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Hydrogen Production From Water Splitting Using Photo-Semiconductor Catalysts
Hydrogen Production From Water Splitting Using Photo-Semiconductor Catalysts
3
Hydrogen Production from Water Splitting
Using Photo-Semiconductor Catalysts
Rufino Manuel Navarro Yerga, Marı´a Consuelo Alvarez-Galván,
Fernando Vaquero, Javier Arenales, José Luis Garcı´a Fierro
Grupo de Energı́a y Quı́mica Sostenibles, Instituto de Catálisis y Petroleoquı́mica (CSIC),
Marie Curie 2, Madrid, Spain
O U T L I N E
storable for extended periods of time. Additionally, the Research in this field was initiated by the pioneering
chemical energy stored in the HeH bond is easily released work conducted by Honda and Fujishima in 19725 in
when it combines with oxygen, yielding only water as a PEC cell that demonstrated that hydrogen generation
a reaction product (Fig. 3.1). Solar energy can be used to via splitting of water was possible using photocatalysts
produce hydrogen in the form of heat (thermochemical3,4), based on n-type TiO2 semiconductor capable of
light (photoelectrochemical (PEC),5 photosynthetic6 or absorbing light energy. This work stimulated the
photocatalytic7) or electricity (electrolysis8). Among research for water splitting using particulate photocata-
them, the most efficient is the production of hydrogen by lysts, which was first realized in 1980 by Lehn et al.,9
water splitting (Eqn (3.1)) using solar light because it Sato and White10 and Domen et al.11 Over the last
does not have the inefficiencies associated with thermal 40 years, many types of photo-semiconductors, with
transformations or with the conversion of solar energy to more than 130 materials including oxides, nitrides,
electricity followed by electrolysis: sulfides, carbides and phosphides have been reported
to act as efficient particle photocatalysts for hydrogen
1 evolution via water splitting. Unfortunately, most of the
H2 O / sunlight / H2 þ O2 (3.1)
2 photocatalysts are only active under UV light irradiation
(ca. 4% of solar irradiation) and the activity under visible
The reaction involves the standard Gibbs free energy
light is quite limited. So far, the maximum apparent
change (DG0) greater than 237 kJ/mol, equivalent to
quantum efficiency (hydrogen yield per number of inci-
2.46 eV per molecule (1 eV/molecule ¼ 96.1 kJ/mol).
dent photons) for overall water splitting over visible
This energy is equivalent to the energy of photons with
light-driven particle photocatalysts records only a few
wavelengths between 1010 and 500 nm. As pure water
percent (5.9%) apparent quantum efficiency over
does not absorb solar radiation, the water splitting needs
Rh2yCryO3/(Ga1xZnx)(N1xZnx) photocatalysts
a photo-semiconductor capable of efficiently absorbing
applied to pure water under visible irradiation.12 The
solar energy and then splitting the molecule in an indi-
low quantum efficiency is still the current ‘‘bottleneck’’
rect way. Because the electrochemical decomposition of
of the hydrogen production from solar light. The effi-
water to hydrogen and oxygen is a two-electron stepwise
ciency values achieved is still far from the quantum effi-
process, it is possible to use photo-semiconductor
ciency of 10% marked as the initial starting point for
surfaces capable of absorbing solar energy to generate
practical application. Consequently, progress in material
electrons and holes that can, respectively, reduce and
science and engineering applied to the development of
oxidize the water molecules adsorbed on photocatalysts.
efficient semiconductors used as photocatalysts is still
a major issue, the design of efficient photo-semicon-
ductor systems for production of molecular hydrogen
1/2 O2 from water splitting being one of the foremost challenges
splitting
in the development of a solar hydrogen economy.1,12e20
This chapter reports the most significant advances
made in H2 production via water splitting and the chal-
lenges that need to be addressed over the next coming
years to verify the feasibility of hydrogen production
by inorganic semiconductors as a competitive process
H2
in the hydrogen economy. Particular attention is given
H 2O H2 to the new materials and strategies reported in the liter-
ature over the past years for developing efficient partic-
ulate photocatalysts for water splitting.
Storage, distribution
use
3.2 PRINCIPLES OF WATER SPLITTING
(combustion, FC) ON PHOTO-SEMICONDUCTOR
1/2 O2
CATALYSTS
3.2.1 Concept
Q, W Water splitting into H2 and O2 is classified as an “up-
FIGURE 3.1 Scheme of generation and use of solar hydrogen as hill” photocatalytic reaction because it is accompanied
energy carrier. (For color version of this figure, the reader is referred to by a large positive change in the Gibbs free energy
the online version of this book.) (DG0 ¼ þ237 kJ/mol, 2.46 eV per molecule). In this
3.2 PRINCIPLES OF WATER SPLITTING ON PHOTO-SEMICONDUCTOR CATALYSTS 45
hν H2
e–
H+
e –
hh++
h+ ½ O2
H2O
FIGURE 3.3 Scheme of the photocatalyst particulate suspension system for water splitting.
