Solar Energy 78 (2005) 581–592

www.elsevier.com/locate/solener

Metal oxide photoelectrodes for hydrogen generation

using solar radiation-driven water splitting
V.M. Aroutiounian *, V.M. Arakelyan, G.E. Shahnazaryan
Yerevan State University, 1 Alek Manookian St., Yerevan 375025, Armenia
Received 28 April 2003; received in revised form 2 February 2004; accepted 10 February 2004
Available online 4 March 2004
Communicated by: Associate Editor Ali Raissi

Abstract
Metal oxide semiconductors are today the most promising materials for photoelectrochemical production of
hydrogen by the method of the photoelectrolysis of water as the problems of the stability of photoelectrodes are
basically solved only for such materials. The aim of this short review paper is the presentation of results in this field
obtained both worldwide and by the authors of this paper. The factors determining the efficiency of photoelectrolysis
and possible ways to increase the photocatalytic activity of semiconductor photoelectrodes are analyzed. It is shown
that the development of new photoelectrodes made of solid solutions and more complicated multicomponent com-
positions are most promising. Possibilities to use porous and nanocrystalline oxide photoelectrodes in photoelectro-
chemistry are also discussed. Photoelectrolysis setups for the photoelectrochemical conversion of solar energy into
hydrogen are briefly described.

2004 Elsevier Ltd. All rights reserved.

Keywords: Oxide semiconductor; Photoelectrode; Water splitting

1. Introduction immersed in the electrolyte solution comprises the basis

When a semiconductor is immersed in a solution, a
charge transfer occurs at the interface because of the
difference in the electron affinity or electrochemical po-
tential of the two phases. The net result is the formation
of space charge regions at the surface of the semicon-
ductor and in the electrolyte. If the semiconductor
electrode absorbs radiation, electrons move towards the
bulk of the n-type semiconductor, while holes move
towards the surface and are injected into the electrolyte
(Fig. 1). Excited electrons have a possibility to pass to
the second electrode, which is connected with the first
electrode through a conductive wire. The second elec-
trode may be metallic or made of other type (p-type)
semiconductor. The combination of two such electrodes
*
Corresponding author. Tel./fax: +374-155-5590.
E-mail address: kisahar@ysu.am (V.M. Aroutiounian).
0038-092X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2004.02.002
of the photoelectrochemical cell. If an aqueous electro-
lyte is chosen, the reaction of water oxidation on the
semiconductor anode and the reaction of hydrogen
reduction on the cathode take place, so we deal in this
case with the photoelectrolysis of water (radiation-dri-
ven water splitting). Photoelectrolysis of water with use
of semiconductor photoelectrodes (PE’s) is a non-pol-
luting, wasteless, renewable method of energy produc-
tion as water is a combustion product of hydrogen.
The problem of coordination of the energetics of an
electrochemical reaction with the spectrum of solar
radiation is a difficult one. It is necessary to solve it in
order to raise the efficiency of photoelectrochemical
conversion (PEC) of solar energy. Photogenerated holes
may cause the oxidation of the semiconductor surface,
producing a blocking layer or the dissolution (corrosion)
of the electrode. The stability and mode of operation of
electrodes can be attained by suitable choice of solution
and redox couple, as well as by the electrode surface.
582 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
e-
-
O There are books and review papers available today,
E E
e-
e- e ϕ fb -
O see, for example, books: Myamlin and Pleskov, 1967;
-
O Ec
hν
H+/H2
H2O/O2
O
+ p + and Dulay, 1993; Linsebigler et al., 1995; Nozik and
Metal Electrolyte Semiconductor
Semiconductor: H2O+ 2p+ = 2H+ + ½ O2↑
Counterelectrode: 2H+ + 2e- = H2 ↑
Total reaction: H2O = H2 +½ O2
Fig. 1. The energetic diagram of photoelectrochemical cells
with n-type semiconductor photoanode and metallic counter-
electrode.
The efficiency of photoelectrochemical production of
hydrogen is determined by a combination of such
factors as imperfections of crystalline structure, bulk
and surface properties of the semiconductor PE’s, their
resistance to the corrosion in aqueous electrolytes, and
ability to drive the water-splitting reaction. Therefore,
research is developing today in two directions: the first
one is further investigations of known semiconductors,
with the aim of optimization of their electrophysical and
photoelectrochemical parameters, and the second one––
discovery and manufacture of new semiconductor PE’s.
After the pioneering work of Fujishima and Honda
(1972), where the possibility to electrolyze water to
hydrogen fuel using a solar-driven TiO2 PE–electrolyte
cell was shown, the main attention of investigators was
attracted to such semiconductor oxides or solid solu-
tions, which are resistant to photocorrosion. Although
impressive results for the efficiency of PE’s made of
conventional semiconductors like Si, GaAs, InP, Cu-
InSe, CdTe, etc., were obtained, only such PE’s could be
used in the photoelectrolysis operation mode for a very
short time and only after a modifying the surface or
coating it with different catalytic metals. Unfortunately,
these semiconductors, used successfully in modern elec-
tronics and solar power engineering, in addition to their
high cost, are unstable in aqueous solutions.
