Hindawi Publishing Corporation

Journal of Nanomaterials
Volume 2015, Article ID 790173, 29 pages
http://dx.doi.org/10.1155/2015/790173

Review Article
Recent Developments in Environmental Photocatalytic
Degradation of Organic Pollutants: The Case of Titanium
Dioxide Nanoparticles—A Review

Mphilisi M. Mahlambi,1 Catherine J. Ngila,1 and Bhekie B. Mamba2

1
Department of Applied Chemistry, University of Johannesburg, P.O. Box 17011, Doornfontein 2028, South Africa
2
Nanotechnology and Water Sustainable Unit, College of Science, Engineering and Technology, University of South Africa,
Florida Campus, Johannesburg 17025, South Africa

Correspondence should be addressed to Mphilisi M. Mahlambi; [email protected]

Received 29 April 2015; Revised 29 July 2015; Accepted 5 August 2015

Academic Editor: Xin Zhang

Copyright © 2015 Mphilisi M. Mahlambi et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

The presence of both organic and inorganic pollutants in water due to industrial, agricultural, and domestic activities has led to the
global need for the development of new, improved, and advanced but effective technologies to effectively address the challenges of
water quality. It is therefore necessary to develop a technology which would completely remove contaminants from contaminated
waters. TiO2 (titania) nanocatalysts have a proven potential to treat “difficult-to-remove” contaminants and thus are expected to
play an important role in the remediation of environmental and pollution challenges. Titania nanoparticles are intended to be
both supplementary and complementary to the present water-treatment technologies through the destruction or transformation
of hazardous chemical wastes to innocuous end-products, that is, CO2 and H2 O. This paper therefore explores and summarizes
recent efforts in the area of titania nanoparticle synthesis, modifications, and application of titania nanoparticles for water treatment
purposes.

1. Introduction is emitted directly into the water system, for example, a pipe
that spews sewage directly into a river, while nonpoint source
The South African National Water Act (Act number 36 of (NPS) pollution refers to diffuse contamination which occurs
1998) specifically states that water resources must remain fit when pollutants enter a water system through runoff, for
for use on a sustainable basis and that their quality must be example, when fertiliser is washed into a river by surface
constantly monitored [1]. Therefore the availability of water runoffs. Water pollutants can be classified as physical (odour,
should be based not only on the quantity but also on the qual- colour, solids, or temperature), biological (pathogens), or
ity of the available water [2]. However, due to agricultural, chemical (organic or inorganic compounds) [1, 2, 5–9].
industrial, and domestic activities the quality of river water Organic pollutants are of more concern than the other types
or groundwater continues to deteriorate due to pollution by because of their carcinogenic and mutagenic effects even after
hazardous materials [3, 4]. Water pollution is defined as the exposure to minute concentrations [10, 11].
direct or indirect introduction of substances into the water
bodies. These pollutants may be harmful to human health 1.1. Organic Pollutants. Organic contaminants have become
or the quality of aquatic ecosystems thus affecting the use of of more concern due to the inability of conventional
amenities and other legitimate uses of water [1]. water-treatment technologies to completely decompose these
The sources of water pollution are categorised as either contaminants in aqueous media [12, 13]. The ubiquitous
a point source or nonpoint source (diffuse sources). Point appearance of organic contaminants in sewage effluents,
source water pollution occurs when the polluting substance groundwater, drinking water, and sludge poses a significant
2 Journal of Nanomaterials

threat to humans and aquatic organisms [14]. Volatile organic aesthetic and malodour problems in water. The organic acids
compounds (VOCs) are known to be toxic and carcinogenic that result from the oxidation of NOM have the capability
and have been implicated in the depletion of the stratospheric to corrode turbines and engineering systems and this affects
ozone layer while also contributing to global warming [10, transportation of contaminants [19, 22, 27, 28]. Thus, under-
15]. These pollutants have been reported as being mutagenic standing the impact of NOM in water-treatment processes is
and hence are responsible for the emergence of antibiotic vital for human health and water-treatment plants as well as
resistance bacteria and genes [16]. industrial processes where pure water is a prerequisite.
Some organic pollutants are referred to as persistent
organic pollutants (POPs) because when they enter the
environment, they do not readily break down and may 1.3. Disinfection By-Products. In the water-treatment pro-
remain there for very long periods of time, for example, cesses, NOM may have adverse effects since it may react
polychlorinated biphenyls (PCBs), and may enter the food with disinfectants (e.g., chlorine or chloramines) resulting
chains and accumulate to levels detrimental to organisms that in the formation of disinfection by-products (DBPs), many
are high up in the food chain [17]. Also organic pollutants of which are either carcinogenic or mutagenic [5, 25, 26,
are a serious threat because they can be transported from 29]. For example, haloacetic acids (HAAs) are a component
the source of contamination through air as vapour or as of DBPs that are considered harmful to human health.
dust particles by water currents or sediments and released These have been found to result in impaired reproductive
in a new environment [17]. Some of these organic pollutants and developmental retardation when tested on laboratory
eventually contaminate groundwater and surface waters; animals [24, 30–33]. Also, trihalomethanes (THMs) have
however, groundwater contamination is likely to be the been classified as possible carcinogens to humans [30, 32, 34,
primary source of human contact with these toxic chemicals 35]. Nitrosamines are another group of DBPs, formed due
[18]. Generally, exposure to organic contaminants could be to the reaction of NOM with disinfectants that have been
through breathing, through ingestion, through drinking, or reported to be a threat to human life due to its carcinogenicity
by skin contact. [32, 36–38].

1.2. Natural Organic Matter. Natural organic matter (NOM) 1.4. Industrial Effluents. Industrial development is directly
is an agglomeration of organic compounds that naturally related to the release of various toxic pollutants into the envi-
occur when animal and plant material break down [19–21]. ronment, especially to aqueous streams, and these pollutants
NOM consists of a wide range of compounds with diverse are harmful and hazardous to the environment [12, 39–41].
chemical properties (due to geographic origin and age of Prevention of industrial pollution is currently a major focus
the decomposing organism) and occurs in all natural water of environmentalists and therefore treatment of industrial
sources [20, 22, 23]. NOM components are a heterogeneous effluents before disposal into the ecosystem is imperative
mixture of complex organic materials which consists of both to protect human life and environmental quality [3, 40,
hydrophilic and hydrophobic components. The hydrophilic 42]. Thus, a constant effort to protect water resources is
components are microbial by-products and contain a higher being made by various government and nongovernmental
proportion of aliphatic carbon and nitrogenous compounds organisations (e.g., US EPA, WHO, and DWAF) through the
with relatively high charge density such as amino acids introduction of increasingly strict legislation covering pollu-
and proteins as well as polysaccharides [22, 24, 25]. Humic tant release into the environment, with particular emphasis
substances (HS) constitute the more hydrophobic fraction on liquid industrial effluents [5, 40, 43, 44]. There are major
of NOM and exhibit relatively high specific ultraviolet types of industries in the industrial complex, for example,
absorbance (SUVA) values due to the presence of a relatively pulp and paper mills, food, pharmaceutical, electroplating,
large proportion of aromatic carbon, phenolic structures, and textile, photographic, mining, and agriculture, to mention
conjugated double bonds [5, 19, 21, 22, 24, 25]. just a few, which do not generate uniform waste streams;
Due to the complexity of NOM no single tool can give its industrial effluents are complex mixtures of chemical and
definitive structural or functional information. Nondestruc- biological compositions that have various environmental
tive spectroscopic techniques appear to be the most useful impacts depending on the source of the toxicant [45, 46].
analytical techniques for NOM characterisation [20]. Treat-
ment options for the removal of NOM include coagulation, 1.4.1. Textile Industry Effluents. Textile-processing industries
the use of magnetic ion-exchange resins, activated carbon, form the economic backbone of most developing countries.
membrane filtration, and advanced oxidation processes [22]. Effluents from textile industries are characterised by a variety
Characterisation of the structure and reactivity of NOM is of chemicals generated from the dyeing, bleaching, and
vital because its presence creates problems in the quality of washing processes [47, 48]. Wastewaters discharged from
drinking water as well as in water-treatment processes [20, textile industries are a serious environmental threat due to
26]. The presence of NOM results in an increased coagulant their characteristic high colour, fluctuating pH, malodour,
and disinfectant dosage resulting in increased sludge. It also high biological oxygen demand (BOD) and chemical oxygen
increases biological growth in water-distribution networks demand (COD), acids, and alkalis as well as various heavy
and may also result in increased levels of heavy metal com- metals that breach environmental standards [48–50]. Dyes
plexes and adsorbed organic pollutants [22]. Furthermore, are soluble in water and even a small amount of dye is highly
the presence of NOM causes membrane fouling as well as visible and reduces the transparency of water bodies [49, 51].
Journal of Nanomaterials 3

Table 1: Molecular structure and chemical properties of Rhodamine B [6, 52–54].