46 3. HYDROGEN PRODUCTION FROM WATER SPLITTING USING PHOTO-SEMICONDUCTOR CATALYSTS
CdS GaP
KTaO3 Si
–1 CdSe
SrTiO3
TiO2
WO3
Potential / V (NHE)
MoS2 + 0.0 V
0
Fe2O3 E0 (H+/H2)
1
+ 1.23 V
E0 (O2/H2O)
FIGURE 3.4 Band gap energy and relative band position of different photocatalysts with respect to the potentials (NHE) for water oxidation/
reduction reactions.
photocatalysts.29 Nevertheless, the improvement on the of metal oxides, metal sulfides, oxysulfides, oxynitrides
efficiency associated to a high crystalline degree of the and composites thereof. Most metal oxide, sulfide and
photocatalyst has much larger effect on the efficiency nitride photocatalysts consist of metal cations with
than that associated with low crystal sizes.30 d0 and d10 configurations. Unfortunately, most of the
photo-semiconductor materials are only active under UV
light and those active under visible light are quite limited.
3.3 PHOTO-SEMICONDUCTOR
MATERIALS FOR WATER SPLITTING
3.3.1 Photocatalysts Active under
The number of elements whose compounds display
photocatalytic activity for water splitting is limited.
UV Irradiation
Elements included in photocatalysts for water splitting Various kinds of semiconducting metal oxides have
are summarized in Fig. 3.5. The photocatalysts are made been reported to act as efficient photocatalysts to split
FIGURE 3.5 Elements included in photocatalysts for water splitting: elements with d10 configuration (red) and elements with d0 configu-
ration (light green). (For interpretation of the references to color in this figure legend, the reader is referred to the online version of this book.)
48 3. HYDROGEN PRODUCTION FROM WATER SPLITTING USING PHOTO-SEMICONDUCTOR CATALYSTS
gaseous or liquid phase water into H2 and O2 under UV 3.3.1.4 Nonoxide Materials
light irradiation. The UV-active photocatalysts can be Sulfides, nitrides and phosphide photocatalysts that
divided into four groups: TiO2 and titanates; tantalates have wide band gap and VB at relatively negative
and niobates; d10 metal oxides and non-oxide materials. potentials compared to oxides have also been reported
as semiconductors for UV-driven photocatalysis. ZnS
3.3.1.1 TiO2 and Titanates has been reported as high-active photocatalyst for
Overall water splitting using particulate TiO210 and hydrogen production from SO2 3 solutions under UV
SrTiO311 under UV light was reported for the first irradiation.47 InP was the sole reported phosphide
time in 1980. Other titanates are known to work as effi- capable of producing hydrogen from aqueous sulfite
cient photocatalysts for water splitting under UV irra- solutions.48 Nitrides of transition metal-cations with
diation. When TiO2 is fused with metal oxides, e.g. d10 electronic configuration (Ga3þ, Ge4þ) are another
La2O3, Sm2O3, metal titanates with intermediate band type of photocatalysts that can split water efficiently
gaps can be obtained. Shibata et al.31 reported that under UV light.49,50
layered titanates (Na2Ti3O7, K2Ti2O5 and K2Ti4O9)
were active in photocatalytic H2 evolution from
aqueous methanol solutions. Perovskite titanates, 3.3.2 Photocatalysts Active under
La2TiO5, La2TiO3 and La2Ti2O7, with layered structures Visible Irradiation
have been also described as materials with high photo-
The number of single-phase materials active under
catalytic activities under UV irradiation.32 Titanates
visible irradiation for water splitting is quite limited.
with cubic-pyrochlore structure R2Ti2O7 (R ¼ Y, Eu,
The photocatalysts active under visible light can be
Ga, La) showed a fairly high activity for overall
divided into three groups: oxides, sulfides and other
water-splitting reaction.33,34
materials.
3.3.1.2 Tantalates and Niobates 3.3.2.1 Oxides
Oxides with layered and tunneling structures are Valence band-controlled photocatalysts having
considered as promising materials to perform efficient a continuous VB formed by atomic orbitals of the
water photodecomposition. According to this fact, tanta- constituent elements have been reported by many
lates and niobates oxides with corner-sharing of MO6 researchers as materials capable of producing H2 from
(M ¼ Ta, Nb) octahedra structure have been considered aqueous solutions under visible light. BiVO4 with
as photocatalysts for water splitting. Tantalates and scheelite structure and Ag3VO4 with perovskite struc-
niobates oxides are highly active for pure water splitting ture were found to show photocatalytic activities for
even without co-catalysts but only under UV light O2 evolution from aqueous silver nitrate solution under
because of their high energy band gap (4.0e4.7 eV).35e39 visible light irradiation.51e53 These oxides possess steep
The high activity of this layered compounds are related absorption edges in the visible light region. The steep
with the easy migration and separation of the photogen- edges indicate that the visible light absorption of these
erated electroneholes through the corner-shared frame- oxides is due to a bandeband transition. In contrast
work of MO6 units.40 with other oxides, the VB of BiVO4 and Ag3VO4 consist
of Bi and Ag orbitals mixed with O2p states that result
3.3.1.3 d10 Metal Oxides in the increase of the VB potentials and the decrease in
Various metal oxides with d10 configuration (In3þ, the band gap energy. Therefore, BiVO4 and Ag3VO4
Ga3þ, Ge4þ, Sn4þ, Sb5þ) have been shown to be effective have the ability to absorb visible light. However, these
for water splitting under UV light. B-Ga2O3 with a band catalysts did not have potential for H2 production
gap of 4.5 eV has been reported as promising photocata- because the CB potentials of the photocatalysts do not
lysts for water splitting under UVevisible irradiation.41 have sufficient overpotential for the reduction potential
Inoue and co-workers investigated photocatalytic proper- of water.
