Fabrication of CaFe

2
O
4
/MgFe
2
O
4
bulk heterojunction for enhanced
visible light photocatalysisw
Hyun Gyu Kim,
a
Pramod H. Borse,
b
Jum Suk Jang,
b
Euh Duck Jeong,
a
Ok-Sang Jung,
c
Yong Jae Suh
d
and Jae Sung Lee*
b
Received (in Cambridge, UK) 16th June 2009, Accepted 31st July 2009
First published as an Advance Article on the web 18th August 2009
DOI: 10.1039/b911805e
A bulk heterojunction photocatalyst of interfacing CaFe
2
O
4
and
MgFe
2
O
4
nanoparticles is highly active for oxidative degradation
of isopropyl alcohol and hydrogen production from water under
visible light, because the exciton easily reaches the interface and
dissociates to minimize recombination.
Tailoring of semiconductor properties by fabricating designed
nanostructures is the key to the performance improvement of
various optoelectronic and photoelectrochemical devices.
1
Instead
of using a single semiconductor, coupling of semiconductors
with other semiconductors, metals, and molecules forming a
junction structure has been found to enhance the performance
of various devices including solar cells,
2
photoluminescence
3
and electrochromic devices,
4
and superhydrophobic surfaces.
5
For instance, one can form uniform pn junction diodes, or
generate multi-junction devices.
6
We have been developing nano-congured particulate
devices by economic solution-based processes for photo-
catalytic applications. Thus, we have fabricated nanoparticle
junctions of CaFe
2
O
4
/PbBi
2
Nb
2
O
9
,
7
WO
3
/W/PbBi
2
Nb
2
O
9
,
8
CdS/AgGaS
2
,
9
and TiO
2
/CdS,
10
which showed enhanced
photocatalytic activity for water splitting and decomposition
of organic compounds compared to the materials with no
junction structure. In the present work, we report a concept
for fabricating a nanocomposite photocatalyst with a
conguration of RuO
2
/MgFe
2
O
4
/CaFe
2
O
4
/Pt. In particular,
two semiconductors form interpenetrating networks on a
nanometre scale constituting a bulk heterojunction (BH)
structure. The material showed unprecedentedly high photo-
catalytic activity as oxide photocatalysts for hydrogen evolution
from water, photocurrent generation, and decomposition of
isopropyl alcohol under visible light (l 4420 nm). This highly
structured material was synthesized by a simple polymer
complex (PC) method.
11
The base materials we chose were metal ferrites of the spinel
structure, i.e., n-type MgFe
2
O
4
(MFO)
12
and p-type CaFe
2
O
4
(CFO).
13
The spinel ferrites are the most important magnetic
materials, yet they also show interesting photocatalytic
properties for hydrogen or oxygen evolution from water.
1216
Desirable properties of these materials as photocatalysts are
resistance to photocorrosion in aqueous solutions and narrow
band gaps near 2 eV that allow the absorption of a large part
of visible light. The Fe d-orbital plays the major role in the
formation of the narrow band as indicated in the band
structure calculation (Fig. S1, ESIw). But their activity as
single phase photocatalysts was low.
As a means to enhance the photocatalytic activity of the
ferrites, we fabricated a bulk heterojunction structure
promoted by two co-catalysts, Pt and RuO
2
. The obtained
particulate device of RuO
2
/MgFe
2
O
4
/CaFe
2
O
4
/Pt is denoted
hereafter as BH CFO/MFO. Fig. 1a shows a transmission
electron microscopy (TEM) image of a typical BH CFO/MFO
particle of 150200 nm decorated with 25 nm clusters on its
surface. The small nanoparticles on the surface were found to
be Pt and RuO
2
by in situ energy dispersive X-ray microanalysis
Fig. 1 (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 heterojunction
promoted by co-catalysts.
