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Nano-ferrites for water splitting: unprecedented high photocatalytic hydrogen
production under visible light
Priti A. Mangrulkar,a Vivek Polshettiwar,*b Nitin K. Labhsetwar,a Rajender S. Varmac
and Sadhana S. Rayalu*a
Received 5th April 2012, Accepted 12th May 2012
Published on 31 May 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30819C

DOI: 10.1039/c2nr30819c
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In the present investigation, hydrogen production via water splitting by nano-ferrites was studied using
ethanol as the sacrificial donor and Pt as co-catalyst. Nano-ferrite is emerging as a promising
photocatalyst with a hydrogen evolution rate of 8.275 mmol h
1 and a hydrogen yield of 8275 mmol h
1
g
1 under visible light compared to 0.0046 mmol h
1 for commercial iron oxide (tested under similar
experimental conditions). Nano-ferrites were tested in three different photoreactor configurations. The
rate of hydrogen evolution by nano-ferrite was significantly influenced by the photoreactor
configuration. Altering the reactor configuration led to sevenfold (59.55 mmol h
1) increase in the
hydrogen evolution rate. Nano-ferrites have shown remarkable stability in hydrogen production up to
30 h and the cumulative hydrogen evolution rate was observed to be 98.79 mmol h
1. The hydrogen
yield was seen to be influenced by several factors like photocatalyst dose, illumination intensity,
irradiation time, sacrificial donor and presence of co-catalyst. These were then investigated in detail. It
was evident from the experimental data that nano-ferrites under optimized reaction conditions and
photoreactor configuration could lead to remarkable hydrogen evolution activity under visible light.
Temperature had a significant role in enhancing the hydrogen yield.

1. Introduction conversion, the need to develop visible light responsive

The energy crisis on a global scale is expected to be one of the
major challenges to be faced in the 21st century with the rapid
depletion of fossil fuels. In response to this looming threat, the
quest of identifying new, renewable and sustainable energy
source therefore becomes imperative. Hydrogen is regarded as a
fuel for the future which has the potential to supplement or even
possibly replace the ever depleting fossil fuels. Photocatalytic
splitting of water by harnessing our abundant source of solar
energy promises to be a cleaner and greener route towards
generation of hydrogen. Many research groups like Kudo
et al.,1–6 Domen et al.,7–11 Anpo et al.,12,13 Nocera et al.14 are
actively involved in studying the photocatalytic water splitting
reaction. Photocatalytic splitting of water into H2 and O2 under
UV radiation has been extensively reported.6,15–17 However,
from the viewpoint of solar energy utilization and its chemical
a
Environmental Materials Division, National Environmental Engineering
Research Institute (CSIR-NEERI, Nehru Marg), Nagpur, India.
E-mail: s_rayalu@neeri.res.in; Fax: +91 7122242828; Tel: +91
7122242828
b
Nanocatalysis Laboratory (NanoCat), KAUST Catalysis Center (KCC),
King Abdullah University of Science and Technology (KAUST), Thuwal,
Saudi Arabia. E-mail: vivek.pol@kaust.edu.sa; Tel: +966 28080302
c
Sustainable Technology Division, NRMRL, U.S. Protection Agency, 26
W. Martin Luther King Dr., Cincinnati, Ohio, USA. Fax: +1 513-569-
7677; Tel: +1 513-487-2701
photocatalysts (>400 nm) becomes indispensable. One of the
main reasons attributed to poor efficiency of TiO2 in photo-
catalytic water splitting lies in its inability to be active in the
visible range. Hence, it becomes essential to develop photo-
catalysts with enhanced visible light activity and high quantum
efficiency for efficient solar energy conversion. Iron oxide is
one of the semiconductors which has a conducive bandgap of
2.0–2.2 eV that enables it to absorb nearly 40% of the solar
radiation. Furthermore, it is abundant and non-toxic. In spite of
the potential advantages of iron oxide, it is not widely
reported in photocatalytic water splitting owing to its high
recombination rate of photogenerated electrons and holes.
Moreover, its conduction band edge is not suitable for hydrogen
evolution. These aspects are majorly responsible in limiting the
application of iron oxide as a photocatalyst for water splitting
reaction.
Recently, nano-science and technology have unfolded new
possibilities towards the development of nano-materials. In
particular, magnetic nano-particles are important in diverse
areas from basic research to various applications in electronics,
biosensors, catalysis and energy.18 They have emerged as
sustainable alternatives to conventional materials as robust high
surface area heterogeneous catalysts and catalyst supports.19
The nano-sized particles increase the exposed surface area of the
active component of the catalyst, thereby enhancing the contact

