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Efficient Co–Fe layered double hydroxide
photocatalysts for water oxidation under visible
Cite this: J. Mater. Chem. A, 2014, 2,
4136 light†
Received 28th November 2013 Sang Jun Kim,a Yeob Lee,a Dong Ki Lee,a Jung Woo Leea and Jeung Ku Kang*ab
Accepted 13th January 2014
DOI: 10.1039/c3ta14933a
www.rsc.org/MaterialsA
We report new Co–Fe LDH water oxidation photocatalysts and their
water oxidation abilities under visible light with different ratios of
transition metals. The layered structure containing more iron dis-
played the highest efficiency, attributed to good crystallinity,
enhanced light absorbance and low charge carrier recombination of
Co–O–Fe oxo-bridges.
Global energy today is primarily obtained via the combustion of
fossil fuels, which generates pollution and results in climate
change.1,2 Articial photosynthesis is considered to be an
appealing method for the regeneration of carbon fuels from
water and carbon dioxide (CO2) using solar energy.3,4 Articial
photosynthesis consists of two important steps—the rst is
water oxidation and the second is the conversion of CO2 into
hydrocarbon fuels (e.g., methanol) using the protons generated
during the rst step. This mimics the natural photosynthesis
process in which electrons from the photosystem II oxidation
catalyst are transferred to photosystem I for the conversion of
CO2 into carbohydrates.5 Visible and ultraviolet light are used
for articial photosynthesis. However, because the energy of
visible light is much higher than the energy of ultraviolet light
at the earth's surface, the photocatalytic reaction can be per-
formed under visible light to use solar energy at maximum
efficiency.
The efficiency of a photocatalyst is determined by its elec-
tronic energy band gap, electron–hole pair lifetime, and charge
mobility.6,7 Some transition metals are attractive as water
oxidation catalysts because they are inexpensive and abundant,
a
Department of Materials Science & Engineering and NanoCentury KAIST Institute,
Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro,
Yuseong-gu, Daejeon 305-701, Republic of Korea. E-mail: jeungku@kaist.ac.kr; Fax:
+82-42-350-3310
b
Graduate School of Energy, Environment, Water, and Sustainability (EEWS), Korea
Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu,
Daejeon 305-701, Republic of Korea. E-mail: jeungku@kaist.ac.kr; Fax: +82-42-350-
3310
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3ta14933a
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and have suitable properties for photocatalyst use.8,9 For
example, hematite (a-Fe2O3), with a band gap of about 2 eV, has
been suggested as a water oxidation catalyst that is able to
harvest a wide range of the solar spectrum.10–12 However, it was
found to have a short hole diffusion length, thus resulting in the
fast recombination of holes with electrons before water oxida-
tion could occur.11–13 Cobalt oxides have also been used as co-
catalysts in water oxidation reactions because of their high
turnover frequencies (TOFs),14 although they were unable to
oxidize water by themselves.15,16 Layered double hydroxides
(LDHs), which are composed of mixed metal oxides with the
chemical formula [M2+1 xM3+x(OH)2]x+[(An )x/n]x $mH2O, have
also been proposed as possible photocatalysts.17–20 Structurally,
they contain stacked brucite-like M2+(OH)2 hydroxide layers in
which some of the M2+ ions undergo isomorphous substitutions
by M3+ ions.18,21 A feature of these structures is the linking of the
metal ions to each other by oxygen atoms.22 The oxo-bridges
(M1–O–M2) block electron–hole recombination via a metal-to-
metal charge transfer (MMCT) mechanism.23 Another advan-
tage is that LDHs can be also prepared on a large scale.17,24
LDHs based on titanium or zinc oxides have been tested for
their photocatalytic abilities in water oxidation.2,17,22 Also, a Co–
Fe LDH was synthesized with a 2 : 1 ratio for Co2+/Fe3+ loading
precursors, but it was not very crystalline.25 Meanwhile, LDHs
with good crystallinity can also be prepared using various
metals and anions as well as different metal ratios. Therefore,
the exploration of photocatalytic ability as a function of the
metal ratio would be meaningful. Oxo-bridges in Fe-based LDH
photocatalysts help to prevent the recombination of holes with
electrons, and thereby overcome the issue related to the short
hole diffusion length.23,26 Depending on the ratio of the two
metals, the number of oxo-bridges connecting different metals
can be increased, which will signicantly affect the water
oxidation abilities of the LDHs.
