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S0043-1354(15)30257-8
DOI:
10.1016/j.watres.2015.09.045
Reference:
WR 11553
To appear in:
Water Research
28 September 2015
Please cite this article as: Lee, K.M., Lai, C.W., Ngai, K.S., Juan, J.C., Recent Developments of Zinc
Oxide Based Photocatalyst in Water Treatment Technology: A Review, Water Research (2015), doi:
10.1016/j.watres.2015.09.045.
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Kian Mun Leea,*, Chin Wei Laia, Koh Sing Ngaic, Joon Ching Juana,b,*
Malaysia
Ehsan, Malaysia
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Nanotechnology & Catalysis Research Centre (NANOCAT), 3rd Floor, Block A, Institute of Postgraduate
School of Science, Monash University, Sunway Campus, Jalan Lagoon Selatan, Bandar Sunway 46150,
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Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul
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Abstract
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Today, a major issue about water pollutions is the residual dyes from different sources (e.g.,
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textile industries, paper and pulp industries, dye and dye intermediates industries,
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pharmaceutical industries, tannery and craft bleaching industries, etc.), and a wide variety of
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persistent organic pollutants have been introduced into our natural water resources or
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wastewater treatment systems. In fact, it is highly toxic and hazardous to the living organism;
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thus, the removal of these organic contaminants prior to discharge into the environment is
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essential. Varieties of techniques have been employed to degrade those organic contaminants
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and advanced heterogeneous photocatalysis involving zinc oxide (ZnO) photocatalyst appears
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to be one of the most promising technology. In recent years, ZnO photocatalyst have attracted
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much attention due to their extraordinary characteristics. The high efficiency of ZnO
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minimizes electron loss during excitation state and maximizes photon absorption. In order to
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further improve the immigration of photo-induced charge carriers during excitation state,
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considerable effort has to be exerted to further improve the heterogeneous photocatalysis
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under UV/visible/solar illumination. Lately, interesting and unique features of metal doping
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or binary oxide photocatalyst system have gained much attention and became favourite
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research matter among various groups of scientists. It was noted that the properties of this
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metal doping or binary oxide photocatalyst system primarily depend on the nature of the
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preparation method and the role of optimum dopants content incorporated into the ZnO
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photocatalyst. Therefore, this paper presents a critical review of recent achievements in the
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Table of Contents
1.1
Properties of ZnO
1.2
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Anionic dopant
2.2
Cationic dopant
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2.3
2.4
Co-dopant
2.5
Couple semiconductor
ZnO loading
3.2
ZnO structure
Substrate concentration
3.4
Solution pH
3.5
Light intensity
3.6
Light wavelength
3.7
Temperature
3.8
Inorganic spesies
4.1
Phenolic compounds
4.2
4.3
Dyes
ZnO photocorrosion
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References
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1.0 Introduction
Today, solar energy, radiant light and heat from the sun, is the most abundant clean
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energy source available. Despite the fact that solar energy strikes our earth in an hour is
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relatively higher than energy consumed by humans for entire year (Lewis 2007). Thus,
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extensive research studies and development of materials that can efficiently harvest solar
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irradiation and used it for green environmental pollution management are essential. In this
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manner, photocatalysis which utilizes our renewable solar energy to activate the chemical
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reactions via oxidation and reduction is a sustainable technology to provide solution for
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environmental issue (Kudo and Miseki 2009). This photocatalysis system has attracted great
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interest from science community as the most promising way to solve the environmental
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problems, especially getting rid of residual dyes pollutants from wastewater stream.
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which must be at least two reactions occurring simultaneously, the first reaction involving
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oxidation, from photo-induced positive holes, and the second reaction involving reduction,
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from photo-induced negative electrons (Fujishima et al. 2008). Several types of promising
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photocatalyst, such as titanium dioxide (TiO2), Zinc oxide (ZnO), Iron(III) oxide (Fe2O3),
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Zirconia (ZrO2), Vanadium(V) oxide (V2O5), Niobium pentoxide (Nb2O5) and tungsten
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trioxide (WO3) have been actively applied in environmental waste management system
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In the field of photocatalysis today, ZnO has emerged as the leading candidate as an
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efficient and promising candidate in green environmental management system because of its
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unique characteristics, such as direct and wide band gap in the near-UV spectral region,
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strong oxidation ability, good photocatalytic property, and a large free-exciton binding
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energy (Janotti and Van de Walle, 2009, Reynolds et al., 1999 and Chen et al., 1998) so that
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excitonic emission processes can persist at or even above room temperature. It is a well-
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known fact that ZnO occurs as white hexagonal crystal or white powder known as zinc white.
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ZnO crystallizes in the wurtzite structure (Figure 1), the same as GaN, but, in contrast, ZnO is
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available as large bulk single crystals (Reynolds et al., 1996). Besides, it is odourless, has a
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bitter taste and insoluble in water. As an important semiconductor material, ZnO has been
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applied in catalysis (King and Nix, 1996), rubber and paint industries, ceramic bodies,
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varistors, fertilizers and in cosmetics (Porter, 1991). However, an obvious hindrance to the
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widespread use of ZnO as a photoelectrode is ZnO exhibited lack of control over its electrical
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conductivity due to the n-type of ZnO crystals, which has been a matter of extensive debate
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and research (Janotti and Van de Walle, 2009, Ogale, 2005, Nickel and Terukov, 2005 and
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Look, 2001). Thus, development of the ZnO with precisely controllable nanoscale features
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photocatalysis, principally on ZnO and modified ZnO, that there is a host of possible
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photochemical, chemical and electrochemical reactions that can occur on the photocatalyst
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surface (Vinu and Madras, 2010). Clearly, with so many varied aspects, photocatalysis is
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summarize an overview of some of the more fundamental aspects, which are in their own
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right extremely scientifically interesting and which also need to be better understood in order
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This review manuscript will be divided into several sections: 1. Introduction of ZnO; 2.
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Strategies
to
improve
ZnO
photodegradation
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efficiency;
3.
Factors
affecting
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ZnO is a wide band-gap semiconductor with large exciton binding energy of 60 meV at room
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temperature (Janotti and Van de Walle, 2009 and Peng et al., 2006). The electrical, optical
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and magnetic properties of ZnO can be altered or improved by the use of ZnO in nanoscale
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itself nicely to a broad range of daily applications that will not leave any risks to human
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health, and environmental impacts (Schmidt-Mende and MacManus-Driscoll, 2007). ZnO has
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pollutants (Anandan et al., 2010, Hasnat et al., 2007 and Peternel et al., 2007). Since ZnO has
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almost the same band gap energy as TiO2 (3.2 eV), its photocatalytic capability is anticipated
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to be similar to that of TiO2. Moreover, ZnO is relatively cheaper compared to TiO2 whereby
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the usage of TiO2 are uneconomic for large scale water treatment operations (Daneshvar et
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al., 2004). The greatest advantage of ZnO is the ability to absorb a wide range of solar
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spectrum and more light quanta than some semiconducting metal oxides (Behnajady et al.,
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2006). The major drawbacks of ZnO are the wide band gap energy and photocorrosion. The
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light absorption of ZnO is limited in the visible light region which is due to its wide band
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energy. This results in fast recombination of photogenerated charges and thus caused low
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ZnO has well-defined crystal structures which are commonly in rocksalt, wurtzite or cubic
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(zinc blende) structure. A rocksalt structure of ZnO can be yielded under high pressure thus
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ZnO in this structure is quite rare. The ZnO wurtzite structure has the highest thermodynamic
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stability among the three structures. It is the most common structure of ZnO (Dubbaka, 2008,
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zgr et al., 2005 and Wang, 2004). ZnO has a hexagonal wurtzite crystal structure at
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ambient pressure and temperature, with two lattice parameters, a and c, values of 0.3296 nm
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and 0.52065 nm, respectively (Dubbaka, 2008 and Baruah and Dutta, 2009). This ZnO
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hexagonal wurtzite space grote structure belongs to the P63mc space group and exhibits a
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(Moore and Wang, 2006). Non-centrosymmetric structure of ZnO is the condition at where
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the space groups lack inversion centre (Maggard et al., 2001). Figure 1 exhibits the unit cell
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of rocksalt, zinc blende and wurtzite structures of ZnO (Morko and zgr, 2009).
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It could be observed that the wurtzite ZnO consists of atoms forming hexagonal-close-
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pack sub-lattices which will stack alternatively along the c-axis (Erhart and Albe, 2006). In
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this case, each Zn2+ sub-lattice contains four Zn2+ ions and surrounded by four O2- ions and
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vice versa, coordinated at the edges of a tetrahedron (Jagadish and Pearton, 2006). This
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tetrahedral coordination will form polar symmetry along the hexagonal axis which induces
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the effect of piezoelectricity and spontaneous polarization in the ZnO wurtzite crystal (Kong
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and Wang, 2003 and Hughes and Wang, 2004). The polarization effect is one of the major
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factors influencing the crystal growth during the synthesis process of ZnO nanostructures
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(Wang, 2004). Figure 1 presents the shaded grey and black spheres denote Zn and O atoms,
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respectively.