In describing the general situation concerning pho-
toelectrochemical production of hydrogen, we noted
continuing large interest in this problem and more than
a thousand publications in this field. It is obvious that it
is impossible in the framework of this short review paper
to present even the fundamentals on the problem of PEC
solar energy to hydrogen fuel using semiconductor PE’s.
where the general principles of operation of photo-
electrochemical converters of solar energy and problems
concerning the efficiency of photoelectrochemical pro-
duction of hydrogen are perfectly described (readers can
Gr€ atzel, 1983; Pleskov, 1985, 1990; Zamaraev and Par-
EF
mon, 1985, 1991; Pleskov and Gurevich, 1986; Kulak,
Eg 1986; Gruzdkov et al., 1991; Fujishima et al., 1999. See
also some of review papers published in last 15 years:
Levy-Clement, 1988; Arutyunyan, 1989; Memming,
Ev
1991; Aroutiounian, 1991, 2000; Yoneyama, 1993; Fox
Memming, 1996; Mills and Le Hunte, 1997; Peral et al.,
1997; Malato et al., 2002; Bak et al., 2002. Earlier papers
can be found, for example, in review papers of Tom-
kiewicz and Fay, 1979; Zamaraev and Parmon, 1980;
Nozik, 1981; Bagdasaryan, 1982; Gerisher, 1982; Trib-
utsch, 1982, 1986; Bicelli, 1983; Heller, 1981, 1984;
Kalyanasundaram, 1985; Aroutiounian, 1985, 1986;
etc.).
At the same time, in our opinion, a systematic pre-
sentation of the results of investigations of the efficiency
of photoelectrolysis achieved today with the use of PE’s
made of metal oxide semiconductors is absent in the
literature of recent years. Such metal oxide semicon-
ductors are the most promising materials for this pur-
pose today, as the problems of stability are basically
solved only for such PE’s. The aim of the present short
review paper is the presentation of results in this field
obtained both in the literature and by the authors of
this paper, as well as our colleagues at Yerevan State
University.
2. Manufacturing of semiconductor oxide PE’s
As starting materials for the fabrication of PE’s made
of very cheap oxides, powders of commonly occurring
TiO2 , ZnO, Fe2 O3 , SrTiO3 and other oxides and mate-
rials have been used in our laboratory. Of course, as a
rule, we are working with good insulators in this case. In
order to minimize ohmic losses in the circuit, it is often
necessary to increase the electroconductivity by many
orders of magnitude in the process of the preparation of
polycrystalline and ceramic PE’s from powders. In
Yerevan State University, different technological meth-
ods of preparation of ceramic, thin film, and polycrys-
talline PE’s were proposed and investigated. We have
experimentally investigated also the electrophysical,
photoelectrochemical, photoelectrical, optical, lumines-
cence, reflection, electroluminescence, electroreflection,
photocorrosion and other properties of metal oxide PE’s
(see, for example, review papers of Aroutiounian, 1985,
1991, 2000 and papers cited there). We consider some
 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
theoretical mechanisms and models in our papers (see
Aroutiounian, 1986, 1991; Aroutiounian et al., 1994,
1997a,b; Arutyunyan et al., 1981, 1992; Arutyunyan,
1989; Margarian et al., 1997; Melicksetian et al., 1997).
Results of these investigations will not be discussed here,
as the aim of this short review paper is rather narrow––
to give the information about the efficiency of the con-
version of solar energy into hydrogen fuel by the use of
metal oxide PE’s.
Photosensitivity is considerable only in the region of
fundamental absorption for photocorrosion-stable oxi-
des (usually in short-wavelength part of the solar spec-
trum). This is the main reason for rather low efficiency
of solar energy conversion encountered in the photo-
electrolysis of water. We succeeded in lowering by many
orders of magnitude the specific resistance of PE’s made
of reduced oxide materials after corresponding techno-
logical procedures. For example, during conversion of
stoichiometric TiO2 to its reduced form (TiO2
x ), we
realized a drop in the dark specific resistance of PE’s of
10–12 orders of magnitude, ZnO to ZnO1
x ––5–7 or-
ders, etc. It led to dramatically decrease ohmic losses in
circuit and a remarkable increase in the efficiency as
compared to non-reduced samples. In particular, the
alloying of semiconductor oxides was usually carried out
at high temperatures in the CO or He atmosphere or in
vacuum, fully adequate to the partial reduction of
semiconductors. The same procedure was undertaken
when we added some impurity atoms to the oxide or
solid solution.
