The Effect of Band Engineering of Semiconductors On Photocatalyic Water Splitting
The Effect of Band Engineering of Semiconductors On Photocatalyic Water Splitting
The Effect of Band Engineering of Semiconductors On Photocatalyic Water Splitting
School of Chemical Engineering, UniversitiSains Malaysia, Engineering Campus, Seri Ampangan, 14300 NibongTebal,
Pulau Pinang, Malaysia, [email protected]
Abstract
The direct conversion of solar energy using a photocatalyst in a water splitting reaction is a source of a sustainable and clean
hydrogen supply. In general, photocatalysts are semiconductors that possess valence and conduction bands. These energy bands
permit the absorption of photon energy to excite electrons in the outer orbitals of the photocatalysts. Photoexcited electron and hole
pairs can subsequently induce a watersplitting reaction to produce hydrogen and oxygen. Photocatalytic water splitting is affected by
the band level and crystallinity of the photocatalyst. Therefore, band engineering using chemical modifications such as cationic and
anionic modification could createa photocatalyst suitable for the large-scale production of hydrogen. In this paper, cationic and
anionic modifications of photocatalysts and the effects of these modifications onphotocatalytic water splitting are reviewed.
Energy Level
Conduction Band
0V
1.23V
Valence Band
Fig.1.Energy structure of an effective photocatalyst
for the overall water splitting reaction
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
195
2. CATIONICMODIFICATION
Transition metals are predominantly used to modify the band
structure of a semiconductor. Examples of cationic additives
include Bi, Mo, Au, Rh, Zr, Pt, Ru, Cr, Ni, V, Fe, La, In and
Ce. TiO2is the most popular photocatalyst and has been widely
modified by various cautions. A cocatalyst and dopants are
incorporated into TiO2 rutile and anatase phase to narrow the
TiO2 band gap, extending the absorption edge from the UV to
visible light region. The Bi-dopedTiO2studied by Naik et al. is
one example of a d10 cationic dopants for TiO2[2]. This nano
composite was synthesized using a soft chemical template free
homogeneous co-precipitation method. A mesoporous
compound formed with a significant red shift in the absorption
edge was formed, indicating its capability of absorbing more
lights with a longer wavelength. After calcination at 400C,
4.3% of the apparent quantum efficiency was achieved at198.4
mol/h of H2. TiO2 films doped with Mo were prepared by Li
et al. using the layer-by-layer method [3]. Optimum Mo
doping enhanced the transformation from the anatase to the
rutile phase and reduced the surface oxygen vacancies that
could promote recombination of the photo induced charges.
The doped TiO2 exhibited photocatalytic activity 3.3 times
higher than the bare TiO2 because the introduction of Mo6+
resulted in a red shift of the absorption edge to the visible
region.
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
196
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
197
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
198
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
199
3. ANIONIC MODIFICATION
In general, oxide photocatalysts possess a large band gap that
is unresponsive to visible light irradiation. (Oxy)nitride
photocatalysts, however, have a narrower band gap and are
responsive to visible light irradiation. The valence band of an
(oxy)nitride photocatalyst consists of a N2p orbital that has a
lower potential than the valence band of the oxide
photocatalyst that is normally formed by the O2p orbital [54].
An (oxy) nitride photocatalyst, therefore has a broader
absorption band in the visible region. Nevertheless, compared
with an oxide photocatalyst, an (oxy)nitride photocatalyst is
typically not thermally stable and undergoes photo corrosion.
Several types of (oxy)nitride photocatalyst that have been
under extensive research recently include GaN, GeN,
perovskiteoxynitride, N-TiO2 and TaON, and these are
discussed in the following section.
Arai et al. demonstrated the preparation of GaN from Ga2S2
using nitridation in a NH3 flow at 1273K for 15 hours [55].
The GaN formed was only active in the UV region. However,
doping divalent ions such as Zn2+, Mg2+ and
Be2+couldtransformGaNinto a visible light responsive material
with high photocatalytic water splitting activity, and further
enhancement could be achieved if RuO2was present as a cocatalyst. Doping with a divalent ion was observed to increase
the concentration and mobility of the holes. An N-doped GaO
and ZnO solid solution was also studied by Parida et al.[56].