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Typically ZnO has a relatively low hardness ranged from 4 to 5 GPa at different
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indentation (Fang et al., 2007 and Kucheyev et al., 2002). This value has to be taken into
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consideration during the processing and designing of ZnO devices. Indentation to the ZnO
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structure will result in significant quenching of excitonic luminescence (Zhang et al., 2014c).
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The crystal orientation of ZnO as seen previously also results in different mechanical
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properties. The a-axis oriented bulk ZnO has lower hardness which is 2 GPa compared to c-
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axis oriented ZnO (Zhang et al., 2014c and Jian et al., 2008). From the aspect of epitaxial
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ZnO, studies have shown that the epitaxial ZnO grown on sapphire has higher hardness than
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the bulk ZnO (Hwang et al., 2007). The hardness is 5.75 GPa for c-axis epitaxial layers
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ZnO has a direct band-gap of 3.37 eV and a large exciton binding energy of 60 meV at
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room temperature with good electro-optical properties and high electrochemical stability (Lu
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et al., 2006 and Tan et al., 2005). The ZnO is very stable chemically, thermally and also
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under high energy radiation (Lu et al., 2006, Tan et al., 2005, Liu et al., 2010, and Rodnyi
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and Khodyuk, 2011). The n-type ZnO semiconductor has wide direct band gap, higher
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electron mobility, high breakdown voltages, and higher breakdown field strength (Liu et al.,
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2010, Rodnyi and Khodyuk, 2011 and Umar, 2009). The optical and electrical properties of
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single crystal wurzite are presented in Table 1. In this manner, ZnO has been used
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specifically in high powered electronic devices such as for field emission devices due to its
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excellent electrical devices. In addition, modified ZnO has also been used for transparent
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generated electron and hole pairs in ZnO would produce UV/blue light (Rodnyi and
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Khodyuk, 2011 and Umar, 2009). Thus, ZnO has been used for short wavelength
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optoelectronics such as UV/blue light emitter applications (Lu et al., 2006). Table 1 shows
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the optical and electrical properties of single crystal wurzite. (Adapted and modified from
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The luminescence properties of ZnO can be characterized using photoluminescence (PL).
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Typical PL spectra exhibited by ZnO nanostructure consist of two regions, which are the UV-
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emission region and broad visible emission (Wang et al., 2007 and Hong et al., 2008b). In
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this case, UV emission which is also termed as deep level emission is attributed to the
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(Hullavarad et al., 2009 and Sharmaa et al., 2010). If the ZnO is highly crystalline, then the
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UV emission would be very high (Hullavarad et al., 2009). The origin of the green band in
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the visible region in ZnO is attributed to various impurities and defects (Morko and zgr,
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2009). The visible emission could be related to the recombination of electrons with oxygen
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vacancies and with photoexcited holes in the valence band and hence its increase in intensity
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Lattice dynamics of a single crystal wurtzite ZnO can be measured by using Raman
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spectroscopy analysis. In a perfect wurtzite ZnO crystal, the 4 atoms per unit cell will
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correspond to 12 phonon modes. The modes are one longitudinal-acoustic (LA), two
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branches. Table 2 presents the most common Raman modes depicted by various authors on
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the value obtained from single crystal wurtzite ZnO at room temperature (Jagadish and
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Pearton, 2006).
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and specific heat (Jagadish and Pearton, 2006). Thermal expansion coefficient of a material is
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the lattice deformation as a function of temperature. ZnO has thermal expansion coefficients
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at the a-axis of = 4.31x10-6 K-1 and c-axis of = 2.49x10-6 K-1 at 300 K (Morko and
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zgr, 2009). Thermal conductivity is defined as the ability of a material to conduct heat. It
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is vital especially when the devices are to be used under high power and high temperature
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conditions. Factors that influence the thermal conductivity in a ZnO semiconductor material
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too as ZnO semiconductor contains a large number of point defects, which make the effect
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significantly felt as in other semiconductors. The typical thermal conductivity values are in
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the range from 0.6 W cm-1 K-1 to 1 Wcm-1K-1. Specific heat is the heat capacity per unit mass
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of material. In fact, the specific heat of a material is influenced by the lattice vibrations, free
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carriers and number of defects presence within a material. The specific heat capacity of ZnO
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1.2.1 Photocatalysis
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(Serpone and Pelizzetti, 1989). It implies that light and a catalyst are necessary to bring about
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species as a result of initial absorption of radiation by another chemical species called the
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photosensitizer.
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which occur at the surface of a catalyst. If the adsorbate is photoexcited first and then
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interacts with the ground state of the catalyst substrate, the process is referred to sensitized
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photoreaction. On the other hand, if the catalyst is photoexcited first and then interacts with
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the ground state adsorbate molecule, the process is a catalyzed photoreaction. In most
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(CO2), water (H2O) and mineral acids in the presence of ZnO particle and reactive oxidising
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species, such as oxygen or air. The photocatalytic reactions were initiated when ZnO particle
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absorbs photons with energies greater than that of its band gap energy from the illumination.
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In this way, photo-induced electron is promoted from the valence band (VB) to the
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conduction band (CB), forming positively hole (hVB+) and electron (eCB-) on the surface of
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eCB + O2 O2
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hVB+ + OH OH
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(Equation 1)
(Equation 2)
(Equation 3)
(Equation
(Equation 5)
hVB+ + R R+ Intermediates
(Equation 6)
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(Equation 7)
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HOO H2O2 + O2
(Equation 8)
H2O2 + O2 OH + OH- + O2
(Equation 9)
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It should be noted the photo-generated holes in the valence band will recombine with the
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photo-excited electrons in the conduction band and dissipates in the form of heat (Equation
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2). Therefore, the presence of oxygen as electron scavengers prolong the recombination of
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electron-hole pair while forming the superoxide radicals (O2) (Equation 3). The reaction of
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hVB+ with OH (Equation 4) may leads to the formation of hydroxyl radicals. The hydroxyl
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radical is an extremely strong, non-selective oxidant (E0 = +3.06 V) which leads to the partial
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or complete mineralisation of organics (Equation 5). Moreover, the high oxidative potential
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of the hole in the photocatalyst also permits the direct oxidation of organic matter to reactive
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produce hydroperoxyl radical (HOO) and subsequently H2O2 (Equations 7-9). The HOO
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also functions as electron scavengers to trap conduction band electrons which further delay
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the recombination process. The general photocatalysis mechanism processes are shown in
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Figure 2.
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The recombination of photogenerated hole (hVB+) and electron (eCB-) is the major
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yield and causes energy wasting. Therefore, the e--h+ recombination process should be
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inhibited to ensure efficient photocatalysis. Metal doping could counter the recombination
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problem by enhancing the charge separation between electrons and holes. In addition, the
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dopants may trap electrons, reducing the chances of electron-hole recombination that
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deactivates the photocatalytic system (Sanchez and Lopez, 1995). Furthermore, the
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generation of hydroxyl radicals and active oxygen species will greatly increase resulted from
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enhancement in charge separation efficiency (Kato et al., 2005). Generally, the concentration
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and ion nature of the dopant, synthesis method and operating conditions significantly affect
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metal dopant into a semiconductor, namely anionic dopant, cationic dopant and rare-earth
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photocatalytic degradation performance compared to that of pure ZnO. In the case of N-ZnO
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system, the existence of isolated N 2p states above the valence band maximum of ZnO
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increased its visible light absorption ability. Hence, the photogenerated electron-hole pairs
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exist between the impurity N 2p states and Zn 3d conduction band. Additionally, the
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narrowing band gap in N-ZnO system requires less energy to photoinduce the charge carriers,
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i.e. electron and hole, under visible light irradiation (Batzill et al., 2006 and Irie et al., 2003).
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In such a way, the photoexcited eCB- could be reacted with surface adsorbed oxygen to
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(Nagaveni et al., 2004, Dong et al., 2009 and Chu et al., 2012). Meanwhile, the hVB+ will
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react with the adsorbed hydroxyl anion to form hydroxyl radicals. These O2- and OH were
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summarized as below:
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(Equation 11)
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H2O OH-ads + H+
(Equation 12)
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OH-ads + hVB+ OH
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(Equation 10)
(Equation 13)
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(Equation 14)
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Guo and co-workers (2009) reported that the increment in photocatalytic activity of carbon-
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doped ZnO could attributed to several reasons. First, the presence of carbon on C-ZnO
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surface enhanced the MB adsorption on the catalyst surface. Second, C-ZnO showed stronger
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UV absorption in comparison to the pure ZnO. Third, the surface oxygen vacancies in the
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ZnO nanostructure induced new energy levels below the conduction band of ZnO, where the
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photo-excited electrons were scavenged by this new energy levels and the recombination of
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electron-hole is avoided. These increased the number of charge carriers, which improved the
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photodegradation efficiency (Lai et al., 2011, Li et al., 2012b, Li et al., 2009, Wang et al.,
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2009a, Maiti et al., 2012, Liu et al., 2009 and Zheng et al., 2007).
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Similarly, the number of oxygen vacancies play a significant role in affecting the
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photoactivity of S-doped ZnO system. During the photocatalytic process, the oxygen
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vacancies and defects become centres to trap photogenerated electrons. As a result, the
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electron-hole recombination process is hindered. Therefore, the higher the amount of oxygen
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vacancy or defect, the better the photocatalytic activity (Patil et al., 2010). Chen et al. (2008)
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synthesized N,S,C-ZnO by precipitation route and found that the interfering of the non-metal
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Some properties of ZnO is important for its practical applications in various fields.