It is reasonable to assume that the impurity atoms
and oxygen vacancies have identical influence on the
properties of PE’s. The following samples have been
synthesized and investigated in our laboratory: TiO2 ÆTa,
Photocurrent, a.u
2
4
0.25
250 350 450
(a)
Fig. 2. (a) Photocurrent spectra of polycrystalline photoelectrodes TiO2
x (1); TiO2 ÆCræ (2), TiO2 ÆVæ (3), and TiO2 ÆMnæ (4); (b)
Photocurrent spectra in the impurity range of photoelectrodes TiO2 doped with Cr in concentrations of 0 at.% (1), 0.5 at.% (2), 1 at. %
(3), and 2.5 at.% (4).
583
Mo, W, Nb, Re, Cr, V, Fe, Mn, Ni, Co, Al, etc.æ,
Fe2 O3 ÆSn, Ge, Zr, Hf, Nb, Ti, Ta, etc.æ, ZnOÆAl, Y, In,
etc.æ, SrTiO3 ÆNb, Cr, La, etc.æ, TiO, etc. (Aroutiounian,
1985, 1991, 2000; Shakhnazaryan et al., 1994; Sarkiss-
yan, 1995; Sarkissyan et al., 1997; Aroutiounian et al.,
1998, 1999, 2000a, 2002b,c, 2003). We manufactured Y–
Ba–Cu–O and Bi–Sr–Ca–Cu–O high temperature
superconductor ceramic with different compositions
containing Li, Cs, Al, Ca, Cr, Na, Fe, Ga, Zr, Hf, Nb,
etc. and studied them as very cheap photocathode
(Sarkisyan et al., 1992).
3. Sensitization of oxide PE’s
It is very important try to shift the sensitivity range of
the PE’s closer to the maximum of the solar spectrum.
We have carried out investigations of the possibility of
PE sensitization to visible light by a doping of oxide
semiconductors with impurities mentioned above (Fig.
2). It was established that the doping of semiconductor
electrodes alter the spectral dependence of photocurrent,
for example, for TiO2 doped with chromium, vanadium
and manganese and ZnO doped with aluminum and
others. Note that PE’s made of TiO2 ÆCræ are sensitive up
to 600 nm, TiO2 ÆVæ––up to 750 nm (see review papers of
Aroutiounian, 1991, 1998b, 2000). Analogous works
were carried out by other authors (Bicelli, 1983; Pleskov
and Gurevich, 1986; Kokorin et al., 1999, 2001, 2003;
Kulak, 1986, etc.).
Note that in a series of papers (see, for example, Khan
and Akikusha, 1999; Khan et al., 2002 and some papers
in the corresponding table in the review paper of Bak
et al., 2002) the noticeably overstated efficiency of solar
Photocurrent, a.u
3
0.25
2
3 1
1
550 650 750 380 460 540 620
λ, nm (b) λ, nm
584 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
Photocurrent, a.u
2
0.25
1
250 450 650
(a)
Fig. 3. Photocurrent spectra of polycrystalline photoelectrodes: (a) TiO2
x (1); TiO2 ÆNb, Cræ (2), and TiO2 ÆNb, Væ (3); (b) ZnO1
x (1);
ZnOÆAlæ (2), and ZnOÆCdæ (3).
energy conversion with the use of the semiconductor
oxide PE’s is claimed. Such efficiency (for example,
11.0% (Khan et al., 2002) for chemically modified TiO2
PE’s 1 or 4.92% (Khan and Akikusha, 1999) for nano-
crystalline Fe2 O3 PE’s) have no any relation to the effi-
ciency of the conversion of solar energy to hydrogen fuel
as in all cases the measurements were carried out under
the 150 W xenon lamp illumination. Note that the radi-
ation spectrum of this lamp considerably differs from the
solar spectrum, especially in the ultraviolet range, which
is very important for flame-produced titanium oxide
PE’s, which have a shift to the shorter-wavelength range
of the spectrum. This circumstance leads to errors. It is
well known that a xenon lamp with a set of narrow-range
interference filters can be used only for some qualitative
estimation mostly for extraterrestrial applications, and
can never be used for quantitative analysis of the effi-
ciency of conversion of solar energy under terrestrial
conditions. Besides, the xenon lamp in the investigations
of Khan et al. (2002) illuminated samples with only half
of the power density, corresponding air mass 1.5. It is not
clear how the efficiency changes under one sun illumi-
nation conditions.
It is difficult to understand how the authors of the
paper by Khan et al. (2002) could report an 11% con-
version efficiency for the flame-produced titanium
dioxide samples, when, according to the data of authors,
the main fundamental absorption range lies in the range
1
In the early eighties, we together with T. Vardapetyan
carefully investigated the possibility of manufacturing chemi-
cally modified TiO2 electrodes using the same technology,
which did not lead to an increase in the efficiency of solar cells
mentioned by Khan et al. (2002).
Photocurrent, a.u
1 3 2
0.25
3
250 350 450 550
λ,nm (b) λ, nm
330–420 nm and tail absorption in the range 420–520
nm. The sum of both ranges corresponds only about 22–
23% of the solar constant. Such ‘‘production’’ is
impossible even for tandem solar cells covering most of
the solar spectrum.
