that the visible-light-driven photoactivity for hydrogen
catalysts, focusing on the refinement of nonoxide-type production was much higher than that of the corresponding
photocatalysts, such as (oxy)nitrides and oxysulfides. These composite prepared through the hydrothermal route (Li
materials absorb visible light in the spectral range 450–700 et al., 2013a,b). The effect of the AgIn5 S8 /TiO2 molar ratio
nm and are stable photocatalysts for the oxidation and in 2 wt% Pt-loaded nanocomposite on the photocatalytic H2
reduction of water (Maeda et al., 2011b). Novel non-TiO2 evolution rate under visible-light irradiation for 3 h reveals
photocatalysts have recently been reviewed by Chao et al. for P25 no H2 evolution, 100.1 μmol/h for pristine AgIn5 S8 ,
(2014). These include Ag3 PO4 -based composites, non-TiO2 and 371.8 μmol/h for the most optimal 1 : 10 molar ratio. It
metal oxides, sulfides, bismuth compounds, and cobalt is proposed that the photoelectrons of AgIn5 S8 easily flow
compounds. toward TiO2 , which acts as a sink for the photoelectrons,
I-III-VI2 ternary semiconductors with chalcopyrite thereby decreasing the charge recombination. At the Pt
structure such as AgInS2 and other Ag-In-S compounds co-catalyst on P25 hydrogen is formed and the photoholes
are attracting widespread attention owing to their narrow in AgIn5 S8 oxidize the sacrificial reagents such as S2− and
bandgaps. Bandgaps are found between 0.8 and 2.2 eV SO3 2− . It is shown that Pt loading on both components of
(Cheng et al., 2008; Dai et al., 2012; Li et al., 2013a). the nanocomposite leads to the highest H2 evolution rate. A
The ternary chalcogenide AgIn5 S8 with a bandgap of possible influence of the different surfaces of anatase and
1.72 eV shows in thin-film form excellent photoelectrical rutile in P25 with 80% anatase and 20% rutile (see Figure 5)
properties (Qasrawi, 2011a, 2011b; Qasrawi et al., 2011) has not been indicated in this work.
and also as photocatalyst for the production of hydrogen The properties of I-III-VI2 semiconductors with chalcopy-
under visible-light irradiation (Chen and Ye, 2007). These rite structure, such as CuInS2 and AgInS2 , can easily be
investigations indicated that AgIn5 S8 may be a suitable modified by introducing defects. In these ternary materials
narrow bandgap semiconductor to couple with TiO2 for not only deviations from stoichiometry can be introduced,
improved performance under visible-light irradiation. Li but also deviations from molecularity, which cannot be intro-
et al. (2013b) have prepared nanocomposites through a duced in binary materials. Schoonman et al. (2005); Perniu
hydrothermal route by using TiO2 (P25) nanoparticles et al. (2005, 2007, 2009) have developed a 3D-Brouwer
and the obtained AgIn5 S8 /TiO2 nanocomposite indeed defect diagram using deviations from stoichiometry, which
revealed enhanced photocatalytic H2 production activity lead to combinations of ionic and electronic defects and
under visible-light irradiation as compared to the pristine deviations from molecularity, which lead to combinations of
AgIn5 S8 prepared using a similar hydrothermal process (Li ionic defects, as will be presented in more detail in the Defect
et al., 2013a, 2013b). A disadvantage of the hydrothermal Chemistry section. While the defect chemistry was focused
preparation route is that the TiO2 nanoparticles are not on CuInS2 and CuSbS2 , the developed 3D-Brouwer defect
dispersed uniformly in the reaction suspension, and this diagram can also be used to describe the defect chemistry of
leads to a non-uniform distribution of the heterojunction other I-III-VI2 semiconductors with chalcopyrite structure.
structure. Li et al. (2013a) adopted a low temperature water Li et al. (2012) reported visible-light-driven photocatalytic
bath deposition process (Lin et al., 2007) and obtained the activity of CuInS2 nanoparticles loaded with 0.5 wt% Ru as
nanocomposite particles with a homogeneously distributed a cocatalyst for H2 evolution in the presence of S2− /SO3 2−

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Production of Hydrogen with Solar Energy 9

ions as sacrificial agent. The cocatalyst acted as an electron in this type of photocatalyst the electric field in the space
trap for the subsequent reduction of H2 O to H2 . charge region in AgCl due to the Schottky junction promotes
The group of Torimoto has reported in-depth studies the charge separation and suppresses recombination. The
of the Ag-based chalcopyrite semiconductor AgInS2 and silver nanoparticles are formed at the surface of AgCl and
has reviewed recent studies relating to the preparation of resulted from the reducibility of glycerol at high temper-
nanoparticles of this chalcopyrite semiconductor and solid atures during the synthesis process. These authors refer
solutions such as ZnS-AgInS2 (Torimoto et al., 2014). The to AgCl as a typical electron conducting semiconductor.
photocatalytic activity of ∼4.4 nm particles of this solid solu- In fact, AgCl, like AgBr and AgI, is an ionic conductor.
tion for hydrogen evolution was investigated. Under visible- Both the Ag interstitial ions and the silver ion vacancies
light irradiation in the presence of 2-propanol as a photohole are mobile point defects, the Ag interstitial ions being
scavenger, the amount of H2 increased linearly with irradi- the more mobile point defects. Optically excited electrons
ation time, regardless of the chemical composition of the and holes are mobile and lead to photoconductivity, the
solid-solution nanoparticles. However, the H2 evolution rate photoelectrons being more mobile than the photoholes.
was strongly dependent on the chemical composition of the These properties lead to a mechanism in which a surface
solid-solution particles. For a specific composition of the Ag interstitial ion, having an effective positive charge,
solid solution between ZnS and AgInS2 a photocatalytic H2 traps a photoelectron. This silver atom interacts with an Ag
evolution rate of 10 μmol h−1 was obtained at 𝜆onset of ∼540 interstitial ion, which subsequently traps a photoelectron. In
nm. When loaded with Ru as a cocatalyst, the evolution rate this way silver clusters are formed at the surface of AgCl.
of solid solution was comparable to that of a CdS nanopar- In the classical silver halide-based photography clusters of
ticle photocatalyst loaded with Ru nanoparticles in the pres- four silver atoms form the latent image, which is chemically
ence of 2-propanol (Torimoto et al., 2014; Takahashi et al., amplified by a factor of 109 , thus creating the negative
2013). It is also shown that controlling the deviation from image. This type of silver cluster formation will also occur
stoichiometry is a good strategy for tuning the optical prop- in the silver halides AgCl, AgBr, AgI, contributing to their
erties of I-III-VI2 nanoparticles (Torimoto et al., 2014). This promising plasmonic photocatalytic behavior. The results
will be further elaborated in the next section, as in several reveal that the red Ag/AgCl photocatalysts exhibit higher
cases not a deviation from stoichiometry is used, but a devia- photocatalytic oxidative and reductive activities than normal
tion from molecularity, which as indicated earlier will result Ag/AgCl and TiO2 photocatalysts.
in combinations of ionic defects. In this section the role of surface structure and morphology
The activities in the field are numerous and it is, therefore, control has not been discussed. As water oxidation occurs
not surprising that the relevant journals present contin- on the surface of the photocatalyst the nanostructure of
uously a large number of highly interesting papers. To a surface will play an important role in determining the
end this section a few recent examples will be presented photocatalytic activity and efficiency. For example, TiO2
briefly, which are focused in particular on special nanoscale exhibits different photocatalytic reactivities on (110) and
structures. Liu et al. (2014) prepared hollow mesoporous (100) surfaces because of the differences in reactive sites and
TiO2 /WO3 fibers with interconnected nanotubes by a energy levels. These aspects are dealt with in an excellent
sol–gel technique and studied the structure and the perspective paper by Yang et al. (2014b).
optical properties, along with photocatalytic behavior. It is interesting to realize that the field of heterogeneous
Sim et al. (2014) prepared and studied the composite photocatalysis has undergone various evolutionary phases
Ag nanoparticles-graphene oxide-TiO2 . The composite related not only to energy but also to environment while
contained 100% anatase. The deposition of Ag contributed indeed the most significant application of environmental
to improved photocatalytic activity in the visible part of photocatalysis; in addition also photoelectrochemical solar
the spectrum owing to the existence of localized surface energy conversion, is the solar water splitting, the purifi-
plasmon resonance (LSPR). Graphene oxide can not only cation of air and water, including self-cleaning surfaces
act as an electron sink, but also as an electron-accepting (Fujishima et al., 2000), are being studied world wide.
mediator depending on the photocatalytic degradation mech- The interdisciplinary nature of the field has recently been
anism. Cai et al. (2014) have discovered the red Ag/AgCl presented by Teoh et al. (2012).
photocatalyst and showed that the optical absorption is
greatly enhanced by LSPR and by Mie scattering of the
Ag nanoparticles. In addition to LSPR, incorporation of 3.3 Photoelectrode materials and PEC cells
noble metal nanoparticles (Ag, Au, Pt) leads to Schottky
junctions. For an ideal photocatalyst the separation of the The landmark papers of Fujishima and Tryk (1968) and
optically excited charge carriers should be optimal and Fujishima and Honda (1972) on the photoelectrochemical