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in the development of ZnO photocatalyst. Although ZnO is a good photocatalyst, the doped
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currently another important technology being used by many researchers. The doped ZnO
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possesses prominent photodegradation performance than the undoped ZnO. Moreover, the
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structural, optical, chemical, electrical and magnetic properties of ZnO can be tuned by the
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addition of selected cationic dopant. The ZnO have been doped with elements such as Al, Sb,
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Mn, Ni, Co have enhanced photocatalytic performance. The cationic doping is performed
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essentially by the addition of transition metals, group I and group V elements. The
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incorporated elements are usually isomorphic to zinc ions, such as Cu2+, Ni2+, Co2+ and Mn2+.
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organic pollutant. In recent years, many photocatalytic studies reveal that the cationic dopant
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strongly improved the photocatalytic activity of ZnO. The results indicated that the cationic
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doped ZnO have better photocatalytic activity than the undoped ZnO. The doped ZnO
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exhibits faster response to the photodegradation of many organic pollutants. The influence of
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The photocatalytic properties of the Se-doped ZnO were compared with the undoped ZnO.
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The Se-doped ZnO showed the higher photodegradation activity towards trypan blue (Dutta
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et al., 2014 and Nenavathu et al., 2013). Methylene blue is commonly used a model organic
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pollutant for the photocatalytic study. A number of transition metals including Cd (Zhang and
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Zeng, 2012), Fe (Kumar et al., 2014a), Hf (Ahmad et al., 2013c) and Pd (Han et al., 2013),
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have been used as dopants. It can be seen from Table 4 that 1.0 M % Fe-doped ZnO shows
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the highest photocatalytic activity among all modified ZnO catalysts towards the degradation
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process of methylene blue. Among all cationic modified ZnO, transition elements modified
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ZnOs have wide popularity in the photodegradation of methyl orange (Karunakaran et al.,
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2011, Zhong et al. 2012b, Saleh and Djaja, 2014, Ahmad et al., 2013a and Wu et al., 2012).
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Enhanced photocatalytic removal of methyl orange upon doping the ZnO with Al was
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previously observed (Xiaoliang et al., 2013, Zhang et al., 2014b and Ahmad et al., 2013b).
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Although many modified ZnO showed enhanced photocatalytic activity, in some cases, the
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doping does not significantly influence the photocatalytic activity. For example,
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photocatalytic removal of methyl orange by 0.9 at. % Ag-loaded ZnO (Karunakaran et al.,
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phenol and organic dye pollutants. Enhanced performance was observed with Na-doped ZnO
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over undoped ZnO in the photodegradation of methyl orange (Xiaoliang et al., 2013) and
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methylene blue (Kim et al., 2013), respectively. Low doping level of K-doped ZnO exhibits
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(Li et al., 2014b), whereas high doping level of K-doped ZnO showed reduced in the
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photocatalytic activity over the undoped ZnO (Benhebal et al., 2012). The results suggested
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appropriate amount of K.
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The photocatalytic reaction begins with the generation of electrons and holes under
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irradiation. These photogenerated charges are moved to the catalyst surfaces separately.
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Electrons react with oxygen molecules to form superoxide anions. Both electrons and holes
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react in the solution lead to the formation of highly oxidising species such as hydroxyl and
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proposed as below:
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(Equation 15)
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(Equation 16)
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O2 + M(n-1)+ O2 + Mn+
(Equation 17)
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(Equation 18)
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(Equation 19)
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When cationic dopant is added to ZnO, the photodegration efficiency of ZnO is improved
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further. Several locations are possible for the cationic dopant deposition: the surface of the
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ZnO, the Zn sites within the lattice of ZnO crystal, and the interstitial sites of the ZnO in
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crystal lattice (He et al., 2012). Dopant also affects the interfacial electron transfer rate and
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recombination rate of the charge carriers. The incorporated elements such as K, Ni, Cu, Pd
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and Cd, could increase the specific surface area of ZnO and reduced the resistivity of ZnO.
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The presence of the dopants could also reduce the activation energy in the photocatalytic
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activity. The effective route leads to the high catalytic efficiency in the new photocatalyst.
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Cation-doped ZnO have a lower band gap energy value, compared to the undoped ZnO.
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When cationic dopants were introduced as impurities in the ZnO crystal lattice, extra energy
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levels are added to the new photocatalyst. The excitation of electrons are effective even with
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lower energy photons. Moreover, the incorporated elements act as electron traps, which
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suppress the recombination of photogenerated holes and electrons. Thus retarding the rate of
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electron-hole pairs formation. The dopants can extend the light absorption range and
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enhanced the photoresponse of the cation-loaded ZnO in visible light range. The overall
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However, high-doping level ZnO could reduce the photodegradation efficiency. This
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could be attributed to the physical defects and the increased oxidation states of cations. The
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excess cations may act as trapping sites for the holes and electrons, and thus promote the
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and O2 free radicals which leads to the reduction in photocatalytic activity. The schematic
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Figure 4.
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Rare earth (RE) metal, another elegant dopant for the photodegradation of organic
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pollutants. Recently, rare earth doped photocatalyst have received much attention. The unique
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photocatalytic and redox properties of RE is important to promote the surface properties and
396
the electron transfer activity of the photocatalyst. The RE-doped ZnO have been reported to
397
exhibit better photocatalytic activity compared to the undoped ZnO. Table 5 summarised the
398
literatures of photocatalytic efficiency studies at undoped and RE-doped ZnOs. The Nd-
399
loaded ZnO are considered to be a popular photocatalyst for the photodegradation study of
400
various organic dyes such as rhodamine B (Kumar and Sahare, 2012), methylene blue
401
(Yayapao et al., 2013a) and methyl orange (Zhao et al., 2014). The data obtained
402
403
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It was also found that the RE-doped ZnO is wide applied in the degradation of methylene
407
blue, such as 3 mol% Dy-ZnO (Yayapao et al., 2013b), 4.8% M ratio Er-ZnO (Yu et al.,
408
2013), 3 mol% Eu-ZnO (Phuruangrat et al., 2014b), 3 mol% Ho (Phuruangrat et al., 2014c)
409
and 1 mol% Nd (Yayapao et al., 2013b). Based on these experimental results, 3 mol% Dy-
410
ZnO irradiated under UV light for 5 h results in the highest photodegradation performance.
411
The photocatalytic degradation of methyl orange was studied by employing the ZnO doped
412
with 1 mol% Eu (Zong et al., 2014) and 3 mol% Nd (Zhao et al., 2014) as photocatalysts. The
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413
results demonstrated that 1 mol% Eu-loaded ZnO has slightly higher efficiency over 3 mol%
414
Nd-loaded ZnO.
The doped semiconducting catalysts are predicted to exhibit better optical properties, high
416
417
contaminants. This could due to the increased particles surface area, reduced of band gap
418
energy, improved adsorption ability of the particle surfaces and dopant-ZnO interfaces. The
419
optical properties of the photocatalyst is significant for the selection of element for its
420
specific applications. The band gap energy values is important in determining the
421
semiconducting ability and also the photocatalytic property of the materials. The doped-ZnO
422
have lower band gap energy values, compared to the individual component of ZnO. The
423
decrease in the band gap is due to the doping of a trace amount of impurity to the ZnO. Under
424
irradiation, more electrons are induced and available in the conduction band. These
425
photogenerated electrons react with oxygen molecules to form superoxide anions. The RE
426
metal on the ZnO surfaces reduced the work function of the adsorbed oxygen interfaces
427
which could improve the oxygen absorption ability. More strong oxidising species such as
428
hydroxyl, peroxy- and superoxy- radicals are produced and therefore increase the rate of
429
430
ZnO also enhanced in addition of the RE dopant. The added RE acts as luminescent centers
431
which could effectively improve the luminescence property of the doped ZnO. RE dopants
432
also act as trapping sites for electrons, and thus promote the separation of photogenerated
433
electrons and holes, which leading to high photocatalytic efficiency (Figure 5).
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435
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2.4 Co-dopants
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The rapid recombination of the electron-hole pairs can also be countered by the presence
438
of co-dopants (Table 6). It can be seen that the co-doped ZnO has been applied in removing
439
dyes, such as Methylene Blue (Senthilraja et al., 2014 and Vignesh et al., 2014), Napthol
440
Blue Black (Subash et al., 2012), Methyl Orange (Zhang et al., 2015), Reactive Red 120
441
(Subash et al., 2013a) and Acid Black 1 (Subash et al., 2013b). It is obvious that the
442
photodegradation efficiency of co-dopants-ZnO is higher than bare ZnO and single dopant
443
ZnO system. This is due to the co-dopants will simultaneously trapped the photogenerated
444
electron from the conduction band of the ZnO and subsequently reduced the recombination
445
rate of electron-hole (Figure 6). Therefore, the photoinduced generation of electron-hole pairs
446
will continue and produced a large amount of highly active superoxide radical anions (O2-)
447
and hydroxyl radicals (OH), which enhanced the photo-decomposition efficiency of the
448
dyes.