Spectra of the flame-produced and oven-produced
samples in Fig. 2 in the paper Khan et al. (2002)
did not compare correctly. Different arbitrary units for
absorbance were used, which led to incorrect
absorbance values for the tail part of the spectrum of
the flame-produced sample in comparison with the
corresponding value for the fundamental absorption of
the oven-produced samples of TiO2 . As seen from Fig.
1 in above-mentioned paper, the X-ray patterns did not
show remarkable changes in band structure for
samples made by different technologies. Proofs for the
creation of a new solid solution with band gap 2.32 eV,
as mentioned in the paper, were absent.
Samples made under flame are more porous in
comparison with oven-produced samples, but it seems
that the authors did not take into account the dramatic
increase of effective surface area of the flame-produced
samples during estimation of the photocurrent density
and efficiency. Correlation between Figs. 3 and 4 in the
paper Khan et al. (2002) at applied potential 0.3 V is
absent. Authors should have subtracted from the stan-
dard potential 1.23 V the value of the potential applied
to full circuit during estimation of the efficiency of the
conversion, which is more than the electrode potential
0.3 V. Water splitting can be realized under short-cir-
cuited conditions. Any data about production of
hydrogen was not given in the paper. Therefore, values
of the efficiency for oxide PE’s reported by Khan and
Akikusha (1999) and Khan et al. (2002) cannot be
considered as true.
 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
2 sensitivity range up to 560 nm was shown for PE’s made
6 6
3
5
1 4
Fig. 4. Photoelectrolysis setup with compound cylindrical
concentrator: (1) body of photoelectrochemical cell; (2) quartz
windows; (3) semiconductor matrix; (4) electrolyte; (5) ion-
exchanging membrane; (6) cylindrical concentrator.
At present, the solar energy–hydrogen conversion
efficiency under conditions of AM1 (‘‘one sun’’) for our
stable ceramic electrodes equals to 1.5–1.9% for TiO2
x ,
TiO2 ÆReæ, and ZnO1
x , ZnOÆAlæ, etc., 1% for Fe2 O3 ÆTi
or Taæ and SrTiO3 ÆLaæ (see review papers of Aroutiou-
nian, 1998b, 2000). Note that despite the fact that the
efficiency of PEC was remarkably increased in compar-
ison with earlier efforts in this field, it is still lower than is
necessary for large-scale practical applications. Further
efforts should be made on the increase in efficiency of
PE’s made of oxide semiconductors in order to reach
commercially desired values.
4. Double doping of PE’s
The main difficulty on the way to achieving high
efficiency in TiO2 and similar oxide PE’s is connected to
their too wide band gap (more than 3 eV) effectively
permitting absorption of only several percent of the
incident solar radiation. Therefore, a possibility to im-
prove characteristics of PE’s made of TiO2 by simulta-
neous doping with donor and acceptor impurities was
investigated. This allows one to sensitize them into the
visible light range and to overcome some difficulties
originating from usual doping with acceptors. In par-
ticular, there is a possibility to increase the concentra-
585
tion of introduced acceptor impurities up to the value
necessary for the splitting of discrete levels in an impu-
rity sub-band and overlapping this sub-band with the
valence band of the semiconductor.
The ceramic semiconductor PE’s made of TiO2
doped simultaneously with Nb (donor) and Cr or V
(acceptor) were manufactured by us, and their charac-
teristics, depending on the types and concentrations of
impurities, were investigated. Extension of the photo-
of TiO2 ÆNb, Cræ (Fig. 3a). The increase of the impurity
concentration was accompanied by an increase of the
photocurrent long-wave maximum. There are spilt dis-
crete levels in the impurity sub-band placed 0.4 eV above
the bottom of the valence band with more than 2 at.%
increase in the chromium concentration. The long-wave
photosensitivity of the TiO2 ÆNb, Væ PE’s exceeds a
photosensitivity stipulated by main transitions in some
cases and covers wavelengths up to 800 nm. The intro-
duction of two types of impurities results, however, in
strong distortion of the crystal lattice, appearance of
many dissipation centers, and an increase of the number
of centers of surface recombination. The above negative
consequences of double doping probably prevail over
the contribution to the long-wave photosensitivity.
Therefore, the efficiency of such PE’s remains low. The
same situation was found in the case of SrTiO3 PE’s
doped with Cr and Ta (Sayama et al., 2002).
5. Tandem cells and solid solutions
Recently, interest in III–V semiconductor alloys has
recommenced. Several groups of investigators have
investigated use of multi-band-gap semiconductor–elec-
trolyte systems for the hydrogen production. Efficient
solar-driven water splitting can be realized by the use of
multilayer tandem solar cells that produce a photovolt-
age value that is higher than the electrolysis potential.