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DOI: 10.1002/9781118991978.hces006
10 Solar Energy

splitting of water with the semiconductor photoanode


material TiO2 under UV irradiation have initiated worldwide
investigations focused on the splitting of water using solar 25

(IPCE.hv)1/2
energy. In the early days of photoelectrolysis, different
semiconducting photoanodes such as cadmium sulfide and 20
cadmium selenide were studied in PEC cells (Gerrard and
Owen, 1977; Chandra et al., 1980; Haneman et al., 1981).

IPCE (%)
In addition to sensitizing TiO2 to visible light by doping 15 2.5 3.0 3.5 4.0
with cation dopants (Maruska and Ghosh, 1979; Borgarello Photon energy (eV)

et al., 1982) dye-sensitization of TiO2 with Ru-compounds 10


Undoped TiO2
has been studied for the photoelectrolysis of water (Mackor
and Schoonman, 1980). Also research focused on stable Undoped TiO2, x2.4
5 C-doped TiO2
PEC cells without the application of either an external
bias or a pH gradient is being studied. Before presenting Fe-doped TiO2

recent developments in electrode materials for PEC cells, 0


attention will be focused on doping of several wide bandgap 2.0 2.5 3.0 3.5 4.0
photoelectrode materials. Photon energy (eV)
While certain transition metal ion dopants, such as Cr and
Fe, shifted the absorption spectrum of TiO2 to the visible part Figure 7. Incident photon-to-current conversion efficiency (IPCE)
of the solar spectrum, the doping did, in general, not improve for undoped, Fe-doped, and C-doped anatase-structured TiO2 ,
the water splitting efficiencies. The hopping of the holes recorded at a potential of 0 V versus SCE. The insert presents the
1
photocurrent spectrum of undoped TiO2 , plotted as IPCE ∕2 versus
over the localized sub-bandgap defect levels of the dopant the photon energy to determine the band gap of TiO2 . Source:
ions is a slow process, compared to hole conduction in the Reproduced with permission from Enache et al., 2004. © Springer.
valence band. Therefore, the metal dopants act as efficient
recombination centers for the optically excited electron–hole
pairs (van de Krol et al., 2008). surface species are responsible for the black coloring of the
Increased interest in water splitting efficiencies and the nanocrystalline nanoporous TiO2 film and do not lead to
sensitization of wide-band gap metal oxides by doping was enhanced photocatalytic activities in the visible part of the
catalyzed by the paper of Asahi et al. (2001) on anion- solar spectrum.
doped TiO2 . In the case of anion-doping with nitrogen and In order to modify the photoelectrochemical properties
carbon the anion wavefunctions show significant overlap of (anatase) TiO2 the effect of codoping with a nonmetal,
with the valence band wavefunctions, which implies that N or C, and a transition metal, Nb or Ta, has been studied
the sub-bandgap defect levels are less localized than for (Hoang et al., 2012; Ma et al., 2011). Son Hoang et al.
cation dopants; hence recombination of the photoexcited (Hoang et al., 2012) have prepared Ta-doped TiO2 and N
electron–hole pairs is less of a problem. Increased photocat- and Ta co-doped TiO2 nanowires. For the dopant Ta a simple
alytic activities of nitrogen- and carbon-doped TiO2 particles solvothermal method was used and the Ta dopant concentra-
have indeed been shown to result in improved photocatalytic tions ranged from 0.11 to 3.47 atomic percent. The N and
activities (Sakthivel and Kisch, 2003; Enache et al., 2004). Ta codoped nanowires were obtained by the nitridation of
To investigate the effect of anion dopants on TiO2 photoan- Ta-doped nanowires in an NH3 flow at 500◦ C. The codoped
odes, we have doped thin films of anatase-structured TiO2 nanowires with the optimum Ta concentration of 0.29 atomic
with carbon by spray pyrolysis under a CO2 /O2 atmosphere, percent revealed a substantial enhancement in photoelectro-
or by an n-hexane treatment (Enache et al., 2004, 2006; chemical performance. Photocurrents reached 0.52 mA/cm2
Enache, 2012; Hoang et al., 2012) and included doping with under AM 1.5 and 0.18 mA/cm2 in visible light (>420 nm).
Fe. Figure 7 presents the photocurrent action spectra of nomi- For N-doped TiO2 the photocurrents are under these condi-
nally pure, Fe-doped, and C-doped anatase-structured TiO2 . tions 0.26 and 0.13 mA/cm2 , respectively. Incident photon to
The incorporation of carbon as a dopant by carrying out current conversion efficiency (IPCE) values of 25% and 44%
the spray pyrolysis thin-film deposition did not lead to an at 350 nm are obtained for N-doped and N and Ta codoped
observable photocurrent in the visible part of the solar spec- TiO2 , respectively. The active spectrum of both materials
trum which is attributed to a too low carbon content (Enache extends to ∼520–540 nm. The N-doped materials have an
et al., 2004). Doping anatase TiO2 with carbon, using a post- amorphous surface layer, which does not form on nitridation
thermal treatment in a hexane-containing ambient, leads to of the N and Ta codoped TiO2 nanowires. The improvement
mainly surface located carbon (Enache et al., 2006). The shown by the codoped material is ascribed to the presence