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450
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Besides metal doping, coupled semiconductor has been proven to enhance the charge
454
separation of electron-hole pair which increase the lifetime of the charge carriers and
455
consequently reduce the recombination of electron-hole (Serpone et al., 1995). Table 7 shows
456
457
cationic dye is widely chosen as the model organic pollutant for the photocatalytic
458
degradation by using ZnO coupling system, such as CdO/ZnO (Saravanan et al., 2011 and
459
Samadi et al., 2014), CeO2/ZnO (Liu et al., 2014), GO/ZnO (Li et al., 2012a and Dai et al.,
460
2014), NaNbO3/ZnO (Xu et al., 2011), RGO/ZnO (Zhou et al., 2012), SnO2/ZnO (Uddin et
461
al., 2012) and TiO2/ZnO (Pant et al., 2012). It can be seen from Table 7 that Graphene Oxide
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(GO) coupled with ZnO shows the highest photodegradation efficiency among the studied
463
coupling system. Similarly, enhanced photocatalytic activity was also observed in the
464
removal of Methyl Orange (MO) by BiOI/ZnO (Jiang et al., 2011), CuO/ZnO (Liu et al.,
465
2008), Cu2O/ZnO (Xu et al., 2010), Fe3O4/ZnO (Hong et al., 2008a and Xia et al., 2011),
466
SnO2/ZnO (Yang et al., 2010) and ZnO2/ZnO (Hsu and Wu, 2005). The decolourization
467
percentage of Rhodamine B (RhB) increased at least twice when Bi2O3/ZnO (Yang et al.,
468
2014), CdS/ZnO (Li and Wang, 2011a), CuO/ZnO (Li and Wang, 2010) and SiO2/ZnO (Zhai
469
et al., 2010) was applied as the photocatalyst. Nevertheless, only 16% enhancement was
470
observed with CeO2/ZnO (Li et al., 2011b). The photocatytic activities of some
471
semiconductors coupled with ZnO have been studied for phenol (Lam et al., 2013b, Feng et
472
al., 2014 and Lam et al., 2014), Acid Black 1 (AB1) (Balachandran and Swaminathan, 2012),
473
Acid Red 88 (AR88) (Sathishkumah et al., 2011), Orange II (OII) (Helali et al., 2010),
474
475
(Lam et al., 2013c), Rhodamine 6G (Rh6G) (Zhang et al., 2014a), Acid Orange 10 (AO10)
476
(Kuzhalosai et al., 2013), 4-chlorophenol (4-CP) (Pozan and Kambur, 2014), Acid Orange II
477
(AOII) (Yu et al., 2011), resorcinol (ReOH) (Lam et al., 2013a), dimethyl phthalate (DMP)
478
(Hsu and Wu, 2005) and 2,4-dichlorophenol (2,4-DCP) (Liao et al., 2010).
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480
481
electrons can flow from one semiconductor with a higher conduction band minimum to the
482
other with a lower conduction band minimum. Moreover, the formation of heterojunction led
483
to a more efficient interelectron transfer between the two catalysts. In this way, the
484
photoinduced electron-hole pairs were separated and the probability of electronsholes pairs
485
recombination was reduced (Shang et al., 2009, Wang et al., 2009b and Peng et al., 2010).
486
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From Table 7, we can conclude that the comparison of photocatalytic activity for different
488
types of coupling system is difficult. This is due to the fact that the photoactivity of catalysts
489
is strongly depend on its band gap, morphology, particle size, porosity, surface area and
490
surface hydroxyl density. Moreover, the irradiation intensity and photoreactor design also
491
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Most of the studies have investigated the effect of catalyst loading on the photocatalytic
498
efficiency (Mrowetz and Selli, 2006, Kositzi et al., 2007, Chatzitakis et al., 2008, Lu et al.,
499
2009 and Hayat et al., 2011). These results indicated that the photodegradation rate initially
500
increases with increasing in the amount of catalyst loaded until it reached an optimum mass.
501
This phenomenon is based on the fact that an increase in the catalyst dosage will enhance the
502
total active surface area and the number of reaction sites on the catalyst surface. As a result,
503
the number of hydroxyl and superoxide radicals increased as well, which facilitates the
504
degradation of the organic pollutants. Thus, the degradation percentage was enhanced.
505
506
photocatalyst dosage was beyond the optimum concentration due to light scattering and
507
508
interaction) leading to a reduction in catalyst surface area available for light absorption and
509
pollutant adsorption, which in turn, reduced the photocatalytic efficiency. On the other hand,
510
one should also noticed that the solution turbidity increase as well. This phenomenon inhibits
511
the penetration of light into the solution. Thus, the photoactivated volume of the suspension
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512
decreases and consequently lowers the degradation rate. These suggested that an optimum
513
catalyst mass should be obtained in order to avoid usage of excess catalyst and to ensure a
514
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The photodegradation efficiency can be improved through the advancement in the ZnO
518
structure. Recently, ZnO nanostructure received a great interest in the photocatalytic study
519
due to their unique structures and properties. The nanostructured ZnO can exists in various
520
521
nanotetrapods, nanoflowers and nanospiral disks, where are different from the bulk ZnO (Lai
522
et al., 2010 and Saravanan et al., 2011). Nanostructured ZnO have a size in nanoscale with
523
higher surface area. A high surface-to-volume ratio offers better physicochemical properties.
524
Nano ZnO possesses better surface effect and quantum effect (Lai et al., 2010). One
525
dimensional ZnO nanorods were used in the photodegradation of methylene blue. The study
526
indicated that the ZnO nanorods with higher specific surface area produces better
527
photodegradation efficiency compared to the nanorods with lower surface area (Assi et al.,
528
2014). A novel sphere of ZnO nanosheets was constructed for the photodegradation of
529
Rhodamine B. This three-dimensional (3D) fluffy structure offers a large surface area with
530
more active sites for reaction. The photocatalytic removal of Rhodamine B indicated a higher
531
rate of degradation compared to other nanostructures due to the larger specific surface area
532
and improved segregation efficiency for electrons and holes (Lai et al., 2010).
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533
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Many reports have showed that the concentration of organic contaminants in aqueous
536
solution has a detrimental effect on the photocatalytic degradation rate (Rabindranathan et al.,
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2003, Akyol and Bayramolu, 2005, Sirtori et al., 2006, Mahalashmi et al., 2007 and Wu et
538
al., 2010). The degradation efficiency reduced when the substrate concentration increased.
539
This is due to the fact that as the concentration of the target pollutant increases, more and
540
more organic substances are adsorbed on the catalyst surface. Therefore, the demand of
541
oxidizing species (OH and O2-) for the degradation of the organics also increases. However,
542
the number of active sites on the catalyst surface remains constant for a fixed catalyst dosage,
543
light intensity and irradiation period. Therefore, the generation of hydroxyl radicals is
544
insufficient since there are only a few active sites available for the adsorption of hydroxyl
545
ions. Furthermore, the photons get intercepted before they can reach to the catalyst surface at
546
547
548
pollutant solution.
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3.4 Solution pH
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Solution pH plays a vital role in photocatalytic water system. pH not only affects the
552
surface charge of the catalyst particles (Haque et al., 2006), but also influences the positions
553
554
industrial wastewater may be discharged at various pH, which make the photocatalytic
555
556
lower than its pKa value. When the pH of solution is greater than the pKa value, the
557
compound deionised and exists as negatively charge species. In addition, the solution pH has
558
559
substrate and charged radicals formed during photodegradation process. Recently, Kosmulski
560
(2006) reported an update of the points of zero charge (pzc) for some semiconductors. The
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561
protonation and deprotonation of organics and photocatalyst surface could occur either in
562
acidic or in alkaline conditions as shown in the following reactions (Equations 20 and 21):
563
(Equation 20)
564
(Equation 21)
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Therefore, the semiconductor surface is positively charged below its pzc value and is
567
negatively charged when exceeded its pzc. According to Shifu and Gengyu (2005), the
568
photogenerated holes (h+) are the predominant oxidising species at low pH, whereas at
569
neutral or alkaline medium, hydroxyl radicals play the major role in oxidising the organic
570
contaminants. However, it should also be noticed that hydroxyl radicals are rapidly
571
scavenged at high pH due to abundance of hydroxyl ions which inhibits its reaction with the
572
pollutant substrate (Davis and Huang, 1989). Thus, suitable pH should be carefully selected
573
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575
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photocatalytic process. It is believed that more radiations fall on the catalyst surface at higher
578
light intensity and hence more hydroxyl radicals are produced, which in turn increases the
579
reaction rate (Shafaei et al., 2010, Mahalakshmi et al., 2007 and Behnajady et al., 2006).
580
581
Hermann (1999) concluded that the reaction rate was proportional to the radiant flux, for
582
< 25 mW cm-2, but varied to square-root dependency (0.5) when above 25 mW cm-2. In an
583
n-type semiconductor such as ZnO and TiO2, the number of photo-induced holes in valence
584
band is much less than the photo-generated electrons in conduction band. This indicated that
585
the photo-generated holes are the limiting active species (Malato et al., 2009). At much
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higher light intensities, the photodegradation rate is independent to the radiant flux (0).
587
Under this condition, the reaction rate only depends on the mass transfer within the reaction.
