Journal of Hazardous Materials 170 (2009) 520–529

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Journal of Hazardous Materials

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Review

Parameters affecting the photocatalytic degradation of dyes

using TiO2 -based photocatalysts: A review
U.G. Akpan, B.H. Hameed ∗
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents the review of the effects of operating parameters on the photocatalytic degradation
Received 19 January 2009 of textile dyes using TiO2 -based photocatalysts. It further examines various methods used in the prepara-
Received in revised form 28 March 2009 tions of the considered photocatalysts. The findings revealed that various parameters, such as the initial
Accepted 11 May 2009
pH of the solution to be degraded, oxidizing agents, temperature at which the catalysts must be calcined,
Available online 18 May 2009
dopant(s) content and catalyst loading exert their individual influence on the photocatalytic degradation
of any dye in wastewaters. It was also found out that sol–gel method is widely used in the production
Keywords:
of TiO2 -based photocatalysts because of the advantage derived from its ability to synthesize nanosized
Parameters
Photocatalytic degradation
crystallized powder of the photocatalysts of high purity at relatively low temperature.
Dopant © 2009 Elsevier B.V. All rights reserved.
Preparation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
1.1. Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
1.2. Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
1.2.1. Titanium dioxide photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
2. Operating parameters in photocatalytic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
2.1. Influence of pH on photocatalytic degradation of dyes in wastewaters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
2.2. Oxidizing agents effect on photocatalytic degradation of dyes in wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
2.3. Catalyst loading effects on photocatalytic degradation of dyes in wastewaters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
2.4. Dopant content effect on photocatalytic activity of photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
2.5. Influence of calcination temperature on the activity of photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
3. Methods of TiO2 -based photocatalysts preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527

1. Introduction and human beings [1]. These deleterious effects of chemicals on

the earth ecosystems are a cause for serious concern. Several of
The effluents, gaseous or liquid produced by some of our indus- these chemicals such as azo dyes, herbicides, and pesticides are
tries are harmful to the health and general well-being of man. When actually present in rivers and lakes, and are in part suspected of
undesirable substances are present in liquid effluents, it can be being endocrine-disrupting chemicals (EDCs) [2–5].
disastrous as their presence pose severe threat to the immediate Konstantinou and Albanis [6] reported that textile dyes and
recipients. Wastewaters from various industries, factories, labora- other industrial dyestuffs constitute one of the largest groups of
tories, etc. are serious problems to the environment. The discharged organic compounds that represent an increasing environmental
wastes containing dyes are toxic to microorganisms, aquatic life danger. About 1–20% of the total world production of dyes is lost
during the dyeing process and is released in the textile effluents
[7]. The release of those colored wastewaters in the environment
∗ Corresponding author. Tel.: +60 4 599 6422. is a considerable source of non-aesthetic pollution and eutrophi-
E-mail address: [email protected] (B.H. Hameed). cation and can originate dangerous byproducts through oxidation,

0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.05.039
 U.G. Akpan, B.H. Hameed / Journal of Hazardous Materials 170 (2009) 520–529 521

Fig. 1. Schematic diagram of photocatalytic process initiated by photon acting on the semiconductor [27].