5202 | Nanoscale, 2012, 4, 5202–5209 This journal is ª The Royal Society of Chemistry 2012

between reactants and catalyst dramatically and mimicking the
homogeneous catalysts. Nanoscale catalysis is being regarded as
a significant area of research capable of providing break-
throughs which can help in raising the performance and reli-
ability of technologies required in hydrogen production. A wide
range of nanoparticles and nano-metal oxides have been
synthesized and studied by various physical and chemical
methods in recent times. The scientific challenge is the synthesis
of specific size and shape nano-catalysts to allow facile move-
ment of the materials in the reacting phase and control over the
morphology of nanostructures to tailor their physical and
chemical properties. However, the rapid advancement of
nanotechnology has made possible the preparation of a variety
of nanoparticles with controllable size, shape, morphology and
Published on 31 May 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30819C
composition.20 The novel physical and chemical properties of
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engineered and designed nanoparticles make them an attractive
option in various environmental applications. As the properties
of nano-materials differ from the bulk phase, it can have an
astonishing impact on their catalytic properties in various
reactions including photocatalytic water splitting for hydrogen
production.21 Nano-structuring can therefore significantly help
in improving the properties of photocatalysts. Most of these
catalytic systems are based on oxides like titania, ceria, etc.22–25
and the use of nano-ferrites for water splitting is largely
untapped, although there are a few reports on hydrogen
production by ferrites but with not much success.26–28 Nano-
ferrites have been reported for thermochemical splitting of
water for hydrogen production.28 However, these processes
operate at high temperatures making the process energy
intensive.
In continuation of our work on advanced nano-materials for
sustainable catalysis,18a,19,29 herein we report nano-Fe3O4 as an
excellent catalyst for hydrogen production through water split-
ting in the presence of a sacrificial donor. It has shown high
potential in hydrogen production with an exceptionally high rate
of photocatalytic hydrogen evolution. Nano-ferrites were tested
under three different reactor configurations. Nano-ferrites have
shown good stability in hydrogen production up to 30 h. The
exceptionally high activity of the nano-photocatalyst is unprece-
dented and to the best of our knowledge is being reported for the
first time. The influence of various operating parameters were
also studied and optimized.
2. Results and discussion
2.1. Catalyst preparation and characterization
Nano-ferrites were prepared by a co-precipitation method using
FeSO4$7H2O and Fe2(SO4)3 in water. In 500 cm3 of water, 13.9 g
of FeSO4$7H2O and 20 g of Fe2(SO4)3 were dissolved. Ammo-
nium hydroxide (25%) was added slowly to adjust the pH of the
solution to 10. The reaction mixture was then continually stirred
for 1 h and the precipitated nano-particles were isolated, washed
with water until the pH reached 7, and then dried under a
vacuum at 60  C.
The catalyst was characterized by X-ray diffraction (XRD)
(Fig. 1) which confirms the formation of single phase Fe3O4
nanoparticles. The crystal structures agree with the corre-
sponding reported JCPDS data (card 19-629). A distinct line
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broadening of the diffraction peaks indicates that the synthesized
ferrites are in the nanometer range. The crystallite sizes were
calculated from Debye–Scherrer formula applied to the major
intense peak and were found to be 12.42 nm.
Transmission electron microscopy (TEM) (Fig. 2) also shows
nanoparticles with spherical morphology and a size range of 10–
12 nm which is comparable to the crystallite size calculated from
the X-ray spectrum. The corresponding SAED patterns for the
Fe3O4 particles are also given in Fig. 2d.
Diffuse reflectance UV-Vis spectra of nano-ferrites was
recorded using a Perkin Elmer spectrophotometer lambda 900
equipped with an integrating sphere. BaSO4 was used as a
reference material. The spectrum is as shown in Fig. 3. The lmax
was observed to be at 449 nm which confirms that nano-ferrite is
active in the visible range of the spectrum. The bandgap energy
was calculated from absorption maxima using following
equation:
Eg (eV) ¼ 1240/lg nm
The bandgap energy was found to be 2.7 eV. This prominent
red shift may be responsible for enhanced charge separation and
increased photocatalytic activity.
2.2. Photocatalytic hydrogen evolution by nano-ferrites
(photoreactor system I or Impinger system)
Photocatalytic water splitting of water by nano-ferrites in the
presence of a sacrificial donor and Pt as co-catalyst was carried
out in a tubular borosilicate glass reactor. The experimental set
up was same as that employed by Mangrulkar et al.30 The
hydrogen evolution rate was observed to be was 8.275 mmol h
1
with a hydrogen yield of 8275 mmol h
1 g
1 for nano-ferrite which
was significantly higher as compared to the hydrogen evolution
rates of 3.08 mmol h
1 and 0.0046 mmol h
1 observed for
commercial TiO2 (Degussa P-25) and Fe2O3, respectively, under
similar experimental conditions. The effect of various operating
parameters that influence hydrogen yield was then investigated in
detail.
Fig. 1 XRD pattern of Fe3O4.
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Fig. 5 Effect of illumination intensity on hydrogen generation by Fe3O4