High hydrogen production efficiency was realized
using a monolithic tandem p-n-GaAs–p-n-GaInP2 –Pt
cell (12.4–16.5%) (Kocha et al., 1998; Khaselev and
Turner, 1998; Khaselev et al., 2001; Gao et al., 1999),
multilayer GaAlAs–Si–CoS (or Pt) and multilayer Ga-
AlAs–Si–RuO2 –Pt cells (18.3%) (Licht, 2001; Licht
et al., 1998, 2001, 2002), as well as triple-junction p-i-n a-
Si (Pt) cells (7.8%) (Khaselev et al., 2001). Such out-
standing results were realized with the use of rather
expensive structures. Of course, the problem of photo-
corrosion of such systems needs to be solved, and exposed
semiconductors should be modified. Results mentioned
above were obtained using stacked multijunction tandem
systems, the top cell of which absorbed higher-energy
photons, whereas subsequent layers absorbed lower-en-
ergy photons. Taking into account an energy balance of
the photoelectrolysis process (1.23 eV is necessary for
586 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
water electrolysis, and overvoltages are really about
1 eV), we can conclude that catalytically active semi-
conductor materials (including oxides) with a band gap
2–2.5 eV can be used as effective catalysts for water
splitting. However, the distribution of photon energies
the over solar spectrum shows that the maximum of en-
ergy conversion corresponds to semiconductor materials
with band gap 1.1–1.4 eV. Elementary semiconductors
and III–V or II–VI compositions, as well as oxides with
such a band gap, are, as a rule, unstable in aqueous
electrolytes. The search for continuous solid solutions of
semiconductor oxides with heightened stability to
photocorrosion, smaller band gap, and best arrangement
of allowed bands on the energy axis, which allows one to
decrease the overvoltage in the system and losses due to
charge carriers overcoming the flat band potential, is very
important. Unfortunately, today’s photoelectrolysis cells
require an additional voltage supply or difference in pH
between cathode and anodic compartments. In all cases,
the use of solid solutions and multicomponent semicon-
ductors opens possibilities to absorb a larger part of the
incident solar photons. Therefore we investigated several
types of solid solutions of semiconductor oxides with the
purpose of increasing the part of the solar spectrum,
which can be absorbed.
One of the ways of improving solar absorption is the
synthesis of new semiconductor phases made of solid
solutions with wide band gap oxide (more than 3 eV)
and rather small band gap oxide (corresponding to the
maximum of the solar radiation spectrum). In this re-
gard, the pair TiO2 (Eg  3 eV)–MnO2 (Eg  1:3 eV) is
of practical interest. The identical phases are present in
their homological series. The similarity of crystalline
structures and electronic configurations of these oxides
enables one to assume the existence of a wide range of
solid solutions in the system TiO2 –MnO2 . Our investi-
gations of solid solutions in the TiO2 –MnO2 system led
to manufacturing semiconductor phases with a degree of
dissolution of MnO2 up to 4 at.%. Such PE’s of the
TiO2 –MnO2 systems are more sensitive in the visible
range of the solar spectrum (Fig. 2a). Thereat, undesir-
able problems arising by the usual doping of TiO2 such
as, the shift of main peak absorption to the short-wave
range and sharp decrease in the integral efficiency of
PE’s, were avoided. However, the synthesis of solid
solutions with large content of MnO2 was accompanied
by the formation of non-photosensitive phases of
MnTiO3 .
We started also investigations of the system TiO2 –
Cu2 O (see also paper Siripala et al., 2003). Mixed TiO2 –
WO3 oxide electrodes were used for photocatalysis of
toluene (Fuerte et al., 2002). The solid solutions made of
ZnO (Eg  3:2 eV) and CdO (Eg  2:1 eV) are also of
definite interest. We synthesized a series of composition
Zn1
x Cdx O ð0 6 x 6 1Þ. The substitution solid solution
is formed at a cadmium concentration up to 10 at.%.
The increase in cadmium concentration in solid solu-
tions results in a displacement of the photosensitivity
maximum and long-wave absorption edge to the long-
wave range (Fig. 3b). It showed that the band gap of
solid solutions is decreased when the cadmium concen-
tration is increased. The efficiency of PE’s made of solid
solutions rises when the cadmium concentration is in-
creased, and reaches a maximum for the composition
Zn0:95 Cd0:05 O. The solubility of CdO in ZnO is limited
by differences in the crystalline structures of these oxi-
des. Two-phase compositions are formed when the
cadmium concentration is more than 10 at.%; a pro-
gressively less photosensitive phase of CdO falls out,
resulting in the decrease in the efficiency of PE’s.
The investigations of PE’s made of solid solutions
have been extended in recent years. Murata et al. (2000)
investigated the solid solutions (Ti, M)O2 , containing 5
mol.% M (M: Nb, Mo, Ta, W). The largest photocur-
rent was observed in the composition (Ti, Nb)O2 , it
exceeded almost 2 times the photocurrent in the pure
TiO2 . Photocatalysts made of solid solutions TiO2 –
In2 O3 and TiO2 –VO2 were obtained (Srivastava et al.,
2000; Karn et al., 2000). These authors reported on the
hydrogen gas evolution rate 14.6 and 16.1 l/h m2 for
TiO2 –In2 O3 and TiO2 –VO2 PE’s, respectively. Elec-
tronic structure compositions InMO4 (M ¼ V, Nb, Ta)
and BiVO4 , promising for water decomposition in the
visible wavelength region, are reported in Oshikiri et al.