Molecular structure Chemical properties

COOH
Class Triphenylmethane
Chemical formula C28 H31 ClN2 O3
Molecular weight 479.02 g⋅mol−1
CH2 CH3
H3 CH2 C + UV absorption maximum 553 nm
N O NCl−

CH2 CH3 CH2 CH3

Rhodamine B

Also, dyes can be mutagens and carcinogens [49, 50], and thus that leachates contain hazardous pollutants like arsenides,
they need to be removed from industrial effluents. PCBs, and sulfanilamides [14, 16, 55, 56]. Commonly used
It is estimated that about 1% to 20% of the total world pesticides from agricultural activities (either domestic or
production of dyes is lost to the environment during syn- large commercial scale) have high recalcitrant organic groups
thesis and dyeing processes. These textile effluents are an and hence are extremely difficult to break down through
environmental burden as they contain a large amount of normal degradation [2, 38, 42, 57]. Also, the use of nitrogen-
azoic, anthraquinonic, and heteropolyaromatic dyes [6, 50]. containing fertilisers causes acidification and eutrophication
The discharge of these highly pigmented synthetic dyes to of ecosystems due to leaching [44, 58, 59]. These nitrogen-
the ecosystem causes aesthetic pollution, eutrophication, and containing pollutants from agricultural activities are usually
perturbations in aquatic life as they hinder light penetration intermediates to the formation of refractory organic pollu-
resulting in decreased photosynthesis [48, 49, 51]. Therefore tants [44].
textile wastewaters need to be treated to acceptable levels to
meet the national discharge standard before being discharged 2. Refractory Organic Pollutants
to the environmental ecosystem.
Degradation of refractory organic pollutants is a challenge
1.4.2. Rhodamine B. Rhodamine B (Rh B) is a type of because these pollutants cannot be degraded using the
triphenylmethane dyes. Triphenylmethane (TPM) dyes are current water-treatment technologies. They are resistant to
extensively used in textile, printing, food, photographic, and aerobic microbial degradation in conventional biological
cosmetic industries [52]. TPM dyes can persist for long peri- treatment processes and the natural environment [44, 60, 61].
ods in the aquatic environment because they are resistant to High-molecular-weight organics are the typical refractory
chemical and biological (bacterial) attacks. Rh B is a common pollutants. The presence of refractory pollutants in industrial
dye in the TPM family, which contains four (4) N-ethyl wastewaters causes problems in the water-treatment system
groups at either side of the xanthene rings (Table 1). It has [46]. These pollutants cause biomass poisoning and die-off
achieved its prominent use due to its good stability as a laser in conventional biological water-treatment systems. Other
material and is one of the major sources of pollution in the techniques such as flocculation, precipitation, or reverse
textile and photographic industry effluent streams [53]. Also, osmosis require posttreatment to dispose of the pollutants
although Rhodamine B is a highly phosphorescent (fluores- while the use of chemical techniques either fails to adequately
cent) dye, its toxicity is not dependent on the synergic effect remove these organic pollutants or results in the formation of
of visible light [52, 54]. As a dye in the TPM family (i.e., azoic, DBPs [28, 33, 36, 44, 62].
anthraquinonic, and heteropolyaromatic dyes), the presence Current water-treatment technologies are designed to
of Rh B in the ecosystem causes aesthetic pollution, eutroph- deal with either organic or inorganic pollutants in an aqueous
ication, and perturbations in aquatic life [6, 50, 52, 53]. medium, but not both. In addition, due to the diversity
and varying chemical properties of organic pollutants these
1.4.3. Other Industrial Effluents. Other sources of industrial technologies fail to remove pollutants to the required lev-
pollution are from surface treatment (mechanical and chem- els. Furthermore, the presence of NOM in water-treatment
ical surface-finishing processes), thermal power stations, processes may have adverse effects since it may react with
and agricultural activities, to name but a few. Effluents disinfectants (e.g., chlorine or chloramines) and result in the
originating from surface-treatment processes contain both formation of DBPs. Therefore the development of techniques
organic and metal pollution from the washing and rinsing that can remove both contaminants simultaneously without
of process baths [43]. Fly ash is the by-product of combus- the production of DBPs would be ideal. Nanocatalysts have
tion in thermal power plants using coal and lignite and is shown the ability to cost-effectively mineralise recalcitrant
mainly used as landfills [39]. However, studies to charac- organic pollutants and reduce metal ions in aqueous media
terise leachate originating from these landfills have indicated producing innocuous products, that is, H2 O and CO2 , and
4 Journal of Nanomaterials

zero-valent metals, respectively. The approaches that we have and 20.0 MPa in the aqueous phase [44, 59]. The mechanism
undertaken in our laboratories in an attempt to address these of wet oxidation seems to take place by means of a free radical.
problems are also described in this review. However, WAO is only effective for aliphatic and aromatic
compounds that do not have halogenated groups. Moreover,
3. Advanced Oxidation Processes (AOPs) investment and operation costs of WAO plants are not feasible
due to excessive temperatures and pressures, while treatment
Due to the aforementioned limitations of the conventional of effluents containing refractory organic pollutants would
water-treatment methods, there is an ongoing research inter- further escalate the operating costs [75, 76].
est to develop more efficient and environmentally friendly
systems for the treatment of recalcitrant organic pollutants. 3.3. Electrochemical Oxidation. Electrochemical oxidation
Advanced oxidation processes (AOPs) have demonstrated processes employ an electrochemical cell to generate oxidis-
the capability to develop such a green system. AOPs provide ing species which are used to destroy organic pollutants at
an effective remediation for the treatment of water since they ambient temperatures [60, 77–79]. The mechanism of elec-
have the ability to completely degrade a variety of organic trochemical oxidation involves three stages which are elec-
pollutants, oxidise heavy metals, and destroy microbial trocoagulation, electroflotation, and electrooxidation [79]:
substances. Advanced oxidation processes exploit the high
−e−
reactivity of hydroxyl radicals as the oxidation driving force RH 󳨀󳨀󳨀→ RH+
resulting in the formation of benign by-products (i.e., H2 O
and CO2 ); hence they are environmentally friendly [41, 63– −H+ (1)
67]. RH+ 󳨀󳨀󳨀→ R∙

R∙ + R∙ 󳨀→ R − R
3.1. Supercritical Water Oxidation. Supercritical water oxida-
tion (SCWO) is a technique that has been proven to destroy Electrochemically, organic pollutants can be oxidised either
highly persistent organic pollutants without the production directly or indirectly. In direct anodic oxidation, the pollu-
of harmful products. SCWO reactions are carried out above tants are adsorbed on the anode before being destroyed by
the critical point of water (374∘ C and 22.1 MPa) and at this the oxidising species (mediator ions) produced at the anode
point the volume of water is three times higher than at room while indirect electrochemical oxidation makes use of strong
temperature, with a density of 0.322 g⋅mL−1 and a dielec- oxidising agents and the pollutants are oxidised in the bulk
tric constant of 5.3 [68–71]. A homogeneous single phase solution [77–79]. Although electrochemical oxidation pro-
results when oxygen and organic compounds are dissolved cesses offer an environmentally friendly prospect, the process
in supercritical water [69, 71, 72]. SCWO has been studied in is economically not viable due to high energy consumption.
the degradation of nitrogenated compounds (e.g., pyridine, Furthermore, fouling of the electrodes has been observed due
aniline, nitrobenzene, and ammonia), phenolic compounds, to either the deposition of oligomers formed during phenol
and radioactive wastes [70]. oxidation or radical combination as an effect of pH [60, 80].
SCWO is regarded as an environmentally friendly pro-
cess, because not only does it produce CO2 and H2 O during 3.4. Photolysis. In photolysis, a chemical compound absorbs
oxidation, but also none of the NO𝑥 and SO𝑥 compounds radiation energy, is elevated to a state of higher energy and
are produced due to the relatively mild operating conditions an excited state, and produces radicals that carry out the
(340∘ C to 400∘ C and 22.29 MPa to 25.33 MPa) [69, 71]. How- photochemical reactions. The source of radiation is either
ever, during the degradation of halogenated hydrocarbons, solar energy or low and medium-pressure mercury lamps
the SCWO process is subject to corrosion problems due to the [27, 33, 81, 82]. In photolysis, the hydroxyl compounds are
formation of acidic conditions as well as fouling problems due generated by water splitting:
to the utilisation of neutralising processes and these are the
ℎ]
major obstacles that have led to the noncommercialisation of H2 O 󳨀→ H∙ + OH∙ (2)
SCWO [71, 73].
These radicals then react with the organic pollutant, splitting
3.2. Wet Oxidation. Wet oxidation, also referred to as wet air it to smaller and more bioavailable compounds [27]. How-
oxidation (WAO), is used to oxidise organic and inorganic ever, photolysis is a poor source of radicals and the radicals
substances, in either suspension or solution forms, in the produced are not efficient enough to fully degrade refractory
presence of an oxidant (water or air) at elevated temperature pollutants due to slow reaction kinetics observed in photoly-
and pressure [44, 61, 74]. WAO technology has a high sis [8]. To accelerate these photochemical processes, metallic
potential for the treatment of effluents containing a high salts called semiconductors which act as catalysts to speed up
content of organic matter and/or hazardous materials for the photochemical processes need to be added, giving rise to
which biological treatment is not feasible [44]. In WAO the so-called advanced oxidation processes [8, 83–85].
technology the organic pollutants are either partially oxidised
into biodegradable intermediate products with low molecular 4. Semiconductor Photocatalysis
weights or completely mineralised to water, carbon diox-
ide, and innocuous end-products at temperatures ranging 4.1. Introduction. Interest in semiconductor photocatalysis
between 125∘ C and 320∘ C and at pressures of between 0.5 MPa has recently risen exponentially because of the potential and
Journal of Nanomaterials 5