588
This is due to the catalyst surface was fully covered by the saturated solids, which limits the
589
mass transfer for both adsorption and desorption. Thus, the reaction rate remains constant
590
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591
592
594
A, UV-B and UV-C, according to its emitting wavelength. The UV-A range has its light
595
wavelength spans from 315 to 400 nm (3.10 to 3.94 eV), while UV-B has wavelength range
596
of 280 to 315 nm (3.94 to 4.43 eV) and the germicidal UV-C ranges from 100 to 280 nm
597
(4.43 to 12.4 eV) (Rincon and Pulgarin, 2005). Ochuma et al. (2007) reported that the UV-A
598
light provides light photons sufficient for photonic activation of the prepared TiO2 in the
599
600
efficiency is higher at 254 nm radiation due to shorter penetration capability of the higher
601
energy photon, which increased the number of electron-hole pairs generated for the
602
decomposition of the target pollutant (Bayarri et al., 2007). However, Venkatachalam et al.
603
604
606
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3.7 Temperature
607
608
atmospheric pressure due to photonic activation. This is beneficial for water purification
609
treatment whereby the heating step can be excluded to conserve energy. The optimum
610
26
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activation energy (Malato et al., 2003). In general, an increase in the reaction temperature
612
may enhance the degradation rate of the organic contaminants, however it may also reduce
613
the adsorptive capacities of the reactant species and dissolved oxygen, which resulted in
614
lower photodegradation efficiency (Hermann, 1999, Gaya and Abdullah, 2008, Chatzitakis et
615
al., 2008 and Kositzi et al., 2007). This is confirmed by Vant Hoff-Arrhenius equation,
616
where the chemical reaction rate constant, k is linearly proportional to exp (-1/T).
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617
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Most of the scientific works indicated that the major energy wasting step in the
620
photocatalytic reaction is the electronhole recombination that prompts low quantum yield.
621
622
photocatalytic process to work more effective. The addition of inorganic oxidants improves
623
the photodegradation rate by: 1) Increasing the number of trapped electrons to avoid
624
recombination of electron-hole pair; 2) Generating more radicals and other oxidising species
625
626
radicals and oxidation rate of intermediate compounds and 4) Avoiding problems caused by
627
low oxygen concentration (Wei et al., 2009, Selvam et al., 2007, and Singh et al., 2007).
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Several inorganic oxidants were studied for their influences towards the photocatalytic
629
efficiency of ZnO photocatalyst, such as H2O2, S2O82-, BrO3-, and SO3-. Hydrogen peroxide,
630
H2O2, a powerful oxidising species and electron acceptor which leading to the increased in
631
the rate of photodegradation of various organics. Upon photoexcitation, electrons and holes
632
were generated on the surface of ZnO photocatalyst. The generated holes and electrons will
633
involve in the production of strong oxidising radicals, which are the main species that
634
responsible for the destruction of organic pollutants. H2O2 accepts a photoinduced electron
635
from the conduction band and form the hydroxyl radical via the redox reaction on the catalyst
AC
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636
surface (Equation 22). H2O2 can also split photolytically to hydroxyl radicals directly as
637
(Equation 22)
639
H2O2 + h 2OH
(Equation 23)
640
The hydroxyl radicals that formed on the ZnO surface are capable of oxidising various
641
organic compounds into less hazardous molecules such as H2O, CO2 and inorganic salts. It
642
was reported that the photodegradation efficiency reached an optimum condition when a trace
643
amount of H2O2 is used in the presence of ZnO (Khattab et al., 2012 and Shanthi et al., 2012).
644
However, it is worth to pinpoint that the excessive amount of H2O2 will suppress the
645
646
radicals (HO2), which is a much weaker oxidant than hydroxyl radicals (OH) as
647
648
649
2014).
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(Equation 24)
651
(Equation 25)
652
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650
654
percentage of organic contaminants, by forming BrO2- and HOBr (Equations 26 and 27),
655
which reduces the recombination rate of the electron-hole pairs (Seyed-dorraji et al., 2009).
656
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657
(Equation 26)
658
(Equation 27)
659
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The presence of persulfate ions, S2O82- in the photocatalytic system showed higher
661
degradation rate by promoting the charge separation and also generating the sulphate radical
662
anion (SO4-), which is a very strong oxidising agent that mineralise a wide range of organic
663
pollutants (reduction potential of SO4- = +2.60 V). The generated SO4- will then reacts with
664
the water molecule to form hydroxyl radicals (Hazime et al., 2014) (Equations 28-31).
S2O8 2- + eCB- SO4- + SO42-
666
667
(Equation 28)
(Equation 29)
(Equation 30)
SC
665
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668
Oxone, SO3- a strong oxidant that intend to react with the electrons from the conduction
670
band of ZnO to form sulphate radicals (SO4-) and hydroxyl radicals under light induction
671
Equations (31-32). The sulphate radicals are easily react with hydroxyl species from water
672
and thus capable of improving the degradation efficiency (Krishnakumar et al., 2010).
HOOSO3- + eCB- SO4- + OH-
674
675
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(Equation 31)
(Equation 32)
Some inorganic ions/electrolytes will tend to retard the photodegradation of ZnO. It was
677
demonstrated that inorganic ions such as Na2SO4, NaCl, NaNO3 and Na2CO3 tend to retard
678
the photedegradation (Krishnakumar et al., 2010). These ions could be deposited on the ZnO
679
surface and the inorganic ions inhibited the degradation. This could be attributed by the
680
blocking of active sites on the surface of ZnO. For example, the inclusion of NaCl retard
681
photodegradation of ZnO which could due to the radical scavenging effect of chloride as
682
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683
Cl- + OH HOCl-
(Equation 33)
684
HOCl + H+ Cl + H2O
(Equation 34)
29
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685
686
687
(Equation 35)
689
(Equation 36)
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This is will pose a major challenge for treating industrial wastewater that may contain high
691
692
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694
Phenolic compounds, persistent organic pollutants (POPs) and dyes are among the most toxic
695
organic compounds have long been a focus of concern due to their gravest threat to human
696
health, marine life and environment. The importance of the removal of organic pollutants in
697
industries wastewater arises due to the toxicity of these pollutants, and their ability to
698
bioaccumulate in the aquatic life and slowly moving to the food chain. Multiple methods
699
have been developed and used to remove the organic pollutants. However, most of these
700
701
expensive or sophisticated instruments, have poor removal efficiency and long turnaround
702
times which make those methods unsuitable for field applications. The ability of advanced
703
704
wastewater has been widely applied. This technology is progressively being used in many
705
industries and even being commercialized in many countries. ZnO has been an attractive
706
707
708
simple, versatile and cost effective treatment technology. Many literature have proven that
709
the decreased in the concentration of the contaminants when ZnO is used as a photocatalyst
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710
711
photodegradation to remove phenolic compounds, POPs and dyes is presented in the Table 8.
712
713
715
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Phenol and its derivatives are one of the most important environmental pollutants which
717
are mainly discharged from textile industries, petrochemical plants, and petroleum refineries.
718
719
the critical environmental issue. Phenolic pollutants are very toxic which can cause lethal for
720
aquatic life even in a low concentration. Wastewaters which containing a significant amount
721
of phenolic compounds should be treated before being discharged to the environment. Some
722
723
biological treatment have limitations in treating the phenolic wastewater. Advanced oxidation
724
process (AOP) offers better advantage in removing of phenolic compounds over conventional
725
methods. Photocatalysis is one of the AOPs which possesses great potential in treating
726
727
elimination of phenolic compounds has been carried by Selvam and co-workers (2007). ZnO,
728
a semiconductor with photocatalytic property was used to detoxify the toxic 4-fluorophenol
729
(4FP) in the studies (Table 8). Mercury lamp is used as a light source, which create electron
730
hole pairs in the ZnO after the photoexcitation. Gaya and co-workers (2009) successfully
731
demonstrated the photocatalytic ability of ZnO to remove 4-chlorophenol (4CP). The source
732
of light was ultraviolet-A (UV-A) and 4CP was completely degraded after 180 min of
733
irradiation.
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734
31
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735
737
environment and human health. The major concern of POP is because they remain for long
738
periods of time in the environment. Therefore, it will bioaccumulate and transport from lower
739
food chain to the higher food chain. Example of these pollutants is fungicides, herbicides,
740
insecticides, and pesticides. As shown in Table 8, these POPs can also be degraded by ZnO
741
under UV light irradiation. Mijin et al. (2009) has also successfully degraded metamitron
742
which is mainly used as herbicides by using ZnO under 300 W of UV light irradiation. The
743
harmful pesticide e.g. dimethoate was completely degraded just within 60 minutes by ZnO
744
745
which is a potential endocrine disrupting compound (EDC) has becoming major concern.
746
747
causes adverse effects on aquatic life. These pharmaceutical compounds such as amoxicillin,
748
749
photocatalyst under UV or solar light irradiation (Elmolla and Chaudhuri, 2010 and
750
Palominos et al., 2009). Lastly, ZnO has proven to be a potential photocatalyst to treat
751
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753
4.3 Dyes
754
Dyes are one of the most important pollutants from the textile industry. Synthetic dyes such
755
as methyl orange, methylene blue and methyl green are mainly used in the paper and textile
756
industries. Several methods have been applied to reduce the impact of these synthetic dyes on
757
aquatic life and environment. Unfortunately, many conventional methods such as membrane
758
separation, adsorption and biological treatments required high operating cost and have
759
32
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reaction has been proposed as an efficient method for the removal of pollutants including
761
dyes. ZnO is among the most popular photocatalyst has been widely used to remove dyes due
762
to its ability to absorb a wide solar spectrum. The successful photodegradation using ZnO in
763
764
80% was achieved after 180 minutes of irradiation with a light intensity of 1060 W m-2
765
(Danwittayakul, et al., 2015). ZnO was applied to degrade orange II under UV illumination.