(photocatalyst dose ¼ 1 mg per 20 ml, time: 4 h).

Fig. 2 TEM images of Fe3O4.

Fig. 6 Effect of irradiation time on hydrogen generation by Fe3O4

(nano-ferrite) (photocatalyst dose ¼ 1 mg per 20 ml, time: 4 h, illumi-
Fig. 3 UV-Vis diffuse reflectance spectrum (DRS) of Fe3O4.
nation: 200 W  2 tungsten lamps).

Fig. 7 Effect of sacrificial donors on hydrogen generation by Fe3O4

Fig. 4 Effect of photocatalyst dose on hydrogen generation by Fe3O4 (photocatalyst dose ¼ 1 mg per 20 ml, time: 4 h, illumination: 200 W  2
(time: 4 h, illumination: 200 W  2 tungsten lamps). tungsten lamps).

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 View Article Online

Table 1 Hydrogen evolution by nano-ferrites in online system

Hydrogen yield
Time (h) (mmol)

2 0.781055
4 0.320214
6 0.17431
8 0.148829
10 0.043909
12 0.036919
14 0.485318
16 0.205499
18 0.218029
20 0.046384
22 0.316559
24 0.093104
Published on 31 May 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30819C

26 0.051748
28 0.21867
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30 0.019955
Fig. 8 Effect of sacrificial donors on hydrogen generation by Fe3O4
(photocatalyst dose ¼ 1 mg per 20 ml, time: 4 h, illumination: 200 W  2
tungsten lamps).

Fig. 11 Comparison of the different photoreactor systems.

Fig. 9 Effect of temperature on hydrogen generation by Fe3O4 (nano-

ferrite) (photocatalyst dose ¼ 1 mg per 20 ml, time: 4 h, without
illumination).

Fig. 12 Plausible reaction mechanism.

2.3. Effect of various parameters on photocatalytic hydrogen

Fig. 10 Schematic of online (photoreactor system II) system.
generation
2.3.1. Effect of amount of catalyst. The amount of photo-
catalyst used is a vital parameter in all photocatalytic reactions.
The effect of amount of nano-ferrite on photocatalytic hydrogen
evolution was studied in the range of 0.5–10 mg per 20 ml of