ties for water splitting of different indates.42,43 The photo- Lee and co-workers54 reported that PbBi2Nb2O9, an
catalytic activity for water decomposition under UV Aurivillius-phase perovskite, acts as photocatalyst
irradiation was considerably large for CaIn2O4, SrIn2O4 capable of producing H2 or O2 from aqueous solutions
and BaIn2O4, which show distorted InO6 octahedra containing sacrificial reagents under visible light.
with dipole moment. Metal oxides with d10 configura- Lv et al.55 developed a new LiCr-(WO4)2 single-phase
tions have distorted octahedral and/or tetrahedral struc- oxide photocatalyst that showed photocatalytic activity
tures (CaSb2O644 Zn2GeO4,45 ZnGa2O446 were also for H2 production under visible light irradiation.
reported to show activity for water splitting under UV RbPb2Nd3O10 Dian-Jacobson phase layered perovskite
irradiation). is also a single-phase oxide that showed photocatalytic
3.4 STRATEGIES TO IMPROVE THE VISIBLE RESPONSE OF UV-ACTIVE PHOTOCATALYSTS 49
activity under visible light. Domen and co-workers56 N N
reported visible light response of RbPb2Nd3O10 with
capacity to produce H2 or O2 from aqueous solutions
under visible light. Li and Ye57 developed binary lead
niobates Pb3Nb2O8 and Pb3Nb4O13, which are visible
light-sensitive photocatalysts. The hybridization of the
Pb6s and O2p orbitals in these niobates is responsible N N N
for the observed visible light response. Melem unit
3.3.2.2 Sulfides
Sulfide photocatalysts, which have narrow band gap
and VB at relatively negative potentials compared to N N
oxides, are good candidates for visible light-driven photo- FIGURE 3.6 Schematic structure of a perfect graphitic carbon
catalysts. Metal sulfide photocatalysts, however, are not nitride sheet constructed from melem units. Source: Adapted from Ref. 63.
stable in the water oxidation reaction under visible light
because the S2 anions are more susceptible to oxidation
than water causing the photo-degradation of the photoca- dependence takes place at longer reaction times. The
talyst.27,58 For that reason, sulfide photocatalysts are not first part of the H2 evolutionetime curve was inter-
suitable for water splitting unless appropriate strategies preted in terms of the surface oxidation of TiSi2 whereas
are designed to minimize the photo-degradation. A the linear part observed at longer illumination times was
common method for reducing the photo-corrosion of the attributed to water splitting.
sulfides under irradiation is by means of the use of suitable Graphitic carbon nitride (g-C3N4, Fig. 3.6) with
sacrificial reagents. Photo-corrosion may be effectively a band gap of 2.7 eV was developed as a promising pho-
suppressed by using a Na2S/Na2SO3 mixture as electron tocatalyst for hydrogen or oxygen production from
donor.59 Using this mixed solution, the photocatalytic water under visible-light irradiation with the assistance
reaction should proceed as follows, avoiding the degrada- of sacrificial reagents.63 The prepared g-C3N4 achieved
tion of sulfide photocatalyst: steady H2 production from water containing triethanol-
amine as a sacrificial electron donor on visible light
Photocatalysts þ hv / e ðCBÞ þ hþ ðVBÞ (3.3) illumination.
Some phosphate semiconductors were also reported
2H2 O þ 2e ðCBÞ / H2 þ 2OH (3.4)
as active photocatalysts for water splitting under visible
þ
SO2
3 þ H2 O þ 2h ðVBÞ / SO2
4 þ 2H þ
(3.5) light. Li9Fe3(P2O7)3(PO4)2 was proven to be an active
photocatalyst for H2 production under visible light irra-
2S2 þ 2hþ ðVBÞ / S2 (3.6)
2 diation using I ions as electron donor.64
S2
2 þ SO2
3 / S2 O2
3 þS 2
(3.7) Graphene oxide semiconductor photocatalyst (Fig. 3.7)
with a band gap of 2.4e4.3 eV can also steadily produce
SO2
3 þS
2
þ 2hþ ðVBÞ / S2 O2
3 (3.8)
H2 from an aqueous methanol solution or pure water
under visible light irradiation as reported recently by
Among the available sulfide semiconductors, nano-
Yeh et al.65
sized CdS is an interesting photocatalyst, since it has
a narrow band gap (2.4 eV) and a suitable CB potential
to effectively reduce the Hþ.59,60 CdS loaded with Pt
co-catalyst shows very high efficiency in light absorp- 3.4 STRATEGIES TO IMPROVE THE
tion and hydrogen production under visible light VISIBLE RESPONSE OF UV-ACTIVE
(apparent quantum efficiency ¼ 25%61). PHOTOCATALYSTS
3.3.2.3 Other Materials As shown in Section 3.3.1, various kinds of semicon-
A new class of titanium semiconductor, titanium dis- ducting metal oxides have been reported to act as effi-
ilicide (TiSi2), which absorbs a wide range of the solar cient photocatalysts to split gaseous or liquid phase
spectrum, has been proposed as a prototype photocata- water into H2 and O2 under UV light irradiation.
