Catalysis Today 185 (2012) 270–277

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Catalysis Today
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Heterojunction semiconductors: A strategy to develop efficient photocatalytic

materials for visible light water splitting
Jum Suk Jang a , Hyun Gyu Kim b , Jae Sung Lee a,∗
a
Department of Chemical Engineering, Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH), San 31 Hyoja-dong, Pohang 790-784,
Republic of Korea
b
Busan Center, Korea Basic Science Institute (KBSI), Busan 609-735, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Heterojunction semiconductors are discussed as a strategy to develop efficient visible light photocatalysts
Received 29 May 2011 for water splitting. The concept has been demonstrated in photovoltaic cells and optoelectronic devices,
Received in revised form 8 July 2011 for which junction-type semiconductors show greatly enhanced efficiency compared to the devices con-
Accepted 11 July 2011
sisting of a single semiconductor. We applied this proven concept to fabricate photocatalysts of inorganic
Available online 1 September 2011
semiconductors. Thus heterojunction structures of Shottky junctions, p–n junctions (or p–n diode), p–n
junctions with Ohmic layer, and bulk heterojunctions were fabricated and their photoactivity was tested
Keywords:
for reduction or oxidation of water under visible light. The formation of heterojunctions results in the
Heterojunction
Photocatalysts
efficient separation of electron–hole pairs to minimize the energy-wasteful electron–hole recombination,
Water splitting which leads to the high photocatalytic activity. As the complexity and sophistication of the photocatalyst
Recombination fabrication increased, the photoactivity also increased. Modern nanomaterial synthetic techniques were
employed to bring into reality the highly engineered material configurations.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction alysts are needed to meet the requirements of future environmental

Sunlight and water is a clean, renewable and most abundant
energy source and natural resource on the Earth, respectively. Their
conversion to hydrogen has been considered as an ideal solution to
counter the depletion and environmental problems of fossil fuels.
Photocatalytic water splitting (PWS) is a promising and sustainable
technology for the purpose, since H2 could be produced directly
from water and solar light through the process. Photocatalysts
that respond to visible light are needed to utilize the main part of
the solar spectrum for production of hydrogen energy by splitting
water. Traditional visible-light photocatalysts are either unstable
in water upon illumination (e.g., CdS, CdSe) [1] or have low activity
(e.g., WO3 , Fe2 O3 ) [2]. Recently, some UV-active oxides are mod-
ified to function as visible-light photocatalysts by substitutional
doping of metals as in Nix In1−x TaO4 [3] and (V-, Fe-, or Mn-)TiO2 [4],
reduction of TiO2 (as in TiOx (x < 2)) [5], and anion doping or making
compounds with N, C, and S (as in TiO2−x Nx [6],TiO2−x Cx [7], TaON
[8], and Sm2 Ti2 O2 S2 [9]). However, these doped materials, in gen-
eral, show only a little absorption in the visible-light region, leading
to low activities [10]. New and more efficient visible-light photocat-
∗ Corresponding author. Tel.: +82 54 279 2266; fax: +82 54 279 5528.
E-mail address: jlee@postech.ac.kr (J.S. Lee).
and energy technologies driven by solar energy.
Like other photocatalytic reactions, PWS is initiated when
a semiconductor photocatalyst absorbs photons with energies
greater than its band gap energy (Eg). This absorption creates
excited photoelectrons (e− ) in the conduction band and holes (h+ )
in the valence band of the semiconductor as schematically shown
in Fig. 1 [11]. The photoelectrons and holes reduce and oxidize
water, respectively, to produce the 2:1 mixture of H2 and O2 by
the following reactions:
Oxidation : H2 O + 2h+ → 2H+ + 1/2O2 (1)
Reduction : 2H+ + 2e− → H2 (2)
Overallreaction : H2 O → H2 + 1/2O2 (3)
The overall reaction involves four-electron transfer (per O2
molecule) and is usually promoted by metal or metal oxide co-
catalysts (denoted as cat 1 and cat 2 in Fig. 1) deposited on the
semiconductor surfaces. These co-catalysts are known to collect
charge carriers and provide catalytic reaction sites for these reac-
tions [12]. The reaction involves the standard Gibbs free energy
change G◦ of 237 kJ/mol or 1.23 eV (per electron). In prac-
tice, some overpotentials are needed to drive the reactions fast
enough, and thus the semiconductor should possess Eg greater than
1.6–1.8 eV to be used for water splitting. In order to absorb a large
part of the visible light irradiation, however, its value should be