766
767
al., 2014). The degradation of methyl green was examined with a completely colour removal
768
after 16 hours at pH 10 by visible light with an intensity of 4.8 W m2. (Mai et al., 2008).
769
ZnO has also found to achieve satisfactorily degradation efficiency in Acid Red 18, (Sobana
770
and Swaminathan, 2007), methyl orange (Xie et al., 2011) and Acridine Orange (Pare et al.,
771
2008).
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772
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775
776
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(Equation 37)
778
(Equation 38)
(O-O2-) + 2hVB+ O2
(Equation 39)
(Equation 40)
779
780
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781
782
783
(Equation 41)
784
33
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It can be seen that the reaction between the positively holes and the surface oxygen of ZnO is
786
the key factor for the dissolution of ZnO. Moreover, the vacant sites on the ZnO surface also
787
lead to photocorrosion of ZnO (Bai et al., 2013 and Chen et al., 2013a). Some studies
788
reported that the photocatalytic activity of ZnO remained after a few cycles (Akyol and
789
Bayramoglu, 2010 and Lee et al., 2015). On the contrary, the photodegradation efficiency
790
reduced significantly under photo-corrosion (Li et al., 2010, Xiao, 2012, and Chen et al.,
791
2013b). A number of studies have been conducted to overcome photo-corrosion of ZnO via
792
surface modification with a layer of polyaniline (Zhang et al., 2009a, Ameen et al., 2011),
793
graphitic carbon (Zhang et al., 2009b), fullerene (Fu et al., 2008), and reduced graphene
794
oxide (Zhang et al., 2013). The formation of a passive layer on the ZnO surface, which is less
795
photo-active suppresses the photo-corrosion rate (Rudd and Breslin; Comparelli et al., 2005).
796
According to Kislov et al. (2009), the occurrence of ZnO photocorrosion was orientation
797
dependent, with only ZnO (0001)-O suffered strong photocorrosion, while ZnO (0001)-O and
798
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800
801
In summary, modified ZnO seems to be the most promising photocatalyst for high
803
804
concluded that reducing the probability of charge carrier recombination rate is one the most
805
significant factors that determine the photocatalytic activity using the modified ZnO
806
807
developed to minimize the recombination losses of charge carriers and extended the spectral
808
809
doping, co-doping and semiconductor coupling with ZnO. Many researchers have been trying
810
to synthesize not only higher active surface area of ZnO photocatalyst but also sunlight-
811
driven ZnO photocatalyst for effective photocatalytic activity. In this manner, addition of
812
electron donors (hole scavengers) or electron mediators with ZnO can further improve the
813
photocatalytic activity by reacting with positive holes (valence band) irreversibly to prohibit
814
815
Continuous efforts have been conducted to achieve the solar-driven ZnO photocatalyst by
816
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technique]. Besides, small band gap semiconductors can inject electrons to the conduction
818
band of large band gap semiconductors, resulting in efficient charge separation and high
819
photocatalytic efficiency (semiconductor coupling). Thus, the energy levels and charge
820
821
system for organic dye, phenolic compounds, and persistent organic pollutants (POPs).
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The industrial application of modified ZnO photocatalyst is anticipated for the future due to
824
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modifications are essential to improve its photocatalytic activity under the direct sunlight
826
irradiation by reducing it band gap energy as well as minimizing the recombination losses.
827
Thus, various potential approaches have been employed to further increase ZnO
828
829
applied in the field of organic dye degradation, phenolic compounds removal, and persistent
830
organic pollutants (POPs) degradation. It was believed that modified ZnO photocatalyst is
831
still permit extensive and in-depth study on the electronic and lattice structure in order to
832
truly understand the effect of different doping / loading with cationic, anionic, small band gap
833
of semiconductor, and elements on ZnO photocatalyst. The modeling work is thus required
834
for better understanding of the photocatalytic oxidation degradation mechanism as well as for
835
designing efficient photoreactor / system for organic dye, phenolic compounds, and persistent
836
organic pollutants (POPs) in our waste water stream. The solid outcomes would be the
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management via advanced photocatalytic oxidation reactions in order to create the healthy
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Acknowledgments
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This
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research
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1494
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1498
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List of Tables
60 meV
0.24 - 0.30 me
0.45 0.60 me
200 cm2V-1S-1
5 50 cm2V-1S-1
2.008, 2.029
SC
<106 cm-3
M
AN
U
RI
PT
Property
TE
D
80 95 %
E2low
101
437
TO (A1)
380
LO (A1)
574
AC
C
EP
E2high
591
TO (E1)
ACCEPTED MANUSCRIPT
Sunlight
(Intensity = 1.08x105 lux)
Rhodamine B (RhB)
Solar simulator
(Intensity = 80 lux)
Methylene Blue (MB)
1000 W Xe lamp
Rhodamine 6G (R6G)
350 W Xe lamp
Bisphenol A (BPA)
350 W Xe lamp
Methyl Orange (MO)
Sunlight
Resorcinol (Rs)
Haibo et
al., 2014
Samadi et
al., 2013
5.4
81.6
Wu et al.,
2013
~ 25.0
93.0
Qiu et al.,
2013
20.0
100
Sun et al.,
2013
~ 55.0 %
100
Patil et
al., 2010
M
AN
U
210
Reference
42.3
SC
13.9
TE
D
EP
AC
C
Experimental
conditions
Catalyst = 1 g/L
[RhB] = 4.8 mg/L
Irradiation time: 30 min
RI
PT
Dopant
100
420
ACCEPTED MANUSCRIPT
Ag
(0.5 M %)
UV lamp
4-Nitrophenol (4-NP)
Al
(10 at. %)
2x20 W UV lamp
Methyl Orange (MO)
Al
(1.5 mol %)
Al
(4.0 M %)
Bi
(5.0 at. %)
UV lamp
Congo Red (CR)
Bi
(5.0 M %)
300 W Hg lamp
Methyl Orange (MO)
Cd
(5 at. %)
9 W UV lamp
Rhodamine B (RhB)
RI
PT
Ag
(0.9 at. %)
8W UV lamp
17
-ethinylestradiol
(EE2)
Hg lamp
Methyl Orange (MO)
TE
D
EP
Ag
(6.7 mol %)
20.0
Reference
Li et al.,
2014c
30.0
Karunakaran
et al., 2011
~ 15.0
100
Divband et
al., 2013
50.0
95.7
Xiaoliang et
al., 2013
20.2
95.9
Zhang et al.,
2014b
13.0
20.0
Ahmad et al.,
2013b
80.0
~ 86.0
Chandraboss
et al., 2013
26.0
46.2
Zhong et al.,
2012b
70.0
98.0
Zhai et al.,
2014
SC
Experimental conditions
M
AN
U
Light source/Pollutant
AC
C
Dopant
ACCEPTED MANUSCRIPT
Co
(12.0 at. %)
2x20 W UV lamp
Methyl Orange (MO)
Co
(0.25 at. %)
150 W Xe lamp
Rhodamine B (RhB)
Cu
(3.0 wt. %)
Cu
(15 wt. %)
350 W UV lamp
Resazurin (Rz)
Cu
(3.0 mol %)