hydrolysis, or other chemical reactions taking place in the wastew- reactions are activated by absorption of a photon with sufficient
ater phase. It must be noted that dyes can present toxic effects and energy (equals or higher than the band-gap energy (Ebg ) of the
reduce light penetration in contaminated waters [8]. catalyst) [26]. The absorption leads to a charge separation due to
Degradation of dyes in industrial wastewaters has therefore promotion of an electron (e− ) from the valence band of the semicon-
received increasing attention and some methods of remediation ductor catalyst to the conduction band, thus generating a hole (h+ )
have been proffered. Traditional physical techniques (adsorption in the valence band (the schematic diagram of the process is pre-
on activated carbon, ultrafiltration, reverse osmosis, coagulation by sented in Fig. 1 [27]). The recombination of the electron and the hole
chemical agents, ion exchange on synthetic adsorbent resins, etc.) must be prevented as much as possible if a photocatalyzed reaction
have been used for the removal of dye pollutants [6,9]. These meth- must be favored. The ultimate goal of the process is to have a reac-
ods only succeed in transferring organic compounds from water to tion between the activated electrons with an oxidant to produce a
another phase, thus creating secondary pollution. This will require a reduced product, and also a reaction between the generated holes
further treatment of solid-wastes and regeneration of the adsorbent with a reductant to produce an oxidized product. The photogener-
which will add more cost to the process. Microbiological or enzy- ated electrons could reduce the dye or react with electron acceptors
matic decomposition [10], biodegradation [11], ozonation [12], and such as O2 adsorbed on the Ti(III)-surface or dissolved in water,
advanced oxidation processes such as Fenton and photo-Fenton cat- reducing it to superoxide radical anion O2 −• [6]. The photogener-
alytic reactions [6,13], H2 O2 /UV processes [14] have also been used ated holes can oxidize the organic molecule to form R+ , or react
for dyes removal from wastewaters. with OH− or H2 O oxidizing them into OH• radicals. Together with
Forgacs et al. [15] noted that traditional wastewater treatment other highly oxidant species (peroxide radicals) they are reported
technologies have proven to be markedly ineffective for handling to be responsible for the heterogeneous TiO2 photodecomposition
wastewater of synthetic textile dyes because of the chemical stabil- of organic substrates as dyes. The resulting • OH radical, being a
ity of these pollutants, and went further to verify that 11 out of 18 very strong oxidizing agent (standard redox potential +2.8 V) can
azo dyes selected for their investigations passed through the acti- oxidize most azo dyes to the mineral end-products. According to
vated sludge process practically untreated. Most textile dyes are this, the relevant reactions at the semiconductor surface causing
photocatalytically stable and refractory towards chemical oxida- the degradation of dyes can be expressed as follows [6]:
tion [16], and these characteristics render them resistant towards
decolorization by conventional biochemical and physico-chemical TiO2 + hv(UV) → TiO2 (eCB − + hVB + ) (1)
methods. All the aforementioned processes have a wide range of TiO2 (hVB + ) + H2 O → TiO2 + H+ + OH• (2)
their deficiencies in the removal of dyes from wastewaters.
+ −
Recent studies [11,17–23] have been devoted to the use of pho- TiO2 (hVB ) + OH → TiO2 + OH• (3)
tocatalysis in the removal of dyes from wastewaters, particularly,
because of the ability of this method to completely mineralize the TiO2 (eCB − ) + O2 → TiO2 + O2 −• (4)
target pollutants [24]. −• + •
O2 + H → HO2 (5)
The present work is slated to review the effects of operating
parameters on the photocatalytic degradation of textile dyes using Dye + OH• → degradationproducts (6)
TiO2 -based photocatalysts. A brief review of the methods of prepa-
ration of the photocatalysts will also be presented. Dye + hVB + → oxidationproducts (7)
−
Dye + eCB → reductionproducts (8)
1.1. Photocatalysis
where hv is photon energy required to excite the semiconductor
Photocatalysis may be termed as a photoinduced reaction which electron from the valence band (VB) region to conduction band (CB)
is accelerated by the presence of a catalyst [25]. These types of region.
522 U.G. Akpan, B.H. Hameed / Journal of Hazardous Materials 170 (2009) 520–529

1.2. Semiconductors are the proofs of enhancement of the efficiency of TiO2 by doping
[23,38–47]. Krishna et al. [48] also reported a 2.6 times higher rate
Semiconductors (such as TiO2 , ZnO, Fe2 O3 , CdS, and ZnS) can coefficient for PHF-TiO2 over TiO2 for the degradation of triazine