(2002). The band gaps are 2.6 and 2.5 eV for InTaO4
and InNbO4 , respectively. The efficiency was effectively
increased after doping such PE’s with Ni (Zou et al.,
2001b).
We manufactured and investigated also new PE’s
made of solid solutions in the system Fe2 O3 (Eg  2:2
eV)–Nb2 O5 (Eg  3:5 eV). An attempt was made to
combine the best characteristics of each material: a
negative flat band potential of Nb2 O5 PE’s for sponta-
neous water photoelectrolysis and sufficiently large
(30%) absorption of solar energy by rather narrow
band gap PE’s made of iron oxide, Fe2 O3 . We synthe-
sized homogeneous phases with FeNbO4 structure. The
region of spectral photosensitivity for PE’s made of solid
solutions of FeNbO4 coincides practically with the re-
gion of spectral photosensitivity of PE’s made of doped
Fe2 O3 and covers the wavelength spectrum from 270 up
to 670 nm. A noticeable negative shift of the flat band
potential took place for the FNbO4 PE’s; the photo-
current onset was observed at smaller external bias than
for the doped Fe2 O3 PE’s. Expected displacement of the
flat band potential to the negative energy range led also
to the increase in the photocurrent for PE’s made of the
solid solution FeNbO4 . The rate of the H2 evolution was
equal to 22.4 lmol/h cm2 for FeNbO4 PE’s under
mercury lamp illumination. The results of the analysis of
the frequency dispersion of real and imaginary parts of
the complex impedance of the electrochemical cell with
 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
the FeNbO4 PE’s showed that slow diffusion processes
in the semiconductor and large capacitance of the
Helmholtz layer on the interface were the reasons for the
modest photocurrent(Aroutiounian et al., 2002a).
The manufacturing and investigations of more com-
plicated, three and four-component compositions, is
also very promising also (Kato and Kudo, 2001; Zou
et al., 2002, 2003; Sato et al., 2002). Perovskite materials
with a generic composition of Am Bm O3m þ 2 (m ¼ 4, 5;
A ¼ Ca, Sr, La; B ¼ Nb, Ti), highly doped with Ni, were
investigated (Kim et al., 1999). The quantum yield of
such catalysts reached 23% under UV irradiation, and
the rate of hydrogen evolution was 402 lmol/h. These
authors obtained also the perovskite photocatalyst
La4 CaTi5 O17 , which produced hydrogen at rate 499
lmol/h. Layered perovskite tantalates RbLnTa2 O7
(Ln ¼ La, Pr, Nb, Sm), were studied; their efficiency
is effectively increased when doped with nickel (Machida
et al., 2000). A new series of photocatalysts with pyro-
chlore structure Bi2 MNbO7 (M ¼ Al3þ , Ga3þ , In3þ ) were
synthesized and investigated (Zou et al., 2001a). The
Bi2 AlNbO7 photocatalyst exhibited the best photocata-
lytic activity with a rate of gas evolution 710 lmol/h
under UV irradiation.
6. Discussion of prospects of the use of porous
and nanocrystalline oxide PE’s in photoelectrochemistry
It is known that nanoparticles of TiO2 , ZnO, Fe2 O3 ,
WO3 , and SnO2 show remarkable photocatalytic activity
and photoconductivity (Uekawa et al., 2002; Yu et al.,
2002; Gao and Zhang, 2001; Wang et al., 2000; Bamw-
enda and Arakawa, 2001). Various applications for
photocatalysis, such as, manufacturing of dye-sensitized
solar cells and low cost photovoltaic devices, removing
pollutants from air and water, are well known. We will
not consider the use of nanocrystalline porous TiO2 and
other oxides in dye-sensitized photoelectrochemical
cells, which are producing electricity (see, for example,
Gr€atzel, 2000). The particle size, lattice strain, specific
surface area and physical properties can be regulated by
the heating time of gels at high temperature during the
particle formation process (usually, by sol–gel method).
Low light absorption and unsatisfactory stability in time
are, unfortunately, typical for nanoparticle systems
today, if the nanoparticle powder is added to a solution.
Besides these systems, photoinduced super-hydrophilic
properties of the photocatalytically active surface of
mesoporous titania thin films were recently used as anti-
fogging, self-cleaning, and biologically active materials
(especially, in Japan) (Fujishima et al., 1999). It was
found that such mesoporous thin films showed higher
photocatalytic activity and better light-induced hydro-
philicit than TiO2 nanometer range thin films. Meso-
porous films are composed of small monodisperse
587
spherical particles of about 15 nm diameter. They also
contain mesopores between the spherical particles, so as
to have higher surface area and surface roughness.
Probably, such films are beneficial to the transfer and
separation of photogenerated electrons and holes inside
of and on the surface of titania. They have much larger
surface area, smaller pore size and larger pore volume.