Table 2: Band gap energies of some semiconductor photocatalysts but they have a void region that extends from the top of
[8, 52, 89]. the highest occupied molecular orbital (HOMO), that is, the
valence band (VB), to the bottom of the lowest unoccupied
Band gap Band gap
Photocatalyst energy Photocatalyst energy molecular orbital (LUMO) which is also referred to as the
(eV) (eV) conduction band (CB). This void region is called the band gap
Si SiC
(𝐸𝑔 ) [8, 18, 98–100]. When the semiconductor is illuminated
1.1 3.0
with light, it absorbs a photon (ℎ]) and when the energy of the
WSe2 1.2 TiO2 rutile 3.02 photon is equal to or exceeds the band gap energy, an electron
𝛼-Fe2 O3 2.2 Fe2 O3 3.1 (ecb − ) is promoted from the VB to the CB leaving a hole
CdS 2.4 TiO2 anatase 3.2 (hvb + ) in the VB (Figure 1) [2, 18, 99–101]. The electron-hole
NaBiO3 2.62 ZnO 3.2 pair then migrates to the surface of the photocatalyst where
V2 O5 2.7 SrTiO3 3.4 it can recombine and dissipate the energy as heat, get trapped
B2 WO6 SnO2
in metastable surface states, or react with electron donors
2.78 3.5
or acceptors adsorbed on the surface of the semiconductor
WO3 2.8 ZnS 3.7 [18]. Generally, the hole oxidises water to form hydroxyl
radicals and initiates a chain reaction that then proceeds to
oxidise organics while the electron can be donated to an
opportunities it offers in a variety of fields. These include
electron acceptor, for example, O2 , leading to the formation of
treatment of environmental pollution, biotissue generation
superoxides or a metal ion that is reduced to its lower valence
and biosensors, medicine (destruction of cancer and viruses),
state and deposited on the catalyst surface [8, 18, 98, 102, 103].
and pharmaceutical industries [7, 18, 86–90]. The major
The mechanism for semiconductor photocatalysis (of a
advantages of semiconductor photocatalysis are that it offers
M(IV) lattice metal, e.g., TiO2 ) can be summarised in the
a good substitute for the energy-intensive treatment methods
following reaction steps [8, 18]:
and has the capacity to use renewable and pollution-free solar
energy. Also, unlike the conventional treatment methods, (i) Excitation of photon greater than band gap resulting
which not only transfer pollutants from one medium to in the formation of electrons (ecb − ) and holes (hvb + ),
another but also transform those to more refractory pollu- that is, charge-carrier generation:
tants, semiconductor photocatalysis converts contaminants
to innocuous products, such as CO2 and H2 O. Furthermore, TiO2 + ℎ] 󳨀→ hvb + + ecb − (3)
the reaction conditions are mild, and the reaction time is
modest and can be applied to aqueous, gaseous, and solid- (ii) Charge-carrier trapping:
phase treatments with the possibility of being both sup- +
plementary and complementary to the present technologies hvb + + TiIV OH 󳨀→ {TiIV OH∙ } (4)
[8, 18, 52, 83, 87, 88]. Semiconductor photocatalysts therefore
have the advantage of not only minimising running costs but ecb − + TiIV OH 󳨀→ {TiIII OH} (5)
also generating the desired product in the most efficient and
effective way. (iii) Charge-carrier recombination producing thermal
energy:
4.2. Properties of Semiconductor Photocatalysts. The defining hvb + + {TiIII OH} 󳨀→ TiIV OH + heat (6)
property of a good semiconductor photocatalyst material is
that the core element making up the material can reversibly +
ecb − + {TiIV OH∙ } 󳨀→ TiIV OH + heat (7)
change its valence state to accommodate a hole without
decomposing the semiconductor (e.g., Ti3+ → Ti4+ in non- (iv) Interfacial charge transfer:
stoichiometric TiO2 ) [8, 18, 91]. The photogenerated holes
+
should be highly oxidizing to produce hydroxyl radicals {TiIV OH∙ } + Red 󳨀→ TiIV OH + Red∙+ (8)
(∙ OH) and the photogenerated electrons should be reducing
enough to produce superoxides from the oxygen [92]. Also, ecb − + Ox 󳨀→ TiIV OH + Ox∙− (9)
the element should have more than one stable valence in the
semiconductor so that it is not decomposed (photocorrosion) where Red is an electron donor (reductant) and Ox is
by the formation of holes (e.g., Zn2+ in ZnO and Cd2+ in CdS an electron acceptor (oxidant).
are photocorroded by the formation of holes) [8, 18, 93–95].
(v) Reduction of metal ions by ecb − , if present:
Furthermore, the semiconductor must have a suitable band
gap, which is highly stable to chemical corrosion, nontoxic, 𝑛ecb − + M𝑛+ 󳨀→ M0 (10)
and generally of low cost [8, 18, 92, 93, 96, 97]. The band gap
energies of some semiconductor photocatalysts are shown in This fundamental phenomenon observed in semiconductor
Table 2. photocatalysts to oxidise (degrade) organic compounds and
reduce metal ions is a promising technique in the treatment
4.3. Mechanism of Photocatalysis. Semiconductor photocata- of refractory organic pollutants and heavy metals present in
lysts do not have a continuum of electronic states like metals, wastewater treatment plants.
6 Journal of Nanomaterials

h Electron
− − M2+ M+
CB Reduction
O2 O2 ∙−

Band gap
Red+∙

M2+ /M3+ Degraded products

VB + Hole + M2+ M3+

OH− ∙
OH

Oxid+∙ Oxidation

Degraded products

Figure 1: Mechanism for semiconductor photocatalysis [18].

5. Nanophotocatalysts in Water Treatment [88, 116–119]. Since the discovery of the phenomenon of
photocatalytic splitting of water on a TiO2 electrode under
Due to industrial and geographical reasons there is always UV light, enormous efforts devoted to titania research have
a difference in the quality of water across the world. It led to promising applications in the fields of photovoltaics,
is therefore acceptable that there is no possibility of one photocatalysis, photoelectrochromics, ceramics, and sensors
solution that can solve all the problems of water contami- [120–126]. As the most promising semiconductor photocat-
nation. Thus, in the design for water-treatment technologies, alyst, TiO2 -based materials are therefore expected to play
nanotechnology will always play a key role. The intrigue of a major role to curb serious environmental and pollution
nanotechnology is the ability to control the manipulation challenges and ease the energy crisis through the use of
of nanoscale (approximately 1 nm to 100 nm) structured renewable solar energy [93, 127–134].
materials and integrate them into large material components,
systems, and architecture that have novel properties and 6.2. Synthetic Methods for TiO2 Nanoparticles. There are a
functions [2, 86, 113, 114]. The merits of using semiconductor number of available techniques for the synthesis of titania
photocatalysts in their nanorange far outweigh their use in nanoparticles and these include sol-gel, sol, hydrothermal,
their bulk form [115]. For example, in the case of adsorption solvothermal, and chemical vapour deposition, to name just
where surface sites of the adsorbent are utilised, diffusion is a few [88, 135, 136]. These synthetic methods are highlighted
usually hindered due to the lack of a porous structure in the in the following subsections. The method used plays a signif-
bulk materials. This is because the surface-to-volume ratio icant role in the shape, size, and photochemical properties of
increases drastically with the decrease of the adsorbent from TiO2 .
bulk to nanodimensions [2, 7, 11, 87, 113].
Also, new physical and chemical properties emerge when 6.2.1. Sol-Gel Method. The sol-gel method is the most com-
the size of a material is reduced to the nanoscale level. monly used technique for the synthesis of TiO2 nanoparticles
The surface energy per nanoparticle increases significantly [137–140]. In a typical sol-gel process, a colloidal suspension
in the nanorange. This increase in surface energy directly (a sol) is formed from the hydrolysis of the precursors, usually
results in an increase in contaminant removal even at low inorganic metal salts or metal inorganic salts such as metal
concentrations. The use of nanocatalysts also results in alkoxides [16, 88]. For titania synthesis, the sol-gel process
less waste generation, especially in posttreatment, since less usually proceeds via an acid-catalysed hydrolysis of titanium
quantity of nanomaterial will be required compared to its (IV) alkoxides followed by condensation [88, 138]. The sol-gel
bulk form. Furthermore, with the use of nanomaterials, novel process has found more extensive use in the synthesis of tita-
reactions can be accomplished at nanoscale due to an increase nia because the reaction takes place at low temperatures, does
in the number of surface atoms which is not possible with not use complicated equipment, results in the formation of
its analogous bulk material, for example, the degradation highly homogeneous and pure products, and allows for mod-
of pesticides by nanoparticles which cannot be done by the ification to produce specific desired products [138, 141–143].
metals in their bulk form [2, 7, 93, 94, 113]. Also, the sol-gel method results in the synthesis of high
surface-area nanomaterials. It also allows for easy control of
6. Titanium Dioxide/TiO2 /Titania shape, size, and distribution, as well as the easy introduction
Photocatalysts of foreign materials into the catalyst lattice and at low
temperatures [135, 141, 144–147]. Moreover, nanomaterials
6.1. Introduction. Among the nanophotocatalysts used in the prepared by this method have a well-crystalline phase and
treatment of environmental wastewater, titanium dioxide, a small crystalline size, which benefit thermal stability and
also known as titania or TiO2 , has been extensively studied photocatalytic activity. Hence, in this study, the sol-gel
Journal of Nanomaterials 7