1000 W Xe lamp
Methyl Orange (MO)
Fe
(1.0 M %)
2x18W UV lamps
Methylene Blue (MB)
Fe
(1.0 M %)
500 W Xe lamp
Rhodamine B (RhB)
Fe
(0.5 wt. %)
Sunlight
(Intensity = 23 W/m2)
2-Chlorophenol (2-CP)
RI
PT
~ 60.0
TE
D
M
AN
U
Cd
(1.2 at. %)
Experimental conditions
AC
C
Reference
Zhang and
Zeng, 2012
~ 70.0
Saleh and
Djaja, 2014
~ 100
~ 90.0
He et al.,
2012
26.0
39.0
Ahmad et al.,
2013a
60.0
90.0
Mohan et al.,
2012
5.1
~ 40.0
Wu et al.,
2012
5.0
42.0
Kumar et al.,
2014a
67.0
94.0
Yi et al.,
2014
~ 65 %
~ 85 %
Ba-Abbad et
al., 2013
SC
Light source/Pollutant
EP
Dopant
ACCEPTED MANUSCRIPT
K
(10 %)
125 W UV lamp
Phenol (Ph)
Li
(10 %)
125 W UV lamp
Phenol (Ph)
Li
(10 wt. %)
1000 W Xe lamp
Methylene Blue (MB)
Mg
(5 wt. %)
125 W Hg lamp
Alprazolam (APZ)
Mg
(5 %)
Mg
(10 %)
Mn
(12.0 at. %)
RI
PT
500 W Xe lamp
Rhodamine B (RhB)
42.1
Reference
Ahmad et al.,
2013c
92.6
Li et al.,
2014b
~ 70.0
~ 60.0
Benhebal et
al., 2012
~ 70.0
~ 75.0
Benhebal et
al., 2012
53.1
100 %
Ganesh et
al., 2012
~ 60.0
~ 80.0
Iveti et al.,
2014
83.0
92.0
Suwanboon
et al., 2013
~ 83.3
100
Etacheri et
al., 2012
~ 60.0
~ 85.0
Saleh and
Djaja, 2014
SC
K
(0.3 %)
M
AN
U
AC
C
Hf
(2 mol %)
Experimental conditions
TE
D
Light source/Pollutant
EP
Dopant
ACCEPTED MANUSCRIPT
Na
(1.86 wt. %)
500 W Xe lamp
Methylene Blue (MB)
Pd
(1.5 at. %)
UV lamp
Methylene Blue (MB)
Pd
(3 M %)
300 W Hg lamp
Methyl Orange (MO)
Sb
(3 mol %)
UV lamp
Methylene Blue (MB)
Sb
(0.03 mol %)
125 W UV lamp
Methylene Blue (MB)
Se
(5 wt. %)
25 W UV lamp
Trypan Blue (TrB)
Se
(5 wt. %)
30 W UV lamp
Trypan Blue (TrB)
RI
PT
2x20 W UV lamp
Methyl Orange (MO)
50.0
Reference
Abdollahi et
al., 2011
55.5
Xiaoliang et
al., 2013
~ 31.8
100
Kim et al.,
2013
68.0
~ 100
Han et al.,
2013
30.0
~ 50.0
Zhong et al.,
2012a
56.0
95.0
Phuruangrat
et al., 2014a
71.9
~ 100
Omidi
18.0
85.0
Dutta et al.,
2014
16.5
86.1
Nenavathu et
al., 2013
SC
Na
(15 at. %)
M
AN
U
6 W UV lamp
o-cresol
AC
C
Mn
(1 %)
Experimental conditions
TE
D
Light source/Pollutant
EP
Dopant
ACCEPTED MANUSCRIPT
RI
PT
1000 W Xe lamp
Rhodamine B (RhB)
30.0
M
AN
U
Sr
(0.1 M %)
Catalyst = 1 g/L
[MO] = 10 mg/L
Irradiation time = 60 min
Catalyst = 1 g/L
[RhB] = 10 mg/L
Irradiation time = 180 min
TE
D
300 W Hg lamp
Methyl Orange (MO)
EP
Sn
(1 M %)
Experimental conditions
SC
Light source/Pollutant
AC
C
Dopant
92.0
Reference
Li et al.,
2013
Li et al.,
2014a
ACCEPTED MANUSCRIPT
Eu
(2 at. %)
Gd
(0.05 mol %)
Ho
(3 mol %)
Nd
(0.04 mol %)
UV lamp
Methylene
Blue
(MB)
125 W Hg lamp
Rhodamine B (RhB)
RI
PT
Reference
Sin et al.,
2014a
56.0
98.0
SC
Eu
(3 mol %)
Yayapao et
al., 2013b
69.3
97.7
Yu et al.,
2013
75.7
95.3
Zong et al.,
2014
75.0
90.5
Phuruangrat
et al., 2014b
~ 60.0
~ 86.0
Sin et al.,
2014b
70.0
100.0
74.8
98.3
Kumar and
Sahare,
2014b
Phuruangrat
et al., 2014c
~ 70.0
100.0
M
AN
U
Er
(4.8%
M
ratio)
Eu
(1 mol %)
Catalyst = 1 g/L
[Phenol] = 20 mg/L
Irradiation time: 300 min
Catalyst = 5 g/L
[MB] = 3.2 mg/L
Irradiation time: 300 min
Catalyst = 0.5 g/L
[MB] = 10 mg/L
Irradiation time: 60 min
Catalyst = 1 g/L
[MO] = 10 mg/L
Irradiation time: 180 min
Catalyst = 1.5 g/L
[MB] = 3.2 mg/L
Irradiation time: 300 min
Catalyst = 1 g/L
[Phenol] = 20 mg/L
Irradiation time: 300 min
Catalyst = 0.3 g/L
[RhB] = 2.4 mg/L
Irradiation time: 60 min
Catalyst = 1.5 g/L
[MB] = 3.2 mg/L
Irradiation time: 300 min
Catalyst = 0.3 g/L
[RhB] = 2.4 mg/L
Irradiation time: 60 min
TE
D
Dy
(3 mol %)
Experimental conditions
EP
Ce
(2 at. %)
Light
source/Pollutant
55
W
compact
fluorescence lamp
Phenol
UV lamp
Methylene
Blue
(MB)
32 W UV lamp
Methylene
Blue
(MB)
100 W Hg lamp
Methyl
Orange
(MO)
UV lamp
Methylene
Blue
(MB)
55
W
compact
fluorescence lamp
Phenol
125 W Hg lamp
Rhodamine B (RhB)
AC
C
Dopant
Kumar and
Sahare, 2012
ACCEPTED MANUSCRIPT
85.0
100.0
SC
RI
PT
Zhao et al.,
2014
98.5
Sin et al.,
2013
M
AN
U
Sm
(1 at. %)
Catalyst = 5 g/L
[MB] = 3.2 mg/L
Irradiation time: 300 min
Catalyst = 1 g/L
[MO] = 15 mg/L
Irradiation time: 45 min
Catalyst = 1 g/L
[2,4-DCP] = 20 mg/L
Irradiation time: 180 min
TE
D
Nd
(3 mol %)
Experimental conditions
EP
Nd
(1 mol %)
Light
source/Pollutant
UV lamp
Methylene
Blue
(MB)
UV lamp
Methyl
Orange
(MO)
55
W
compact
fluorescence lamp
2,4-dichlorophenol
(2,4-DCP)
AC
C
Dopant
72.2
ACCEPTED MANUSCRIPT
83.9
Catalyst = 3 g/L
[NBB] = 123 mg/L
Irradiation time: 40 min
53.0
EP
Catalyst = 3 g/L
[AB1] = 123 mg/L
Irradiation time: 40 min
61.2
Reference
88.9
~100
Senthilraja
et al., 2014
60.1
100
Subash et
al., 2012
~5.0
53.3
98.9
Zhang et
al., 2015
55.0
79.0
65.0
93.0
Vignesh et
al., 2014
71.1
71.1
70.6
~100
Subash et
al., 2013a
43.8
59.0
63.9
~100
Subash et
al., 2013b
TE
D
Catalyst = 1 g/L
[MO] = 30 mg/L
Irradiation time:
Catalyst = 0.375 g/L
[MB] = 0.48 mg/L
Irradiation time: 180 min
Catalyst = 3 g/L
[RR120] = 294 mg/L
Irradiation time: 30 min
94.9
M
AN
U
Catalyst = 3 g/L
[MB] = 96 mg/L
Irradiation time: 60 min
RI
PT
ZnO
SC
Experimental conditions
AC
C
Co-dopants
Light source /
M1-M2Pollutant
ZnO
Ag-Au-ZnO 4x8W medium
pressure Hg lamp
Methylene Blue
(MB)
Ce-Ag-ZnO Sunlight
(1.25x105 lux)
Napthol Blue
Black (NBB)
Er-Al-ZnO
18 W LED lamp
Methyl Orange
(MO)
Ni-Th-ZnO 300 W Xe lamp
Methylene Blue
(MB)
Zr-Ag-ZnO Sunlight
(1.25x105 lux)
Reactive Red 120
(RR120)
Zr-Ag-ZnO 4x8W medium
pressure Hg lamp
Acid Black 1
(AB1)
ACCEPTED MANUSCRIPT
Bi2O3/ZnO
(11.7 wt.%
Bi2O3 )
4 x 8 W medium
pressure Hg lamp
Acid Black 1
(AB1)
250 W projection
lamp
Methylene Blue
(MB)
Solar simulator
Methylene Blue
(MB)
CdO/ZnO
(5 wt.%
CdO)
CdO/ZnO
(20 %
CdO)
CdS/ZnO
(1:3)
300 W Xe lamp
Rhodamine B
(RhB)
CdO/ZnO = N/A
[MB] = 9.6 mg/L
Irradiation time = 360
min
CdO/ZnO = 0.4 g/L
[MB] = 3.2 mg/L
Irradiation time = 240
min
CdS/ZnO = 0.5 g/L
[RhB] = 24 mg/L
Irradiation time = 90 min
RI
PT
Reference
Jiang et al.,
2011
85.0 %
Yang et al.,
2014
56.4
98.4
Lam et al.,
2013b
78.0
~ 100
100
Balachandran
and
Swaminathan,
2012
Saravanan et
al., 2011
Samadi et al.,
2014
~ 45.0
100
Li et al.,
2011a
SC
~ 15.0
M
AN
U
55 W compact
fluorescence lamp
Phenol
BiOI/ZnO = 1 g/L
[MO] = 10 mg/L
Irradiation time = 240
min
Bi2O3/ZnO = 1 g/L
[RhB] = 4.8 mg/L
Irradiation time = 180
min
Bi2O3/ZnO = 1 g/L
[Phenol] = 19.8 mg/L
Irradiation time = 360
min
Bi2O3/ZnO = 4 g/L
[AB1] = 185 mg/L
Irradiation time = 90 min
TE
D
Bi2O3/ZnO
(1 at.%)
Experimental conditions
EP
Bi2O3/ZnO
(1:23)
Light source /
Pollutant
500 W tungsten
halogen lamp
Methyl Orange
(MO)
300 W Xe lamp
Rhodamine B
(RhB)
AC
C
Coupling
system
BiOI/ZnO
(1:1)
ACCEPTED MANUSCRIPT
CuO/ZnO
(8 mol%
CuO)
CuO/ZnO
(1:2)
Cu2O/ZnO
(1.5 M
Cu2O)
Cu2O/ZnO
(70 %
Cu2O)
200 W tungsten
halogen lamp
Methyl Orange
(MO)
500 W tungsten
halogen lamp
Orange II (OII)
RI
PT
15 W UV tube
Methyl Orange
(MO)
150 W Tungsten
halogen lamp
Acid Red 88
(AR88)
300 Xe lamp
Rhodamine B
(RhB)
Reference
Li et al.,
2011b
67.4
Liu et al.,
2014
50.0
90.0
Liu et al.,
2008
Sathishkumah
et al., 2011
37.0
100
Li et al., 2010
30.0
73.0
Xu et al.,
2010
No decolourization.