But again, a higher degradation rate was detected for
mesoporous titania.
Note that new applications of nanocrystalline and
microporous semiconductors (including improved pho-
tocatalytic activity) open new directions in photoelect-
rochemistry of semiconductors (see, for example, review
papers Tomkievich, 2000; Lewis, 2001). In order to
better understand the physical, optical, and photoelect-
rochemical processes at the porous PE–electrolyte
interface, we started theoretical consideration of trans-
port phenomena at such an interface making the fol-
lowing assumptions, which should be confirmed
experimentally.
Note that a dramatic increase in specific surface area
and correspondingly available active sites, as well as
fractal phenomena, lead to changes of the charge car-
rier’s transport phenomena in porous materials (see, for
example, Aroutiounian and Ghoolinian, 2000, 2003;
Aroutiounian et al., 2000b; Aroutiounian and Ghuli-
nyan, 2003). Along with free diffusion in the energy
bands, we have to take into account the drift of charge
carriers in the inner electric field arising due to an in-
crease of band gap of the porous electrode because of
the size quantization phenomena in non-uniform porous
media (especially near the interface). The latter changes
not only optical properties and the rate of reaction in a
drastic manner, but also the electrical properties of
nanocrystalline porous electrodes. We have to take into
account hopping processes. It is evident that the density
of different traps will be very high as a consequence of
very high surface-to-volume ratio. The major part of the
electrical current will be flow via traps by the percolation
mechanism. On the other hand, high porosity can lead
to a decrease in the surface recombination velocity at the
semiconductor–electrolyte interface (in contrast to the
case of the contact of porous media with ambient air).
Note that an increase in the band gap at a porous
electrode made of a relatively narrow band gap semi-
conductor can lead to radical changes in the stability to
corrosion and oxidation of PE’s, and a passivation of
electrical defect sites on the semiconductor surface. We
expect the band bending to be reduced in the porous
electrode, which will favor the electron transport.
Kinetics of heterogeneous reactions needs further stud-
ies. Above-mentioned peculiarities of porous PE’s make
theoretical analysis of transport phenomena and corre-
sponding computer simulations very complicated and
stubborn. But it is necessary to do as we expect an in-
crease in the current through PE and their efficiency due
588 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
to the increase in the concentration of free charge car-
riers, their mobility and, as a rule, electroconductivity of
the electrode.
7. Photoelectrolysis equipment
It is well known that colloids of TiO2 catalysts are
widely used now for cleaning water, environmental
media, photosynthesis, etc. We will not discuss such
applications of oxides; there are many investigations in
this field (see, for example, Ilysz et al., 2002; Hernandez-
Alonso et al., 2002; Tripanagnostopoulos et al., 2002;
Saiton and El-Ghetany, 2002). Descriptions of how the
photolysis of water can become an important segment of
wastewater treatment technology related to the degra-
dation of very persistent toxic compounds is given for
example by Malato et al. (2002) and Aguando et al.
(2002). Such a pilot plant is working now at Plataforma
Solar la Almeria (Spain).
In order to obtain hydrogen under natural conditions
and investigate the efficiency of solar energy conversion,
several versions of the photoelectrolysis equipment have
been created and tested at Yerevan State University
(Aroutiounian, 1991, 2000). One of these equipment
versions is presented in Fig. 4.
With the first equipment version, hydrogen had been
obtained on PE’s with small area (1.5–2 cm2 ) at high
concentration of solar radiation (up to 50 W/m2 ). The
equipment had a concentrator in the form of a parabolic
mirror with the area of 0.2 m2 , having the photoelec-
trolysis cell in its focus. This equipment, with PE’s from
reduced and doped TiO2 , allows producing 0.04 l/h
hydrogen. However, such equipment, despite the low
cost of PE’s, is not economically profitable because of
the rather expensive parabolic mirror and tracking sys-
tem. Besides, additional water-cooling is necessary at
such concentrations of solar radiation.
A matrix of PE’s with overall area up to 550 cm2 was
used in other versions of photoelectrolysis equipment.
The first setup had no concentrator; in the second, the
solar radiation concentration had been doubled using a
parabolic-cylindrical concentrator. Other technologies
proposed by us allow preparing large area electrodes
with the use of a metallic sheet covered by TiO2 powder
and conductive glue. These systems did not require a
complicated tracking system. The engine placed in the
lower part of the apparatus was switched on several
seconds every hour to rotate the equipment around the
vertical axis by 15 grad. With this equipment, supplied
with a parabolic-cylindrical concentrator and the rutile
PE’s matrix with area of about 100 cm2 , the output was
equal to 0.046 l/h of solar hydrogen. Output of 0.028 l/h
was realized without the concentrator. The solar radia-
tion density was about 80 mW/cm2 , and the electrolyte
and PE’s matrix, after operating for a long time, were
heated up to no more than 60 C. That is why the
necessity for a cooling system did not arise.