a
Busan Center, Korea Basic Science Institute (KBSI),
Busan 609-735, Korea
b
Eco-friendly Catalysis and Energy Laboratory (NRL),
Department of Chemical Engineering, Pohang University of Science
and Technology (POSTECH), San-31 Hyoja-dong,
Pohang 790-784, Korea. E-mail: jlee@postech.ac.kr;
Fax: 82-54 279 5528; Tel: 82-54 279 2266
c
Department of Chemistry, Pusan National University,
Pusan 609-735, Korea
d
Korea Institute of Geoscience and Mineral Resources,
Daejeon 305-350, Korea
w Electronic supplementary information (ESI) available: Experimental
procedures, calculated band structures, elemental mapping, at band
potential measurements, photocurrent measurements, and time course
of hydrogen evolution. See DOI: 10.1039/b911805e
This journal is c The Royal Society of Chemistry 2009 Chem. Commun., 2009, 58895891 | 5889
COMMUNICATION www.rsc.org/chemcomm | ChemComm
(EDAX) carried out during the microscopic study. The
composition of CFO/MFO was also conrmed by elemental
mapping analysis with in situ EDAX, which clearly showed
that the elements of Ca, F, Mg, and O were uniformly
distributed forming the BH CFO/MFO particle (Fig. S2, ESIw).
According to high resolution (HR) TEM in Fig. 1b, the
150200 nm BH particle was made of many randomly mixed
and interfacing 2030 nm particles.
The structure of this nanoparticle assembly was investigated
by X-ray diraction (XRD). Fig. 2 displays XRD patterns of
the CFO/MFO BH particles along with individual CFO and
MFO particles, all prepared by the PC method. CFO (Fig. 2b)
had an orthorhombic phase (space group, Pnam; a = 9.23,
b = 10.7, c = 3.02 A

)
15
and MFO (Fig. 2c) had a cubic phase
(Fd

3m; a = 8.36 A

).
16
The XRD for CFO/MFO (Fig. 2a)
showed the co-existence of individual phases of CFO and
MFO. The size of individual particles was estimated to be
ca. 25 nm by application of Scherrer equation to the
half-widths of the diraction peaks. The formation of the
separate phases may be due to dierent structures of the two
ferrites (orthorhombic vs. cubic) and the considerable size
dierence between Ca
2+
(0.99 A

) and Mg
2+
(0.65 A

).
For comparison, CFO/MFO was also prepared by the
conventional solid-state reaction (SSR) method by heating a
ground mixture of CaCO
3
, MgCO
3
, and Fe
2
O
3
at 1300 1C.
But very little crystallization was observed even at the high
temperature (Fig. 2b). Thus, an advantage of the PC method
was to produce highly crystalline products under typical
synthesis conditions. From TEM and XRD, it is conrmed
that the particle shown in Fig. 1a is the agglomerate of
interfacing CFO and MFO nanoparticles of ca. 25 nm.
As discussed, the interpenetrating structure seen in Fig. 1b is
made of two ferrite phases. When n-type MFO and p-type
CFO make the interface, a pn diode heterojunction is formed.
There are many such junctions randomly distributed in the
large particle forming a bulk heterojunction. The conceptual
structure of the BH is schematically shown in Fig. 1c.
Fig. 1d shows a band diagram for a single p-CFO/n-MFO
heterojunction. Band gap energies were determined by
UV-visible diuse reectance spectroscopy to be 1.9 eV and
2.0 eV for CFO and MFO, respectively. These values are in
good agreement with the reported values.
14
and represent the
most desired band gap energies for photocatalytic water
splitting. The band positions were obtained by at band
potential measurements (Fig. S3, ESIw). Note that they
straddle the reduction (0.0 V) and oxidation potentials
(1.23 V) of water, showing the possibility of hydrogen and
oxygen generation from water. This pn heterojunction was
further loaded with Pt and RuO
2
co-catalysts to facilitate the
faster electronhole transfer to the electrolyte.
The working principle of such a multi-junction device can be
explained with reference to Fig. 1e. Under thermal equilibrium,
the Fermi levels align when a junction is formed between two
semiconductors having opposite majority carriers. Then, the
band edges of the semiconductor adjust to the Fermi energy
as depicted. When photons are absorbed by the device,
electronhole pairs or excitons are generated. The excitons
diuse in each semiconductor and break up when they arrive
at the junction. According to the potential established across
the pn junction, holes move to the p-CFO side and electrons to
the n-MFO side. The co-catalyst Pt provides sites for electron
collection and reduction reactions, whereas RuO
2
becomes the
site for hole collection and oxidation reactions. These 25 nm
particles form Schottky junctions with underlying semi-
conductors. Thus, the net eect of the heterojunction device is
the ecient separation of electronhole pairs to minimize the
energy-wasteful recombination.