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water. The hydrogen yield with respect to varying dose is shown
in Fig. 4. It was observed that initially the photocatalytic activity
increased with increase in the photocatalyst dose up to 1 mg and,
later on, the activity decreased with increase in dose. At a lower
dose, the number of active sites is also lower, resulting into lower
hydrogen evolution. On increasing the dose, initially the
hydrogen evolution increases but if the dose is further increased
then, after travelling a certain distance on an optical path,
turbidity impedes the further penetration of light in the reactor,
indicating the limitation in the light penetration.31 This leads to a
decrease in the hydrogen yield. The optimum photocatalyst dose
was observed to be 1 mg per 20 ml of water.
2.3.2. Effect of co-catalyst. The addition of co-catalyst has
Published on 31 May 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30819C
been one of the modes to enhance the photocatalytic activity of
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semiconductors in hydrogen evolution. Platinum (Pt) has been
studied extensively and has proved to be an efficient co-catalyst.
The metal (Pt) acts as an electron trap for the electron migrating
to the surface, thereby preventing recombination of electrons and
holes, thus consequently enhancing the photocatalytic activity.
The effect of addition of Pt to this reaction system was also
studied. Platinum was added in the form of chloroplatinic acid
which was photo-deposited on the semiconductor surface during
the course of the reaction. It was found that the hydrogen yield
dramatically decreased in the absence of platinum; a yield of
458 mmol h
1 g
1 of photocatalyst was obtained as compared to
8275 mmol h
1 g
1 of photocatalyst in its presence. The amount of
platinum was also varied from 0.013 cm3 (0.095 mg Pt) to
0.052 cm3 (0.285 mg) for 20 cm3 of water. The optimum amount
of platinum was observed to be 0.095 mg. At a higher amount of
platinum, the hydrogen yield decreased. This can be explained on
the basis of the fact that increased amount of metal particles may
reduce the photon absorption. Moreover, the metal may act as
recombination centre for photogenerated electrons and holes
thereby reducing the photocatalytic activity.
2.3.3. Effect of illumination intensity. The effect of illumina-
tion on the catalytic activity of nano-ferrite was investigated. An
experiment was carried out in the dark (without illumination)
while keeping all the experimental conditions unchanged. It was
observed that practically no hydrogen evolution occurred at
ambient temperature in the absence of light. Varying the illu-
mination intensity of the tungsten filament lamps (200 W and
400 W) had an impact on the hydrogen yield. Negligible
hydrogen evolved at 200 W; however the hydrogen yield
increased with increase in the illumination intensity. The
hydrogen evolution rate was observed to be 8.275 mmol h
1
(hydrogen yield of 8275 mmol h
1 g
1) when the illumination
intensity was 400 W. The effect of illumination intensity is as
shown in Fig. 5. It is clearly evident that with the increase in the
illumination intensity, the number of incident photons also
increases. This results in the increase in the conduction band
electrons, increasing the hydrogen yield.
2.3.4. Effect of irradiation time. The photocatalytic hydrogen
evolution by nano-ferrites was studied by varying the irradiation