act as sensitizers for light-induced redox-processes due to the elec- monoazo compound Pricion red MX-5B.
tronic structure of the metal atoms in chemical combination, which
is characterized by a filled valence band, and an empty conduction 2. Operating parameters in photocatalytic processes
band [28]. Upon irradiation, valence band electrons are promoted
to the conduction band leaving a hole behind. These electron–hole In photocatalytic degradation of dyes in wastewaters, the fol-
pairs can either recombine or can interact separately with other lowings are operating parameters which affect the process: pH of
molecules. The holes may react either with electron donors in the solution to be degraded, and the pH of the precursor solu-
the solution, or with hydroxide ions to produce powerful oxidiz- tion (catalyst’s solution during preparation of catalyst); oxidizing
ing species like hydroxyl (oxidation potential 2.8 V) or superoxide agent, calcination temperature, dopant content, and catalyst load-
radicals [29]. ing. These parameters will be considered one after the other as they
In other word, semiconductor materials are materials whose influenced the photocatalytic processes of the degradation of dyes
valence band and conduction band are separated by an energy in wastewaters.
gap or band-gap. When a semiconductor molecule absorbs pho-
tons with energy equal or greater than its band-gap, electrons in 2.1. Influence of pH on photocatalytic degradation of dyes in
the valence band can be excited and jump up into the conduction wastewaters
band, and thus charge carriers are generated. In order to have a pho-
tocatalyzed reaction, the e− –h+ recombination, subsequent to the The interpretation of pH effects on the efficiency of dye pho-
initial charge separation, must be prevented as much as possible todegradation process is a very difficult task because of its multiple
[30]. roles [6]. First, is related to the ionization state of the surface accord-
Among all these semiconductors, the most widely used semi- ing to the following reactions,
conductor catalyst in photoinduced processes is titanium dioxide
(TiO2 ). Though TiO2 has the disadvantage of not being activated by TiOH + H+ = TiOH2 + (9)
visible light, but by ultraviolet (UV) light, it is advantageous over
TiOH + OH− = TiO− + H2 O (10)
the others in that it is chemically and biologically inert, photo-
catalytically stable, relatively easy to produce and to use, able to as well as to that of reactant dyes and products such as acids
efficiently catalyze reactions, cheap and without risks to environ- and amines. pH changes can thus influence the adsorption of dye
ment or humans [26]. molecules onto the TiO2 surfaces, an important step for the photo-
catalytic oxidation to take place [49]. Bahnemann et al. [50] have
1.2.1. Titanium dioxide photocatalyst already reviewed that acid-base properties of the metal oxide sur-
Titanium dioxide (TiO2 ) or titania is a very well-known and well- faces can have considerable implications upon their photocatalytic
researched material due to the stability of its chemical structure, activity.
biocompatibility, physical, optical and electrical properties. It exists Second, hydroxyl radicals can be formed by the reaction between
in four mineral forms [31], viz: anatase, rutile, brookite and titanium hydroxide ions and positive holes. The positive holes are considered
dioxide (B) or TiO2 (B). Anatase type TiO2 has a crystalline struc- as the major oxidation species at low pH, whereas hydroxyl radicals
ture that corresponds to the tetragonal system (with dipyramidal are considered as the predominant species at neutral or high pH
habit) and is used mainly as a photocatalyst under UV irradiation. levels [51]. It was stated that in alkaline solution, • OH are easier
Rutile type TiO2 also has a tetragonal crystal structure (with pris- to be generated by oxidizing more hydroxide ions available on TiO2
matic habit). This type of titania is mainly used as white pigment surface, thus the efficiency of the process is logically enhanced [52].
in paint. Brookite type TiO2 has an orthorhombic crystalline struc- Similar results are reported in the photocatalyzed degradation of
ture. TiO2 (B) is a monoclinic mineral and is a relatively newcomer acidic azo dyes and triazine containing azo dyes [9,53,54], although
to the titania family. TiO2 , therefore is a versatile material that has it should be noted that in alkaline solution there is a Coulombic
applications in various products such as paint pigments, sunscreen repulsion between the negative charged surface of photocatalyst
lotions, electrochemical electrodes, capacitors, solar cells and even and the hydroxide anions. This fact could prevent the formation of
as a food coloring agent and in toothpastes [32]. • OH and thus decrease the photoxidation.