In the equipment with a Fresnel lens and rutile PE’s
(Vardapetian and Vartanyan, 1991), the output of
hydrogen was 7 l/h; the size of the equipment (in mm)
was 3600 · 2300 · 300, the size of one PE was 1 cm2 . The
weight of this solar-hydrogen equipment was about 80
kg. Mean efficiency of solar energy conversion to
hydrogen was less than 3%. Cheap nickel electrodes were
used. In order to compensate for the overpotential, sil-
icon photoelectric cells, illuminated through the Fresnel
lens, were used. Polycrystalline rutile PE’s were manu-
factured by the layer-by-layer sintering technique. A
new type of photoelectrochemical converter an aerobic
one, was discussed by Arutyunyan and Vardapetyan
(1983).
The equipment for effective production of hydrogen
using a silicon photovoltaic array and an electrolyzer is
well known. It is much more expensive in comparison
with a setup for direct photolysis of water by use of
metal oxide semiconductor PE’s. For example, for the 5
kWp setup, the photovoltaic hydrogen production and
storage was evaluated (Hollmuller et al., 2000). Results
of our investigations were reported by Pleskov et al.
(1985). Silicon solar cell array had the area about 950
cm2 and 9% efficiency. The electrolyzer with a solid
polymer electrolyte had 80%––efficiency of conversion.
So, more than 7% efficiency of solar–hydrogen conver-
sion was realized. The information about solar–hydro-
gen studies in Armenia reported also earlier
(Aroutiounian, 1993, 1996, 1998a,b, 2000).
8. Conclusion
After the pioneering work of Fujishima and Honda
(1972), where authors have shown the possibility to split
water to hydrogen fuel and oxygen using a solar-driven
TiO2 –electrolyte cell, the main attention of investigators
was attracted to semiconductors which are resistant to
the photocorrosion in aqueous electrolytes. Researchers
focused their attention on oxide semiconductors (TiO2 ,
ZnO, SrTiO3 and other oxides) and cheap technologies
for manufacturing materials and PE’s using such oxides,
as the problems of the stability of PE’s were basically
solved only for such materials. Different technological
methods of the preparation of ceramic, thin film, and
polycrystalline PE’s were proposed and investigated.
The best efficiency for photoelectrolysis of water was
detected in metal oxide PE’s, which were partially re-
duced and contained an optimal concentration of cor-
responding impurities (one or two types). The
correspondingly doped PE’s had the photoabsorption
sensitivity range extended to the visible part of the solar
spectrum, which increased the efficiency of PEC. At-
tempts were made to prepare effective PE’s with nar-
 V.M. Aroutiounian et al. / Solar Energy 78 (2005) 581–592
rower band gap and lower overpotential. New types of
oxide compositions like high temperature superconduc-
tors and others can also be used for the preparation of
rather effective photocathodes.
The best realized value for the efficiency of stable
direct conversion of solar energy into hydrogen energy
using ceramic metal oxide PE’s is near 2%, without any
concentrators of solar energy. Setups for photoelectrol-
ysis of water realized in Armenia and other countries
contained matrices made of very cheap ceramic and thin
film PE’s.
One of the ways to obtain stable PE’s, which will be
sensitive in the visible range of solar spectrum, is the
synthesis of new semiconductor phases made of solid of
wide band gap oxide (no more than 3 eV) and rather
small band gap oxide (corresponding to the maximum of
the solar radiation spectrum). In this regard, the pairs
TiO2 –MnO2 , ZnO–CdO, Fe2 O3 –Nb2 O5 , TiO2 –WO3 ,
TiO2 –In2 O3 , TiO2 –VO2 , etc. as well as complicated
oxides like perovskite materials with a generic compo-
sition of Am Bm O3m þ 2 (m ¼ 4, 5; A ¼ Ca, Sr, La; B ¼ Nb,
Ti), which were highly doped with Ni, RbLnTa2 O7
(Ln ¼ La, Pr, Nb, Sm), and pyrochlore structures
Bi2 MNbO7 (M ¼ Al3þ , Ga3þ , In3þ ), Bi2 AlNbO7 , etc.,
were synthesized and investigated. For such photocata-
lysts, the rate of the hydrogen evolution was 402–710
lmol/h (0.01–0.016 l/h). In all cases, investigation of
solid solutions and multicomponent semiconductors
opens possibilities to absorb a larger part of incident
solar photons is very important.
Discussion of the prospects for the use of porous and
nanocrystalline oxide PE’s in photoelectrochemistry was
given. The short review of the problem of photoelec-
trolysis of water into hydrogen fuel presented in this
publication shows that this field is rapidly widening in
recent years and is again very topical.
Acknowledgements
Valuable contributions to the solar–hydrogen con-
version in Armenia were made by Drs. A. Sarkissyan, J.
Panossyan, V. Meliksetyan, A. Markaryan, A. Arake-
lyan, T. Vardapetian, G. Stepanyan, and other col-
leagues at Yerevan State University.
Part of investigations in the field in recent years was
carried out in the framework of the ISTC A-322 and
CRDF AE1-373 grants.
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