0920-5861/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2011.07.008
 J.S. Jang et al. / Catalysis Today 185 (2012) 270–277
Fig. 1. A model that illustrates the principle of photocatalytic water splitting.
less than ca. 2.2 eV. In addition, for the facile electron and hole
transfer to reduce and oxidize water, the conduction band should
be located at a potential more negative than the reduction poten-
tial of water (0.0 V vs. NHE), while the valence band more positive
than oxidation potential of water (1.23 V vs. NHE) as indicated in
Fig. 1. Therefore, the photocatalytic materials for visible light water
splitting should satisfy these two requirements of proper band gap
energy (1.6–1.8 eV < Eg < 2.2 eV) and band positions. Other require-
ments for photocatalytic materials include durability in aqueous
electrolyte solutions, competitive cost, high crystallinity with little
defects, and good conductivity.
In contrast to single photocatalysts, heterojunction semicon-
ductors are an efficient system for electron–hole separation to
minimize the energy wasteful electron–hole recombination. It has
been demonstrated in photovoltaic cells and photoelectrochemical
(PEC) cells that junction semiconductors show greatly enhanced
activities compared to the devices consisting of a single semi-
conductor. For example, the fundamental unit of current silicon
solar cells is made of p–n junction of p-type and n-type silicon.
Nozik constructed an n-TiO2 /p-GaP diode electrode for a PEC cell,
which was found to be much more active than either n-TiO2 or
p-GaP single-component electrode for the decomposition of water
[13,14]. Multi-junction solar cells of remarkable energy conversion
efficiencies have been reported [15].
There are several junction types: (i) Schottky junction, (2)
p–n diode, (3) p–n junction with Ohmic layer, and (4) bulk
heterojunction. In this critical review, we highlight particulate
versions of the heterojunction semiconductors that we have
developed for photocatalytic applications based on these four het-
erojunction types. There have been many reports on composite
photocatalysts, but not many works deliberately fabricated the het-
erojunctions to improve the performance of the photocatalysts,
or attributed the observed improvements to the junction effects.
New concepts and methods are explored to fabricate more effi-
cient photocatalysts by utilization of modern material processing
techniques. These heterojunction photocatalysts are highly active
under visible light and stable under typical photocatalytic reaction
conditions.
2. Experimental
2.1. Photocatalyst preparation
The basic catalyst PbBi2 Nb2 O9 was synthesized by the conven-
tional solid-state method. Thus, a stoichiometric mixture of PbO
(Aldrich, 99.999%), Bi2 O3 (Aldrich, 99.99%), and Nb2 O5 (Aldrich,
99.999%), was ground in a mortar. The pelletized powders were
calcined at 1123 K for 24 h in static air and sintered at 1323 K for
24 h. The oxide form of doping component (WO3 , TiO2 ) was added
in the precursor mixture to synthesize doped photocatalysts. The
271
sol–gel route was adopted to synthesize the CaFe2 O4 nanoparti-
cles. A stoichiometric ratio of Ca(NO3 )2 ·4H2 O (Aldrich, 99.999%)
and Fe(NO3 )3 ·9H2 O (Aldrich, 99.999%) was mixed in 30% aqueous
NH3 solution, and the mixture was stirred at room temperature
for 24 h. The composite of CaFe2 O4 /PbBi2 Nb2−x Wx O9 was made
by hydrothermal treatment of preformed PbBi2 Nb1.9 W0.1 O9 and
CaFe2 O4 sol at 150 ◦ C for 7 day to obtain 2 wt% CaFe2 O4 loading on
PbBi2 Nb1.9 W0.1 O9 .
The W on surfaces of PbBi2 Nb2−x Tix O9 powders was deposited
by using a cold-wall CVD chamber with a shower-head. The base
pressure of the reactor was below 10−3 Torr, and the operating
pressure was in a range of 0.1–1 Torr during the W deposition. The
white colored tungsten salt, viz., W(CO)6 with a high vapor pressure
was used as the source for metal oxide chemical vapor deposition
(MOCVD). The solid tungsten hexacarbonyl source was contained
in a stainless steel bubbler. During the W deposition, the bubbler
temperature was maintained at 80 ◦ C. Delivery line was also heated
to 110 ◦ C to prevent the source condensation. Argon was used as
a carrier gas with the flow rate of 1.5 mol/s. Deposition tempera-
ture was varied from 450 to 500 ◦ C. Thus produced W metal-loaded
PbBi2 Nb2−x Tix O9 catalysts were then oxidized in air (25 ␮mol/s) at
473 K for 1 h.
The synthesis of CaFe2 O4 was carried out by the polymer com-
plex method. Calcium acetate monohydrate (Ca(CH3 CO2 )2 , 99.0%,
Aldrich), magnesium carbonate (MgCO3 , 99.9%, Aldrich), ethylene