lyst for the water-splitting reaction.62 This photocatalyst However, most of metal oxide photocatalysts are unable
presents two phases of hydrogen evolution when the to split pure water under visible light. This is mainly due
reaction is conducted under specific conditions. At short to the fact that as the band gap energy of the metal oxide
reaction times, the system shows a nonlinear depen- becomes smaller, the CB edge shifts more positively.66 To
dence for H2 evolution, whereas a nearly linear overcome this difficulty, suitable band engineering is
50 3. HYDROGEN PRODUCTION FROM WATER SPLITTING USING PHOTO-SEMICONDUCTOR CATALYSTS
Light
Anti-bonding π
CB
H+/H2
O O O
O O
BG
O O
Ox/Red O O O
MeOH
O2/H2O O
O2p VB
FIGURE 3.7 Energy-level diagram of semiconducting graphene oxide. Source: Adapted from Ref. 65.
required in order to develop new photocatalysts for photocatalysts do not record photoactivity because
water splitting under visible light irradiation when start- dopants in the photocatalysts act not only as visible light
ing with wide band semiconductors. absorption centers, with an absorption coefficient
dependent on the density of dopants, but also as recom-
bination sites between photogenerated electrons and
3.4.1 Band Gap Engineering holes.67 Furthermore, the impurity levels created by
The ability to adjust and fine-tune band gap and dopants in the photocatalysts are usually discrete, which
band positions is essential in developing visible light- would appear disadvantageous for the migration of the
responsive photocatalysts for H2 production. Three photo-generated holes.68 Therefore, it is important to
approaches toward band engineering have been fine-tune both the content and depth of the cation substi-
reported: cation or anion doping; VB modification; and tution in the structure of the host photocatalysts to
solid solution formation. develop visible light-driven water-splitting photocata-
lysts. Metal ions may be incorporated into the photoca-
3.4.1.1 Cation or Anion Doping talysts by chemical methods such as impregnation and
The replacement of cations or anions in the lattice of precipitation or by the advanced ion-implantation tech-
a wide band gap semiconductor has often been used nique that allows for the incorporation of cations by the
for enhancing the visible light response of wide band impact of high-energy ions accelerated by high voltage
gap photocatalysts (UV-active). (50e200 keV).69e71
The replacement of cations in the crystal lattice of Anion doping is another approach undertaken to
a wide band gap semiconductor may create impurity enhance the visible light response of wide band gap
energy levels within the band gap of the photocatalyst (UV-active) semiconductors. As in wide band gap oxide
that facilitates absorption in the visible range, as semiconductors, the top of the VB consists of O2p atomic
depicted in Fig. 3.8. Although a cation-doped photocata- orbitals and partial replacement of oxide anions by other
lyst can induce visible light response, most of these anions such as nitrogen,72,73 sulfur74 or carbon75 has
photocatalytic properties of Cd1xZnxS solid solutions 1000-fold, thus making light absorption efficient even
with different Zn concentration (0.2 < x < 0.35). The with only a dye monolayer on each particle. Nature, in
solid solution between CdS and ZnS showed a blue shift fact, uses a similar means of absorption enhancement
of the absorption edge with the increase in Zn concentra- by stacking the chlorophyll-containing thyalkoid
tion. The photocatalytic activity of samples increases membranes of the chloroplast to form the grana struc-
gradually when the Zn concentration increases from tures. An intriguing feature in the nanocrystalline TiO2
0.2 to 0.3. The change in activity for H2 production for films is that the charge transport of the photoinjected
these samples arises mainly from the modification of electrons passing through all the particles and grain
the energy level of the CB as the concentration of Zn boundaries is highly efficient, the QY being practically
increased in the solid solution photocatalyst. unity.