time. It can be seen from the Fig. 6 that on increasing the irra-
diation time, the hydrogen evolution rate decreases. The
hydrogen evolution rate decreased from 8.275 mmol h
1 of
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photocatalyst to 3.125 and 1.96 mmol h
1 of photocatalyst for an
illumination time of 4 h, 6 h and 8 h, respectively. This decrease
in the hydrogen evolution can be attributed to the exhaustion of
the sacrificial donor. Also, in a batch system a progressive decline
in the hydrogen evolution is observed on increased irradiation
time owing to the backward reactions as well as the pressure
build up in the gas phase.32
2.3.5. Effect of sacrificial donor. The addition of suitable
sacrificial donors or hole scavengers which can react with the
valence band holes and prevent the recombination reaction is
considered as an effective means of increasing the efficiency of
photocatalytic reaction. Initially, three different sacrificial
donors were tested under identical conditions to evaluate the
most effective one in photocatalytic hydrogen evolution (Fig. 7).
The hydrogen yield was in the order of ethanol > methanol >
monoethanolamine. This may be due to the fact that ethanol is
more amenable to oxidation as compared to methanol and
monoethanolamine. In the case of the alcohol–water mixture, H+
is also generated by the interaction of the conduction band holes
with water and alcohol33 as per the following equations:
2h+ + H2O / 2H+ + ½O2 or H+ + _OH
2h+ + C2H5OH / 2H+ + CH3CHO
In addition to water and ethanol, intermediates like acetalde-
hyde could be formed during the course of the reaction leading to
further generation of H+. These H+ are then reduced to H2 by the
electron trapped at metal site. Further studies were hence carried
out with ethanol as sacrificial donor.
2.3.6. Effect of amount of sacrificial donor. The amount of
sacrificial donor was varied with respect to water in order to
optimize the ratio of ethanol : water. The ethanol : water ratio
was varied viz 1 : 10, 1 : 20 and 1 : 40 and the effect on photo-
catalytic hydrogen evolution was studied. It was observed that
the optimum ratio of ethanol : water was 1 : 20 resulting in
hydrogen evolution rate of 8.275 mmol h
1. In the case of 1 : 10
and 1 : 40, the hydrogen evolution rate was 0.715 and 0.7 mmol
h
1, respectively. At a ratio of 1 : 40, a lower amount of sacrificial
donor might be responsible for decreasing the hydrogen evolu-
tion rate while in case of 1 : 10 an increased amount of sacrificial
donor may lead to increase in the evolution of oxygen and other
gases as compared to hydrogen (Fig. 8).
2.3.7. Effect of replenishment of sacrificial donor. One of the
factors responsible for decreased hydrogen yield on prolonged
irradiation time was considered to be the exhaustion of the
sacrificial donor. Moreover, since during the course of the pho-
tocatalytic reaction, the sacrificial donors are consumed, it
becomes imperative to replenish the donor in order to sustain the
reaction. Experiments were carried out wherein the sacrificial
donor was replenished after every 4 h. It was observed that
during the first 4 h (first cycle), the hydrogen evolution rate was
8.275 mmol h
1 followed by 7.431 and 4.366 mmol h
1 for second
and third cycles, respectively. In the fourth cycle, no hydrogen
evolution was observed in spite of replenishment of sacrificial
This journal is ª The Royal Society of Chemistry 2012