glycol (C2 H6 O2 , Kanto Chemicals), citric acid (C6 H8 O7 , Wako) and
iron nitrate nonahydrate (Fe(NO3 )3 9H2 O, 99.99%, Aldrich) were
used as starting materials. The citric acid (CA) was added into water
under constant agitation, at 60–70 ◦ C. Next, the salts of calcium car-
bonate and iron nitrate hydrate were dissolved in citric acid–water
solution to obtain metal–citrate complex. Finally, ethylene glycol
(EG) was added to the mixture to yield a mass proportion of 60% CA
to 40% EG. The mixture was kept on hot plate (80 ◦ C) till it became
a transparent colorless solution. The colorless solution was then
heated at 130 ◦ C for several hours to obtain a polymeric gel. The
viscous polymeric product was pyrolyzed at about 300–500 ◦ C to
form the precursor powders. Thus obtained powder was pressed
in the form of pellets, which were calcined at 500–1200 ◦ C for 2 h
in an electric furnace to obtain nanocrystalline CaFe2 O4 /MgFe2 O4 .
RuO2 was first loaded on CaFe2 O4 /MgFe2 O4 photocatalyst by an
impregnation method, and then, 1 wt% of Pt metals were deposited
on RuO2 /CaFe2 O4 /MgFe2 O4 photocatalysts by using a photodepo-
sition method using metal H2 PtCl6 under a 450-W Xe-arc lamp
(Oriel) with UV cut-off filter ( ≥ 420 nm) and then was dried in
an oven at 373 K in air for 2 h.
2.2. Characterization and photocatalytic reactions
The crystal structure photocatalysts thus obtained were deter-
mined by X-ray diffractometer (Mac Science Co., M18XHF), and
272 J.S. Jang et al. / Catalysis Today 185 (2012) 270–277
the morphology was determined by scanning electron microscopy
(SEM, Hitachi, S-2460N) and high-resolution transmission elec-
tron microscopy (HRTEM, Phillips model CM 200). Light absorption
property was determined by UV/Vis diffuse reflectance spec-
troscopy (Shimadzu, UV 2401).
The photocatalytic reactions in aqueous solution were car-
ried out at room temperature in a closed system using a 450-W
Xe-arc lamp (Oriel) with UV cut-off filter ( > 420 nm) placed
in an inner irradiation-type 200-mL Pyrex reaction cell. The
H2 evolution was examined in an aqueous solution (distilled
H2 O(170 mL) + CH3 OH(30 mL)), and the O2 evolution in an aque-
ous AgNO3 solution (0.05 mol L−1 , 200 mL), both containing 0.3 g
of the catalyst. The quantum yield (QY) was calculated as twice the
number of generated H2 molecules or four times the number of gen-
erated O2 molecules divided by the number of photons absorbed
by the photocatalyst. The number of absorbed photons was deter-
mined with a light flux meter (1815-C, Newport) with the light
sensor attached to the photocatalytic reactor.
3. Results and discussion
3.1. Schottky junction photocatalysts
The Schottky junction is a commonly adopted strategy to induce
an effective charge separation in optoelectronic devices, photocata-
lysts or photoelectrochemical cells [16,17]. In general, the Schottky
junction consists of n- or p-type semiconductor (SC) and a metal
contact spread over SC [13,14]. These single Schottky junction semi-
conductors are the most common type of photocatalysts, which
can be fabricated with nanoscale metal islands on semiconductor
surface. The Schottky junction forms an electric field that facili-
tates the separation of photogenerated electrons and holes [18–20].
Most of particulate semiconductor photocatalysts employ a metal
or a metal oxide forming the Schottky junction, called co-catalyst.
Without it, the semiconductor alone shows little or no activity. The
critical role of the co-catalyst has been demonstrated in a recent
example by Domen et al. who developed Rh/Cr2 O3 (core/shell)
nanoparticles photodeposited on (Ga1−x Znx )(N1−x Ox ) [21,22]. The
carefully designed co-catalyst suppressed water formation from
the back-reaction of evolved H2 and O2 during the water splitting
reaction.
Our example of Schottky junction photocatalyst is
Pt/PbBi2 Nb2 O9 [23]. The semiconductor PbBi2 Nb2 O9 , is an
Aurivillius-phase layered perovskite, and 1 wt% Pt was loaded
on its surface by the photodecomposition method. As shown in
Fig. 2a, Pt forms islands of 5–8 nm on the surface of PbBi2 Nb2 O9
forming a Schottky junction. Thus, PbBi2 Nb2 O9 represents an
undoped, single phase oxide photocatalyst with Eg of 2.88 eV. This
small band gap was attributed to the formation of a hybrid valence
band between O2p and Pb6s/Bi6s orbitals as revealed by the band
structure calculation [23].
The operation of a Schottky junction photocatalyst is depicted
schematically in Fig. 2b. Across the n-type semiconductor/metal
junction, the electric field is established as depicted. Visible light is
absorbed by the semiconductor creating electron–hole pairs. Pho-
