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Procedia Engineering 45 (2012) 993 – 997

2012 International Symposium on Safety Science and Technology

Application of photocatalytic technology in environmental safety
JIANG Lijuan, WANG Yajun*, FENG Changgen
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China

Abstract

With the environmental safety becoming the research focus, water environmental security, as an updating research direction has also been
the concern. Nano-titania photocatalysis can prevent environmental pollution from the sources and ensure the fundamental productions in
the industry. The applications of nano particle photocatalytic technology in environmental safety are reviewed. Emphasis is put on the
applications of nano-titania photocatalytic technology in wastewater treatment, and the latest achievements in scientific research of nano
particle photocatalytic technology in wastewater treatment are given. Besides, it is also pointed out that the technology of using nano-
titania as photocatalyst has some obvious disadvantages in the actual treatment process of environmental safety. Lastly, the development
trend of photocatalytic technology is discussed.

© 2012 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of the Beijing Institute of
Technology. Open access under CC BY-NC-ND license.

Keywords: environment safety; photocatalysis; nano-titania; wastewater treatment

Nomenclature
K constant
k constant of reaction rate (min-1)
C concentration of reactant (g/L)
C0 the initial concentration of reactant (g/L)
Kapp apparent first-grade reaction kinetics constant (min-1)
t response time (min)
r reactant reaction rate (g L-1 min-1)

1. Introduction

Environmental expert Lester R. Brown is the first person who introduced safety concept into the environment in 1977 [1].
In 1988, the United Nations environment programme put forward the concept of environmental safety [2]. Environmental
safety has both narrow and broad concepts. The narrow concept of environment safety is the harmful effects of people’s
health caused by the environmental pollution and damage, and the broad one refers to human and national survival
development free from environmental pollution and persecution [3]. With the environmental safety becoming the research
focus, water environmental safety, as an updating research direction, has also been the concern. Many researchers thought
water environment safety refers to water pollution problems. The problem of the water environment from pollution and
contamination by various types of discharges (such as heavy metals, dyes, pesticides) is now the focus of attention all over
the world.

* Corresponding author. Tel./fax: +86-10-68912941.

E-mail address: yajunwang@bit.edu.cn

1877-7058 © 2012 Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
doi:10.1016/j.proeng.2012.08.271
994 JIANG Lijuan et al. / Procedia Engineering 45 (2012) 993 – 997

Although various methods (such as microorganism method, adsorption method, ion exchange method) have been used to
treat sewage, the application of these methods is restricted due to high cost, poor degradation efficiency, second-pollution
and complicated technology. Photocatalysis is a kind of chemical method, which appears to be quite promising because of
its simplicity, low cost, nontoxic, high degradation efficiency, and excellent stability. Semiconductor photocatalysis is a new
method of sewage treatment which was developed in 1972 [4]. It has been received much attention as a potential solution to
the wastewater treatment and stop the deterioration of the environment.

2. Photocatalysis mechanism

The catalytic activity of TiO2 originates from its electronic structure and photoelectric characteristics. The band theory
can be used to explain the photocatalytic reaction principle [5]. TiO2 has a band gap which consists of valence band and
conduction band, and the band gap energy is 3.2 eV. When the surface of TiO2 is irradiated with light which is equal to or
greater than the band gap energy of TiO2, its surface will be stimulated and produce hole-electronic pair, which has the
ability of oxidation and reduction [6]. Expression is as equation (1).

TiO2+hv e-+h+ (1)

The produced h+ can oxidize OH- and H2O on the surface of TiO2 to OH, and OH can almost oxidize all pollutants
adsorbed on the surface of TiO2 [7]. Theoretically speaking, any metal ions whose reduction potential is more positive than
the edge of TiO2’s conduction band can be reduced by e-. The process of photocatalysis is shown as Fig 1 [8].

Fig. 1. The process of photocatalysis

Photocatalytic mechanism is that: (1) Formation of charge carriers by a photon; (2) Charge carrier recombination to
liberate heat; (3) Initiation of an oxidative pathway by a valence-band hole; (4) Initiation of a reductive pathway by a
conduction-band electron; (5) Further thermal (e.g., hydrolysis or reaction with active oxygen species) and photocatalytic
reactions to yield mineralization products; (6) Trapping of a conduction-band electron in a dangling surficial bond to yield
Ti(III); (7) Trapping of a valence-band hole at a surficial titanol group.
At present, photocatalytic reaction kinetics is generally described by a classic model Langmuir-Hinshelwood
adsorption kinetic model [9]. The expression is as equation (2).

r=dC/dt=kKC/(1+KC) (2)

where, r is catalytic reaction rate, C is mass concentration, t is reaction time, k is photocatalysis reaction rate constant, K is
Langmuir adsorption constant.
When C «1, the equation can be simplified as:

lnC0/C=kKt=Kappt (3)

where, Kapp is apparent first-order kinetics rate constant, C0 is the initial concentration of pollutants.