process was used for the synthesis of TiO2 nanoparticles as particle size, narrow size distribution, and dispersity [159–
well as the introduction of metal ions into the crystal lattice 162]. Also the versatility of this method is seen in that it can
of the TiO2 nanoparticles. be employed to synthesise TiO2 nanoparticles and nanorods
with or without the aid of surfactants.
6.2.2. Sol Method. This method is also referred to as the
nonhydrolytic sol-gel process and usually involves the reac- 6.2.5. Chemical Vapour Deposition (CVD) Method. Chemical
tion of titanium chloride with oxygen donating materials, for vapour deposition (CVD) is a process in which materials in
example, metal alkoxides or organic ethers [88, 148–152]. The a vapour state are condensed to form a solid-phase material
reaction between Ti–Cl and Ti–OR leads to the formation [88, 163]. This process alters the mechanical, electrical,
of Ti–O–Ti bridges. The alkoxide groups are formed in thermal, optical, corrosion resistance, and wear-resistance
situ by the reaction of titanium chloride with alcohols or properties of various substrates [163]. CVD has been used to
ethers. The length of the alkyl substituent of the alcohols form free-standing bodies, films, and fibres and to infiltrate
affects the reaction speed (the longer the chain, the faster fabric to form composite materials and, recently, in the
the reaction) but not the average particle size. However, fabrication of various nanomaterials [164, 165]. Chemical
the variation of the halogen (e.g., TiF4 and TiI4 ) affects the vapour deposition of titanium dioxide is usually carried
average particle size [88, 153]. Also, the shape and size of out through the reaction of titanium tetrachloride (TiCl4 )
the titania nanoparticles can be controlled by the addition with oxygen or through the thermal reaction of a titanium
of a surfactant. For example, TiCl3 was added to a solution alkoxide such as Ti(OPri)4 , which already displays the Ti–
of trioctylphosphine oxide (TOPO) and lauric acid and the O4 tetrahedral motif of the titanium dioxide lattice in its
reaction conditions controlled to produce either diamond- chemical structure [165–167].
shaped, bullet-shaped nanocrystals or a mixture of branched CVD processes usually take place within a vacuum
and unbranched TiO2 nanorods [88, 153–155]. chamber. If no chemical reaction occurs within the reaction
chamber, the process is called physical vapour deposition
(PVD). In CVD processes, the gaseous precursor compounds
6.2.3. Hydrothermal Method. Hydrothermal synthesis of chemically react on a heated substrate surface and the
nanoparticles takes place under controlled temperature deposition reaction is driven by thermal energy. The reactions
and/or pressure in an autoclave [88, 127]. The reaction takes usually happen in an inert atmosphere in the presence of
place in an aqueous medium. The hydrothermal process is a gas, for example, N2 , Ar, or He [163–165, 167]. Moreover,
effective for selective crystallisation of anatase titania from the reaction conditions in a CVD process can be tuned
the amorphous phase. However, the presence of the Cl− ion to determine the phase, size, and morphology of the TiO2
(from the precursor, TiCl3 ) results in the formation of a mix- nanostructures.
ture of anatase and the brookite phases. Thermal treatment
of the amorphous phase below 300∘ C results in a mixture 6.3. Properties of TiO2 Nanoparticles. Titanium dioxide has
of the anatase and the brookite phases due to a solid-state gained prominence for use as an environmental remediation
epitaxial growth mechanism. At temperatures above 300∘ C catalyst to completely mineralise organic and inorganic con-
the formation of only the anatase phase is achieved because taminants because of its outstanding characteristics. These
the dissolution/precipitation mechanism dominates [88, 127]. include high thermal stability, high photocatalytic activity,
The hydrothermal process is thought to be environ- high resistance to chemical and photocorrosion, nontoxicity,
mentally friendly since the reactions are carried out in a and dielectric properties as well as being inexpensive [168–
closed system and the contents can be recovered and reused 172]. The photocatalytic activity of TiO2 depends on its crystal
after cooling down to room temperature [53]. Moreover, phase, crystallinity, particle size, lattice impurities, density
proper and careful control of the hydrothermal processing of surface hydroxyl groups, and the surface area. Titania
conditions allows for the control over the physical properties has three (3) phases, namely, anatase (tetragonal), rutile
of titania such as crystallite size and form, surface area, (tetragonal), and brookite (orthorhombic), and the anatase
contamination, morphology and phase, uniform distribution phase of titania is the most photoreactive of the phases
and high-dispersion, and stronger interfacial adsorption [121, 172–174]. Of the three phases, the anatase phase has
properties [53, 88, 127]. the smallest particle sizes (<50 nm), high concentrations of
surface hydroxyl (OH) groups, and a high surface area, hence
6.2.4. Solvothermal Method. The solvothermal method is the high photocatalytic activity [169].
almost identical to the hydrothermal method except that However, the band gap of anatase TiO2 is 3.2 eV and can
it uses nonaqueous solvents [88, 156, 157]. However, in the only be activated under UV light irradiation with wavelength
solvothermal method the temperature can be elevated much of 387 nm [117, 175–177]. This high-energy band gap rules
higher than in the hydrothermal method and a variety of out the use of solar energy as the photoactivity source. The
organic solvents with high boiling points can be used. With UV source requires large quantities of electrical energy which
the solvothermal method there is a better control of the would result in high costs in practical applications [52].
size, shape, and the crystallinity of the TiO2 nanoparticle Moreover, titania is characterised by low quantum yields (i.e.,
distributions than hydrothermal methods [158]. Thus the low electron transfer rate) resulting in high electron-hole
solvothermal method has been found to be a versatile method pair recombination which results in the termination of the
for the synthesis of a variety of nanoparticles with controlled photocatalytic reactions [41, 104, 168, 178–180]. As a result, a
8 Journal of Nanomaterials

number of reformative initiatives have been investigated as a the rate of electron-hole pair recombination and the pho-
means of overcoming these drawbacks. tocatalyst can also cause thermal instability [57, 176]. It is
therefore imperative to avoid this by taking into consideration
the adequate amount of the dopant (metal) when preparing
6.4. TiO2 Modifications. The main aim for titania modifica-
doped titania [105, 194]. This is because when the dopant
tions is to reduce the band gap of titania thus shifting its
level passes the optimal limit, which usually lies at a very low
optical response to the visible-light region and to reduce
dopant concentration, the metal ions act as recombination
the rate of electron-hole pair recombination to increase its
centres resulting in reduced photoactivity. The presence
photoreactivity [105, 132, 180]. TiO2 modifications result in
of adequate amounts of metal doping (optimal limit) also
the “decrease” of the band gap by means of introducing a
ensures that the metal particles only act as electron traps
donor level on the valence band (Figure 2). The paramount
hence aiding electron-hole separation [105, 195].
condition for titania modification is to ensure that the anatase
phase is maintained. The most common techniques used for
6.4.2. Anion Doping. Anion doping of titania has increased
TiO2 modifications include anion doping, dye sensitizers,
recently and has been reported to shift the absorption edge
the use of binary oxides, and metal-ion doping. These are
towards the visible-light region and increase the photocat-
discussed in the following subsections.
alytic activity [16, 102, 119, 176, 196–199]. The narrowing of the
band gap is as a result of the mixing of either the p or the 2p
6.4.1. Metal-Ion Doping. Doping of titanium dioxide nano- states of the halogen (X) with the 2p states of the oxygen (O)
particles with transition and noble metal ions for the degra- atom in the valence band of the TiO2 nanoparticles [88, 196,
dation of organic pollutants is the most studied phenomenon 197]. However, the mixing of the p states of the halogen and
and has been found to enhance both the photoresponse and the 2p states of the O atom has the most positive effect on
photoresponse and photocatalytic activity of TiO2 nanopar- the band gap narrowing as it induces some states which act as
ticles under visible-light irradiation [47, 96, 105, 142, 181–191]. shallow donors on the valence band [88]. The anion therefore
The electronic states of titania can be decomposed into three traps holes resulting in less recombination of the electron-
parts: 𝛿 bonding of O p and Ti 𝑒𝑔 orbitals or states that are hole pair and displaces the surface OH groups increasing the
located in the lower region, 𝜋 bonding of O p𝜋 and Ti 𝑒𝑔 states rate of electron scavenging by O2 resulting in the formation
in the middle energy region, and O p𝜋 states in the higher of an increased yield of superoxide radicals [103]. Anions
energy region (Figure 3). The bottom of the lower CB has the therefore undergo innersphere ligand substitution reactions
Ti d𝑥𝑦 orbital and contributes to the metal-metal interactions with surface hydroxyl groups.
due to 𝛿 bonding of the Ti t2𝑔 –Ti t2𝑔 states. The top of the
lower CB consists of the Ti t2𝑔 states that are antibonding 6.4.3. Dye Sensitizers. Organic dyes have been widely em-
with the O p𝜋 states. The upper CB is characterised by the ployed as sensitizers for titanium dioxide nanomaterial to
𝛿 antibonding orbitals between the O p𝛿 and Ti 𝑒𝑔 states improve its optical properties as they are light absorbing
[88]. chromophores [6, 84, 88, 125, 193, 200]. Organic dyes are
During metal-ion doping, the energy due to the metal- usually transition-metal complexes with low-lying excited
ion dopant either lies at the top of the valence band or states, for example, polypyridine, phthalocyanine, and met-
produces midgap states. When the atomic number of the alloporphyrin complexes. The metal centres for the dyes
dopants is increased, the localised level shifts to lower energy include Ru(II), Zn(II), Mg(II), Fe(II), and Al(III), while
thus significantly contributing to the formation of the valence the ligands include nitrogen heterocycles with delocalised
band with the O p and Ti 3d electrons. This results in the 𝜋 or aromatic ring systems. The conduction band usually
band gap narrowing due to the introduction of electron states acts as a mediator for transferring the electrons from the
into the band gap of TiO2 resulting in the formation of a new excited sensitizer to the substrate on the titania surface [84,
lowest unoccupied molecular orbital (LUMO) [88]. Basically, 125, 187].
metal ions provide a “cushion” on the valence band (the donor These organic dyes act as both sensitizers and substrates
level) which results in the “decrease” in the band gap. and are normally linked to the TiO2 nanoparticle surfaces
Metal doping should be differentiated from metal ions via functional groups. The various interactions between the
codissolved in a photodegraded solution and noble metals dyes and the TiO2 nanoparticle substrates include covalent
deposited on the semiconductor surface [88, 105]. Metal ions attachment by directly linking groups of interest or via link-
(dopants) are therefore incorporated into the TiO2 lattice ing agents, electrostatic interactions via ion-exchange, ion-
resulting in a “decrease” between the valence band and the pairing, or donor-acceptor interactions, hydrogen bonding,
conduction band hence altering the band gap energy thereby van der Waals forces, or hydroxyl groups [84, 88, 95]. Most
shifting the absorption band to the visible-light region dyes of interest link via direct covalent bonding with the
[47]. Metal-ion dopants are nanoscale metal semiconductor functional groups that are on the TiO2 surface. Carboxylic
contacts that act as electron scavengers hence resulting in and phosphonic acid derivatives react with the hydroxyl
increased photocatalysis [192, 193]. groups to form esters, while amide linkages are obtained via
It is worth noting that although the introduction of metal- the reaction of amine derivatives on TiO2 [88, 95]. However,
ion dopants on the titania lattice drastically shifts the absorp- dye sensitizers are not stable and are usually prone to
tion edge to the visible-light region, it can also result in thermal instabilities which result in increased recombination
reduced photocatalytic activities. Metal doping can increase centres. Furthermore, they are susceptible to damage from
Journal of Nanomaterials 9