toelectrons slide down the bent conduction band to the metal and
holes move up towards the electrolyte inducing electron–hole sep-
aration. Here, the conduction band position of SC and work function
of the metal should be matched as in Fig. 2b to allow the pho-
toelectrons to flow from SC to the metal. The other role of metal
is to provide catalytic sites for the reduction of water to produce
hydrogen. These factors are expected to contribute to an improved
efficiency.
3.2. Heterojunction between two p–n semiconductors
A p–n junction is formed by joining p-type and n-type semicon-
ductors in close contact. It forms an elementary building block of
almost all semiconductor electronic devices such as diodes, tran-
sistors, solar cells, and light emitting diodes (LED). As p–n type
semiconductors are joined, electrons near the p–n interface tend
to diffuse into the p-region. As electrons diffuse, they leave posi-
tively charged ions in the n-region. Similarly, holes near the p–n
interface begin to diffuse into the n-type region leaving ions with
negative charge. The regions nearby the p–n interfaces lose their
neutrality and become charged, forming the space charge region
or depletion layer. Then the electric field is created such that elec-
trons and holes diffuse in opposite direction to reduce the chance
of recombination.
We have tried to apply this concept of p–n heterojunction
to the synthesis of particulate photocatalysts [24]. This type of
junction structures reported in the literature includes CaFe2 O4 -
PbBi2 Nb1.9 W0.1 O9 [24], CdS–AgGaS2 [25], CoAl2 O4 –Fe2 O3
[26], CuBi2 O4 –WO3 [27], Cu–Ti–O nanotube arrays [28],
and so on [29–31]. Here a heterojunction photocatalyst of
CaFe2 O4 –PbBi2 Nb1.9 W0.1 O9 is discussed. As the suitable n-type
semiconductor, we employed PbBi2 Nb2 O9 , the layered perovskite
semiconductor discussed above [23]. The material was doped with
hexavalent tungsten WVI to obtain n-type PbBi2 Nb1.9 W0.1 O9 . In
addition to the valency, the similarity of its size (0.74 nm) to that
of NbV (0.78 nm) was also considered in the choice of tungsten
dopant. CaFe2 O4 is a p-type semiconductor with the band gap
of 1.9 eV as reported earlier [24]. In order to combine these two
semiconductor particles to form a p–n junction, we devised the
configuration of the diode particles: (i) nano-crystals of p-CaFe2 O4
on the surface of (ii) n-PbBi2 Nb1.9 W0.1 O9 as submicron-sized
base material. Thus, CaFe2 O4 nanoparticles and PbBi2 Nb1.9 W0.1 O9
submicron particles were synthesized individually by sol–gel
and solid-state reaction methods, respectively. Then, produced
individual components were combined in by a hydrothermal
reactor (150 ◦ C for 7 days) to obtain CaFe2 O4 nano-islands formed
over larger particles of PbBi2 Nb1.9 W0.1 O9 .
Fig. 3a shows a HRTEM image of a typical
CaFe2 O4 –PbBi2 Nb1.9 W0.1 O9 heterojunction photocatalyst par-
ticle. It clearly exhibits the existence of nano-islands dispersed
over the perovskite base material. The magnified view of a nano-
island reveals the nanocrystallinity of 5–10 nm CaFe2 O4 (Fig. 3b)
and it also shows a highly crystalline, layered base material cor-
responding to PbBi2 Nb1.9 W0.1 O9 (layer thickness 0.4 nm, Fig. 3c).
The phase identification was also confirmed by elemental analysis
with in situ energy-dispersive X-ray microanalysis (EDX) carried
out during the microscopic study. Each island forms a nanoscale
p–n junction at the interface, which plays a crucial role in the
photocatalytic process.
The working principle of p–n heterojunction is shown with an
energy band model for one p–n junction (Fig. 3c). Here, band posi-
tions were determined by the flat-band potential measurements
[32]. At thermal equilibrium, the Fermi levels of two semiconduc-
tors align. When the device is immersed in an electrolyte, the band
edges of the conduction and valence bands bend as indicated. The
operation of the p–n heterojunction is initiated by the absorption of
the band-gap photons in both p–n semiconductors. Photogenerated
holes and electrons separate under the influence of the electric field,
corresponding to the energy diagram in Fig. 4c. Thus, holes move to
the p-CaFe2 O4 side, and electrons to the n-PbBi2 Nb1.9 W0.1 O9 side.
To establish this charge flow, the band positions of two semicon-
ductors should stagger as shown with that of p-type semiconductor
located at a more negative potential. The net effect of the p–n
diode formation is efficient separation of electron–hole pairs by
physically separating reduction and oxidation sites, which limits
 J.S. Jang et al. / Catalysis Today 185 (2012) 270–277 273