Prepared from a solid state reaction, the GaO-ZnO was added
to different nitrogen precursors such as urea, glycine,
hexamine and pyridine. N-doping reduced the band gap from
4.1 to 2.6 eV and extended the absorption band further into the
visible light region. An apparent quantum efficiency of 5.1%
by visible light irradiation was achieved using glycine as the
N-precursor. Kamata et al. added Into the oxynitride
photocatalyst to form Ga-Zn-In oxynitride[57]. The absorption
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
200
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
201
CONCLUSIONS
Cationic and anionic modification of semiconductors is
successfully employed in band engineering using different
types of preparation methods such as hydrothermal, solid state
reactions and polymerized complex methods for the purpose
of improving the photocatalytic water splitting reaction.
Enhanced hydrogen evolution has been achieved by
broadening absorption of the light wavelength, efficient
charge separation and the formation of a new band level to
facilitate the mechanism of the water splitting reaction. This
review also indicates the trend of utilizing visible light
irradiation in the water splitting reaction. Although the
hydrogen rate is not yet comparable to that of UV light
irradiation, visible light sensitive photocatalysts have greater
potential because solar irradiation mostly consists of the
visible spectrum. Further research should be performed
concerning various strategies to enable a hydrogen economy
to be realized as soon as possible before irreversible damage
done onto environment by a fossil fuel based economy.
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
202
ACKNOWLEDGMENTS
The authors wish to express appreciation to theMyBrain
15Programme, USM Short Term Grant (Grant No. 60311051)
for the financial support provided.
REFERENCES
[1] Fujishima A, Honda K. Electrochemical photolysis of
water at a semiconductor electrode. Nature 1972;238:3738.
[2] Naik B, Martha S, Parida KM. Facile fabrication of
Bi2O3/TiO2-xNx nanocomposites for excellent visible light
driven photocatalytic hydrogen evolution. International
Journal of Hydrogen Energy 2011;36:27942802.
[3] Li C, Zhang D, Jiang Z, Yao Z, Jia F. Mo-doped titania
films: preparation, characterization and application for
splitting water. New Journal of Chemistry 2011;35:423429.
[4] Lin HY, Chang YS. Photocatalytic water splitting for
hydrogen production on Au/KTiNbO5. International Journal of
Hydrogen Energy 2010;35:84638471.
[5] Lunawat PS, Kumar R, Gupta NM. Structure sensitivity of
nano-structured CdS/SBA-15 containing Au and Pt cocatalysts for the photocatalytic splitting of water.
CatalysisLetter 2008;121:226233.
[6] Feil AF, Migowski P, Scheffer FR, Pierozan MD, Corsetti
RR, Rodrigues M, et al. Growth of TiO2 nanotube arrays with
simultaneous Au nanoparticles impregnation: photocatalysts
for hydrogen production. Journal of Brazilian Chemical
Society 2010;21:13591365.
[7] Chiarello GL, Selli E, Forni L. Photocatalytic hydrogen
production over flame spray pyrolysis-synthesised TiO2 and
Au/TiO2. Applied Catalysis B: Environment 2008;84:332339.
[8] Rosseler O, Shankar MV, Du MKL, Schmidlin L, Keller N,
Keller V. Solar light photocatalytic hydrogen production from
water over Pt and Au/TiO2(anatase/rutile) photocatalysts:
influence of noble metal and porogen promotion. Journal of
Catalysis 2010;269:179190.
[9] Chen JJ, Wu JCS, Wu PC, Tsai DP. Plasmonic
photocatalyst for H2 evolution in photocatalytic water splitting.
The Journal of Physical Chemistry C 2011;115:210216.
[10] Hisatomi T, Maeda K, Takanabe K, Kubota J, Domen K.
Aspects of the water splitting mechanism on (Ga1-xZnx)(N1-xOx)
photocatalyst modified with Rh2-yCryO3 cocatalyst. The
Journal of Physical Chemistry C 2009;113:2145821466.
[11] Hisatomi T, Miyazaki K, Takanabe K, Maeda K, Kubota
J, Sakata Y, et al. Isotopic and kinetic assessment of
photocatalytic water splitting on Zn-added Ga2O3
photocatalyst loaded with Rh2-yCryO3 cocatalyst. Chemical
Physics Letter 2010;486:144146.
[12] Kumagai N, Ni L, Irie H. A visible-light-sensitive water
splitting photocatalyst composed of Rh3+ in a 4d6 electronic
configuration,
Rh3+-doped
ZnGa2O4.
Chemical
Communications 2011;47:18841886.
[13] Ma R, Kobayashi Y, Youngblood WJ, Mallouk TE.
Potassium niobate nanoscrolls incorporating rhodium
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
203
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
204
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
205
__________________________________________________________________________________________
Volume: 02 Issue: 11 | Nov-2013, Available @ http://www.ijret.org
206