The possible application for this material as a photocatalyst in a Third, it must also be noted that TiO2 particles tend to agglom-
commercial scale water treatment facility is due to several factors: erate under acidic condition and the surface area available for dye
adsorption and photon absorption would be reduced [49]. The
(a) Photocatalytic reaction takes place at room temperature. degradation rate of some azo dyes increases with decrease in pH
(b) Photocatalytic reactions do not suffer the drawbacks of pho- as reported elsewhere [55].
tolysis reactions in terms of the production of intermediate The study of Baran et al. [56] also showed that the degradation
products because organic pollutants are usually completely of Bromocresol purple dye under acidic condition was better than
mineralized to non-toxic substances such as CO2 , HCl and water in alkaline medium, and that the molecules are positively charged.
[33–36]. Precisely, after the solution was acidified from pH 8.0 to pH 4.5,
(c) The photocatalyst is inexpensive and can be supported on var- a six-fold increase in adsorption efficacy was observed. Such an
ious substrates such as, glass, fibers, stainless steel, inorganic increase in adsorption efficacy could not be explained only through
materials, sand, activated carbons (ACs), allowing continuous changes of the TiO2 surface (probably caused by a change of pH)
re-use. [57].
(d) Photogenerated holes are extremely oxidizing and photogener- The mechanism of the photocatalytic reaction in the presence of
ated electrons reduce sufficiently to produce superoxides from TiO2 consists of a free radical reaction initiated by UV light [56]. The
dioxygens [37]. mechanism may depend on the ability of the degraded compound
to be adsorbed on the surface of the catalyst. The extent of such
The effectiveness of TiO2 photocatalyst can be enhanced by dop- adsorption depends on many factors, and one of it is the charge of
ing metal and non-metal ions into it. The following investigations the degraded compound. It was found that in photocatalytic degra-
 U.G. Akpan, B.H. Hameed / Journal of Hazardous Materials 170 (2009) 520–529 523

Table 1
pH influence on the photocatalytic degradation of various pollutants and an insecticide.

Pollutant type Light source Photocatalyst Tested pH range Optimum pH Ref.

Fast Green FCF UV TiO2 3.0–11.0 4.4 [19]

Patent Blue VF UV TiO2 3.0–11.0 11.0 [19]
Salicylic acid UV TiO2 1.0–11.0 2.3a [22]
Orange G UV Sn/TiO2 /AC 1.0–12.0 2.0 [23]
BRL UV K-TiO2 4.5–11.8 7.2 [38]
Methyl orange UV Pt-TiO2 2.5–11.0 2.5 [39]
Orange G Visible N-TiO2 1.5–6.5 2.0 [43]
Acid Red B UV Ce-TiO2 1.5–7.0 1.5 [44]
4-Chlorophenol UV N-TiO2 2.0–5.0 3.0a [45]
Orange II Solar Zn-TiO2 3.0–10.0 3.0 [46]
Bromocresol purple UV TiO2 4.5 and 8.0 4.5 [56]
a
pH of precursor solution (catalysts solution during preparation of catalysts).