Herein, we report highly efficient Co–Fe LDH water oxidation
photocatalysts under visible light and having different water
oxidation abilities with different ratios of transition metals.
Scheme 1 illustrates the Co–Fe LDH structure and the water
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Scheme 1 Schematic illustration of a Co–Fe layered double hydroxide
structure and its catalysis of water oxidation. This reaction proceeds
under visible light because of its suitable bandgap.
oxidation reaction under visible light. Three Co–Fe LDHs were
synthesized by the co-precipitation method under an inert
atmosphere with cobalt and iron ratios of 2.23, 3.33, and 4.16
(Table S1†), which were denoted as CFL2, CFL3, and CFL4,
respectively.
Fig. 1a shows the powder X-ray diffraction (XRD) patterns of
crystals of the three Co–Fe LDHs; peaks that were characteristic
of an LDH structure were clearly observed.27 In the case of CFL4,
the (003), (006), (012), (110), and (113) peaks (JCPDS Card no.
50-0235, Fig. S1(a)†) were observed at 11.48 , 23.13 , 33.02 ,
59.05 , and 60.35 , respectively. The (003) basal plane spacing
was determined to be 7.7 Å (Scheme 1).27,28 The peak corre-
sponding to the (110) plane was very distinct, signifying a
regular arrangement of the metal ions in the Co–Fe LDH.29,30
Meanwhile, CFL2 and CFL3 had more basal and non-basal
peaks, such as (101), (009), (015), (009), (018), (0012), and (1013).
This meant that CFL2 and CFL3 had higher crystallinities than
CFL4, including non-basal planes. Further experiments
(Fig. S2†) show that LDHs less than low cobalt and iron ratios of
Fig. 1 (a) PXRD patterns of various Co–Fe LDHs. (b) HR-TEM image of
CFL2. (c) Co K-edge and (d) Fe K-edge XANES spectra of a Co–Fe LDH
(CFL4).
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2.23 (CFL2) have poor crystallinities. Fig. 1b, S3a and b and
S4a–c† show high-resolution transmission electron microscopy
(HR-TEM) images of the Co–Fe LDHs. The small round particles
in Fig. S4a† demonstrate the agglomeration of LDH particles.
The magnied image in Fig. S3b† reveals ne striped layers
indicative of a layered structure. In particular, the lattice spac-
ings of 0.263 and 0.232 nm in Fig. 1b and S3a† correspond to
the (012) and (015) planes of Co–Fe LDH, respectively. Finally,
the energy-dispersive spectrometry (EDS) images in Fig. S3d–f
and S4d–f† conrmed that cobalt and iron were well dispersed
in the structure.
The anions located between the interlayers were identied by
Fourier transform infrared (FT-IR) spectroscopy (Fig. S5†). The
strong broad band at 3442 cm 1 was attributed to the stretching
mode of the –OH bonds in the hydroxide layer, which are
marked as red spheres in Scheme 1, and water between the
hydroxide layers.31 Deformation of the H–O–H angle in water
produced the characteristic small bands at 1633 and 1556
cm 1.30,32 The peaks at 1384 and 1353 cm 1 resulted from the
asymmetric stretching of carbonate anions in the interlayer
region.33,34 The splitting of the CO32 peak was attributed to the
presence of both C–O and C]O bonds.22 Several metal-ion-
related bands for M–O or M–OH stretching modes occurred at
low frequencies. Despite the presence of other anions such as
NO3 in the solution, the FT-IR results suggested that the Co–Fe
LDHs contained CO32 in the interlayers. This is because CO32
has good affinity towards the hydroxide layers and water
molecules in the interlayer,35 and the anion neutralizes the
charge in the LDH structure.