Pollutant∗
− (LUMO)
e

Pollutant
(HOMO)

h − − M2+ M+
CB
Reduction

Narrow band gap

O2 O2 ∙−

Wide band gap

Visible light UV light
TiO2 Pollutant+∙
𝜆 ≥ 380 nm
Degraded products
M2+ /M3+
Donor level
VB + + M2+ M3+

OH− ∙OH

Pollutant+∙
Oxidation

Degraded products

Figure 2: Band gap (effect of doping) and photocatalysis mechanism of TiO2 [18, 104, 105].

Ti-O𝛿 ∗ Upper CB
Ti eg states

Ti-O𝜋 ∗

Ti t2g states M-M𝜋 ∗

M-M𝜋 Lower CB
M-M𝛿 ∗

M-M𝛿

GAP
O p𝜋 states
O p𝜋

VB O p𝛿 states
Ti-O𝜋

Ti-O𝛿

Figure 3: Bonding diagram of TiO2 [18].

reactive oxygen species (ROS) which destroy the catalyst the coupling oxide is activated under visible light, it is
[92, 176]. believed that the metal oxide will absorb visible light and the
photocatalytic activity of the titanium dioxide will be used to
6.4.4. Binary Oxides. Binary metal oxides like TiO2 /SiO2 , mineralise organic pollutants. The metal oxides also enhance
TiO2 /ZrO2 , TiO2 /WO3 , TiO2 /Fe2 O3 , TiO2 /SnO2 , TiO2 / the separation properties of titania suspended particles from
Ln2 O3 , and TiO2 /RuO2 systems have been applied in the pho- solution and thus decrease the effect of beam splitting by
tocatalytic degradation of environmental pollutants under agglomerated particles [118]. Moreover, the metal oxides act
visible light [3, 95, 118, 124, 140, 201–207]. The photoactivity as supports of the catalysts [10]. However, some of the metal
of these binary oxides was found to be enhanced because oxides are thermodynamically unstable, for example, RuO2 /
the metal oxides increased the acidity of the titania surface. TiO2 , thus resulting in electron-hole pair recombination and
The surface acidity takes the form of surface hydroxyls and significantly decreasing the photocatalytic activity [95].
accepts holes generated by illumination of the catalyst and Other techniques that have been used to shift the absorp-
oxidises the adsorbed molecules [118, 204]. Basically, since tion edge of titania towards the visible-light region and
10 Journal of Nanomaterials

reduce the rate of electron-hole pair recombination include 211, 226–229]. Secondly, it has low quantum efficiency due
carbon nanotube-titania composites, metal-anion codoping, to the low rate of electron transfer to oxygen resulting in
mounting TiO2 on activated carbon exfoliated graphite, and a high recombination of the photogenerated electron-hole
polymeric substrates, for example, chitosan [116, 130, 208– pairs [226, 227, 230]. Thirdly, when used in a suspension,
213]. For the purposes of this research metal-ion-doped tita- titanium dioxide aggregates rapidly due to its small size (4 nm
nia will be synthesised and investigated for its photocatalytic to 30 nm) and its aggregates may cause scattering of the
properties under visible-light irradiation. light beam resulting in loss of catalytic efficiency [66, 211,
231]. And lastly, the application of powdered TiO2 catalysts
6.5. TiO2 Applications requires posttreatment separation to recover the catalyst from
water. This is normally difficult, is energy consuming, and
6.5.1. Industrial Applications. The existing and potential is economically not viable for use in water-treatment plants
applications of titanium dioxide nanomaterials include tooth- [12, 66, 156, 211, 230]. Therefore new research initiatives need
paste, paint, UV protection, photovoltaics, photocatalysis, to be explored to counter these challenges.
sensing, electrochromics, and photochromics. The photo- One of the major challenges facing scientists and govern-
catalytic properties of TiO2 have found application, as well ment bodies is the development of materials using “clean”
as potential application, in the manufacture of self-cleaning energy applications, the so-called Green Science, to relieve
surfaces, air cleaning devices, and self-sterilising devices the environmental burden due to pollution. TiO2 has the
[88, 92, 194, 214, 215]. Photochromic and electrochromic potential to be that green material and hence so much
compounds (with a redox potential above the conduction research has been ongoing to try and harness its potential
band edge of titania) exhibit different colours in different applications. To achieve this, doping metals into the TiO2
oxidation states, and TiO2 acts as an electron conductor lattice is an effective strategy to reduce the band gap and shift
between the conduction band and the photo/electrochromic the absorption edge towards the visible-light range [57, 84,
material. Electrochromic devices like electrochromic win- 105, 107, 191, 227, 232, 233]. However, the amount of the metal-
dows, displays, contact lenses, catheters, and spectacles with ion dopant when preparing doped titania is important. This
TiO2 as the electron conductors have been synthesised and is because when the dopant level passes the optimal limit,
commercialised [131, 216–218]. Also, biomedically, TiO2 has (∼0.4%), the metal ions then act as recombination centres
shown much potential in cancer therapy (endoscopic-like resulting in reduced photoactivity [105, 194].
instruments) due to its antitumor activity [92]. Also, TiO2 nanoparticles can be supported on catalyst
supports. This would help improve the photocatalytic activ-
6.5.2. Environmental Applications. The photocatalytic prop- ity and potential application of the titania nanoparticles.
erties of TiO2 make it an important semiconductor in appli- Furthermore, to avoid the aggregation and posttreatment
cations in environmental remediation. Titanium dioxide has challenges, TiO2 can also be assembled onto different sub-
shown tremendous ability not only as a sensor for chemical, strates and fabricated into different types of titania thin films
biological, and various gases (H2 , NO𝑥 , CO, etc.) even at [150, 211, 214, 234–237]. The advantage of using thin films is
low concentrations, but also to photocatalytically degrade that they are known to be chemically stable and possess a
and self-clean the contaminated environment [88, 200, 219– high dielectric constant, a high refractive index, and excellent
222]. Moreover, the degradation of organic pollutants and transmittance; therefore they have the ability to retain the
reduction of metals to their zero oxidation states have been photocatalytic activity of the assembled catalysts [236].
earmarked as one of the peak applications of TiO2 for the
treatment of river water, groundwater, the drainage water 7. Catalyst Supports
from fish-feeding tanks, and industrial wastewater [57, 65, 91,
92, 117, 223, 224]. Furthermore, photodegradation of organic 7.1. Introduction. A support material is very important in
pollutants by titanium dioxide results in the formation of catalysis because it determines the catalytic activity of a
innocuous products and therefore eliminates the problems catalyst [238, 239]. Catalyst supports are porous and have
associated with the recalcitrant DBPs [18, 83, 174, 175, 225]. high surface areas [44, 240, 241]. The electronic interactions
Although titania has the ability to completely degrade organic between the support and the catalyst bring about slightly
refractory pollutants and to be coused with the existing water- acidic conditions which increases the rate of electron transfer
treatment technologies, its large-scale industrial application thus reducing the rate of electron-hole combination. Also,
in drinking-water treatment is still considered to be miles supports result in an increased adsorption ability and stability
away. of the catalyst and hence increase the rate of oxidation
of organic pollutants [44, 76, 242, 243]. Moreover, catalyst
6.6. Problems Associated with TiO2 Applications. The use of support materials do not only shift the band edge towards the
TiO2 in suspension form is efficient due to its large surface visible-light energy region but also have the ability to disperse
area but there are four major technical challenges that restrict the supported catalysts thus preventing them from agglom-
its large-scale application and its use in water-treatment erating and also helping to improve catalyst separation from
technologies. Firstly, it has a relatively wide band gap (∼3.2 eV, posttreatment wastes [130, 238, 243–247]. These conditions
which falls in the UV range of the solar spectrum), and are therefore important since they enhance the photocatalytic
therefore it is unable to harness visible light thus ruling out activity and the application of the supported TiO2 catalysts.
sunlight as the energy source of its photoactivation [9, 16, The common types of supports used for catalysts include
Journal of Nanomaterials 11