Combination of ZnS with AgInS2 and CuInS2 to Whereas much pertinent information has been gath-
produce solid solutions (CuAgIn)xZn2(1x)S2 is other ered over the years on the overall performance of dye
strategy followed to improve the optical absorption of sensitized semiconductor systems, more precise data
ZnS in the visible range.105e107 The optical absorption about the details of the electron injection and recapture
of these materials can be adjusted between 400 and process are required. The rapid nature of these reactions
800 nm depending on solid solution composition. requires application of fast kinetic techniques which, in
(CuAgIn)xZn2(1x)S2 solid solutions showed high photo- the case of solid semiconductor powders, is very diffi-
catalytic activities for H2 evolution from aqueous solu- cult. Similar effects have been observed with a number
tions containing sacrificial reagents, SO2 3 and S2, of different sensitizers such as porphyrins and
under visible light irradiation. Loading solid solutions Ru(bipy)2þ3 derivatives or Fe(CN)4 6
112
surface-
with co-catalyst improved the photocatalytic activity. derivatized TiO2 particles. In all these cases, the back-
Pt loaded on (AgIn)0.22Zn1.56S2 showed the highest electron transfer from the semiconductor particle to
activity for H2 evolution with an apparent QY of 20% the oxidized sensitizer occurred with a rate that was
at 420 nm. several orders of magnitude slower than the forward
Other ternary sulfides comprising In3þ and one type injection. Thus, the combination of a sensitizer with
of transition metal cation (Cd2þ, Zn2þ, Mn2þ, Cuþ) are a colloidal semiconductor particle affords a molecular
also investigated as photocatalysts for water splitting device for light-induced charge separation. The question
under visible light. However, up to now, the efficiency should be addressed why in this system the rate of the
achieved over these photocatalyst is very low. For back-reaction is so much smaller than that of the
example, a quantum efficiency of only 3.7% at 420 nm forward electron transfer. One might assume the fact
was reported for the most active Na14In17Cu3S35 photo- that recapture of the CB electron has a large driving force
catalyst.108 Recently,109 a solid solution was reported to placing this reaction in the inverted region where the
be formed from AGa5S8 and AIn5S8 (A ¼ Cu or Ag), rate drops with increasing heat release. In addition,
which are active under visible light, with relatively entropic factors should be considered. If there is only
high QY (15%). They were active from aqueous solutions one sensitizer cation available at the surface, the back-
containing electron donors. reaction is associated with a significant entropy decrease
which amounts to ca. 67 J/K mol.
Light harvesting can also be improved by incorporating
3.4.2 Dye Sensitization a multicomponent system possessing several chromo-
An effective strategy for populating the CB of UV phoric molecular components. This kind of antenna
photocatalyst is by excitation of a chromophore such system absorbs the incident light and channels the excita-
as an organic dye. However, the development of effi- tion energy to a common acceptor-reaction center. Porphy-
cient dye-sensitized solar cells using single-crystal semi- rins, the main chromophores of natural photosynthesis,
conductor electrodes was precluded by poor light have been the obvious candidates for the design of artifi-
harvesting efficiencies and low photocurrent densities. cial antenna systems. Another interesting series of polynu-
The photosensitization of wide band gap semicon- clear species of large nuclearity, which because of their
ductors such as TiO2 by adsorbed dyes has been studied shape can be called “dendrimers” or “arborols”,
since the late 1960s.110,111 The earlier photo-electrochem- has been obtained using Ru(II) and/or Os(II) as metal
ical studies focused on flat electrodes, but these systems centers, bis-bipyridine-type ligands as bridging groups
were facing an intrinsic problem. Only the first mono- and bipyridine-type terminal ligands.113,114 Following
layer of adsorbed dye results in efficient electron injec- a modular synthetic strategy known as “complexes-as-
tion into the semiconductor, but the light harvesting metals/complexes-as-ligands”, such polynuclear species
efficiency of a single dye monolayer is very small. In can be obtained with a high degree of synthetic control
a porous film consisting of nanometer-sized TiO2 parti- in terms of the nature and position of metal centers,
cles, the effective surface area can be enhanced bridging ligands, and terminal ligands. The energy of
3.5 STRATEGIES TO IMPROVE THE PHOTOGENERATED CHARGE SEPARATION 55
the metal-to-ligand charge transfer excited state of each High crystalline degree of the photocatalyst has a positive
unit depends on metal and ligands in a well-known and effect on transport of photo-excited carriers, as the density
predictable way. Thus, synthetic control translates into of defects caused by grain boundaries, which act as recom-
control on the direction of energy flow within these bination centers of electrons and holes, decreases when
molecules. particle crystallinity increases. Apart from that, crystalline
For some practical purposes (e.g. to bind at an inter- size also influences the electronic properties of the photo-
face with good surface coverage), one-dimensional catalyst. It has been reported that the band gap of a crystal-
(1D) antenna systems might be more convenient than line semiconductor is a function of the particle size,
highly branched ones. A 1D antenna requires stepwise increasing the band gap of photocatalysts with the
energy transfer along a chain of molecular components, decrease in particle size to nanometer range.
and the maximum length of the system (i.e. number of Taking into account the effects of particle size on light
components) depends critically on the driving force absorption, charge-carrier dynamics and surface area,
demand of each energy-transfer step. The possibility to much effort has been made to control the synthesis of
obtain efficient energy migration along chain-like materials in order to optimize the particle size, crystal-
systems has been checked with the cyano-bridged linity morphology and defects of photocatalysts at the
pentanuclear species. These results suggest that in nanometric scale.