On top of the heterojunction formation, an ingenious feature
of the present device is the formation of a bulk heterojunction,
which is made of many interfacing heterojunctions of 2030 nm
(Fig. 1c). The introduction of the BH dramatically improved
the eciency of organic solar cells.
17
In the BH, electron
donor and acceptor molecules are blended together. If the
domain size in either material is similar to the exciton diusion
length, then wherever an exciton is photogenerated, it is likely
to diuse to the interface and break up. The situation is more
suitable for high eciency than a planar heterojunction,
or bi-layer device, where much longer diusion of the exciton
is required to reach the interface. The device proposed
here is an all-inorganic version of BH, where p-type and
n-type semiconductors form interpenetrating networks on a
nanometre scale, and high eciency is expected by the same
principle.
The optical properties of BH CFO/MFO were probed by
UV-visible diuse reectance spectroscopy as shown in
Fig. 3a. The spectra show the red shift in the absorption with
increasing calcination temperatures from 900 to 1200 1C, and
accordingly the color palettes demonstrate the hue variation.
As mentioned, the absorption edge around 620 nm is most
suitable for the visible light photocatalysis. Thus CFO/MFO
oers an additional advantage due to this desirable optical
property which is a key factor in designing a high eciency
photocatalyst.
Fig. 2 X-Ray diraction patterns of CFO/MFO, CFO and MFO
synthesized by the PC method, and CFO/MFO prepared by SSR
method.
5890 | Chem. Commun., 2009, 58895891 This journal is c The Royal Society of Chemistry 2009
Fig. 3b shows the time curves for CO
2
evolution from the
photooxidation of isopropyl alcohol (IPA) under visible light
(l Z 420 nm) for BH CFO/MFO, WO
3
/W/PbBi
2
Nb
1.9
Ti
0.1
O
9
and TiO
2x
N
x
. It clearly shows that BH CFO/MFO is more
ecient than the others yielding the most CO
2
from the
photooxidation reaction. The CO
2
production stopped when
the light was turned o and the reaction resumed
at the same rate when the light was turned on again. The
superiority of the BH photocatalyst was also demonstrated in
photocurrent generation from an aqueous solution containing
acetate (donor) and Fe
3+
(acceptor) under visible light as
shown in Fig. S4.w
The BH CFO/MFO photocatalyst was also used in
photocatalytic hydrogen evolution from an aqueous solution
of methanol as a hole scavenger. As listed in Table 1, our BH
CFO/MFO photocatalyst with co-catalysts of Pt and RuO
2
yields the highest activity. The rate of hydrogen evolution
remained almost the same even after several runs with
intermittent evacuation (Fig. S5, ESIw). The quantum yield
(QY = 2 number of H
2
molecules generated per absorbed
photon) for hydrogen evolution was 10.1%, which represents,
to the best of our knowledge, the highest number ever reported
for oxide photocatalysts. The CFO/MFO prepared by the
conventional SSR method showed little activity for hydrogen
evolution. The single component photocatalysts, CFO
and MFO with co-catalysts of Pt and RuO
2
, showed low
activity, suggesting the importance of the BH structure.
The WO
3
/W/PbBi
2
Nb
1.9
Ti
0.1
O
9
is a highly optimized photo-
catalyst with an ohmic junction sandwiched between
pn semiconductors.
8
This junctioned photocatalyst was,
however, less active than CFO/MFO(PC) with the bulk
heterojunction structure.
In conclusion, we have demonstrated a concept to fabricate
a highly ecient photocatalyst conguration of bulk hetero-
junction. As a proven concept in organic solar cells,
17
it has
been successfully applied here to fabricate photocatalysts of
inorganic semiconductors. Upon light absorption, excitons are
generated in both semiconductors. The excitons diuse to the
pn interface and dissociate into free carriers, and electrons
and holes diuse in opposite directions at the heterojunction.
For a homojunction of a single semiconductor or a planar
heterojunction, the diusion distance for the exciton would be
long and the electronhole recombination would take place
before it reaches the interface. In a bulk heterojunction where
p- and n-type semiconductors are dispersed interfacing each
other, the probability that the exciton will reach the interface
and dissociate is higher, especially when the domain size of the
semiconductor particles is similar to the exciton diusion
length. This would lead to enhanced photocatalytic activity.