alumina (𝛾-Al2 O3 ) supports, carbon supports, and carbon- synthesised by this method have some drawbacks. For exam-
covered alumina (CCA) supports. ple, their textural properties are dependent on the amount
of carbon deposited and the type of the hydrocarbon used;
7.1.1. Alumina Supports. 𝛾-Alumina as a catalyst support hence the carbon coating is nonuniform [254]. Furthermore,
has a high surface area, good mechanical properties, and increasing the degree of surface coverage of the alumina by
numerous pores as well as the ability to disperse the active carbon through CVD results in the aggregation of carbon on
metal phase [238, 239, 247, 248]. However, its exclusive use the alumina surface and this decreases the apparent surface
as a support has been found to have some disadvantages. area and pore volume which are key to catalytic activity of
For example, its acidity results in low catalytic activity of the supported catalysts.
the supported catalysts. Furthermore, its reactive surfaces Another method used to synthesise CCA involves the
form unwanted metal oxides upon calcination. The reactive impregnation of alumina with sucrose solutions [198, 238,
surfaces of alumina react with the promoter ions resulting 250, 253, 257]. In this method the sucrose-impregnated
in the formation of oxides which lower the catalytic activity alumina is dried in an oven and the pyrolysis of the sucrose
of the catalysts [238, 247–249]. The strong interactions of takes place in an inert atmosphere at elevated temperatures
the alumina support with the metal atoms are therefore (600∘ C to 700∘ C) to produce CCA supports. The CCA
undesirable since it is detrimental to the catalyst activity. supports produced by the impregnation of sucrose have a
uniform carbon layer; hence this is regarded as a better
7.1.2. Carbon Supports. Carbon has also been used to support method than CVD of organic compounds. Lately, Sharanda
catalysts. Carbon supports have mild interactions with the et al. have synthesised CCA supports using an adsorption-
supported metals and have a neutral surface, good thermal equilibrium method [254, 261]. In this method highly reactive
conductivity, and high surface area with controlled pore compounds like acetylacetone and isocyanates form surface
volume. Carbon is also resistant to nitrogen poisoning and complexes with the OH groups of the alumina via the C=O
contains variable surface functional groups [246, 248–251]. and N=C=O bond openings, respectively. Upon pyrolysis,
However, it also has some undesirable properties that limit its a carbon coating is expected to form on the surface of
use as a catalyst support. It has poor mechanical properties the alumina. The equilibrium adsorption method has the
and a low surface area. Moreover, it is also microporous advantage of forming better CCA supports since the interac-
and has poor adsorption properties and hence catalysts may tion between the C and alumina is a chemical process and
be deposited on the micropores thus making their photo- not a physical or mechanical one like in the case of CVD
catalytic effect trivial [238, 246, 248–251]. These properties and sucrose impregnation. Hence, for the purposes of this
therefore make the sole use of carbon as a support material study, the adsorption-equilibrium method was adopted for
inapplicable. the synthesis of CCA supports.

7.2. Carbon-Covered Alumina (CCA) Supports. As described 7.4. Applications of CCA Supports. CCA supports have found
before, the sole use of either carbon or alumina as support utilisation as supports for hydrotreating catalysts in the
materials has some shortcomings. A support system that Fischer-Tropsch conversion of heavy crude oil into light
exploits the merits of both carbon and alumina can provide fractions [252, 258]. Also, CCA supports have a high surface
an ideal support system. This is because it overcomes their area and high adsorption affinity for both organic and
shortcomings while improving their advantages. In this inorganic compounds (Al2 O3 is a polar adsorbent and C is
system, the alumina is coated with a thin layer of carbon prior a nonpolar adsorbent). These properties have been exploited
to catalyst impregnation which results in a support material and CCA supports have been used as packing material for
that possesses both the textural and mechanical properties high-performance chromatography [249, 260, 261]. Recently,
of alumina and the favourable surface properties of carbon Jana and Ganesan [255] have synthesised CCA in the form
[238, 250, 252–255]. The properties of this carbon-covered of foams and increased its surface area and also enhanced
alumina (CCA) support include reduction of the alumina its adsorptive properties. Due to their high catalytic activity
acidity (∼ by 90%) due to the presence of carbon; increased and stability, CCA supports have been used to support Ru
electron-charge transfer and reduced metal-support interac- catalysts in the synthesis of NH3 [262]. Ag nanoparticles have
tions resulting in increased catalytic activity; and increased been used in CCA supports and used to remove bacteria in
mechanical strength and increased surface area [238, 239, drinking water [239]. Since not much work has been done on
247, 252–254, 256, 257]. CCA supports are therefore superior the environmental application of CCA-supported catalysts,
catalyst supports due to the integration of the properties of this research therefore seeks, for the first time, to support
both the carbon and alumina. anatase TiO2 nanoparticles on CCA supports and apply them
in the degradation of organic pollutants.
7.3. Synthesis of CCA Supports. The most common approach
to the synthesis of CCA supports is based on the “pyrolyzabil- 8. CCA-Supported TiO2 Nanoparticles
ity” of organic compounds, such as cyclohexene, acetylene,
or ethane, on the surface of alumina at elevated temperatures Titania nanoparticles have been recently attached on CCA
(600∘ C to 700∘ C) in the flow of nitrogen, that is, chemical supports and used for the photocatalytic degradation of Rho-
vapour deposition (CVD) of organic compounds [247, 249, damine B under visible-light irradiation [263]. Metal-doped
254, 258–260]. However, it has been found that the materials titania has also been supported on these CCA supports. Ag,
12 Journal of Nanomaterials

Co, Ni, and Pd were used as the metal dopants [106]. The CCA tetrahedral motif of the TiO2 in its chemical structure, or
supports were synthesised from glucose and an impregnation TiCl4 is reacted with oxygen to form the T–O4 tetrahedral
method was used to attach the nanoparticles on the supports. motif. These are thereafter deposited on a substrate at elevated
According to the results obtained, attaching the titania temperatures in a vacuum to form the titania thin films [165,
nanoparticles on the CCA supports greatly enhanced their 236, 268, 269]. CVD offers good control of film structure and
photocatalytic activity. Both these CCA/TiO2 and CCA/m- composition, excellent uniformity even on highly irregular
TiO2 nanoparticles had a large surface area due to the porous substrates (conformal deposition), and a sufficiently high
nature of the CCA supports, and they were highly active growth rate thus applicable for synthesis of multilayer struc-
under visible-light irradiation and exhibited less electron- tures [268, 270–272]. To realise the desired physicochemical
hole combination due to the presence of C (which acts as properties of a material, a suitable substrate surface must
electron traps) on the supports. Also, the band gap of the be exposed to a suitable growth environment (temperature,
CCA-supported titania nanoparticles was highly reduced. pressure, and chemical composition) especially in the gas
The decrease in the band gap of the CCA-supported catalysts phase conditions close to the substrate surface [270].
was found to be much higher than the decrease of 0.14 eV The factors that affect the physicochemical properties
which is usually observed for carbon doped titania. The SEM of the thin films are the choice of precursors, carrier gas,
images (Figure 4) revealed that the carbon formed a layer on and their respective flow rates, the total pressure in the
top of the alumina and that the nanoparticles were success- reactor, the substrate temperature, the distance between the
fully impregnated on the highly porous CCA supports. substrate and the nozzle head, and the water-vapour content
Figure 5 showed that the catalysts were successfully in the whole reaction chamber [270, 273]. However, CVD is
impregnated onto the CCA supports. The authors also not a straightforward process and is complicated to control.
revealed that the catalysts were evenly distributed on the CCA The deposition rates, uniformity, and film properties change
supports. Uniform distribution is a distinguishing feature when one inert gas is replaced by another, a different-sized
of CCA supports due to their high adsorption and porous substrate is used, a different reactor loading is applied, or
nature. The CCA-supported catalysts were found not to have an identical process is applied in a different reactor setup
lost their crystallinity which would have inversely affected the [270]. Moreover, the vacuum equipment is expensive and
photocatalytic activity of the catalysts. due to the complicated nature of the reaction kinetics in the
CVD reactors CVD processes developed in the laboratory are
9. Thin Films difficult to scale up to industrial scales [166, 235, 270].