strongly coupled systems of this type, energy migration
between isoenergetic adjacent molecular components
takes place efficiently. The presence of a higher-energy 3.5.1.1 Advanced Synthesis Approaches
“stopper” on one end and a lower-energy “trap” at the Nanostructured photocatalysts have the potential to
other end is sufficient to give directionality to the overall reduce the extent of electronehole recombination due
process. to short charge transfer distances, and reactant adsorp-
tion and product desorption can be enhanced due to
the high surface area offered by nanostructures. A crit-
3.5 STRATEGIES TO IMPROVE THE ical issue of aqueous dispersions of semiconductor
PHOTOGENERATED CHARGE powders conductive to visible light excitation is stability.
SEPARATION Taking into account the importance of the structural
characteristics (crystalline phase, crystalline size and
Apart of the electronic properties of the photo- geometrical surface area) in the control of band structure
semiconductors, the precise design of the bulk and and in the concentration and mobility of photocatalyst
surface properties from the semiconductor is essential charges, studies have been conducted on the influence
to control the interrelation between its electronic, of preparation methods on the photophysical properties
microstructural and surface properties. In the search of CdS.116,117 Improvement in CdS photoactivity is
for more efficient photocatalysts for water splitting, observed from preparation methods that lead CdS
the control of the synthesis of the material to tailor phases with good crystallinity and few crystal defects.
its crystallinity and morphology at the nanometric Different approaches have been undertaken over
scale is very important, because these properties the last two decades to synthesize semiconductor systems.
have a major influence on the rate of water-splitting Salt precursors like Cd(NO3)2, Cd(ClO4)2 and Na2S
reaction. All these approaches have been nicely dis- have often been used for synthesis of IIeIV nanopar-
cussed in a recent review by Best and Dunstan.115 ticles in aqueous media.118 Some other organometallic or
TOP/TOPO (tri-n-octylphosphine/tri-n-octylphosphine
3.5.1 Nanodesign: Controlling the Size oxide)-based synthesis have been used for preparing
Cd-calcogenides (CdX, X ¼ S, Se, Te).119 The particle diam-
and Form eter of IIeIV nanoparticles can be adjusted by using
The water-splitting reaction at the photocatalyst inter- a combination of the cation, calcogenide precursor and
face occurs if charge carriers (electrons and holes) gener- stabilizing agents. Among the stabilizing agents,
ated in the bulk of the semiconductor by absorbed light thiols,120,121 surfactants,122,123 phosphates,124 zeolites and
can reach the surface during their lifetime and manage to microporous oxide films125 remain prominent. A some-
find suitable reaction partners, protons for electrons and what different approach must be followed to synthesize
water molecules for holes. The transport of photo-excited the other class of IIIeV semiconductors due to the increase
carriers is determined by the crystal size, the crystalline in covalent bond strength in IIIeV lattices.126 Molecular
structure, the nature and number of structural defects beam epitaxy,127 colloidal methods based upon TOP/
and the surface properties of photocatalysts. To have an TOPO128,129 along with the more widely employed deha-
efficient charge-carrier dynamics, the diffusion length of losilylation reactions have often been used to synthesize
charge carriers must be longer than the particle size. GaP, InP, GaP and GaAs nanoparticles.130
56 3. HYDROGEN PRODUCTION FROM WATER SPLITTING USING PHOTO-SEMICONDUCTOR CATALYSTS
Oxide semiconductors can be synthesized relatively the titania VB that shifts the absorption edge of titania to
easily due to their stability in an aqueous media. The around 540 nm. The nitrogen-doped titania nanotube
most common method involves a metal salt or alkox- arrays were synthesized by anodizing titanium foil in
ide combined with an acid or base catalyst to seed an NH4F/H2O water electrolyte containing ethylene
crystal growth and maintain particle size at about glycol at 55 V.140 Nanotube array samples up to about
5 nm.131 This is similar to the solegel based technique, 130 mm in length and average pore diameter of
where particle growth drops before the formation of 95 13 nm with wall thickness of 20 5 nm were
a gel. This method can be used to synthesize several prepared by changing the anodization time. Ti anodiza-
oxide nanoparticles, e.g. TiO2, ZnO, and films, where tion in fluorine-containing electrolytes yields amor-
a slightly different solegel method is used for pellet phous nanotube arrays, hence elevated temperature
preparation. oxygen annealing is needed to maintain titania stoichi-
ometry and reduce lattice defects. However, annealing
3.5.1.2 Anisotropic Photocatalysts the nitrogen-incorporated samples at high tempera-
and Other Structures tures in an oxygen-rich environment generally removes
Generating anisotropic photocatalysts particularly the nitrogen by oxidation. Therefore, incorporated
with 1-D or longitudinal structures such as nanotubes, nitrogen within the nanotube sample can be maintained
nanorods, nanowires and nanoribons has been widely by limiting the oxygen flow across the sample during
explored. Physically, these structures may offer exploit- annealing.