Fig. 2. TEM images of 1 wt% Pt–PbBi2 Nb2 O9 and a schematic energy band model of Schottky junction.

Fig. 3. Proposed photocatalytic nanodiode consisting of p-CaFe2 O4 and n-PbBi2 Nb1.9 W0.1 O9 : (a) HRTEM image showing nanocrystalline p-CaFe2 O4 islands decorating a large
n-PbBi2 Nb1.9 W0.1 O9 particle, (b) schematic of the p–n heterojunction working for water oxidation, and (c) an energy band model of a p–n heterojunction (after Ref. [24]).

Fig. 4. (a) Schematic illustration of fabrication process of PNHO. (b) Typical HRTEM of the fabricated PNHO showing WO3 nanodimensional entities stacking over the surfaces
of perovskite base material. (c) Cross-sectional schematic of a typical single WO3 -encapsulated W layer that stacks over base material. (d) Schematic energy band model
diagram of the system (after Ref. [34]).
274 J.S. Jang et al. / Catalysis Today 185 (2012) 270–277

Fig. 5. (a) A TEM image of a CFO/MFO particle. (b) A HRTEM image of interfaces between semiconductor nanoparticles. (c) A schematic model of interpenetrating domains
of CFO (white) and MFO (gray). (d) An energy band diagram showing band gap energies and band positions of p-CFO and n-MFO: CB, conduction band; VB, valence band. (e)
Operating principle of a BHJ promoted by co-catalysts (after Ref. [46]).

the energy-wasteful electron–hole recombination. By introducing experimental observations, we propose a schematic model for
semiconductors of different band gap energies, the configuration PNHO as illustrated in Fig. 4c. The WO3 -encapsulated W layer on
can also extend the range of absorbed light in solar spectrum. These PbBi2 Nb1.9 Ti0.1 O9 appears to play a critical role of Ohmic junction in
effects will lead to the higher photocatalytic activity. Formation of the photocatalytic process. Its presence was confirmed by observ-
heterojunction between semiconductors of the same kinds or with ing both W0 and W6+ in X-ray photoelectron spectroscopy (XPS)
a neutral semiconductor can also contribute to the charge separa- analysis where the deconvolution of peaks indicated a WOx /W kind
tion if their band positions are correct for charge transfer in the of configuration in the Ar+ etched samples which otherwise domi-
desired directions [33]. But without band bending cross the deple- nantly showed peaks only due to WO3 .
tion region, the beneficial effect on charge separation should be less The working principle of PNHO is schematically shown in Fig. 4d.
pronounced than p–n junction semiconductors. Again, the band positions for PbBi2 Nb1.9 Ti0.1 O9 were determined
from the flat band potential measurements. Upon absorption of
3.3. Heterojunction with Ohmic layer the band gap photons both in the p–n semiconductors, the holes
and electrons are separated in space-charge regions of respective
It has been noted that the interface between two semicon-
ductors forming p–n heterojunction would contain an ample
amount of defects that could hamper charge transfer pro-
cesses by trapping charge carriers. In an attempt to alleviate
the problem, we have adopted the concept of a p–n hetero-
junction structure with the Ohmic junction (PNHO) [34]. Thus,
PNHO photocatalyst powders were fabricated with the configu-
ration of p-semiconductor/metal/n-semiconductor by combining
solid-state reaction (SSR) with chemical vapor deposition (CVD).
Thus, WO3 /W/PbBi2 Nb1.9 Ti0.1 O9 photocatalyst was fabricated by
depositing the tungsten metal clusters over the p-type perovskite
base material by CVD with W(CO)6 , and later partly oxidizing the
surfaces of these W clusters to obtain n-WO3 overlayers on the top
of metallic W layers. Fig. 4a illustrates the schematic fabrication
process of WO3 /W/PbBi2 Nb1.9 Ti0.1 O9 . The WO3 is a well-known
n-type semiconductor, and PbBi2 Nb1.9 Ti0.1 O9 is derived from
PbBi2 Nb2 O9 doped with Ti4+ in order to obtain p-type semicon-
ductivity.
Fig. 4b shows a HRTEM image of typical PNHO particles
that clearly exhibit the existence of 30–40 nm WO3 clusters
stacking over the surface of a large PbBi2 Nb1.9 Ti0.1 O9 parti-
cle of 150–200 nm. The phase identification was also confirmed
by elemental analysis with in situ EDX analysis. Based on the Fig. 6. Optical transitions probed by UV–vis spectroscopy for various photocatalysts.
 J.S. Jang et al. / Catalysis Today 185 (2012) 270–277 275