3. Application of photocatalysis in wastewater treatment

The problem of wastewater from pollution and contamination by various types of discharges is now the focus of attention
all over the world. As a potential technology to solve the energy crisis and control environmental pollution, photocatalysis
has been studied widely in recent years. The main application areas in catalysis are photocatalytic electrolysis of water,
environmental protection, solar cells, storage equipment and so on, especially the application in wastewater treatment. The
pollutants in waste water can be divided roughly into organic pollutants and inorganic pollutants.
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3.1. Photocatalytic degradation of organic pollutants

Organic pollutants such as dye, pesticide, pharmaceutical waste, exist widely in wastewater, which are very harmful to
the biological safety and ecological system. Especially toxic and difficultly degradable organic pollutants (such as heavy
metal pollutants, dye, pesticide) have a long half-life, and only trace can lead to biological variation [10]. TiO2
photocatalysis, as a green catalytic technology, can almost degrade all organic pollutants without selection. Studies show
that more than 3 000 kinds of difficultly degradable organic compounds can be degraded by TiO2 photocatalytic technology.
The applications of TiO2 photocatalytic degradation of organic pollutants in wastewater is shown in Table 1.

Table 1. TiO2 photocatalytic degradation of organic pollutants

Wastewater type Pollutant Catalyst Ref.

Methyl orange Y-TiO2-HPW [11]
Alkaline red dye TiO2-Fenton [12]
Dye wastewater
Rhodamine 6G TiO2 [13]
Anthraquinone dye N-TiO2 [14]
Amoxicillin
TiO2 [15]
Penbritin
Pharmaceutical wastewater
Cloxacillin
TiO2 [16]
Oxolinic acid
Kappa furan pesticides TiO2 [17]
Armour mix phosphorus TiO2 [18]
Pesticide wastewater
Alon TiO2-SBA [19]
Organophosphorus pesticide TiO2 [20]
TNT
Explosives wastewater RDX TiO2 [21]
HMX
Chlorine hydroxybenzene wastewater Chlorinated phenol TiO2 [22]
Nitrobenzene wastewater Nitrobenzene H3PW12O40/TiO2 [23]

From the late 1960s, the application research of TiO2 photocatalytic degradation of organic pollutants is always a
fascinating field. The degradation of many different model compounds has been studied and it has been clearly shown that
most of the organic pollutants present in water can be fully decomposed.

3.2. Photocatalytic removal of inorganic pollutants

The inorganic wastewater pollutants mainly include heavy metal pollutants, cyanide-containing waste, NO2--containing
waste, and so on. Photocatalytic removal of inorganic pollutants usually has two kinds of mechanism: photocatalytic
reduction and photocatalytic oxidation [24]. Heavy metal ions mainly come from waste water discharge of manufacture
leather, metallurgical industry and electroplate factory, which have characteristics such as toxic, long half-life, vivo
enrichment, difficult to degrade, etc. The applications of TiO2 photocatalytic removal of inorganic pollutants in wastewater
is shown in Table 2.
Currently more research on photocatalytic treatment of heavy metal pollutants in effluent is focused on the removal of
Hg(II), Pb(II), Cr(VI) [25,29]. The photocatalytic mechanism is as equation (4) (Mn+ represents metal oxide, and M
represents the photocatalysis product).

Mn++e- M (4)

Cyanide (especially free cyanogen root) is also severely poisonous, mainly coming from metallurgy industry, especially
gold mines, electroplating industry and other corresponding chemical industry. The cyanide emission has increased in those
fields recently. TiO2 photocatalysis can effectively reduce poisonous substances CN- to CO2 or CO32- and nontoxic N2 [27].
The reaction is as equation (5).
996 JIANG Lijuan et al. / Procedia Engineering 45 (2012) 993 – 997

Table 2. TiO2 photocatalytic removal of inorganic pollutants

Wastewater type Pollutant Catalyst Mechanism Ref.

Hg(II) TiO2 [25]
Photoreduction
Cr(VI) ZrO2 [26]
Heavy metal pollutants
Mn(II)
TiO2 Photooxidation [24]
Ti(I)
Cyanide-containing waste CN- TiO2 Photooxidation [27]
-
NO2 -containing waste NO2- Fe3+/TiO2/SiO2 Photooxidation [28]

CN-+1/2O2+h+ [OCN-] CO2(CO32-)+1/2N2 (5)

NO2- is a dangerous environment pollutant which can cause cancer; especially low concentration NO2- is more stable, and
not easily decomposed. The research on photocatalytic treatment of NO2- in water has been a large amount of relevant
reports [28,30-32]. It is the photocatalytic reactions premise step that NO2- is adsorbed in the surface of the catalyst. The
expression is as equation (6).

NO2-+h+ NO3- (6)

4. Conclusions

TiO2 photocatalysts become widely used to treat effluent in the field of water environmental safety, for that it possesses
many merits such as high photocatalytic activity, excellent stability, harmless to human beings, low cost and so on.
However, the application of TiO2 photocatalysis is restricted due to the poor quantum efficiency and the fact that it could
only absorb the UV light which is just 4% of sunlight. The developing directions of photocatalysis are seeking catalysts with
higher catalytic performance, expanding the light responding range of photocatalysts. To solve these problems, many
methods, including noble metal deposition, coupled semiconductor, ion modification, were proposed to enhance the
photocatalysis efficiency and optimize their energy band configurations for specific applications. Besides, based on
photocatalytic reactions with redox reaction occurring simultaneously, we can design reasonable photocatalytic reaction
systems, to simultaneously photocatalytic treat two or more pollutants.

Acknowledgements

This research was funded by the Basic Research Foundation of Beijing Institute of Technology, China under Grant No.
20110242020.

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