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Production of Hydrogen with Solar Energy 11

of fewer recombination centers from charge compensation


H
effects. Ta on a Ti site has an effective charge +q and N on
TiO2–H H TiO2–N
an O site has an effective charge −2q. Here, we anticipate
N
on the use of the Kröger-Vink defect notation, which will be
introduced later.
Ma et al. (2011) studied compensated and noncompen- Melted Al
TiO2 TiO2–x
sated codoped anatase TiO2 with the nonmetal dopant, N
Reduction VO
or C, and the transition metal, Nb or Ta in order to modify
the photoelectrochemical properties of the doped systems.
Codoped systems are constructed with different proportions TiO2–I
and dopant species. The dopant formation energies and elec- I TiO2–S
tronic properties of codoped anatase TiO2 are calculated to S
study the stability and visible-light photoactivity by first-
principles density functional theory. The calculated results Figure 8. A schematic evolution from stoichiometric TiO2 to
demonstrate very interestingly, that the codoping with tran- nonstoichiometric TiO2−x and subsequently to nonmetal-doped
sition metals facilitates an enhancement of the concentration TiO2− X (X = H, N, S, I). Source: Reproduced with permission from
of N and C dopants, which they refer to as p-type dopants. Lin et al., 2014. © Royal Society of Chemistry.
Both Nb and Ta on Ti sites will have an effective charge +q
and also these dopants can charge compensate the effective an oxide ion vacancy with an effective charge +2q, symbol
negative charges of the nonmetal dopants. If TiO2 would be VO ⋅⋅ , which is charge compensated by two electrons with an
doped with either N or C, its effective negative charge −2q, effective charge −q, symbol e′ .
could be compensated with oxide ion vacancies, which have Lin et al. (2014) have introduced an elegant process for the
an effective charge +2q. incorporation of large concentrations of nonmetal dopants
The calculations reveal that especially for the 1 : 2 charge in TiO2 , using large deviations from stoichiometry in TiO2 .
compensated codoped Nb-C-Nb and Ta-C-Ta systems the Oxide ion vacancies can be introduced by thermal treat-
energy gap becomes smaller thus enhancing the optical ment in inert ambient, hydrogen reduction, as well as other
absorption. Furthermore local trapping of optically excited reduction methods, for example, by molten Al and black
charge carriers is eliminated improving carrier mobility and coloration of TiO2 occurs. Lin et al. used molten Al to reduce
conversion efficiency. The authors point out that it is impor- P25 nanocrystals and as a result oxygen-deficient amorphous
tant to control the proper proportion of the transition metal layers surrounding the crystalline TiO2 cores are obtained.
and nonmetal dopants so that improved photoelectrochem- The average thickness of the amorphous layers is ∼4 nm.
ical properties can be achieved (Hoang et al., 2012). Figure 8 presents a schematic evolution of their process.
It is well known that nonstoichiometric TiO2 is an n- The amorphous shells in the Al-reduced P25 samples loose
type semiconductor due to an oxygen deficiency. The lattice lattice ordering with a large number of oxide ion vacancies,
reaction is charge compensated by electrons (lattice reaction 4), which
can convert Ti4+ into Ti3+ ions. The schematic core-shell
OO x ↔ VO ⋅⋅ + 1∕2 O2 + 2e′ (4) structures are presented in Figure 9.
The hydrogenation of the nonstoichiometric shells was
Here, the Kröger-Vink defect chemical notation (Kröger, achieved in a thermal plasma furnace by a hydrogen plasma
1964) is used. An oxide ion with an effective charge 0q, for 4 h at 500◦ C. N-, S-, and I-doped black titania resulted
symbol OO x , leaves the lattice as oxygen, thereby creating on a thermal treatment at the same conditions of temperature

Al X

Reduction Doping

TiO2 TiO2@TiO2-x TiO2@TiO2-X

Figure 9. Schematic core-shell structures of TiO2 @TiO2−x and TiO2 @TiO2− X with the Ti4+ , oxide ion vacancies, and X sites in green,
white, and orange, respectively. Source: Reproduced with permission from Lin et al., 2014. © Royal Society of Chemistry.