able advantages such as higher surface-area-to-volume Decorating nanorods or wires with nanoparticles or
ratio compared with spherical particles, aligned pores, thin layers is another recent approach to develop effi-
and wavelength-specific light trapping. cient photocatalysts for water splitting. Jang et al.141
Compared to powder and planar systems, nanotubes reported optimized H2 production on decorated CdS
and nanowires enhance charge separation and photo- nanowires with TiO2 nanoparticles in the presence of
current response. It was demonstrated that photo- hole scavengers and a Pt co-catalyst. Effective charge
conversion efficiency of TiO2 nanowires is almost twice separation was found to occur in the 1D CdS system
that of spherical nanoparticles.133 The aspect ratio also and this led to improved photo-catalytic activity. Similar
plays a key role on the performance. Photon absorption ideas have been investigated by many groups, including
and photocurrent density increase with the aspect ratio CdS-decorated TiO2 nanowires,142,143 Au nanoparticles
of the nanotube. Therefore, the charge transfer at the on TiO2,144 and CdS nanorods.145
semiconductoreelectrolyte interface is enhanced, Synthesis of photocatalysts possessing alternate
limiting electronehole recombination processes at the morphologies such as cube, pyramid and fractals has
tube surface and in the bulk.134 This observation opens also been extensively reported in recent years.
the door for new designs of efficient photo-catalysts Compared with the anisotropic design, these 3D struc-
for water splitting. Following this line, Mahajan et al. tures are bound by their facets, each of which is energet-
recently showed that TiO2 nanotube arrays are highly ically unique. In principle, the photocatalytic redox sites
stable with respect to activity and morphology and can as well as sites for preferential adsorption of reactants
yield H2 without any noticeable decrease in rate for at are dictated by the facets. For TiO2, different groups
least one month.132 have reported the tailored synthesis of anatase single
Doping of nanotubes is also common practice to crystals with a high percentage of the highly reactive
harvest the fraction of visible light. Modified tubular {001} facets.146,147 Nanostructured anatase TiO2 with
arrays have been shown to produce eight times the a large percentage of other exposed high-energy facets
photocurrent density of un-modified arrays,135 and 20 {010} and {100}, respectively, exhibited much higher
times the current density of nanoparticulate films.136 activities than that of commercial anatase powders. In
Similar work has been reported for ZnO nanotubes the same way, Shen et al.148 found that the photocatalytic
and wires through Cd doping to reduce the band gap activity of ZnIn2S4 was greatly affected by the crystal
from 3.4 to 3.0 eV.62 TiO2 nanotube arrays formed by plane space along the c-axis, the increasing d (001) space
anodic oxidation of titanium137 have very high surface greatly improved the photocatalytic activity. A similar
areas,138 comparable to porous titania nanoparticle effect of the surface nanostructured was also observed
films, and proven photocatalytic properties. Although on La-doped NaTaO3.149
the TiO2 band gap, 3.0 and 3.2 eV for rutile and anatase, Ordered mesoporous materials have also been
respectively, restricts excitation wavelengths to less explored as photocatalysts. The mesoporous photocata-
than about 400 nm, Varghese et al.139 have succeeded lysts possess two major beneficial characteristics: high
in incorporating nitrogen into the nanotubes during surface area and nanoscale channel wall of mesopores
anodization, with a subsequent heat treatment resulting that can facilitate the transfer of photogenerated elec-
in crystallized nanotubes with N2p states formed above trons and holes to the surface, avoiding their
3.5 STRATEGIES TO IMPROVE THE PHOTOGENERATED CHARGE SEPARATION 57
H2
e–
H+
H20
h+
O2
recombination in the bulk (Fig. 3.12). Mesoporous photoexcitation, electrons and holes generated in the
tantalum oxide,150 tantalum nitride151 and g-C3N4152 sheets cause redox reactions with water molecules adja-
have been reported as mesoporous structures with cent to the layers.
higher photoactivity than bulk counterparts.
Metal oxide nanosheets are another class of materials
studied as photocatalysts110,153,154 because of their 3.5.2 Loading of Co-catalysts
morphological characteristics (Fig. 3.13). These Although some of the photocatalysts developed to
compounds consists on negatively charged corner- date (CdS, tantalates, layered compounds) can decom-
and/or edge-shared MO6 (M ¼ Ti, Nb, Ta) octahedral pose water without co-catalysts, most require the
units that stack to form a two-dimensional (2D) layered loading of a suitable co-catalyst to obtain a high
structure interleaved with alkaline cations to compen- activity and reasonable reaction rates. The deposition
sate for the negative charge of the sheets. Upon of noble metals (e.g. Pt, Rh) or metal oxides (e.g.