dation, the adsorption level on unmodified TiO2 is higher for dyes alytically degraded at lower pH, while others do so at higher pH.
with a positive charge (cationic) than for those with a negative All these may be attributed to the nature of the pollutant to be
charge (anionic) [58]. As the charge depends on the pH of a given degraded. Therefore, it is important to study the nature of the pol-
solution, it follows that both pH and the nature of a particular dye lutants to be degraded, and determine the probably right pH to
influence the photocatalyst activity [9,29,59–62]. photocatalytically degrade them.
The degradation rate of azo dyes increases with decrease in pH Influence of pH of the solution of precursor on the photo-
[6]. At pH <6, a strong adsorption of the dye on the TiO2 particles is catalytic activity of Ni-TiO2 photocatalyst on the degradation of
observed as a result of the electrostatic attraction of the positively 4-chlorophenol under UV light had also been studied [45]. In this
charged TiO2 with the dye. At pH >6.8 as dye molecules are nega- case, photocatalysts were prepared at different pH range (2.0–5.0),
tively charged in alkaline media, their adsorption is also expected and calcined at the same temperature, 500 ◦ C. The photocatalytic
to be affected by an increase in the density of TiO− groups on the activity of N-doped TiO2 nanoparticles was found to increase as the
semiconductor surface. Thus, due to Coulombic repulsion the dyes pH decreased from 5.0 to 3.0. Further decrease in pH to 2.0 affected
are scarcely adsorbed [63,64]. the photocatalytic activity of the catalyst negatively. Hence, the
The effects of pH on photocatalytic degradation of dyes have optimum pH for that particular catalysts’ preparation was 3.0. The
been studied by many Researchers [1,19,23,38,39,42–44,56,65]. In reason advanced for the adverse effect of low pH on the photocat-
studying the effects of pH on the photocatalytic degradation of dyes, alyst performance is that the possible increase of H+ concentration
two things must be borne in mind; one, industrial effluents may may restrain hydrolyzation of Ti(OBu)4 and thereby reduces the
not be neutral, and two; pH of the reaction mixture influences the crystal size of the prepared N-doped TiO2 nanoparticles. Again,
surface-charge-properties of the photocatalysts [17]. too low pH such as 2.0 would result in phase transformation from
Sleiman et al. [11] reported on the influence of pH on the pho- anatase to rutile [67].
tocatalytic degradation of Metanil Yellow, an anionic dye with a
sulphonate group, over TiO2 photocatalyst under UV illumination. 2.2. Oxidizing agents effect on photocatalytic degradation of dyes
Their results indicated that the process efficiency is not consid- in wastewater
erably affected over a wide range of pH (4–8). They added that
the interpretation of pH effect can be principally explained by a Reports show that oxidizing agents have a great deal of influence
modification of the electrical double layer of the solid–electrolyte on the photocatalytic degradation of dyes. It was demonstrated
interface, which consequently affects the sorption–desorption pro- by Saquiba et al. [19] that hydrogen peroxide (H2 O2 ), ammonium
cesses and the separation of the photogenerated electron–hole persulphate ((NH4 )2 S2 O8 ) and potassium bromate (KBrO3 ) have
pairs at the surface of the semiconductor particles. Their study also individual influence on the degradation of Fast Green FCF (1) and
explained that since Metanil Yellow is an anionic dye and has a Patent Blue VF (2) using Hombikat UV 100 and Degussa P25 as
sulphonate group, its adsorption is favored at low pH (the extent of respective photocatalysts. Their results revealed that potassium
adsorption is almost two-fold at pH 4.0 compared to that at neu- bromate and ammonium persulphate had a beneficial effect on the
tral pH). The results of their findings showed that the nature of the degradation rate for the decomposition of dye 1 in the presence of
substance to be degraded affects the operating pH of the system. UV 100; whereas in the case of dye 2, all the electron acceptors were
Zhiyong et al. [46] in their work – ZnSO4 -TiO2 doped cat- found to enhance the rate markedly in the presence of P25.
alyst with higher activity in photocatalytic processes, reported Huang et al. [39] also studied the effect of adding H2 O2 on the
on the effect of pH on the photocatalytic degradation of Orange decolorization of methyl orange. The decolorization rate was found
II, an anionic dye with –SO3 group. Their results showed that to increase with increase in H2 O2 concentration. The experiment
the photocatalytic activity was most favored at a lower pH was conducted at the concentration range of 0.4–2 mM/l H2 O2 .
(3.0), but went on at a slower and inefficient rate at pH 10.0. They reported an optimum addition of 1.2 mM/l H2 O2 for photo-
It is important to note that the photocatalytic degradation of catalytic decolorization of methyl orange solution by Pt modified
some dyes is more effective at about neutral pH [38], and TiO2 loaded on natural zeolite. Actually, addition of H2 O2 enhanced
others in alkaline medium [19]. It has earlier been reported the reaction. Zhiyong et al. [47] also reported that addition of
that in alkaline medium, there is a greater probability for the H2 O2 (1 mM) to methyl orange solution mediated TiO2 Degussa
formation of hydroxyl radical (• OH), which can act as an oxi- P25 (0.5 g/l) under sunlight irradiated photocatalyst brought about
dant, thus increasing the rate of photodegradation of the dye methyl orange degradation in 1 h.
[66]. Oxygen is required as electrons scavenger to keep the photocat-
In summary, Table 1 presents pH influence on the photodegra- alytic reaction, and the amount of oxygen going into the system is an
dation of various dyes. The table reveals that different dyes have important parameter. The air (oxygen) flow into the photocatalytic
different activity in photocatalytic reaction. Some are photocat- system should be well regulated, as poor flow of oxygen can bring
524 U.G. Akpan, B.H. Hameed / Journal of Hazardous Materials 170 (2009) 520–529