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12 Solar Energy

and time under an NH3 : Ar = 2 : 1 gas flow at atmospheric fourfold increase in hydrogen production and a five times
pressure, or by reaction with an S and I2 atmosphere, respec- enhancement of the cell efficiency compared to the PEC
tively. cells with an unmodified CdS photoanode. A maximum
The oxide ion vacancies are required for the X dopants, power conversion efficiency of 2.7% was achieved. Electro-
which diffuse into the amorphous shells and occupy the chemical investigations suggest that the TiO2 film on CdS
oxide ion vacancies. Disordered shells are not significantly reduces the interfacial charge recombination and induces
thicker after the nonmetal doping and the crystal size of the a downward shift of the flat band potential in these PEC
black TiO2 @TiO2−x crystals is not increased. In compar- cells, indicating that interfacial charge recombination is
ison to reported doping of TiO2 with nonmetal dopants, essentially critical for both hydrogen production and solar
the amorphous structure of the shells allows faster diffu- electricity (Zhong et al., 2012).
sion of the nonmetal dopants, while in addition the oxide BiVO4 exhibits a high activity for photocatalytic water
ion vacancy concentration is much larger. Lin et al. (2014) oxidation but cannot realize overall water splitting without
have characterized the photocatalytic activities of all these external bias potential, because its conduction band edge is
materials in detail and concluded that the dopants X reduced slightly more positive than the proton reduction potential
electron–hole recombination and further increased effec- (Hong et al., 2011). Ho-Kimura et al. (2014) have synthe-
tively visible-light absorption and hence visible-light photo- sized a BiVO4 /TiO2 junction composite photoanode, using
catalysis was improved. a solution-based metal-organic decomposition method. The
Radecka et al. (2007) have equilibrated polycrystalline photocurrent was increased by a factor of ∼4, using this
TiO2−x at 1220–1420 K in a flow of Ar + 7 vol% H2 gas composite photoanode with good stability, as compared to
mixture and determined gravimetrically the deviation from BiVO4 under 100 mW/cm2 irradiation, resulting in an ∼5-
stoichiometry x. The reduced samples revealed the coexis- fold enhancement in the IPCE at 400 nm. The enhancement
tence of rutile-structured TiO2 and Tin O2n−1 Magnéli phases. of the IPCE is ascribed to the ultrafine film structure and more
The polycrystalline materials were investigated as photoan- importantly, to facile rectifying electron transfer across the
odes in a photoelectrochemical cell and the photocurrent junctions.
response to an applied voltage was studied. It was found that While among the binary photocatalysts and photoanode
for x = ∼0.006 the nonstoichiometric material exhibited the materials TiO2 has been studied most intensively, of the few
best photoelectrochemical performance. ternary metal oxide photocatalysts and photoanode mate-
Walsh and Wills (2010) have presented a concise review rials, bismuth vanadate, BiVO4 , is to date considered as
on Magnéli phase titanium suboxide materials, which a promising photoanode material, exhibiting visible light
were X-ray diffractive and identified as a distinct series of response. Of the different BiVO4 polymorphs, the mono-
compounds having the above-mentioned general formula clinic scheelite (clinobisvanite) is the photoactive phase with
with 3 < n < 10. Magnéli phases also exist for other transi- a band gap of 2.4 eV and absorbs UV and visible light up
tion metal oxides. The Tin O2n−1 materials exhibit oxide ion to 520 nm (Tokunaga et al., 2001). This phase is stable
vacancy ordering, are black, chemically robust in concen- in aqueous solutions with pH in the range 3–11 (Abdi
trated alkaline and acidic solutions (Li et al., 2010a), and et al., 2012). Several studies reported the use of BiVO4 as a
exhibit metallic conduction. No literature was found using photoanode (Long et al., 2008; Li et al., 2010), but in general
Magnéli phases with for values of n > 8 could be of interest the water splitting activity is low. The overall performance of
for anion doping. In general, Magnéli phases of titanium BiVO4 is limited by poor carrier transport properties (Abdi
oxide and other transition metal oxides are used in energy and van de Krol, 2012). The nature of the carrier transport
conversion technologies (Walsh and Wills, 2010; Li et al., in undoped and 1% W-doped BiVO4 photoanode thin films
2010a). has been studied using TRMC (Abdi et al., 2013a). TRMC
Recently, TiO2 has been studied in a different config- is an electrode contactless technique in which the varia-
uration as a component of an advanced photoanode. tion in reflected microwave power from a sample surface
Doctor-blade prepared nanocrystalline films of CdS were is measured after exciting the sample with a nanosecond
studied as photoanode in two different PEC cells by Zhong pulsed laser (Kroeze et al., 2004). For undoped BiVO4 a
et al. for hydrogen production and solar electricity (Zhong carrier mobility of ∼4.4 × 10−2 cm2 /Vs was obtained and
et al., 2012). The performance of these PEC cells with this value is much lower than carrier mobility values for
nanocrystalline CdS photoanodes could be significantly several state-of-the-art semiconducting photoelectrodes for
improved by a surface modification with thin amorphous PEC water splitting suchas hematite, Fe2 O3 (0.5 cm2 /Vs),
TiO2 films. It has been shown that the surface modification tungsten trioxide, WO3 (10 cm2 /Vs), and copper(I) oxide,
has a similar effect on these two PEC cells. PEC cells with Cu2 O (6 cm2 /Vs) (Abdi et al., 2013a). Hence, this observa-
a CdS/TiO2 (1.8 wt% TiO2 content) photoanode revealed a tion supports the poor carrier transport properties of undoped

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DOI: 10.1002/9781118991978.hces006
Production of Hydrogen with Solar Energy 13

BiVO4 . For W-doped (1%) BiVO4 the carrier mobility is of 0.12 mA/cm2 , measured at 0.3 V against the saturated
∼2.2 × 10−4 cm2 /Vs, a factor of 20 lower than that obtained calomel reference electrode (SCE), with a result that is 4.3
for undoped BiVO4 (Abdi et al., 2013a). Tungsten on a vana- times that of bare BiVO4 . The light source was an Xe lamp
dium lattice site has an effective charge +q and is charge (300 W) with a cut-off filter (𝜆 ≥ 420 nm). The photocatalytic
compensated by an electron with an effective charge −q. activity of O2 evolution is also enhanced to a maximum and
Only in the TRMC signal of the W-doped samples charge follows the same trend with increasing the loading of CoPi.
carrier trapping is observed and the trap levels are related to They attribute the enhancement of photocatalytic activity
the ionized tungsten donor states. By trapping an electron the and photocurrent density to the cocatalyst and electrocata-
dopant has no longer an effective charge +q, that is, WV x . lyst, which lower the activation energy and the overpotential
The AM-1.5 photocurrent-voltage curves of undoped and for water oxidation of photocatalysis and electrocatalysis,
W-doped BiVO4 reveal that both photoanodes at V >1.5 V respectively (Wang et al., 2012b). In order to further demon-
versus reversible hydrogen electrode (RHE) approach strate the role of CoPi, 0.1 wt% of this cocatalyst was loaded
a plateau and the photocurrent plateau of the W-doped on the solid solution Bi0.5 Y0.5 O4 , which is a semiconductor
photoanode is ∼30% higher than that of the undoped and thermodynamically able to split water, but its activity is
photoanode. Both photoanodes were provided with a 30-nm very low. The activities of oxygen and hydrogen were low,
thin film of electrodeposited cobalt phosphate (CoPi) as indicating that CoPi is not effective as a reduction cocatalyst
a cocatalyst to ensure fast water oxidation kinetics. The like Pt. Loading with 0.1 wt% Pt indeed increased H2 produc-
plateau is in agreement with the poor electron transport tion; however, the overall water splitting is still low. Overall
limiting the photocurrent (Abdi and van de Krol, 2012; Abdi water splitting was achieved by using both cocatalysts, that
et al., 2013a) and that W-doping increases the concentration is, Pt-Bi0.5 Y0.5 O4 -CoPi (Wang et al., 2012b).
of free electrons (Abdi et al., 2013a,b; 2013). Besides CoPi, CoBi has been studied as a water oxidation
In order to improve the performance of a BiVO4 cocatalyst to improve the PEC activity and stability of a
photoanode, which suffers from poor electron transport, BiVO4 photoanode (Ding et al., 2013). The cocatalyst is
Zhang et al. (2014) introduced a conductive Al-doped ZnO electrodeposited on BiVO4 in the form of ∼20 nm particles.
inverse opal network into this photoanode to reduce the The atomic ratio has been determined to be Co : B : Na =
distance between the location where the charge carriers are 5 : 2 : 1 and it is inferred that the chemical formula could
optically excited and where they are scavenged. The Al- be NaCo5 (BO3 )2 O5-x . Through loading the CoBi cocatalyst,
doped ZnO inverse opal network collects the photoelectrons a remarkably lowered potential is required for the same
for the photoanode and this composite structure provides a photocurrent as for the bare photoanode (Xe lamp, 300 W,
photocurrent threefold higher than the BiVO4 photoanode 𝜆 > 420 nm). In addition, the onset potential is shifted from
without the conducting inverse opal network. Besides ∼−0.23 V to ∼−0.55 V against SCE and the photocurrent
doping or an oxygen-evolving cocatalyst, this design has the substantially increased both in sodium sulfate and sodium
potential to be applied to other materials for PEC cells to borate electrolytes. These results indicate a decrease of the
improve collection of optically excited charge carriers and water oxidation overpotential and that more electrons and
solar energy conversion efficiencies (Zhang et al., 2014). holes are used for water oxidation and reduction, respec-
As the oxygen evolution is kinetically the key step in the tively (Ding et al., 2013). The cocatalyst does not exhibit
photocatalytic water splitting, cocatalysts are indeed being a photoresponse. Bare BiVO4 suffers photocorrosion; in
studied to lower the activation potential for oxygen evolu- that, the surface ratio of V/Bi decreases significantly on
tion and especially low-cost Co-based catalysts CoOx and irradiation with a considerable drop in photocurrent. It
CoPi have demonstrated good performance as water oxida- is shown that the cocatalyst suppresses the corrosion of
tion cocatalysts (Pendlebury et al., 2011; Zhong et al., 2011; vanadium effectively. Practical PEC water splitting was
Wang et al., 2012b). A particularly effective and easy-to- studied using a two-electrode system with the CoBi -BiVO4
synthesize cocatalyst is amorphous CoPi, a catalyst, devel- photoanode and Pt as counter electrode. In this PEC cell
oped by the group of Nocera, which has attractive features photocurrent starts at ∼0.3 V versus Pt, while at least 0.6 V
such as the low overpotential, low cost, and self-repair prop- is needed with a bare BiVO4 photoanode. A dark current is
erty (Kanan and Nocera, 2008; Esswein et al., 2011). observed only at a bias >1.23 V.
Wang et al. (2012b) compared the behavior of BiVO4 The work of Chunmei Ding et al. reveals that the
powder loaded with CoPi as a cophotocatalyst with BiVO4 CoBi cocatalyst obviously reduces the water oxidation
film electrodes also loaded with CoPi as a cocatalyst. The overpotential, promotes the charge transfer across the
cocatalyst was photochemically deposited on the bare photoanode–electrolyte interface, enhances the stability of
electrode and increasing the deposition time afforded a the BiVO4 semiconductor, and thus results in an improved
further increase in the photocurrent density to a maximum PEC water splitting activity (Ding et al., 2013).