The salient feature of our synthesis technique (polymer
complex method) is the one-pot production of the two
separate semiconducting, stable metal oxide phases of
nano-dimensions. Attaining such conguration otherwise
would be a challenging task for such stable metal oxides.
This work has been supported by KBSI grant (No. 28035)
and Hydrogen Energy R&D Center.
Notes and references
1 G. A. Somorjai, F. Tao and J. Y. Park, Top. Catal., 2008, 47, 1.
2 I. Gur, N. A. Fromer, M. L. Geier and A. P. Alivisatos, Science,
2005, 310, 462.
3 J. S. Steckel, J. P. Zimmer, S. Coe-Sullivan, N. E. Stott, V. Bulovic
and M. G. Bawendi, Angew. Chem., Int. Ed., 2004, 43, 2154.
4 Y. Ohko, T. Tatsuma, T. Fujii, K. Naoi, C. Niwa, K. Kubota and
A. Fujishima, Nat. Mater., 2003, 2, 29.
5 Z. Liu and M. Miyauchi, Chem. Commun., 2009, 2002.
6 K. Q. Peng, Z. P. Huang and J. Zhu, Adv. Mater., 2004, 16, 73;
Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayer, B. Gates, Y. Yin,
F. Kim and H. Yan, Adv. Mater., 2003, 15, 353.
7 H. G. Kim, P. H. Borse, W. Choi and J. S. Lee, Angew. Chem., Int.
Ed., 2005, 44, 4585.
8 H. G. Kim, E. D. Jeong, P. H. Borse, S. Jeon, K. Yong, J. S. Lee,
W. Li and S. H. Oh, Appl. Phys. Lett., 2006, 89, 064103.
9 J. S. Jang, D. W. Hwang and J. S. Lee, Catal. Today, 2007, 120,
174.
10 J. S. Jang, W. Li, S. H. Oh and J. S. Lee, Chem. Phys. Lett., 2006,
425, 278.
11 G. Liu, Y. Zhao, C. Sun, F. Li, G. Q. Lu and H. M. Cheng,
Angew. Chem., Int. Ed., 2008, 47, 4516.
12 L. G. J. De Haart and G. Blasse, Solid State Ionics, 1985, 16, 137.
13 Y. Matsumoto, M. Omae, K. Sugiyama and E. Sato, J. Phys.
Chem., 1987, 91, 577.
14 U. Steinike and K. Tkacova, J. Mater. Synth. Process., 2000, 8,
197; S. Zhuiykov, T. Ono, N. Yamazoe and N. Miura, Solid State
Ionics, 2002, 152153, 801.
15 B. F. Decker and J. S. Kasper, Acta Crystallogr., 1957, 10, 332.
16 L. Passerini, Gazz. Chim. Ital., 1930, 60, 389.
17 G. Yu and A. J. Heeger, J. Appl. Phys., 1995, 78, 4510; J. J.
M. Halls, C. A. Walsh, N. C. Greenham, E. A. Marseglia,
R. H. Friend, S. C. Moratti and A. B. Holmes, Nature, 1995,
376, 498.
Fig. 3 (a) UV-visible diuse reectance spectra of CFO/MFO
prepared at dierent temperatures; (b) CO
2
evolution from photo-
oxidation of isopropyl alcohol under visible light with dierent
photocatalysts. K: CFO/MFO(BH), m: WO
3
/W/PbBi
2
Nb
1.9
Ti
0.1
O
9
and : TiO
2x
N
x
.
Table 1 Photocatalytic activities for H
2
evolution from aqueous
solutions
a
Catalyst
Band gap energy Hydrogen evolution
E/eV l
ab
/nm
mol
gcat.
1
h
1
QY
(%)
CFO/MFO(PC) 2.00 620 82.7 10.1
CFO/MFO(SSR) 2.00 620 Trace Trace
CFO 1.90 652 1.40 0.16
MFO 2.00 620 4.55 0.57
WO
3
/W/PbBi
2
Nb
1.9
Ti
0.1
O 2.79 443 49.3 6.51
a
Catalyst 0.3 g; light source, 450 W W-Arc lamp (Oriel) with UV
cut-o lter (l Z 420 nm). Reaction was carried out in a solution of
methanol 30 ml + distilled water 170 ml.
This journal is c The Royal Society of Chemistry 2009 Chem. Commun., 2009, 58895891 | 5891