204 J. Adv. Oxid. Technol. Vol. 18, No. 2, 2015 ISSN 1203-8407 © 2015 Science & Technology Network, Inc.
The Photocatalytic Performance of Benzene- Modified TiO
2
Photocatalysts under UV-vis Light Irradiation
Ewelina Kusiak- Nejman*, Agnieszka Wanag, Łukasz Kowalczyk, Beata Tryba, Joanna Kapica-Kozar,
Antoni W. Morawski
West Pomeranian University of Technology, Szczecin, Institute of Chemical and Environment Engineering,
Pułaskiego 10,70-322 Szczecin, Poland
Abstract:
In this study a photocatalytic performance of new carbon-modified titanium dioxide photocatalysts was discussed.
Benzene was used as carbon precursor. It was found that the photocatalytic activity of obtained samples increases
with the increase of modification temperature and decrease of carbon concentration present in TiO
2
/C samples.
This could be related to the kind of interactions between TiO
2
surface and carbon from thermal decomposition
of benzene. The higher calcination temperature the less carbon deposits on the surface of modified samples and
the higher probability of the Ti and C interaction confirmed by means of UV-vis/DR studies. It was proved that
the photocatalytic activity of carbon modified titania nanomaterials strongly depends on carbon content in
TiO
2
/C photocatalysts. Modification of starting TiO
2
with benzene is a promising method especially by taking
into account the mineralization of phenol and the co-products of its degradation.
Keywords: photocatalysis, carbon-modified TiO
2
, benzene precursor, phenol photodegradation, UV-vis light
Introduction
Among various semiconductors, TiO
2
is widely
known as the most useful photocatalyst because of its
special optical and electronic properties, low cost,
chemical stability and nontoxicity. However, because
of its large band gap of 3.20 eV only the small
fraction (UV) of solar light (about 2-3%), can be
utilized. In order to increase the efficiency of photo-
catalytic processes in the presence of titanium dioxide
many studies have been carried out. There are many
ways to improve TiO
2
properties and one of them is
carbon modification. This process can be carried out
with several methods (1): heating or combustion of
Ti/TiO
2
in a carbonaceous gas atmosphere, pyrolysis
of precursors containing Ti and carbon or carbonization
of different carbonaceous species deposited on the
surface of TiO
2
.
For this purpose many of the carbon precursors
can be used, such as: n-hexane (2-4), poly(vinyl
alcohol) or poly(ethylene terephthalate) (5-9), citric
acid (10), cellulose (11-12), glucose (13), sucrose
(14-15), poly(divinylbenzene) (16) and formaldehyde
polymers (17-20). Commonly used method to
introduce carbon into TiO
2
lattice is thermal treatment.
Khan et al. (21) used for this purpose combustion of
Ti metal sheet in a natural gas flame with controlled
amounts of oxygen. Thereby obtained reduction of
the energy gap to 2.3 eV. Whereas other researchers
*Corresponding author; E-mail: Ewelina.Kusiak@zut.edu.pl
used combustion of Ti precursors with various fuels
(22-24). Thanks to that it was possible to obtain
photocatalyst able to be activated in visible light
region and 3-times more efficient in phenol
degradation under solar light irradiation compared to
commercial TiO
2
P25. Thermal treatment was also
applied by Hahn et al. (25), to receive C/TiO
2
photo-
catalyst able to absorb whole range of visible light.
They used acetylene as a carbon precursor. Carbon
can be also added to TiO
2
by heating TiO
2
or its
precursors in the vapour of cyclohexane (26), ethanol
(27-29) or with other alcohols (30-35). Carbon-doped
titania obtained this method (26) has much better
photocatalytic activity for gas-phase photo-oxidation
of benzene under irradiation of artificial solar light
than pure titania. The photocatalytic activity in azo
dyes decomposition of modified P25 (29) was two
times higher than for unmodified P25. Moreover,
after the process such prepared photocatalysts showed
better sedimentation and filtration. It is due to the
change of their surface character from hydrophilic to
hydrophobic (27). Modified TiO
2
photocatalysts were
also used for NO
x
oxidation in air (34). The experi-
mental results showed that up to 70% of NO
x
could
be oxidized in a continuous flow type reaction system
under irradiation with visible light. Other researchers
modified TiO
2
by calcinations of hydrolysis product
from Ti precursors and heat treatment with urea and
thiourea (36-38) or tetrabutylammonium hydroxide
(39-42). These studies showed that carbon addition to
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