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
14 Solar Energy

While good performing BiVO4 photoanodes are not oxidation. Several recent studies describe the influence of
limited by slow water-oxidation kinetics anymore, the poor surface treatments (Le Formal et al., 2012; Sivula, 2013).
charge carrier separation due to the slow electron transport in Surface modification of a thin-film photoanode, prepared
BiVO4 needs to be improved (Abdi and van de Krol, 2012). by atmospheric-pressure chemical vapor deposition (CVD),
The electrical conductivity of BiVO4 can be increased by by either a catalytic (Co) or a surface passivating overlayer
doping with W, a donor-type dopant; however, this increases (Al2 O3 ), reveals a reduction and a cathodic shift of the
the concentration of electrons and does not affect the low charge accumulation, following the observed change in
intrinsic electron mobility. Abdi et al. (2013) have reported photocurrent onset (Le Formal et al., 2012). Characteriza-
an elegant strategy to improve charge carrier separation. tion of the photovoltage transients suggests the presence
Usually, a good charge carrier separation is obtained by of surface states causing Fermi level pinning at small
creating a heterojunction. These authors have shown that applied potential. The accumulation of photogenerated
doping BiVO4 with tungsten raises the Fermi level of BiVO4 holes at the semiconductor-aqueous electrolyte interface
which implies that when undoped and W-doped BiVO4 are has been rationalized with surface state models (Sivula,
brought into contact, the Fermi energy levels equilibrate by 2013). Surface control and trap passivation layers improve
electron transfer from the W-doped region to the undoped hematite’s performance for the photoelectrolysis of water.
region of BiVO4 , thereby creating a depletion layer at the Brown et al. (2012) have studied the oxygen evolution of
interface between the doped and undoped material. This hematite in alkaline aqueous solution under a bias potential
n+ –n homojunction contributes to charge separation in the during visible-light irradiation in order to shed light on
bulk of the material. For a BiVO4 photoanode with a 10-step the role of electron holes and charge identified with soft
gradient in W doping, starting from 1% at the back-contact X-ray spectroscopy. These are an oxygen 2p hole transition
interface to 0% at the BiVO4 -electrolyte interface a charge into the charge transfer band and an iron 3d type hole into
carrier-separation efficiency increase of ∼60% at 1.23 the upper Hubbard band. Both types of holes contribute to
versus RHE was obtained. This improvement reveals that the photocurrent, contrary to earlier speculations. Besides
a gradient in the dopant concentration is a highly effective the large overpotential, the short diffusion length of the
method to enhance charge carrier separation in highly doped photoholes is limiting the photoresponse of hematite
semiconductor photoanodes. These authors also show that photoanodes. Values for the hole diffusion length are in the
the gradient-doped W-BiVO4 photoanode, provided with order of 0.5–4 nm (van de Krol et al., 2008; Le Formal et al.,
an electrodeposited 30-nm thick CoPi cocatalyst layer, and 2012) and have stimulated the development of high aspect
using a textured Asahi VU-type conducting glass, exhibited ratio nanowire electrodes in order to avoid hole transport
a photocurrent of ∼3.6 mA/cm2 at 1.23 V versus RHE, even limitations. High aspect ratio morphologies can be obtained
better than the photocurrent reported recently for the best by thermal oxidation of metallic iron. Oxidation of iron foil
CoPi catalyzed W-doped BiVO4 photoanode (Abdi et al., at 800◦ C results in nanobelts with a diameter of 50–100 nm,
2013). while a similar treatment at 450◦ C results in the formation
A tandem PEC-PV device was constructed by combining of high aspect ratio nanoflakes (van de Krol et al., 2008).
this optimal photoanode with a 2-jn a-Si superstrate PV cell Nanorod arrays with a primary rod diameter of 4–5 nm
(Abdi et al., 2013), the PV cell being placed behind the PEC reveal a significant blue-shift, showing that one-dimensional
cell. In this tandem configuration, photons with energies less quantum confinement can occur (Vayssieres et al., 2005).
than the bandgap of BiVO4 are absorbed by the a-Si/a-Si PV However, as the 𝛼-Fe2 O3 photoanodes still require a bias
structure. A stable AM-1.5 photocurrent of ∼4 mA/cm2 is voltage to split water, the blue shift does not lead to an
achieved and because the Faradaic efficiency of this system upward shift of the conduction band.
is 100% (Zhong et al., 2011), this corresponds to a solar-to- A hierarchically nanostructured photoanode composed
hydrogen conversion efficiency of ∼4.9%, which is a very of iron oxides is reported to improve the efficiency of a
promising result (Abdi, 2013). hematite photoanode (Yang et al., 2014a). The composite
Hematite, 𝛼-Fe2 O3 , is widely recognized as a potential photoanode comprises Ti-doped 𝛼-Fe2 O3 nanorods which
candidate for the production of solar hydrogen via water are decorated with an undoped hematite underlayer and
splitting. Hematite has a nearly ideal band gap and absorbs 𝛽-FeOOH nanobranches. The Ti-doped hematite nanorods
visible light. The properties of nanostructured hematite reveal enhanced separation of the photogenerated charge
photoanodes have attracted widespread attention (van de carriers and the underlayer increases the photocurrent
Krol et al., 2008; Sivula, 2012). The intrinsic optoelectronic density and also improves the onset potential. The epitax-
properties of 𝛼-Fe2 O3 have limited its performance, a major ially grown 𝛽-FeOOH nanobranches further increase the
drawback being the large required overpotential (0.4–0.6 V photocurrent and induce a positive shift of the onset poten-
anodic of the flat band potential) required to drive the water tial due to an increase in flat-band potential. It is shown