NiO, RuO2) onto photocatalyst surfaces is an effective
way of enhancing photocatalyst activity.23e25 The co-
catalyst improves the efficiency of photocatalysts, as
shown in Fig. 3.14, as a result of the following: (1)
the capture of CB electrons or VB holes from the pho-
tocatalysts,155 thereby reducing the possibility of
electronehole recombination and (2) the transference
of electrons and holes to surface water molecules,
thereby reducing the activation energy for the reduc-
tion (Fig. 3.14(A))/oxidation (Fig. 3.14(B)) of water.156
The activity of the co-catalysts is found to be strongly
H2 dependent on the quantity of co-catalysts deposited on
the photocatalyst surface. When the amount exceeds
e– h+ a critical limit, the co-catalysts act as electronehole
H+ recombination centers, reducing the efficiency of the
H20
host photocatalyst.
Noble metals such as Pt and Rh are excellent
O2 promoters for H2 evolution but can also catalyze a back-
ward reaction, forming water from H2 and O2, limiting
FIGURE 3.13 Scheme of photogenerated charge separation on their usefulness as co-catalysts for photocatalytic overall
metal oxide nanosheets. water splitting. To avoid the backward reaction,
58 3. HYDROGEN PRODUCTION FROM WATER SPLITTING USING PHOTO-SEMICONDUCTOR CATALYSTS
(A) (B)
hv > Eg
Reduction Oxidation hv > Eg
cocatalyst cocatalyst
H2O O2
H2
H+
e– H2O
h+
O2 H2
h+ e–
H+
FIGURE 3.14 Photocatalyst surface modification by addition of co-catalyst to facilitate the hydrogen (A) or oxygen (B) evolution in water
splitting.
transition-metal oxides that do not exhibit activity for 3.6 CHALLENGES AND OPPORTUNITIES
water formation from H2 and O2 are usually applied
as co-catalysts for overall water splitting. NiOx was Photocatalytic H2 production via water photolysis
successfully applied as an H2 evolution co-catalyst offers unique opportunities to develop a C-free fuel
when loaded on the surface of SrTiO3.11 RuO2 was also and sustainable energy system. As shown in the
applied as co-catalyst for overall water splitting over preceding sections, the structural and electronic struc-
KTi4O9,157 Na2Ti3O7,158 and b-Ge3N4.159 ture of photocatalyst material is the core of the photoca-
Mixed NieCr and RheCr oxides were used as co- talytic H2 production technology. Significant advances
catalysts on (Ga1xZnx)(N1xOx) for photocatalytic over- have been achieved in the design and development of
all water splitting.99 Core-shell structured nanoparticles unique photocatalysts that can split water into H2 and
(with a noble metal or metal oxide core and Cr2O3 shell) O2. Several types of semiconductors including oxides,
were presented as a new type of co-catalysts for overall nitrides and sulfides have been reported to act as effi-
water splitting.160 In these coreeshell structured nano- cient photocatalysts for photolysis of water. Among
particles, the Cr2O3 shell can suppress water formation these photocatalysts, higher QY are reported under UV
being permeable to the evolution of H2 (Fig. 3.15). light for NiO/NaTaO3 (56% QY).38 Although this yield
Among the noble metals and metal oxides examined is very high, results have only a limited value for prac-
as nanoparticulated cores, Rh was the most effective in tical H2 production because UV light accounts for only
enhancing photoactivity. about 3e4% of solar radiation energy. Therefore, utiliza-
tion of solar energy on a large scale requires the develop-
ment of photocatalysts capable of splitting water
efficiently under visible light (l ~ 600 nm).
Cr2O3 shell Currently, the number of visible light-driven photo-
H2
catalysts is limited. However, many oxides, sulfides,
oxynitrides and oxysulfides have recently been found
hv > Eg Noble metal
H+ or to be active for H2 and O2 evolution under visible light
Metal oxide irradiation. So far, the maximum quantum efficiency
core
over visible light-driven photocatalysts achieves only
a few percent at wavelengths as long as 500 nm Cr/
e– RheGaN/ZnO (2.5% QY).160 This value is still far
H2O
from the QY of 10% marked as the initial starting point
h+ for practical application.161 Thus, the development of
new photocatalysts is still a major issue.
O2 Novel photocatalysts are expected to be developed,
whereas the existing ones should be optimized. Nano-
Photocatalysts structured photocatalysts are expected to be a future
bulk trend, since these nanostructures display much better
performance than their bulk counterparts. There is
FIGURE 3.15 Scheme of hydrogen evolution on core/shell nano- no general rule to say what kind of material is more
structured nanoparticles as co-catalyst. appropriate, because there is no existing photocatalyst
REFERENCES 59
that meets all the requirements, and all candidates Acknowledgments
have their own virtues and drawbacks. Definitely,
The present work was performed within the research programs sup-
metal oxide photocatalysts are considered promising ported by the CAM and MICINN (Spain) under Projects S2009ENE-
candidates as they are cheap and display good resis- 1743 and PIB2010Z-00531. F.V. would also like to acknowledge financial
tance to corrosion even though they show low support from the MICINN (Spain) through the FPI Program.
photonic efficiency. Among the metal oxides, TiO2
has been and will be one of the most important photo-
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