Table 1
Band gap energies and photocatalytic activities for H2 and O2 evolution.

Catalysts Band gap energy Hydrogen evolution Oxygen evolution

Eg (eV) ab (nm) ␮mol/h Q.Y. (%) ␮mol/h Q.Y. (%)

RuO2 /MgFe2 O4 /CaFe2 O4 /Pt 2.0 620 82.7 10.1 – –

WO3 /W/PbBi2 Nb1.9 Ti0.1 O9 2.79 443 49.3 6.1 741 41
CaFe2 O4 /PbBi2 Nb1.9 W0.1 O9 2.75 450 34.8 4.2 675 38
PbBi2 Nb2 O9 2.88 431 7.6 0.95 520 29
CaFe2 O4 1.99 623 Trace 0 Trace 0
TiO2−x Nx 2.73 451 Trace 0 221 14

Catalysts loaded with 1 wt% Pt, 0.3 g; light source, 450 W W-Arc lamp (Oriel) with UV cut-off filter ( ≥ 420 nm). Reaction was performed in aqueous methanol solution for
H2 generation (methanol 30 ml + distilled water 170 ml) or in an aqueous AgNO3 solution for O2 generation (0.05 mol/l, 200 ml).

semiconductors and become available for redox reactions. Accord-
ingly, the generated minority carriers, viz., holes in n-type and
electrons in p-type semiconductors, move to the front of the sur-
face and are injected to the electrolyte solution to initiate oxidation
and reduction reactions, respectively. In addition, the photogen-
erated majority carriers in each semiconductor are then bound
to migrate towards the Ohmic W layer interfaced between two
semiconductors, where the carriers undergo nonradiative recom-
bination. Thus, one-photon is lost by this recombination. Yet the
remaining electron–hole pair can promote the redox reactions at
the semiconductor-fluid interface, thereby facilitating the reduc-
tion reaction on p-PbBi2 Nb1.9 Ti0.1 O9 and the oxidation reaction
on n-WO3 . In addition to this physical separation of the reduc-
tion and oxidation sites, PNHO provides higher net photon energies
needed for the redox reactions by partial addition of two band
gaps (Eg-composite), while individual band gaps (Eg-p and Eg-
n) still absorb visible light. The large energy difference between
photoelectron and hole (Eg-composite) also reduces the chance
of recombination as for the large band-gap UV active photocata-
lysts. These effects lead to the higher photocatalytic activity. For
the operation of PNHO, the work function of the Ohmic layer metal
should be matched with band positions of two semiconductors so
that electrons of n-SC and holes of p-SC are drawn to the Ohmic
layer.
3.4. Bulk heterojunction
The concept of bulk heterojunction (BHJ) originated from poly-
mer photovoltaic cells, which showed dramatically improved
efficiency [35,36]. In the BHJ, electron donor and acceptor
molecules are blended together. If the domain size in either mate-
rial is similar to the exciton (electron–hole pair) diffusion length,
then wherever an exciton is photogenerated, it is likely to diffuse to
the interface and break up. The situation is more suitable for high
efficiency than a planar heterojunction, or bi-layer device, where
much longer diffusion of the exciton is required to reach the inter-
face. The device proposed here is an all-inorganic version of BHJ,
where p-type and n-type semiconductors form interpenetrating
networks on nano-scale, and high efficiency is expected by the
same principle. Although there is no precedent examples claim-
ing BHJ formation, there are many examples in the literature of
two semiconductors forming interpenetrating networks on nano-
scale: CdS–TiO2 [37], MoS2 –CdS [38], Pb[Zrx Ti1−x ]O3 (PZT)–TiO2
[39], LaVO4 /TiO2 [40], and so on [41–45].