Cobalt and iron K-edge X-ray absorption near-edge structure
(XANES) spectra were obtained to determine the cobalt and iron
oxidation states in the metal hydroxide layer. Fig. 1c shows the
cobalt K-edge XANES spectra of different cobalt oxides (CoO,
Co2O3, Co3O4) and the Co–Fe LDH. All the spectra showed a pre-
edge shoulder around 7710 eV, attributed to quadrupole-
allowed electronic transitions from the 1s orbital to the 3d
orbital.36 The position of the main absorption edge around 7727
eV was similar for both Co–Fe LDH and CoO, caused by a dipole
transition from the 1s orbital to the 4p orbital. The XANES results
provide evidence that there is Co–O bonding with a Co2+ oxida-
tion state in the Co–Fe LDH. Also, the iron K-edge XANES spectra
of Fe2O3, Fe3O4, and Co–Fe LDH are plotted in Fig. 1d. In the
same manner, the pre-edge around 7113 eV and the main edge
around 7132 eV could be attributed to the 1s to 3d and the 1s to
4p transitions, respectively.37 In this graph, Fe2O3 and Co–Fe
LDH had similar main edges and shapes. This indicated that
iron was present as Fe3+ bonded with oxygen in the Co–Fe LDH.
Fig. 2a and S6† show the UV-Vis diffuse reectance spectra of
the Co–Fe LDHs, which were converted by the Kubelka–Munk
function and linear extrapolation to energy vs. F(R). All the
Co–Fe LDHs could absorb the visible light wavelengths,
especially below 550 nm. The peak below 500 nm corresponding
to the 2.25 eV band gap is due to the metal-to-metal charge
transfer (MMCT) leading to efficient water oxidation, while the
peaks above 500 nm were attributed to the metal-to-ligand
charge transfer (MLCT) giving a small contribution to water
oxidation.17,22 The MLCT could be explained by a hexaaquo
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Journal of Materials Chemistry A
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Fig. 2 (a) UV-Vis reflectance spectra of Co–Fe LDHs. (b) UPS of Co–
Fe LDH (CFL4). (c) Schematic model for the band structure of a Co–Fe
LDH having a proper band edge to produce oxygen using visible light.
cation, [M(H2O)6]n+, having a similar environment of transition
metals in the LDH.38 The cobalt hexaaquo cation ([Co(H2O)6]2+)
and the iron hexaaquo cation ([Fe(H2O)6]3+) have pink (mixed
red and a little blue) and pale violet colors, respectively.39,40
Therefore, their absorption regions are green (480–550 nm),
orange (590–630 nm), and yellow (550–590 nm). In other words,
this material absorbed mainly green light from the cobalt cation
with a small amount of yellow and orange light from cobalt and
iron cations. 630 nm corresponds to the absorption edge of the
yellow color and the quantum yield of the water oxidation
reaction17,22 sharply was found to be decreased as the wave-
length increased. Therefore, the efficient water oxidation is
mostly attributed to the green light, while the yellow light at
around 630 nm attributed to the MLCT gives a marginal
contribution to the reaction. Ultraviolet photoelectron
spectroscopy (UPS) experiments, as seen in Fig. 2b, were used to
ascertain whether the Co–Fe LDHs could be used as
photocatalysts for water oxidation. The valence band maximum
(VBM) was calculated from the double tangent of the kinetic
energy of the electrons released from the valence band of the
Co–Fe LDH. The calculated VBM level of the Co–Fe LDH was 0.9 V
vs. the normal hydrogen electrode (NHE) at pH 7.0, while the
conduction band minimum (CBM) was 1.35 V vs. NHE at pH
7.0. The band gap energy was determined from the UV-Vis spec-
trum, and the electronic band structure of Fig. 2c suggested that
the Co–Fe LDH would be suitable for water oxidation as its VBM
level was lower than that for water oxidation (0.818 V, H2O–O2).