about an adverse effect on the photocatalytic reaction as reported simple one-carbon molecular structure as a hole scavenger to inves-
elsewhere [17]. tigate its effect on nitrate reduction. The oxidation of formic acid
Konstantinou and Albanis [6] affirmed that H2 O2 and S2 O8 2− to carbon dioxide is straightforward and involves minimal inter-
were beneficial for the photoxidation of the dyes of different chemi- mediate product [74,75]. Also, formic acid is capable of forming
cal groups including azo dyes. This is in conformity with the findings reducing radicals, which could help in the reduction reaction [76].
of Augugliaro et al. [68] and, Saquib and Muneer [69]. The reactive Rengaraj and Li [73] confirmed from their study that without the use
radical intermediates (SO4 −• and • OH) formed from these oxidants of the sacrificial hole scavenger (formic acid), there was no catalytic
by reactions with the photogenerated electrons can exert a dual activity of either TiO2 or Bi3+ -TiO2 in the nitrate solution. They also
function: as strong oxidant themselves and as electron scavengers, agreed that there is an optimal dosage of the scavenger that must
thus inhibiting the electron–hole recombination at the semicon- be used for the photodegradation of nitrate in the specific reaction
ductor surface [26] according to the following equations: considered.
Putting all together, there is the need to consider the effect of
H2 O2 + O2 −• → • OH + OH− + O2 (11) oxidizing agent in the photocatalytic degradation of textile dyes.
H2 O2 + hv → 2• OH (12)
2.3. Catalyst loading effects on photocatalytic degradation of dyes
− • OH −
H2 O2 + eCB → + OH (13) in wastewaters

S2 O8 2− + eCB − → SO4 2− + SO4 −• (14)

The effects of catalyst loading on photocatalytic degradation
SO4 −• + H2 O → SO4 2− + • OH + H+ (15) of dyes in wastewaters have been studied [6,19,38,39,43,77].
Konstantinou and Albanis [6], in their review of TiO2 -assisted pho-
It must be noted that the addition of peroxide increases the rate tocatalytic degradation of azo dyes in aqueous solution reported
towards real reaction with adequate oxygen supply, because the that in any reactor system, the initial rates were found to be
solution phase may at times be oxygen starved as a result of either directly proportional to catalyst concentration, indicating the het-
oxygen consumption or slow oxygen mass transfer. The presence of erogeneous regime. They further observed that there is a limit of
persulphate positively affects the mineralization rate, despite the catalyst concentration that must be used for the photodegrada-
decrease of pH as the oxidant properties of the system probably tion of a particular pollutant in wastewater, above which the rate
prevail on the effect of pH reduction. of photocatalysis will even decrease. This is in agreement with
Other works [23,43] have also revealed the effect of oxidants in recent reports [17,19,38,39,43,77]. Konstantinou and Albanis [6]
photocatalytic reactions. It was pointed out as part of their find- also reported an enhanced degradation rates for optimum catalyst
ings that one practical problem in using TiO2 as photocatalysts is loading up to 0.4–0.5 g/l. This seems to vary from recent reports as
the undesired electron–hole recombination, which in the absence shown in Table 2, though one of the reports agrees with their report.
of proper electron acceptor or donor, is extremely efficient and The reason generally advanced for this is that the increase in
thus represents the major energy-wasting step, thereby limiting the the amount of catalyst increases the number of active sites on
achievable quantum yield. They therefore opined that, one strat- the photocatalyst surface, which in turn increase the number of
egy to inhibit electron–hole recombination is to add irreversible hydroxyl and superoxide radicals. Again, when the concentration
electron acceptors to the reaction system, and they used H2 O2 to of the catalyst increases above the optimum value, the degradation
study its effect on photodegradation of Orange G (OG) on the N- rate decreases due to the interception of the light by the suspen-
doped TiO2 under different light sources. The results indicated that sion [17]. Sun et al. [43] added that as the excess catalyst prevent the
there was an optimal dosage of H2 O2 , at which the degradation illumination, • OH radical, a primary oxidant in the photocatalytic
efficiency of OG on the N-doped TiO2 attained the height. At higher system decreased and the efficiency of the degradation reduced
dosage of H2 O2 beyond the optimum, the degradation efficiency accordingly. Furthermore, the increase of catalyst concentration
of OG decreased. This was because the very reactive • OH radicals beyond the optimum may result in the agglomeration of catalyst
and valence band holes could be consumed by H2 O2 itself as given particles, hence the part of the catalyst surface become unavailable
in Eqs. (16)–(18) [70,71]. At the same time, radical–radical recom- for photon absorption, and degradation rate decrease [39].
bination as a competitive reaction must be taken into account, as
described in Eq. (19) [6]. 2.4. Dopant content effect on photocatalytic activity of
• OH • photocatalysts
+ H2 O2 → HO2 + H2 O (16)
• OH •
+ HO2 → O2 + H2 O (17) Dopants contents on photocatalytic activity of photocatalysts
have been investigated [44,78–83]. The results of Bouras et al. [78]
+ +
TiO2 (hVB ) + H2 O2 → TiO2 + O2 + 2H (18) revealed that the photocatalytic degradation of Basic Blue 41 dye
HO• + HO• → H2 O2 (19) under UV light was more favored in the presence of pure TiO2 , than
in the presence of Fe-doped TiO2 . A continuous decrease in the per-
As both • OH and hVB + are strong oxidants for organic pollutants, centage degradation of the dye from 80 to about 1 as the dopant
the photocatalytic degradation of OG will be inhibited in the con- content increased from 0 to 30 at% Fe was observed. The same trend
dition of excess of H2 O2 . Furthermore, H2 O2 can be adsorbed onto was observed for Cr-TiO2 and Co-TiO2 , though at varying % reduc-
TiO2 particles to modify their surfaces and subsequently decrease tion. This is a pointer to the fact that transition metals TiO2 -doping
its catalytic activity [72]. can at times be detrimental to the photocatalytic degradation of
Again, the wavelength and intensity of the light sources affect some dyes.
the H2 O2 performance as oxidizing agent in photocatalytic degra- On the other hand, metal–TiO2 -doping is always advanta-
dation of organic pollutants. This was also demonstrated by Sun et geous to the photocatalytic degradation of dyes in wastewaters as
al. [23]. Their findings revealed that the optimal dosage of H2 O2 for depicted in Table 3, but for Bouras et al. [78]. The optimum dopant,
photodegradation of OG under sunlight was 5.0 mM/l, while under either mol% or wt% vary from catalyst to catalyst. Table 3 shows
visible light was 15.0 mM/l. the effect of dopant content on photocatalytic activity of photocat-
In order to improve on the performance of photocatalytic reac- alysts; and from the table, % optimum dopant vary from 0.06 to 1.0
tion of Bi3+ doped TiO2 , Rengaraj and Li [73], used formic acid with a for degradation of dyes in wastewater, and 1.25–2.25 for hydrogen
 U.G. Akpan, B.H. Hameed / Journal of Hazardous Materials 170 (2009) 520–529 525