donor which could be attributed to the deactivation of catalyst
due to adsorption of various species.
2.3.8. Effect of reaction temperature. Ferrites are usually
reported for thermochemical splitting of water involving high
temperatures. The effect of temperature on the photocatalytic
activity of nano-ferrites was investigated at three different
temperatures (30, 75 and 100  C). The experiments were carried
out in airtight glass vials (photoreactor system III). The optimum
amount of catalyst was added to each of the vials while
remaining parameters were kept constant. The glass vials were
then evacuated and then were heated in a water bath for main-
taining the temperatures. (The system was not illuminated.) The
effect of temperature is as shown in Fig. 9. It was observed that
Published on 31 May 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30819C
practically no hydrogen evolved at 30  C and 75  C in the
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absence of illumination. However, at 100  C the hydrogen
evolution rate was 3.792 mmol h
1. This elucidates the fact that
the reaction is not purely thermochemical in nature and illumi-
nation has a pronounced effect on the hydrogen yield.
2.4. Photocatalytic hydrogen evolution by nano-ferrites
(photoreactor system II or online system)
The manual injection of hydrogen through gas collector in the
case of photoreactor system I is prone to human error. More-
over, the system was not observed to be leak proof which further
led to conservative hydrogen yield. Photocatalytic hydrogen
evolutions were carried out in photoreactor system II wherein the
outlet of the reactor was directly connected to a gas chromato-
graph. The schematic of the online photocatalytic system is as
shown in Fig. 10. The hydrogen evolved was collected periodi-
cally and evaluated every 2 h by online gas chromatograph. The
sacrificial donor was replenished every 10–12 h. The hydrogen
yield is summarized as in Table 1. It was observed that nano-
ferrite was stable up to 30 h and the cumulative hydrogen yield
was 98.79 mmol h
1 g
1 and the rate of hydrogen evolution was
observed to be 98.79 mmol h
1 which is remarkably higher to that
observed in the case of photoreactor I (8.275 mmol h
1). The
photoreactor system II was observed to be reproducible in terms
of hydrogen yield. A similar experiment was carried out at
elevated temperature (85–100  C), keeping all the parameters
constant, and it was observed that there was a nearly threefold
increase in the hydrogen yield. The cumulative hydrogen yield
was 352 mmol h
1 g
1 while the rate of hydrogen evolution was
352 mmol h
1. This underlines the impact of temperature on the
photocatalytic activity of nano-ferrites. However, at elevated
temperature the catalyst was stable only up to 22 h.
2.5. Photocatalytic hydrogen evolution by nano-ferrites
(photoreactor system III or vial system)
As mentioned previously, temperature alone has no effect on the
photocatalytic activity of nano-ferrite and the irradiation of
photons increases the photocatalytic activity of nano-ferrites. To
further substantiate this fact, photocatalytic hydrogen evalua-
tions were carried out in photoreactor system III. It was observed
that the hydrogen evolution rate increased by nearly seven fold.
The hydrogen evolution rate was observed to be 59.55 mmol h
1.
The temperature of the reaction mixture was observed to be
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70–75  C. Since no hydrogen was evolved when the reaction was
carried out at the same temperature in the absence of illumina-
tion, it was concluded that incident photons and temperature had
a synergistic effect leading to enhanced hydrogen yield.
2.6. Comparison of the different photoreactor configurations
It was observed that photoreactor configuration had a
pronounced effect on the hydrogen yield. The reaction condi-
tions like temperature and dilution were seen to vary with respect
to the different reactors which influenced the hydrogen evolution
rate. The hydrogen evolution rate and hydrogen yield in the case
of different reactor configurations are as shown in Fig. 11. It was
observed that the Impinger system represents a photocatalytic
system wherein the hydrogen yield is mostly influenced by irra-
diated photons. The temperature was maintained by water
circulating through the reactor system and hence the influence of
temperature on the photocatalytic reaction was not seen. On the
other hand, in the case of the vial system, the temperature of
the system (85  C) and absence of a cooling system simulate the
hydrothermal conditions in the reactor. The increased tempera-
ture may facilitate the gasification of sacrificial donor aiding
the suppression of recombination reaction. This, in addition to
the irradiated photons, leads to a remarkable increase in the
hydrogen evolution rate. Hence, in case of vials, the system is not
purely photocatalytic but thermo-photocatalytic in nature.
2.7. Plausible reaction mechanism
Most of the reports on hydrogen production by ferrites involve
the thermochemical splitting of water at high temperatures. The
reaction mechanism generally involves a two step reaction
occurring at elevated temperatures as follows:34
Fe3O4 / FeO + 1/2O2
H2O + 3FeO / Fe3O4 + H2
However, in the present investigation the reaction temperature
was observed to be in the range of 75–100  C which is too low for
the mechanism to be solely thermochemical splitting of water.
Moreover, practically no hydrogen evolution was observed at
75  C in the absence of illumination. Hence, it can be concluded
that the reaction is not solely thermochemical but (photo)ther-
mochemical in nature. A possible reaction mechanism (as shown
in Fig. 12) could be:
 On illumination of the catalyst, photons of light fall at the
surface of Fe3O4, resulting in charge separation which in turn
gives rise to valence band holes and conduction band electrons.
 The sacrificial donor (ethanol) helps in suppressing the holes
thereby favouring the forward reaction.
 The conduction band electrons then reduce the proton at the
surface of co-catalyst (Pt) into hydrogen. Increased temperature
of 85–100  C may lead to increased oxidation of alcohol by holes
leading to decrease in recombination reaction with consequent
increase in hydrogen evolution rate of 59.55 mmol h
1 not
reported before for ferrite based systems. The reaction mecha-
nism is similar to that proposed by Douglas and Young for
ferritins involving Fe(O) OH with a bandgap of 2.5–3.5 eV.35
Nanoscale, 2012, 4, 5202–5209 | 5207