As mentioned earlier, the tendency of titanium dioxide 9.2. Liquid-Phase Deposition. Liquid-phase deposition
nanoparticles to aggregate and scatter incident light as well (LPD), unlike CVD, is referred to as a unique soft process in
as the need for posttreatment recovery has made its large- which a metal oxide or hydroxide forms thin films through
scale application economically impractical [91, 211, 264]. This ligand-exchange (hydrolysis) equilibrium deposition at low
had led to the exploration of a number of techniques to try temperatures [232, 274]. The substrate is immersed in the
and immobilise TiO2 nanoparticles on solid supports not precursor solution (soft-solution deposition) and thereafter
only to solve posttreatment problems but also to facilitate the the substrate is calcined at high temperatures to obtain crys-
renewable use of the catalyst [66]. Also, TiO2 thin films retain talline thin films [232, 275]. LPD is a cost-effective method,
the photocatalytic properties of its powder form. TIO2 thin is regarded as environmentally friendly, and produces
films can still be applicable in gas sensors, electrodes for solar smooth, uniform, and dense thin films with good adherence
cells, electrochromic applications, as gate oxides of metal- [235, 275]. However, the thermal treatment of the thin films
oxide-semiconductor field transitions, laser applications, and has been reported to affect the adhesion properties of the
photocatalytic degradation of pollutants [150, 264–267]. nanoparticles on the substrate [235].
Although immobilised titania is less photocatalytically
active than suspended titania particles due to reduced surface 9.3. Dip Coating. In dip coating the substrate is slowly
area and less porosity, the merits of using immobilised titania immersed in a titanium dioxide precursor solution, for
still far outweigh the disadvantages as it provides new avenues example, TTIP, TiCl4 , or TiCl3 and then slowly pulled out at
in the practical utilisation of titania. The techniques used a fixed rate. The coated substrate is then immediately dried in
for synthesis of TiO2 thin films include CVD, dip coating, furnace before calcination at elevated temperatures (400∘ C
sol-gel, spin coating, spray pyrolysis, sputtering, liquid-phase to 500∘ C) [65, 276–278]. Sometimes a complexing agent
deposition, and layer-by-layer (LbL) self-assembly. The sub- and a wetting additive are added to stabilise the solution
strates used include glass, single-crystal silicon, or polymeric and enhance film adherence [279]. Dip coating is also
substrates. Some of these thin-film synthesis techniques are regarded as a simple, cost-effective technique and it produces
discussed in the following subsections. uniform coatings with controllable film thickness [277, 280].
However, just like in LPD, the thermal treatment of the thin
9.1. Chemical Vapour Deposition. Chemical vapour deposi- films affects the adhesion properties of the nanoparticles on
tion (CVD) is a versatile method that can be used for the the substrate [235].
synthesis of a number of materials. To synthesise TiO2 thin
films by CVD, either a titanium alkoxide such as titanium 9.4. Spray Pyrolysis. Spray pyrolysis (SP) is a simple tech-
isopropoxide (TTIP) is used, which already has the Ti–O4 nique that requires a precursor solution (e.g., TiCl3 , TiCl4 ,
Journal of Nanomaterials 13

(a)

(b) (c)

(d) (e)

Figure 4: SEM images of CCA and CCA/TiO2 nanoparticles [106].

Ti(OEt)4 , or TTIP dissolved in water, ethanol, or other sol- surface morphology of the deposited films [281–283]. The SP
vents), an atomiser, and a heated substrate [156, 281]. In an method is attractive because it is inexpensive and uses simple
SP process the solution is atomised into small droplets and the facilities, results in rapid film growth, large surface-area sub-
droplets are transported by a gas to the heated substrate where strate coverage, and homogeneity, and has the potential for
they form thin films upon immediate approach or impinge- mass production [156, 283–286].
ment on the substrate (Figure 6). The source of the atomic However, SP has some drawbacks. Poor film quality is
mist (aerosol which produces large droplets or ultrasonic observed due to vapour convection in the hot zone because
spraying which produces smaller droplets) determines the the vapour formed on the heated substrate may hinder the
14 Journal of Nanomaterials

(a) (b)

(c) (d)

Figure 5: TEM images of the CCA-supported titania nanocatalysts [106].

Gas Air pressure result in the formation of thin films with many cracks due
valve meter Filter to precipitate shrinkage [284]. Also, SP can result in the
Air
compressor deposition of powder on the substrate.
Controller
Liquid Liquid flux 9.5. Sol-Gel Technique. The sol-gel technique is the most
valve meter
Spray Pump
widely used method for the synthesis of TiO2 thin films.
nozzle Controller The solution precursors are used to make the sol, and the
substrate is immersed in the sol and substrate gelation occurs.
Precursor These substrates are then aged and calcined at elevated
Substrate
temperatures to produce the thin films [185, 287]. The sol-
gel method has been widely used in the synthesis of titania
Temperature thin films because it is a simple and cost-effective method
controller
that results in the formation of high porosity, low density and
Heater low refractive index, high nanoparticle homogeneity, tunable
particle size, and high substrate coating [185, 227, 234, 288–
Figure 6: Schematic representation of the spray pyrolysis method 290]. The pH of the sol, the ageing time, amount of surfactant
[107].
template, amount of hydrolysis retardant, and calcination
temperature play an important role in the quality of the thin
films produced [288]. However, the sol-gel method has some
source vapour from attaching to the substrate due to the drawbacks. For example, during the ageing of gels and drying
temperature difference. Also, as the source liquid vaporises of films, the sols produce vapours which cause environmental
on the substrate due to thermal decomposition it may pollution [287]. Also, the thermal treatment of the thin films
Journal of Nanomaterials 15

NH
SO2 N
OSO3 − Na+

HO3 S
N
N N−+
I

SO3 − Na+
CO2 −
OHNa+
NaPSS PAZO PVS PAPSA PSMDEMA

SO3 −
O− Na+
NH2 + N +
O +N

S N+ Cl−
R

HN

SPAN R-PHPyV PTAA PMPyA PDDA

NH2
N
NH2
HN
N
NH
N
NH3 + Cl−
HN

SO3 H NH2

PAH PAMPSA PEI

Figure 7: Examples of polyelectrolytes used in LbL thin-film synthesis.

affects the adhesion properties of the nanoparticles on the can thus provide solutions for surface modifications and
substrate [235]. fabrication of thin films; that is, it permits multifunctional
assemblies of materials since it allows deposition on surfaces
9.6. Layer-by-Layer (LbL) Self-Assembly of almost any shape and kind [109, 295].
9.6.1. Introduction. The layer-by-layer (LbL) self-assembly
technique is a technology that enables the nanoconstruction 9.6.2. Fabrication of LbL Thin Films. Sequential deposition
of multifunctional films on solvent-accessible surfaces. It also of polyelectrolytes (polyanions and polycations) on solid sur-
allows for the design of functional surfaces and surface- faces leads to the build-up of multilayer LbL thin films [108,
based nanodevices in a “build-to-order” fashion, that is, 296, 297]. The LbL self-assembly technique is a physisorp-
the capacity to build standard or mass-customised prod- tion process independent of size and topology of the sub-
ucts upon receipt of spontaneous orders without forecasts strate; however, parameters like solution concentration, ionic
[109]. Furthermore, the LbL technique exceeds simple self- strength, solvent composition, and temperature play an
organisation under equilibrium conditions by making it important role in the multilayer build-up [292, 295, 298].
possible to arrange many different materials at will with Examples of polyelectrolytes used for LbL thin-film fabrica-
nanoscale precision [12, 109, 291–294]. The LbL technique tion are shown in Figure 7.
16 Journal of Nanomaterials

the purposes of this study the dipping deposition process was

preferred.

3 9.6.3. Applications of LbL Thin Films. There are a num-

2 4
ber of unprecedented “reagents” or materials for LbL film
deposition and these include polymers (linear or branched),
1
colloids (polymeric, metallic, or oxidic), biomacromolecules
(DNA/proteins, polynucleotides, bioaggregates, and contact
lenses), and nanoparticles (for environmental application)
[293, 296, 297, 299]. Due to the variety of materials used for
LbL thin-film fabrication, its application is therefore spread
across a variety of disciplines which include electric and
Figure 8: Schematic of the LbL electrolyte spraying deposition
process [108]. electronic devices (rectifiers, transistors, and switches), film
coating, micropatterning, nanobioreactors, photocatalysis,
and drug-delivery systems [300–302]. Biomedically, thin-
film coating on medical devices can improve biocompatibil-
+ + + + +
−− − − −

ity, reduce immunological response, and enhance targeted

−− − − −

+ + +
− − −− −− − − − −

+
−− −−

+
− − −− −− − − − −

+
−− −−

+ + + + + + drug delivery [294]. The LbL self-assembly technique has also

+ + + + +
+ + + been applied in the synthesis of thin-film microcapsules that
−

+ +
−

+ + + +
−

+ + + disintegrate on the target site hence improving drug or DNA

−− −− −− − −

++
−− −− −− − −

+ (1) Polyanion + (3) Polycation

Substrate

− −

+
− −

+ + + ++ delivery to their active site [298, 299, 303–307]. Also, LbL thin
+ +
+ (2) Wash + (4) Wash + + films have been applied to assemble semiconductor catalysts
+
+ + + + + + +
(especially TiO2 ) and applied in the degradation of organic
−

+ + + + +
−

+
− −

+ +
− −

+ + +
− −

+ pollutants for environmental remediation [12, 293, 308]. LbL

+ +
−

+ + + +
−

+ + + + + self-assembly of TiO2 on thin films can therefore go a long

way to overcome the problems associated with the practical
application of suspended TiO2 nanoparticles.