The photocatalytic abilities of the Co–Fe LDHs were also
tested under visible light (400 nm < l < 700 nm) using a 300 W
xenon lamp tted with UV and IR lters. The total amount of
evolved oxygen is shown in Fig. 3a. CFL2 produced about 45
mmol oxygen from water over 3 h in the presence of light and
AgNO3 as an electron scavenger. Oxygen was generated at a
uniform rate, indicating that the Co–Fe LDH generated charges
at a steady rate upon the absorption of visible light. CFL3 and
CFL4 also produced oxygen under the same conditions, albeit in
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Fig. 3 (a) Time-dependent evolved oxygen under visible light by Co–
Fe LDHs, CoO, and Fe2O3. (b) UV-Vis reflectance spectra of a Co–Fe
LDH (CFL4) suspension. The reduction of Ag+ ions into Ag nano-
particles induced a color change.
lower amounts compared to CFL2. The main reason for the
reduced production was the number of oxo-bridges connecting
the two different metals. In the photocatalytic reactions of
LDHs, the oxo-bridges play signicant roles. CFL2 had more
oxo-bridges than CFL3 or CFL4 because a greater amount of
iron atoms allowed more connections with cobalt. Furthermore,
CFL2 was more crystalline than CFL3 and CFL4, especially with
respect to the non-basal planes which indicate the crystallinity
of the metal hydroxide layer. Also, CFL2 absorbed more visible
light than the other Co–Fe LDHs according to the UV-Vis
spectra. In control experiments, we found that hematite and
cobalt oxides produced only about 5 mmol and 0.7 mmol oxygen,
respectively, under the same conditions. This indicated that the
bonds formed between the Co and Fe ions in the LDH structure
hindered the recombination of charge carriers, thereby
increasing its catalytic efficiency. The Ni–Ti and Cu–Ti LDH
structures reported in our previous study22 evolved about 200
mmol g 1 and 125 mmol g 1 oxygen, respectively, during a 3 h
catalytic test. This demonstrated that the Co–Fe LDH catalysts
for water oxidation under visible light were more than 450%
more efficient compared to titanium-embedded structures.
Fig. S7† shows that the color of the Co–Fe LDH suspension
was intensied as the irradiation time increased, which was
attributed to the reduction of Ag+ ions into Ag nanoparticles.29
From the UV-Vis reectance spectra of a Co–Fe LDH (CFL4)
suspension shown in Fig. 3b, it was apparent that most of the
light was reected at the start of the photocatalytic reaction.
However, the reectance decreased gradually as the reaction
proceeded, implying that the Co–Fe LDH oxidized water.
Conclusions
In summary, we prepared Co–Fe LDH photocatalysts with
various Co–Fe ratios which exhibited highly efficient water
oxidation under visible light. Among the three Co–Fe LDHs, the
sample containing more iron displayed the highest efficiency.
This enhanced efficiency was attributed to the Co–O–Fe bridges
in the LDH structure, which suppressed the fast recombination
of holes with electrons. The nature of this bonding was eluci-
dated by various experimental techniques, and the suitability of
the Co–Fe LDHs as water oxidation photocatalysts was
demonstrated by optical measurements. We expect that this
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Communication
work will lay a foundation for studies that will use transition
metals to increase the photocatalytic efficiency of LDHs for
water oxidation.
Acknowledgements
Published on 14 January 2014. Downloaded by Memorial University of Newfoundland on 18/07/2014 09:04:05.
This research was supported by the Korea Center for Articial
Photosynthesis (KCAP) located in Sogang University (2009-
0093881) and the Global Frontier R&D Program (2013-073298)
on Center for Hybrid Interface Materials (HIM) funded by the
Ministry of Science, ICT & Future Planning. In addition, J. K.
Kang was supported by the National Research Foundation of
Korea (2010-0029042, 2011-0028737, 2011-0031407, 2012-
0001174). The XANES analysis was supported by PAL through
the abroad beamtime program of the Synchrotron Radiation
Facility Project under MEST and has been performed under the
approval of the NSRRC (BL01C1).
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