Table 2
Effects of catalysts loading on the photocatalytic degradation of dyes in wastewaters.

Pollutant Light source Photocatalyst Range of catalyst wt. (g/l) Optimum wt. cat. (g/l) % Degradation Ref.
a b
Fast Green UV TiO2 0.5–4.0 [19]
b
Acid Blue UV TiO2 0.5–4.0 2.0 [19]
Orange G UV Sn/TiO2 /AC 5.0–15.0 12.5 99.1/h [23]
Everdirect Blue (BRL) UV K-TiO2 0–2.0 1.5 – [38]
Methyl orange UV Pt-TiO2 0.5–6.0 3 90.5c [39]
Methyl orange Visible SiO2 -TiO2 0–1.0 0.055 – [77]
a
Continuous increase.
b
Not indicated.
c
Time not indicated.

production. Any further increase in dopant content, exert negative amount of dopant at the surface of TiO2 could notably screen the
effect on the activity of photocatalyst. Liao et al. [81] showed that TiO2 from the UV light and inhibit the interfacial electron and hole
there is a particular ratio of Zn to Ti that must produce an opti- to transfer, which would result in a low photo-activity [80]. On
mum degradation of methyl orange. Using two different surfactants the other hand, Xin et al. [85] observed that the excessive oxygen
(sodium dodecyl benzene sulphonate (DBS) and sodium dodecyl vacancies and dopant (Cu) species can become the recombination
sulphonate (SDS)) Zn/Ti ratio of 0.25/1.0 gave the highest reaction centers of photoinduced electrons and holes, and that the excessive
rates at calcinations temperatures of 600, 700, and 800 ◦ C. Zhiyong P-type Cu2 O can cover the surface of TiO2 , leading to decrease in the
et al. [46] also reported on the effects of doping TiO2 with ZnSO4 . photocatalytic activity of the photocatalyst.
They observed that there was a great deal of enhancement in the
discoloration of Orange II by doping TiO2 with different mol% Zn. 2.5. Influence of calcination temperature on the activity of
Their report also showed that a doping level as high as 4 mol% Zn photocatalysts
seemed to affect adversely the surface area of TiO2 precluding reac-
tant absorption. Their optimum doping level seems to be 2 mol% Zn. Depending on the method of the preparation and the end usage
Boron- and cerium-codoped TiO2 has also been reported [44]. The of the TiO2 or doped TiO2 photocatalysts, calcination temperatures
contents of different dopants at various ratios also exerted different have prominent influence on the activity of the prepared photo-
effects on the photocatalytic activity of the prepared photocatalyst. catalysts. Yu et al. [45] prepared nitrogen-doped TiO2 nanoparticle
In this case, the best doping content was 1.6 and 0.5 wt% B and Ce catalyst and analyzed its catalytic activity under visible light. In
respectively. their work, the influence of the calcination temperature on photo-
Li et al. [80] offered explanation for the continuous increase in catalytic degradation of methylene blue (MB) under UV irradiation
activity of photocatalyst with increase in dopant content until it was examined. The N-doped TiO2 samples were subjected to var-
reaches the optimum. One, using alkaline earth metals, the metal ious calcination temperatures ranging from 300 to 700 ◦ C. The
oxide (MO) deposited on the TiO2 particles can form a space charge results of their investigations revealed that the photocatalytic
layer, which can separate the photoinduced electron–hole pairs. As activity of the prepared photocatalysts increased with increase in
the concentration of dopants increases, the surface barrier becomes temperature from 300 to 500 ◦ C. At 500 ◦ C, it reached the maximum,
higher and the electron–hole pairs within the region are efficiently because of complete crystallization of anatase at this temperature.
separated by the large electric field. Two, due to the difference in However, the catalytic activity of the N-doped TiO2 decreased with
electron negativity between Ti and M, the Ti–O–M formed via M2+ further increase of calcination temperature from 500 to 700 ◦ C. This
entering into the shallow surface of TiO2 could promote the charges was also found to be consistent with their TEM analysis, which
to transfer, resulting in an increase of photocatalytic activity. Three, showed that at 600 ◦ C and above, a mixture of anatase and rutile
alkaline earth metal ion doping can cause a lattice deformation and phases of the sample were formed.
produce defects in the crystal. The defects can inhibit the recombi- The effect of calcination temperature on the photocatalytic
nation of electron–hole pairs and, eventually, enhance the activity. activity of Zn-TiO2 has also been investigated on the photocat-
When in excess, the existence of dopant on the particle surface alytic degradation of Rhodamine B [84]. Their results also revealed
of TiO2 lessens the specific area of TiO2 , impedes the adsorption of that the photocatalytic activity of Zn-TiO2 rapidly increased and
reactant and thus, inhibits the photocatalytic activity [84]. Excess was optimum at 500 ◦ C as the calcination temperature increased

Table 3
The effect of dopant contents on photocatalytic activity of photocatalysts.

Degraded pollutant and hydrogen production Light source Photocatalyst Range of doping (%) Optimum doping (%) Ref.

Acid Orange 7 UV Pt-TiO2 0–2.0 2.0 [40]

Orange II Suntest lamp ZnSO4 -TiO2 0–6.0 2.0 [46]
Methyl orange UV (Pt-TiO2 pillared clay) 0–2.0 0.5 [79]

Hydrogen production [80]

Be-TiO2 0–4.5 1.25
Mg-TiO2 0–4.5 1.25
Ba-TiO2 0–4.5 2.25
Ca-TiO2 0–4.5 2.25
Sr-TiO2 0–4.5 2.25

Methyl orange UV ZnO-TiO2 0–0.5 0.25 [81]

Bisphenol A UV Ag-TiO2 0–2.0 1.0 [82]
Nitride Visible Sm3+ -TiO2 0–2.0 0.5 [83]
Rhodamine B UV Zn-TiO2 0–2.0 0.5 [84]
Rhodamine B UV Cu-TiO2 0–3.0 0.06 [85]
526 U.G. Akpan, B.H. Hameed / Journal of Hazardous Materials 170 (2009) 520–529

Table 4
Effects of calcinations temperature on surface areas, pore volumes and pore sizes of photocatalysts [38].

Samples TC (K) AS (m2 /g) Micropore surface areaa (m2 /g) External surface areaa (m2 /g) VP (cm3 /g) V␮P a (cm3 /g) Pore sizeb (Å)

TiO2 -400 673 119.4 1.4 118.0 0.394 – 103.0

TiO2 -550 823 57.7 – 57.7 0.252 – 37.0
TiO2 -700 973 18.8 – 18.8 0.121 – 209.0
TiO2 -850 1123 1.48 1.0 0.5 0.016 – 645.9
K1-400 673 94.2 9.0 85.0 0.300 0.0035 118.1
K1-550 823 60.0 5.9 54.0 0.288 0.0023 177.8
K1-700 973 40.9 5.1 35.8 0.294 0.0021 278.2
K1-850 1123 7.8 1.5 6.3 0.027 0.0006 158.5
K4-400 673 68.3 7.9 60.4 0.249 0.0028 180.3
K4-550 823 25.4 4.3 21.0 0.143 0.0018 242.9
K4-700 973 22.8 2.0 20.8 0.113 0.0007 198.9
K4-850 1123 10.8 2.5 8.3 0.045 0.001 204.2

TC : calcination temperature, AS : surface area, VP : pore volume, V␮P : micropore volume.

a
t-Plot method.
b
BJH adsorption/desorption average pore diameter.