Fig. 7. A schematic summary of (a) Schottky junction, (b) p–n heterojunction between two semiconductors, (c) p–n heterojunction with Ohmic Layer, and (d) bulk
heterojunction.
276 J.S. Jang et al. / Catalysis Today 185 (2012) 270–277
Here this concept is exploited with a configuration of RuO2 /n-
MgFe2 O4 (MFO)/p-CaFe2 O4 (CFO)/Pt [46], These spinel ferrites are
the most important magnetic materials, yet they also show inter-
esting photocatalytic properties for hydrogen or oxygen evolution
from water [47–51]. Desirable properties of these materials as pho-
tocatalysts are resistance to photocorrosion in aqueous solutions
and narrow band gaps near 2 eV. But their activity as single phase
photocatalysts was very low. As a means to enhance the photocat-
alytic activity of the ferrites, a bulk heterojunction structure was
fabricated, which was promoted by two co-catalysts, Pt and RuO2 .
Fig. 5(a) shows a TEM image of a typical BHJ CFO/MFO particle
of 150–200 nm decorated with 2–5 nm clusters on its surface. The
small nanoparticles on the surface were found to be Pt and RuO2 by
in situ EDX analysis. The elemental mapping with EDX also clearly
showed that the elements of Ca, Fe, Mg, and O were uniformly
distributed over the BHJ particle, confirming the composition of
CFO/MFO. According to HRTEM image in Fig. 5(b), the 150–200 nm
BHJ particle was made of many randomly mixed and interfacing
20–30 nm particles. When n-MFO [45] and p-CFO [47] make the
interface, a p–n diode heterojunction is formed in nano-scale. There
are many such junctions randomly distributed in the large par-
ticle forming a bulk heterojunction. The conceptual structure of
the BHJ is schematically shown in Fig. 5(c). Fig. 5(d) shows a band
diagram for a single p-CFO/n-MFO heterojunction. To form BJH, it
is essential to have separate phases of p- and n-semiconductors
instead of solid solution or mixed phase. Our synthesis technique
(polymer complex method) provided one-pot production of the
two separate semiconducting, stable metal oxide phases of nano-
dimensions. The formation of the separate phases was confirmed by
X-ray diffraction analysis and it may be due to different structures
of the two ferrites (orthorhombic vs. cubic) and the considerable
size difference between Ca2+ (0.99 Å) and Mg2+ (0.65 Å).
This bulk heterojunction was further loaded with Pt and RuO2
co-catalysts to facilitate the faster electron–hole transfer to the
electrolyte. The working principle of such a multi-junction device
can be explained with reference to Fig. 5(e). Like p–n junction dis-
cussed above, a nano-scale p–n junction is formed at the interface.
When photons are absorbed by the device, electron–hole pairs or
excitons are generated. The excitons diffuse in each semiconductor
and break up when they arrive at the p–n junction. According to the
potential established across the junction, holes move to the p-CFO
side and electrons to the n-MFO side. For a homojunction of a single
semiconductor or a planar heterojunction, the diffusion distance
for the exciton would be long and the electron–hole recombina-
tion would take place before it reaches the interface. In the bulk
heterojunction where p- and n-type semiconductors are dispersed
interfacing each other, the probability that the exciton reaches the
interface and dissociates is higher, especially when the domain size
of the semiconductor particles is similar to the exciton diffusion
length. The co-catalyst Pt provides sites for electron collection and
reduction reactions, whereas RuO2 becomes the site for hole collec-
tion and oxidation reactions, although in reality these co-catalysts
should be dispersed randomly on both types of semiconductors. All
these factors would lead to enhanced photocatalytic activity.
3.5. Photocatalytic activity for reduction or oxidation of water
The UV–visible diffuse reflectance spectra of various photocata-
lysts are compared in Fig. 6 and the band gap energies determined
from them are summarized in Table 1. As a reference photocatalyst,
nitrogen-doped TiO2 (TiO2−x Nx ) was employed for comparison. Our
PbBi2 Nb2 O9 sample, being a single phase material, showed a steep
onset of absorption spectrum around green wavelengths sweeping
major visible region. This sharp absorption edge indicates single