3. Conclusions
We discovered extraordinary property of nano-Fe3O4 in photo-
catalytic water splitting to produce hydrogen. It has shown
significantly high photocatalytic activity under visible light
irradiation. The hydrogen evolution rate observed was 8.275
mmol h
1 of photocatalyst as compared to 0.0046 mmol h
1 of
photocatalyst for commercially available iron oxide under
similar experimental conditions. Altering the photoreactor
configuration led to a sevenfold increase in the hydrogen evolu-
tion rate (59.55 mmol h
1). Nano-ferrite was found to be stable up
to 30 h. The cumulative hydrogen evolution rate was observed to
be 98.79 mmol h
1. Temperature was observed to play an
important role in the enhancement of photocatalytic activity of
Published on 31 May 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30819C
nano-ferrites in water splitting reaction in the presence of sacri-
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ficial donor.
4. Experimental section
4.1. Synthesis of nano-ferrites
In 500 cm3 of water, 13.9 g of FeSO4$7H2O and 20 g of Fe2(SO4)3
were dissolved. Ammonium hydroxide (25%) was added slowly
to adjust the pH of the solution to 10. The reaction mixture was
then continually stirred for 1 h and the precipitated nanoparticles
were isolated, washed with water until the pH reached 7, and
then dried under a vacuum at 60  C.
4.2. Characterization
The phase of nano-ferrites was determined by X-ray diffraction
in an MMS X-ray diffractometer with a Cu Ka source in the 2q
range of 10–70. The data were collected with a step of 1 per min.
TEM micrographs were recorded on a Phillips CM 20 TEM
microscope at an operating range of 200 kV. Diffuse reflectance
UV-Vis spectra of nano-ferrite was recorded on Perkin Elmer
spectrophotometer lambda 900 equipped with an integrating
sphere. BaSO4 was used as a reference material.
4.3. Experimental procedure for photocatalytic water splitting
Photocatalytic water splitting experiments were carried out in
three different reactor configurations.
4.3.1. Photoreactor system I (Impinger). The experimental set
up was the same as that employed by Mangrulkar et al.30 The
photocatalytic experiments were carried out in a tubular boro-
silicate glass reactor. 20 cm3 of distilled water was placed in the
reactor and a known amount of photocatalyst, i.e. nano-ferrite,
was added to it. Ethanol was used as a sacrificial agent and a
known amount, i.e. nearly 1 ml, was added to the reaction
solution. A small amount of platinum solution (0.013 cm3) was
added as co-catalyst. A condenser was fitted at the top of the
reactor to which a gas collector was attached for collecting the
evolved gas. The reactor was then evacuated to remove the air in
the headspace above the reaction mixture. The reaction mixture
was continuously stirred to ensure that the photocatalyst was in
suspension. The reaction was carried out for period of 4 h.
Hydrogen evolved was determined by gas chromatography (GC,
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Shimadzu 2014, MS-5A column, TCD detector and nitrogen
carrier gas).
4.3.2. Photoreactor system II (online). 20 ml water was placed
in a tubular borosilicate glass reactor. A known amount of
photocatalyst, i.e. nano-ferrite, was added to it. The ratio of
water : ethanol was maintained at 20 : 1 and 0.0264 cm3 of Pt
solution (H2PtCl6$6H2O) was then added to it. A condenser was
fitted at the top of reactor to maintain the temperature of the
reaction mixture. The system was connected to GC and was
purged with nitrogen at a rate of 40 ml min
1 in order to ensure
an inert atmosphere. The reaction mixture was continuously
stirred to ensure that the photocatalyst was in suspension. The
system was then illuminated under artificial radiation (tungsten
filament bulb) for a desired period of time. The hydrogen
produced was directly analyzed on a GC-TCD without a gas
collector in between.
4.3.3. Photoreactor system III (vials). 10 ml water was placed
in a borosilicate glass vial and to it a known amount of photo-
catalyst was added. Ethanol was added as sacrificial donor. The
ratio of water : ethanol was maintained at 20 : 1. To it 0.013 cm3
of Pt solution (H2PtCl6$6H2O) was then added. The vial was
quickly sealed with aluminium crimp with the aid of a crimper.
The system was then properly evacuated and was illuminated
under artificial radiation (tungsten filament bulb) for a desired
period of time. The reaction mixture was continuously stirred to
ensure that the photocatalyst was in suspension. The hydrogen
produced was analyzed on a GC-TCD.
Acknowledgements
Financial support from the CSIR-Network projects NWP0022
and NWP-56 is greatly acknowledged. One of the authors, Priti
A. Mangrulkar, would also take the opportunity to sincerely
acknowledge the Council of Scientific and Industrial Research
(CSIR) India for granting the Senior Research Fellowship. The
authors would also like to thank Director, CSIR-NEERI for
providing research facilities.
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