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
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DOI: 10.1002/9781118991978.hces006
Production of Hydrogen with Solar Energy 15

that 𝛽-FeOOH decreases the charge transfer resistance a Schottky mechanism, that is,
across the photoanode–aqueous electrolyte interface. The
interfaces between these different iron oxides demonstrate 0 ↔ 2VFe ′′′ + 3VO ⋅⋅ (7)
a new possibility for improving the efficiency of a hematite
photoanode (Yang et al., 2014a). Here, 0 represents the perfect lattice. The formation of
intrinsic electronic defects is given by lattice reaction (8):
3.4 Defect chemical aspects 0 ↔ e′ + h⋅ (8)
The thermal generation of intrinsic point defects can intro- It should be noted here that these lattice reactions are taken
duce a combination of cation and anion vacancies (Schottky from van de Krol (2012) and that lattice reactions (6) and (7)
disorder), a combination of a cation vacancy and a cation represent better lattice reactions (2.14) and (2.23) from van
interstitial (Frenkel disorder), or a combination of an anion de Krol (2012).
vacancy and an anion interstitial (anti-Frenkel disorder. Stan- For this doped hematite the following electroneutrality
dard examples are VMg + VO (MgO), Agi ⋅ + VAg (AgCl),
′′ ′′ ′

condition is necessary in order to derive all defect concen-


or Fi + VF ⋅ (CaF2 ) where the defect chemical notation of

trations as a function of p(O2 ).


Kröger-Vink is used (Kröger, 1964). Schottky disorder is
generated at surfaces or dislocations, while Frenkel and anti- 3[VFe ′′′ ] + [e′ ] = 2[VO ⋅⋅ ] + [h⋅ ] (9)
Frenkel disorder are generated in the bulk of a material. In a
particular material only one of these intrinsic defect mecha- For the material M2 O3 , doped with XO2 , van de Krol and
nisms will occur. It is common practice to dope a material in Grätzel have derived the defect concentrations as a function
order to control the concentration of an intrinsic point defect, of p(O2 ) and show an example of a Brouwer diagram of log
thereby affecting properties of a material in some way. For 1
defect concentrations versus log p(O2 ) ∕2 . Brouwer diagrams
instance, this engineering on an atomic scale can enhance the can be very helpful in the study of metal oxide photoelec-
concentration of certain ionic point defects and thereby the trodes because they reveal which ionic and electronic defects
ionic conductivity or the n- or p-type electrical conductivity. dominate in a certain p(O2 ) regime. In case of binary mate-
Selected dopants may improve the optical absorption of wide rials, only deviations from stoichiometry occur.
band gap semiconductors, enhance the catalytic activity at In the case of ternary metal oxides, such as BiVO4 , doping
the surface of a semiconductor, or influence the minority with a binary metal oxide, such as WO3 , usually leads to
charge carrier diffusion length. In addition to influencing highly charged, undesired, ionic point defects, in this case
ionic point defect concentrations, deviations from stoichiom- ′′′
VBi . To avoid these undesired defects co-doping with
etry will affect both ionic and electronic defect concen- Bi2 O3 is used (Abdi and van de Krol, 2012; Slapbach and
trations, as illustrated by lattice reaction 4 in the previous Züttel, 2001; Sorokin, 1964). Also for the ternary metal
section. There are many examples of influencing ionic and/or oxides deviations from stoichiometry can be described using
electronic disorder by doping binary materials and specific the lattice reaction (4). In addition to deviations from stoi-
examples for photoelectrode materials are presented by van chiometry, deviations from molecularity can be introduced.
de Krol and Grätzel (2012). Doping hematite with zinc oxide The solid-state synthesis of BiVO4 from Bi2 O3 and V2 O5
will increase the concentration of the oxide ion vacancies can easily lead to small deviations from molecularity, if one
according to the following lattice reaction: of these precursor oxides is present in even a small excess.
The lattice reactions are:
2ZnO → 2ZnFe ′ + 2OO x + VO ⋅⋅ (5)
Bi2 O3 → 2 BiBi x + 2VV ′′′′′ + 3OO x + 5VO ⋅⋅ (10)
The two zinc ions on iron lattice sites have an effec-
tive negative charge, which is compensated by the effective V2 O5 → 2 VBi ′′′ + 2VV x + 5OO x + 3VO ⋅⋅ (11)
charge of the oxide ion vacancy. If this doping reaction will
be performed in an oxygen-containing atmosphere, electron Lattice reaction (10) reveals more point defects to be
holes will be formed as is shown in lattice reaction (6): formed than in reaction (11) are formed, while in addition
the effective charge of the vanadium ion vacancy is larger
2ZnO + 1∕2O2 → 2ZnFe ′ + 3OO x + 2h⋅ (6) than that of the bismuth ion vacancy. Both these differences
indicate that the solubility of V2 O5 in BiVO4 will exceed
In this case, hematite exhibits p-type conductivity. The that of Bi2 O3 . In both cases only combinations of ionic point
intrinsic ionic defects are thermally generated according to defects are formed, hence deviations from molecularity may

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
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This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
16 Solar Energy

S lattice reactions are possible:


Deviation from
stoichiometry In2 S3 ↔ 2VCu ′ + 2InIn x + 3SS x + VS ⋅⋅ (15)
ln2S3
Deviation from
CulnS2 molecularity In the other lattice reactions a larger number of point
Cu2S defects occur, including point defects with effective charges
of + or −3q, which make these lattice reactions less favor-
Cu ln able. Lattice reactions (13) and Wang et al. (2012a) are there-
fore preferred.
Figure 10. Schematics of deviations from stoichiometry and The combinations of a deviation from stoichiometry and
molecularity in CuInS2 . molecularity are exemplified in the following lattice reac-
tions:
lead to different properties of nominally pure BiVO4 and
this holds true for synthesis of undoped ternary and more Cu2 S + 1∕2S2 (g) ↔ CuCu x + CuIn ′′ + 2SS x + 2h⋅ (16)
complex materials.
Dai et al. (2012) and Torimoto et al. (2014) have studied The effective charge of the antisite Cu ion is now charge
tuning of optical properties of chalcopyrite-type AgInS2 by compensated by two electron holes lattice reaction (12).
controlling a deviation from stoichiometry. In these mate-
rials, the Ag content was varied, which means that the mate- In2 S3 + 1∕2S2 (g) ↔ 2VCu ′ + 2InIn x + 4SS x + 2h⋅ (17)
rial’s properties were governed by varying concentrations of
ionic point defects, characteristic for deviations from molec- In the In-rich material the effective charge of the copper
ularity. The work on AgInS2 was compared with literature ion vacancies is charge compensated by the two electron
data for CuInS2 with deviations from molecularity (Torimoto holes (lattice reaction 12).
et al., 2014). As a consequence, deviations from stoichiom- For all the lattice reactions equilibrium constants and
etry and molecularity require a 3D-Brouwer diagram in order electroneutrality conditions can be presented and the defect
to determine the predominant defect pairs. concentrations can then be expressed as a function of the
The defect chemistry of CuInS2 has been reported in relevant equilibrium constants, p(S2 ), and the activities of
detail (Schoonman et al., 2005; Perniu et al., 2005, 2007, the precursor binary metal sulfides (van de Krol, 2012;
2009). Deviations from stoichiometry and molecularity are Schoonman et al., 2005; Perniu et al., 2005, 2007, 2009).
schematically exemplified in Figure 10. The 3D-Brouwer diagram is presented in Figure 11.
Brouwer diagrams of Log defect concentrations versus As stated earlier, the development of a 3D-
Log p(S2 ) and Log defect concentrations versus the Log Brouwerdiagram for CuInS2 can also be applied to develop
activities of the precursor binary metal sulfides, that is, Cu2 S the complete defect structure of other I-III-VI2 materials. In
and In2 S3 were derived and used to construct a 3D-Brouwer general, it is important for the interpretation of properties of
diagram. Here, several basic defect chemical lattice reactions ternary and more complex materials to take both deviations
will be presented in order to illustrate a deviation from stoi- from stoichiometry and molecularity into account.
chiometry and a deviation from molecularity. The deviation It is common practice to investigate diffusion or ionic
from stoichiometry is illustrated with the lattice reaction: conductivity in order to determine the formation enthalpy
of intrinsic point defects and to assign, in case one cation
vacancy and one anion vacancy are formed according to
1∕2 S2 (g) + VS ⋅⋅ ↔ SS x + 2h⋅ (12)
a Schottky mechanism, half of the formation enthalpy to
each intrinsic point defect. In fact, the formation enthalpy
For a Cu-rich material, an antisite copper ion is created of each point defect is different, which leads to a space
along with a sulfide ion vacancy: charge potential difference between bulk and surface and this
space charge goes unnoticed for bulk materials. However,
Cu2 S ↔ CuCu x + CuIn ′′ + SS x + VS ⋅⋅ (13) if the length scale goes down to the nanoscale this space
charge and its effect on materials properties can no longer
It should be mentioned here that for a Cu-rich material be ignored. For TiO2 with Schottky disorder the surface will
two more lattice reactions can describe the incorporation of be positively charged because of surface Ti⋅⋅⋅⋅ ions if the
excess Cu2 S (Perniu et al., 2005, 2007, 2009). formation enthalpy of titanium ion vacancies is smaller than
For an In-rich material the following lattice reaction is that of the oxide ion vacancies. Within the nanostructured
used as an example, as also for the In-rich material three TiO2 the positive surface charge is compensated by a space

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
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DOI: 10.1002/9781118991978.hces006
Production of Hydrogen with Solar Energy 17

log is,
[defect]
KS = [VTi ′′′′ ] [VO ⋅⋅ ]2 (19)

Cui Figure 12 presents the position-dependent concentrations


of the cation and anion vacancies, comprising the ionic space
Vin
VCu
Ini
charge, along with the electrical potential (R. van de Krol,
Vs Delft, 2010 personal communication).
h
e
log ps2 For promising and new materials for photocatalytical
and/or photoelectrochemical splitting of water using solar
log aCu2S log aIn2S3 energy it is important to have detailed insight into the
intrinsic defect structure of a material. This knowledge is
log [defect]
required in order to select appropriate dopants to enhance
the concentration of a desired point defect and to contribute
Ini to the understanding of the mechanism of the production of
VCu hydrogen under irradiation of a particular material.
Cui
Vs
h
log ps2 Vin 4 HYDROGEN SOURCES: THE BLACK
e
SEA
log log aIn2S3
aCu2S Besides water also aqueous solutions of hydrobromic acid
(HBr) were investigated for converting HBr into H2 (g)
Figure 11. The 3D-Brouwer diagram for CuInS2 , including devia- and Br2 (l) using solar radiation. Here, photocorrosion is
tions from stoichiometry and molecularity. a serious problem. The photoanode was stabilized against
photocorrosion using a PEDOT:PSS coating, while low
charge of the titanium ion vacancies and at some distance of loadings of rhodium sulfide or Co- and Ni-substituted RuS2
the surface the electroneutrality condition nanoparticles were used as cathode electrocatalysts in place
of platinum. A photoelectrochemical device comprising
2 [VTi ′′′′ ] = [VO ⋅⋅ ] (18) a single-junction GaAs solar cell electrolyzes HBr with
simulated sunlight as the only energy input. A substantial
holds good as for bulk materials. In order to obtain the improvement in the performance of this GaAs-based photo-
concentration of the oxide ion vacancies in the space charge synthetic cell was observed (Singh et al., 2014; Ivanovskaya
region, the Schottky defect equilibrium constant is used, that et al., 2013).

Concentration

Tisurf VTi′′′′
Bulk: 2VTi′′′′ = Vo

Vo
Tisurf Osurf′′

ϕ (V) Electrical potential


gvm gvx
0

Schottky defects −0.2

Figure 12. Schottky defects created at the surface with the indicated difference in formation enthalpy, here presented as gV , of the individual
point defects. The ionic space charge potential difference between surface and bulk depends on this difference.

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
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DOI: 10.1002/9781118991978.hces006
18 Solar Energy