Helali et al.,
2010
SC
CuO/ZnO
52.3
M
AN
U
18 W Hg lamp
Methylene blue
(MB)
TE
D
CeO2/ZnO
(10 %
CeO2)
Experimental conditions
EP
Light source /
Pollutant
8 W UV light
Rhodamine B
(RhB)
AC
C
Coupling
system
CeO2/ZnO
(1:5)
ACCEPTED MANUSCRIPT
GO/ZnO
GO/ZnO
MoO3/ZnO
(1 at. %)
RI
PT
Reference
Sakthivel
et al.,
2002
55.0
83.0
Hong et
al., 2008
52.0
82.8
Feng et
al., 2014
85.0
93.6
Xia et al.,
2011
25.0
100
Li et al.,
2012a
M
AN
U
SC
-Fe2O3/ZnO =1 g/L
[DCA] = 5 mmol
Irradiation time = 120 min
TE
D
Fe3O4/ZnO
(10 wt.%
Fe3O4)
Experimental conditions
EP
Fe3O4/ZnO
(1:4)
Light source /
Pollutant
500 W medium
pressure Hg lamp
Dichloro acetic
acid (DCA)
30 W UV light
Methyl Orange
(MO)
575 W metal
halide lamp
Phenol
500 W high
pressure Hg lamp
Methyl Orange
(MO)
300 W Xe light
Methylene Blue
(MB)
10 x 10 LED lamp
Methylene Blue
(MB)
55 W compact
fluorescence lamp
2,4-dichlorophenoxyacetic
acid (2,4-D)
AC
C
Coupling
system
-Fe2O3
/ZnO
(0.5 wt.%
-Fe2O3)
Fe3O4/ZnO
(1:10)
Dai et al.,
2014
56.4
98.4
Lam et al.,
2013c
ACCEPTED MANUSCRIPT
SiO2/ZnO
(5 wt.%)
SnO2/ZnO
(5 wt.%)
SnO2/ZnO
(1:2)
SnO2/ZnO
(1:1)
57.8
100
Lam et al.,
2014
~ 55.0
~ 100
Zhang et
al., 2014a
15.0
90.0
Zhou et
al., 2012
Zhai et al.,
2010
84.0
100
Kuzhalosai
et al., 2013
~ 35.0
~ 60.0
Yang et
al., 2010
80.0
100
Uddin et
al., 2012
RI
PT
Reference
SC
Nb2O5/ZnO = 1 g/L
[Phenol] = 20 mg/L
Irradiation time = 40 min
RGO/ZnO = 0.1 g/L
[Rh6G] = 10 mg/L
Irradiation time = 10 min
RGO/ZnO = 0.4 g/L
[MB] = 9.6 mg/L
Irradiation time = 150 min
SiO2/ZnO = N/A
[RhB] = 4.8 mg/L
Irradiation time = 100 min
SnO2/ZnO = 5 g/L
[AO10] = 226.2 mg/L
Irradiation time = 60 min
SnO2/ZnO = 1.33 g/L
[MO] = 20 mg/L
Irradiation time = 100 min
SnO2/ZnO = 1 g/L
[MB] = 10 mg/L
Irradiation time = 40 min
M
AN
U
RGO/ZnO
(1:2)
150 W Hg lamp
Rhodamine 6G
(Rh6G)
12 W UV lamp
Methylene Blue
(MB)
UV light
Rhodamine B
(RhB)
8 W UV light
Acid Orange 10
(AO10)
4x40 W UV lamp
Methyl Orange
(MO)
125 W high
pressure Hg lamp
Methylene Blue
(MB)
NaNbO3/ZnO = 1 g/L
[MB] = 10 mg/L
Irradiation time = 60 min
TE
D
RGO/ZnO
Experimental conditions
EP
Nb2O5/ZnO
Light source /
Pollutant
2 x 125 W Hg
lamp
Methylene Blue
(MB)
Natural sunlight
Phenol
AC
C
Coupling
system
NaNbO3
/ZnO
(10 wt.%)
Xu et al.,
2011
ACCEPTED MANUSCRIPT
ZnO2/ZnO
(75:25)
ZrO2/ZnO
ZrO2/ZnO
(1:2)
8 x 8 W low
pressure Hg lamp
2,4-dichlorophenol (2,4-DCP)
Reference
75.0
Pozan and
Kambur,
2014
Yu et al.,
2011
SC
RI
PT
41.0
M
AN
U
WO3/ZnO
(2 at.%)
TE
D
WO3/ZnO
(2 at.%)
Experimental conditions
EP
TiO2/ZnO
(80:20)
Light source /
Pollutant
UV lamp
Methylene Blue
(MB)
16 W UV-B lamp
4-chlorophenol
(4CP)
15 W UV light
Acid Orange II
(AOII)
55 W compact
fluorescence lamp
Resorcinol
(ReOH)
8 x 12 W UV light
Methyl Orange
(MO)
15 W Hg lamp
Dimethyl
phthalate (DMP)
AC
C
Coupling
system
TiO2/ZnO
100
66.0
Pant et al.,
2012
70.0
100
Lam et al.,
2013a
20.0
45.0
Hsu and
Wu, 2005
40.0
80.0
Liao et al.,
2010
Sherly et
al., 2014
ACCEPTED MANUSCRIPT
Phenylhydrazine
75 W medium pressure
mercury lamp,
ZnO = 0.25 g L-1
Ortho-nitrophenol
30 W UV-C lamp,
ZnO = 0.05 g
Herbicides
Metamitron
EP
AC
C
Fungicides
2-phenylphenol
(OPP)
RI
PT
SC
4-chlorophenol
(4CP)
Degradation rate
M
AN
U
Phenolics
4-fluorophenol
(4FP)
Experimental conditions
TE
D
Pollutant
Reference
Selvam et al.,
2007
Gaya et al.,
2009
NezamzadehEjhieh and
KhodabakhshiChermahini,
2014
Assi et al.,
2014
Khodja et al.,
2001
Mijin et al.,
2009
ACCEPTED MANUSCRIPT
Pesticides
Dimethoate
Pharmaceuticals
Amoxicillin
(AMX),
Amplicillin
(AMP),
Cloxacillin
(CLX)
Tetracycline (TC)
RI
PT
Evgenidou et
al., 2005b
Elmolla and
Chaudhuri,
2010
SC
Daneshvar et
al., 2007
Evgenidou et
al., 2005a
Zsigmind,
2014
M
AN
U
Imidacloprid
Reference
TE
D
Dichlorvos
Degradation rate
EP
Insecticides
Diazinon
Experimental conditions
AC
C
Pollutant
Palominos et
al., 2009
ACCEPTED MANUSCRIPT
Orang II
(OII)
(b) Cationic dyes
Acridine Orange
(AO)
Methylene Blue
(MB)
AC
C
Reference
Sobana and
Swaminathan,
2007
Xie et al.,
2011
Siuleiman et
al., 2014
Pare et al.,
2008
Mai et al.,
2008
EP
Methyl Green
(MG)
RI
PT
SC
Methyl Orange
(MO)
Degradation rate
M
AN
U
Dyes
(a) Anionic dyes
Acid Red 18
(AR18)
Experimental conditions
TE
D
Pollutant
Danwittayakul
et al., 2015
ACCEPTED MANUSCRIPT
SC
RI
PT
Caption of Figures
M
AN
U
Figure 1. Structures of ZnO consist of (a) rocksalt (cubic), (b) zinc blende (cubic) and (c)
AC
C
EP
TE
D
ACCEPTED MANUSCRIPT
M
AN
U
SC
RI
PT
AC
C
EP
TE
D
M
AN
U
SC
RI
PT
ACCEPTED MANUSCRIPT
AC
C
EP
TE
D
surface.
SC
RI
PT
ACCEPTED MANUSCRIPT
AC
C
EP
TE
D
M
AN
U
Figure 7. The band structure of a composite photocatalyst, prepared by a mixture of wideand narrow-band-gap photocatalysts.
ACCEPTED MANUSCRIPT
Highlight
ZnO has emerged as one of the leading photocatalyst candidate.
AC
C
EP
TE
D
M
AN
U
SC
RI
PT