band gap absorption and is expected to be beneficial for high photo-
activity [10]. The spectrum of CaFe2 O4 –PbBi2 Nb1.9 W0.1 O9 powders
showed a slight red shift of the absorption edge from the base mate-
rial PbBi2 Nb2 O9 giving Eg of 2.75 eV, and WO3 /W/PbBi2 Nb1.9 Ti0.1 O9
PNHO showed Eg of 2.79 eV.
The photocatalytic activity of the heterojunction photocatalysts
discussed above was evaluated for two half-reactions of water split-
ting; hydrogen evolution from an aqueous solution of methanol as
a hole scavenger and oxygen evolution from an aqueous solution of
silver nitrate as an electron scavenger. The results are summarized
in Table 1. The quantum yield (QY) is defined as 2 × number of H2
molecules (or 4 × number of O2 molecule) generated per absorbed
photon. The exact comparison among different heterojunction pho-
tocatalysts is not possible because compositions are not the same.
Yet, the data are still interesting because all photocatalysts with
similar band gap energies were tested under the same reaction
conditions.
The single phase PbBi2 Nb2 O9 photocatalyst forming a Schottky
junction with Pt showed hydrogen evolution corresponding to QY
of 0.95%. The QY for oxygen evolution was very high at 29%. The ref-
erence photocatalyst, Pt-loaded TiO2−x Nx , showed trace amount of
H2 evolution, but QY for O2 evolution was ca. 12%. The high QY for O2
evolution indicates that PbBi2 Nb2 O9 has high oxidation potential.
Indeed, the activity of PbBi2 Nb2 O9 for oxidative decomposition of
isopropyl alcohol was about twice as high as that of TiO2−x Nx [23].
The p–n heterojunction catalyst of CaFe2 O4 –PbBi2 Nb1.9 W0.1 O9
exhibited better performance than single phase Pt/PbBi2 Nb2 O9
even without any co-catalyst. The QY for hydrogen evolution was
greatly improved to ca. 4.2%. The QY of O2 evolution over p–n het-
erojunction catalyst was estimated to be ca. 38%. When Ohmic
layer was introduced to form PNHO (WO3 /W/PbBi2 Nb1.9 Ti0.1 O9 ),
the QY for hydrogen evolution was further increased to 6.1% and
that for O2 evolution was estimated to be ca. 41%. To the best of
our knowledge, this is the highest value ever reported for the reac-
tion over semiconductor photocatalysts under visible light. Finally,
the BHJ photocatalyst (RuO2 /n-MgFe2 O4 /p-CaFe2 O4 /Pt) showed a
very high QY for H2 evolution of 10.1%, which also represents the
highest QY for H2 evolution ever reported for oxide photocatalysts
[46]. The results in Table 1 thus demonstrate that formation of het-
erojunctions is a successful strategy to fabricate highly efficient
photocatalysts.
4. Conclusion
This critical review discussed heterojunction semiconductors
as an effective strategy to develop a highly efficient photocata-
lyst working under visible light for water splitting. The concepts
of heterojunction are summarized in Fig. 7. These proven con-
cepts in solar cells and other optoelectronic devices have been
successfully applied here to fabricate photocatalysts of inor-
ganic semiconductors. The formation of heterojunctions results
in the efficient separation of electron–hole pairs to minimize the
energy-wasteful electron–hole recombination, which leads to the
high photocatalytic activity. As the complexity and sophistica-
tion of the photocatalyst fabrication increased, the photoactivity
also increased. Modern nanomaterial synthetic techniques were
employed to bring into reality the highly engineered material con-
figurations. At the present time, our results as well as those of
other groups show still low efficiencies of solar light-to-hydrogen
conversion. Also, the photoactivity reported here was obtained in
sacrificial agent systems (CH3 OH and AgNO3 ), which have a lim-
ited practical value. There still remains the grand challenge to find
materials to absorb more photons from solar light and convert them
to chemical energy more efficiently with minimal loss by charge
recombination. These materials could be utilized to their maxi-
mal potential by applying concepts of heterojunction formation
introduced in this review.
 J.S. Jang et al. / Catalysis Today 185 (2012) 270–277
Acknowledgment
This work was supported by Hydrogen Energy Center and Korea
Center for Artificial Photosynthesis (KCAP) funded by the Ministry
of Science and Technology of Korea.
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