Hydrogen sulfide (H2 S) has been used in PEC cells to then of hydrogen sulfide (Scranton, 1977). The anaerobic
produce hydrogen under visible-light irradiation (Kainthla conditions are generated in the deepest parts of the Black
and O’M Bockris, 1978; Grzyll et al., 1989; Milczarek et al., Sea and are believed to be produced by sulfur-containing
2003), the rationale being the thermodynamic possibility to bacteria. The concentration gradient of hydrogen sulfide
produce hydrogen from H2 S with much less energy than reveals a steady increase until 1000 m and reaches a value
from H2 O. The thermodynamic potential for splitting water of 9.5 mg/L around 1500 m, and 10.2 mg/mL at 2000 m.
into hydrogen and oxygen is 1.23 V, compared to 0.171 V Above the bottom the concentration of hydrogen sulfide
for H2 S. In addition to hydrogen, electrolysis of H2 S is
reaches 13.5 mg/L (Brewer & Spencer, 1974). At ∼2000
producing polysulfides, a valuable product (Scranton, 1977).
m the concentration of methane is ∼0.2 mg/L. An oxygen-
Kainthla and Bockris (Kainthla and O’M Bockris, 1978)
hydrogen sulfide interface is established at 140–200 m
studied the photoelectrolysis of H2 S in a PEC cell with a
chemically deposited thin n-CdSe film as photoanode and below the surface of the periphery and reaches 60–70 m
platinum as cathode. The PEC cell revealed a 97% current in the center of the Sea (K. Petrov, personal communi-
efficiency to hydrogen. If the hydrogen produced in the PEC cation). The total sulfide production in the sediments of
cell is used in a H2 -air fuel cell for electricity generation the Sea is estimated as 10,000 tons per day of which
a practical efficiency of 10.6% can be achieved. Milczarek 1/3 to 1/4 is lost at the oxygen–hydrogen sulfide inter-
et al. (2003) studied a two-compartment PEC cell comprising face (Sorokin, 1964). The level of H2 S containing waters
an n-CdS photoanode immersed in an aqueous sulfide solu- is close to reach the depth of the Bosporus and hence
tion, a Nafion membrane, Pt cathode, and a sulfuric acid may create a severe environmental problem in the Sea of
solution as the dark component electrolyte. Effects of the Marmara.
concentrations of the electrolyte, membrane surface, and A possible process design for the use of Black Sea water
cathode materials on the performance of the PEC cell were for hydrogen production can be based on pumping the sea
studied in order to reach a high quantum yield of H2 produc- water from a depth of at least 1000 m into an absorbent
tion. Light to hydrogen conversion efficiencies of 12% were column containing sodium hydroxide in order to separate
observed under sunlight conditions. The direct splitting of
H2 S from the sea water. By regenerating the absorbent mate-
H2 S stoichiometrically into S and H2 has been studied by Ma
rials, HS− and NaOH are released and NaHS and NaOH are
et al., 2008 using CdS-based photocatalysts under visible-
either directed to commercial electrolyzers, connected to a
light irradiation. Ethanolamine was used as a H2 S solvent
and reaction media at room temperature. Raman spectra combination of PV solar cells and small-scale wind turbines
revealed that the produced sulfur comprised S4 2− and S6 2− . for the production of hydrogen, or using up-scaled PEC
The hydroxyls of the reaction media were found to be crucial cells. Besides hydrogen polysulfides are formed (Scranton,
for the hydrogen production. The electrochemical evaluation 1977).
revealed that the potential of H2 S splitting in ethanolamine Yamamoto et al. ( 2013) reported recently a fuel cell
was lowered substantially and that the photoelectrons could that converts chemical energy generated by seabed hot
be fully used to reduce protons for hydrogen production. water spouts and the cold ocean water around them. Hot
The authors propose a free-radical-related one-electron elec- water spouting out of the seabed contains large amounts
trochemical oxidation process on a Pt electrode (Ma et al., of hydrogen sulfide that easily release electrons. The
2008). surrounding ambient sea water, on the other hand, contains
The conversion of H2 S, being beneficial from both envi- large amounts of oxygen that easily receive electrons. The
ronmental and energy standpoints, did Petrov (Petrov, 1991) fuel cell’s electricity comes from it converting the reaction
to propose to use the hydrogen sulfide in the Black Sea of hydrogen, separated from hydrogen sulfide in the hot
for the large-scale production of hydrogen and sulfur in the
water, and oxygen in the ambient seawater. With regard to
electrolytic stage of a solar-wind-hydrogen energy system
the Black Sea, such a fuel cell could generate electricity
(SWHES).
in the oxygen-rich—hydrogen sulfide-rich interfacial area.
The Black Sea is an elliptical basin with an area of about
423,000 km2 . It is the largest of the world’s anoxic basins A detailed description of this type of fuel cell is beyond
and is almost completely isolated from the Mediterranean the scope of this article. The engineering challenges would
with only a connection through the Bosporus and the Dard- require a multinational approach of the countries around the
anelles. The Black Sea has a unique composition in that Black Sea, but in general the extracting of H2 S from Black
90% of the sea water is anaerobic and contains methane Sea waters would not only be beneficial from environmental
(CH4 ) and hydrogen sulfide (Scranton, 1977; Petrov, 1991). as well as energy standpoints, but would keep the Black Sea
The concentrations of methane are substantially smaller alive.

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces006
Production of Hydrogen with Solar Energy 19

5 CONCLUDING REMARKS The improved properties are ascribed to a high built-in poten-
tial in a metal-insulator-semiconductor-like device (Michael
The worldwide search for optimal materials to be used as et al., 2013). While it is not a custom to introduce a new
a photocatalyst or as a photoelectrode for the production of topic in this section, the simplicity of this protection against
the energy carrier hydrogen by splitting water under solar photocorrosion, as reported by Stanford University, could be
irradiation has shown impressive progress. In this article, explored more widely.
a literature review is presented in order to illustrate this As stated in the Introduction section, one of the main
progress. As has been stated before, the field is very active requirements of a hydrogen economy is the availability of a
and the relevant scientific journals present continuously a clean and efficient technology for producing hydrogen using
large number of highly interesting papers. Therefore, it has sustainable energy sources. It is evident that photocatal-
been possible to also include papers, which were published ysis and photoelectrolysis using solar energy will become
even a few weeks before the submission of this contri- feasible as a result of successful materials research and engi-
bution. While binary materials such as, TiO2 , hematite 𝛼- neering. However, it is also necessary to further develop
Fe2 O3 , WO3 , and CdS are still being investigated in great a hydrogen infrastructure for fuel cell cars, stationary fuel
detail, more complex ternary and quaternary materials are cells for household use, hydrogen mixed with natural gas
attracting increasing attention. Doping, deviations from stoi- for power plants and related infrastructure, such as refueling
chiometry and, in particular for the more complex mate- stations and, for instance, import terminals.
rials, deviations from molecularity are explored to improve
photocatalytical and photoelectrochemical properties. It is
shown, for instance, that anion-doping of TiO2 is not easily RELATED ARTICLES
achieved, but if a high density of oxide ion vacancies is intro-
duced via a reduction process, anion-doping is facilitated, Brief Introduction to Solar Energy Utilization
thereby reducing electron–hole recombination, increasing Basic Photovoltaic Theory
visible-light absorption and, hence improving visible-light Photovoltaics: Comparison of PV Cell Types
photocatalysis. Also, codoping, for instance, TiO2 with tran- Distributed Energy Systems Based on Water Electrolysis
sition metals (Nb and Ta) facilitates anion-doping with N Driven by Renewable Electricity
Introduction: Clean Energy Conversion Technologies
and C. For charge-compensated codoping the band gap
High Temperature Electrolysis for Hydrogen or Syngas
energy becomes smaller thus enhancing the optical absorp-
Production from Nuclear or Renewable Energy
tion. Increasing the concentration of electrons in BiVO4 is
Clean Energy-Based Production of Hydrogen: An Energy
achieved with the donor-type dopant W, but this dopant does
Carrier
not improve the poor charge carrier separation in BiVO4 .
Hydrogen Production by Electrolysis and Photoelectrochem-
However, it raises the Fermi level and a contact between
ical System
undoped and W-doped BiVO4 creates a homojunction, which
contributes to charge separation in the bulk. It is shown that
a gradient in the dopant concentration (1 – 0% in 10 steps)
is a highly effective method to improve charge carrier sepa- REFERENCES
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