from 300 to 500 ◦ C. Further increase in the calcination temperature 3. Methods of TiO2 -based photocatalysts preparation
from 500 to 900 ◦ C resulted in lower photocatalytic activity of the
prepared catalyst. The reason given for this is that the increase in Many methods have been reported for the production of TiO2
calcination temperature beyond 500 ◦ C can promote the transfor- nanopowders such as chemical solution decomposition (CSD) [86],
mation of anatase to rutile, which has little photocatalytic activity. chemical vapour decomposition [87–90], two-step wet chemical
In the same vein Zhiyong et al. [46] considered the effect of cal- method [91], sol–gel [22,23,42,44,45,77,79–85,92–114], ultrasonic
cination temperature on the ZnSO4 -TiO2 coated Raschig ring (RR) irradiation [115,116], ethanol thermal and hydrothermal [117–120].
photocatalytic degradation of Rhodamine B, and Orange II. In their The most widely used TiO2 in photocatalysis is commercial Degussa
study, the calcination temperature was fixed at 500 ◦ C, and the var- P25 produced by flame hydrolysis of TiCl4 at temperatures greater
ied parameter was the calcination time. Their findings revealed than 1200 ◦ C in the presence of hydrogen and oxygen. Recent lit-
that the catalyst treated at 500 ◦ C and 2 h led to the best enhance- erature [22,23,42,44,45,77,79–85,92–114] revealed that sol–gel is
ment during the discoloration of Rhodamine B. They went further the most commonly used method for the preparation of photocat-
to ascribe this trend to the diffusion of Zn-ions into TiO2 lattice. alysts, whether only TiO2 or doped TiO2 . The advantage of these
On the other hand, the discoloration of Orange II was acceler- methods (wet chemical methods, which include sol–gel) is that
ated using the photocatalyst calcined at 500 ◦ C for 5 h. The results they facilitate the synthesis of nanometer sized crystallized TiO2
also showed that there was a retrogressive effect on the discol- powder of high purity at relatively low temperature [115]. Other
oration of Orange II with ZnSO4 -TiO2 /RR calcined at 500 ◦ C for Researchers used modified sol–gel method [121,122], ultrasonic
7 h. This, they also attributed to an increase in the rutile content assisted sol–gel method [72], aerogel method [123], method simi-
in the TiO2 sample, hence lowering the photocatalytic activity of lar to sol–gel [38], sol–gel and photo-reductive decomposition [39],
the catalyst. At lower calcination time (3 h), the discoloration rate precipitation [43,124], two-step wet chemical method [91], and
of Orange II was lower than that of 5 h. Therefore, the optimum extremely low temperature precipitation [125].
time from their study for the calcination of ZnSO4 -TiO2 /RR is 5 h at
500 ◦ C.
Sun et al. [23] also studied the effect of calcination temperature 4. Conclusion
on photocatalytic activity of Sn(IV)/TiO2 /AC on the photocatalytic
degradation of Orange G. Their results showed that photocatalytic Various operational parameters affect the effectiveness or activ-
activity of the prepared catalyst was significantly influenced by the ities of TiO2 -based photocatalysts. It is therefore necessary to study
calcination temperature and that; the optimal calcination temper- the nature of the sample to be degraded, as this will provide a clue
ature was 550 ◦ C. Their XRD revealed that the sample calcined at on the type of photocatalyst to be used in its degradation. Some
550 ◦ C contained both anatase and rutile phases of TiO2 , which reactive dyes are degraded at higher pH, while others at lower pH;
may explain the higher photocatalytic activity for the degradation hence in photocatalytic degradation of dyes in wastewaters, the
of OG. This appears contradictory to the position of Yu et al. [45], reaction should be undertaken at the proper pH. Oxidizing agents,
Zhiyong et al. [46] and Liu et al. [84]. Nevertheless, the calcination calcination temperature and catalyst loadings are found to exert
temperature influence on the photocatalytic activity of the cata- their individual influence on the photocatalytic degradation of any
lyst depends on the end usage of the catalyst. The instance of Chen dye. Therefore, to study effectively, the photocatalytic degradation
et al. [38], where they prepared K+ -doped TiO2 photocatalysts is a of any dye all the aforementioned parameters must be given due
typical example of this. In their investigations, the effects of cal- considerations. It is also discovered that many methods are used in
cinations temperature on the surface areas, pore volume and pore the preparation of TiO2 -based photocatalysts. Nevertheless, sol–gel
sizes, together with its effects on the photocatalytic degradation method is widely used because the method facilitates the synthe-
of Everdirect Supra Blue BRL dyes were studied. The results of the sis of nanometer sized crystallized TiO2 -‘based catalysts’ powder of
effects on calcinations temperature on surface areas, pore volumes high purity at relatively low temperature.
and pore sizes are presented in Table 4. Five sample types were con-
sidered in their study – 0, 4.6, 6.7, 9.0 and 14.3 % mole fractions of
K+ doped onto TiO2 and were designated as TiO2 , K1 , K2 , K3 , and Acknowledgement
K4 respectively. Their results on the effects of calcination temper-
ature, on the degradation of RBL showed that sample K1 degraded The authors acknowledge the research grant provided by Uni-
at a faster rate than the others, and its optimum calcinations tem- versiti Sains Malaysia under the RU Grant Scheme (RU Grant No.:
perature was 973 K (700 ◦ C). 814005) that resulted in this article.
 U.G. Akpan, B.H. Hameed / Journal of Hazardous Materials 170 (2009) 520–529 527

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