9.7. Layer-by-Layer TiO2 Thin Films. The use of titania in

powder form has the tendency to aggregate and scatter
1 2 3 4 incident light and there are difficulties associated with the
recovery of powdered titania after treatment; hence its large-
scale application is economically not viable. TiO2 has been
Figure 9: Schematic of the LbL electrolyte dipping deposition assembled on substrates using different methods and applied
process [109]. in catalytic environmental remediation processes. However,
since the other TiO2 thin-film fabrication methods have some
drawbacks like film cracking, poor adhesion to substrate, the
use of high temperatures, expensive equipment, and a high
To synthesise LbL thin films, a substrate is either dipped level of expertise required, the LbL self-assembly provides
in or sprayed with oppositely charged polyelectrolytes. Also, a better alternative. LbL thin films are synthesised at low
solutions can be allowed to flow over the substrate. During temperature (room temperature), simple equipment is used,
spraying (Figure 8) the electrolyte sprayed on the substrate the films require no thermal treatment, and strong adhesion
should not accumulate on the surface but flow away quickly, between nanoparticles, electrolyte, and substrate is ensured
driven by gravity, and only a thin film of liquid which typically due to the strong electrostatic interactions [12].
dries within minutes should initially remain on the surface. The TiO2 nanoparticles assembled by the LbL self-
Because the thickness of the adhering solution is very thin, assembly technique were found to be well separated and
any spray droplet arriving at the surface immediately fuses highly accessible for the photocatalytic processes. Also, the
with the liquid film and will replace liquid draining off. Spray amount of the nanoparticles deposited was easily controllable
coating is a fast and convenient application for large surface [12, 293]. When compared to other methods like drop-casting
areas. Thus, this setup provides for mild but permanent and spin-coating, the LbL assembled TiO2 show superiority
agitation as driven by the draining solution [108]. in terms of film stability and catalyst reusability (thin film
During the dipping method (Figure 9), the substrate is can be used a number of times with the same efficiency).
dipped alternately in oppositely charged polyelectrolytes. Also, the LbL method has no limit to the number of TiO2
Each dipping step is followed by a rinsing step to remove layers that can be assembled and the higher the number of
excess polyelectrolyte in contact with the surface. The wash- the layers the more the catalytic activity [12]. The use of LbL
ing is important because it avoids the formation of polyelec- synthesised thin films therefore overcomes the problems
trolyte clusters in solution and hence it ensures homogeneity associated with the use of powdered TiO2 as well as the
and uniformity of LbL films. Also, the dipping method forms other thin-film assembly techniques and is attractive for
thicker films than the spraying method [108, 109]. Thus for practical application in continuous water-treatment and
Journal of Nanomaterials 17

(a) (b)

(c) (d)

Figure 10: SEM images of 1, 3, 5, and 10 bilayers of the m-TiO2 nanoparticles thin films [110].

environmental remediation processes. However, little have 11. Titania Mixed-Matrix Membranes
been reported in recent literature on the assembly and use of
metal-doped titania by the LbL method. Recently, membrane separation technologies have been
found to be cheap and fast, chemically stable, and highly
10. Metal-Ion-Doped TiO2 LbL Thin Films selective. They can also be easily integrated with other water-
treatment strategies [309–311]. Because of these properties,
The immobilization of metal-ion-doped titania on glass slides they have been found more favourable to be used for water-
by the LbL method has been reported recently [110]. This treatment processes. Membrane techniques do not require
study reveals that the metal-ion-doped titanium dioxide addition of chemical substances and therefore it is easy to
nanoparticles were successfully attached on glass slides and increase their capacity (modular system). The separation
there was an increase in the number of particles and thin-film process is in a continuous mode and therefore applicable in
thickness with increase in the number of bilayers (Figure 10). mild environmental conditions [312]. Membrane processes
PAH and PSS electrolytes were used to immobilise these m- can therefore be used in diverse industrial sectors such as
TiO2 nanoparticles on the glass slides as thin films. The pho- pharmaceutical, water treatment, chemical, food processing,
tocatalytic efficiency of the PAH (PSS/mTiO2 ) thin films was electronics (fuel cells), metallurgy, and biotechnology [311,
studied using Rhodamine B under visible-light illumination. 313–317].
These thin films were highly active towards the photocatalytic Although using polymeric membranes has major benefits
degradation of Rhodamine B under visible-light illumination over the conventional water-treatment technologies, their
and did not lose their photocatalytic activity and strength susceptibility to fouling is a major drawback [309, 318].
even after five cycles. This study shows a great stride in the Foulants may be either crystalline, particulate, thermal,
use of metal-doped titania nanoparticles as it eliminates the colloidal, microbial (biofouling), or organic fouling [309, 314,
problems associated with aggregation and posttreatment and 318]. Polysulfone (PS) has been widely used to synthesise
thus increases the chances for easy use in water treatment. membranes. PS membranes are relatively cheap, have a
18 Journal of Nanomaterials

(a)

(c)
(b)

Figure 11: SEM micrographs of the CCA/TiO2 mixed matrix membranes: (a) surface morphology, (b) cross section, and (c) nanoparticles
within the polymer matrix [111, 112].

superior film-forming ability, strong thermal and chemical For such purposes, nanoparticles like TiO2 , Al2 O3 , ZrO2 , Cu,
stability, and acidic and alkaline resistance, and hence have Ag, and SiO2 have been utilised in the past [309, 311, 318, 325].
been widely used in many applications [318, 319]. These mem- Recently CCA-supported free TiO2 (CCA/TiO2 /PSf) and
branes have good mechanical and anticompaction properties. Pd-doped titania (CCA/Pd-TiO2 /PSf) nanoparticles have
However, like any other membranes, PS membranes have been embedded within a polysulfone matrix to synthesise
limitations to be used in water-treatment processes because mixed matrix membranes [111, 112]. In these studies, both
they easily get fouled, have a low permeate flux, and are the CCA/TiO2 /PSf and the (CCA/TiO2 /PSf) membranes
hydrophobic in nature [310, 311, 320], hence the need to were found to be highly photoactive for the discolouration
modify their properties. of Rhodamine B under visible-light irradiation. The CCA-
Current research in membrane technology develop- supported nanoparticles were distributed both within and
ment is focussed on the improvement of antifouling and on the surface of the membranes (Figure 11). These studies
hydrophilicity properties while maintaining or improving revealed that only a minimal amount of the nanoparticles can
their throughput characteristics [310, 311, 319, 321]. This can be be incorporated within the polymer matrix without compro-
attained by either bulk or surface modification which changes mising the mechanical properties. Increasing the amount of
the chemical structure of the membranes. Also, inorganic the nanoparticles to about 0.5% resulted in weakening of the
nanoparticles can be incorporated through the membrane mechanical properties of the nanoparticles. The presence of
matrix or on the surface [309]. Although this phenomenon the nanoparticles also enhanced the permeate flux as well as
is still under debate, it is widely accepted that the thermo- the fouling behaviour of the PSf membranes. This is thus a
dynamic state and kinetic properties of the system and how great step that eliminates not only the problems associated
they vary during processing govern the structure formation with posttreatment and aggregation but also fouling of the
pathway of the membrane. Also, physical parameters like membranes and thus provides a better alternative in finding
the temperature, the composition of the casting solution, the means to deal with water-treatment problems.
composition of the nonsolvent bath, and the surrounding
atmosphere play a pivotal role in determining the synthetic 12. Conclusion
pathway as well as the final membrane structure [322, 323].
Incorporating inorganic nanomaterials into polymeric mem- From the literature discussed, the health risks associated with
branes has been found to improve the chemical stability, the the presence of pollutants in water due to the failure of con-
thermal stability, the permeation, and the mechanical as well ventional water-treatment technologies to effectively remove
as the antifouling resistance of membranes [313, 318, 321, 324]. organic and inorganic pollutants have been highlighted. It
Journal of Nanomaterials 19

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R. G. Palgrave, and R. G. Egdell, “Nitridation of nanocrystalline
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cheaper alternative that can be used in conjunction with
“Effect of metal doping into Ce0.5 Zr0.5 O2 on photocatalytic
the already existing water-treatment technologies, especially activity of TiO2 /Ce0.45 Zr0.45 M0.1 OX (M = Y, La, Mn),” Journal
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alternative for the use since it harnesses the green solar energy
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Conflict of Interests [13] H. Choi, E. Stathatos, and D. D. Dionysiou, “Photocatalytic
TiO2 films and membranes for the development of efficient
The authors declare that there is no conflict of interests
wastewater treatment and reuse systems,” Desalination, vol. 202,
regarding the publication of this paper. no. 1—3, pp. 199–206, 2007.
[14] G. V. Lowry and K. M. Johnson, “Congener-specific dechlorina-
Acknowledgment tion of dissolved PCBs by microscale and nanoscale zerovalent
iron in a water/methanol solution,” Environmental Science and
The authors are grateful to the Department of Applied
Technology, vol. 38, no. 19, pp. 5208–5216, 2004.
Chemistry, University of Johannesburg, South Africa, for
constantly supporting our research program on nanomateri- [15] W. Nam, J. H. Park, and G. Y. Han, “Enhanced photocatalytic
oxidation properties in Pt-TiO2 thin films by grounding,”
als, especially their financial support.
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