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ScienceDirect
Titanium dioxide-based antibacterial surfaces
for water treatment
Changseok Han1, Jacob Lalley2, Devi Namboodiri3,
Keeley Cromer2 and Mallikarjuna N Nadagouda2
The field of water disinfection has gained much interest since
waterborne diseases caused by pathogenic microorganisms
directly endanger human health. Antibacterial surfaces offer a
new, ecofriendly technique to reduce the harmful disinfection
byproducts that form in medical and food processing
industries. Titanium dioxide (TiO2) photocatalysts have been
extensively studied to prepare antibacterial surfaces due to
their environmentally favorable properties. The studies
demonstrate TiO2 improves the efficiency of disinfection by the
effective inactivation of pathogenic microorganisms (i.e.,
Escherichia coli, Enterococcus faecalis, Staphylococcus
aureus, Pseudomonas putida, and Listeria innocua). TiO2
photocatalysts decompose natural algal toxins such as
microcystin-LR and cylindrospermopsin under solar light
irradiation. On the basis of literature review, these antibacterial
surfaces may be applied to hospital, food, ceramic, and
building industries or to environmental remediation where
bacteria inactivation is required to ensure the safety of human
health and the environment.
Addresses
1
ORISE Post-doctoral Fellow, The U.S. Environmental Protection
Agency, ORD, NRMRL, STD, CPB, 26 W. Martin Luther King Jr. Drive,
Cincinnati, OH 45268, USA
2
The U.S. Environmental Protection Agency, ORD, NRMRL, WSWRD,
WQMB, 26 W. Martin Luther King Jr. Drive, Cincinnati, OH 45268, USA
3
Seven Hills High School, 5400 Red Bank Road, Cincinnati, OH 45227,
USA
Corresponding author: Nadagouda, Mallikarjuna N
(nadagouda.mallikarjuna@epa.gov)

Current Opinion in Chemical Engineering 2016, 11:4651

This review comes from a themed issue on Materials engineering
Edited by Thein Kyu and Jai A Sekhar

http://dx.doi.org/10.1016/j.coche.2015.11.007
2211-3398/Published by Elsevier Ltd.

Introduction
Water disinfection is a significant process for drinking
water treatment since it is directly related to the reduction
of waterborne diseases caused by pathogenic microorganisms [13]. Chlorination is a common technique used for
water disinfection to inactivate or kill pathogens in water
Current Opinion in Chemical Engineering 2016, 11:4651

treatment plants. However, there are several disadvantages. During chlorination, harmful compounds known as
disinfection byproducts (DBPs) are produced due to a
reaction of chlorine and natural organic matter (NOM) in
water. DBPs contain carcinogens (i.e., trihalomethanes
(THMs) and haloacetic acids (HAAs)) and are associated
with bladder concerns that may contribute to adverse
productive effects [4,5]. Moreover, it has been reported
that after chlorination, multidrug resistant (MDR) pathogens (i.e., Acinetobacter baumannii, and Pseudomonas aeruginosa) grow and survive [5,68]. Although new,
alternative techniques, such as UV-disinfection and ozonation, have been studied and employed in water treatment plants to solve these problems, complications
regarding residual of pathogens have still been reported
[5]. Therefore, there is a need to develop a reliable
method of disinfection, which is free from the production
of DBPs and effective at killing or inactivating pathogens.
Also, further studies are required to ensure that new
techniques do not have adverse effects to the safety of
human health and the environment.
One alternative approach of disinfection is utilizing antibacterial surfaces. Antibacterial surfaces offer a different
technique compared to conventional disinfection since
water-containing pathogens require contact with the antibacterial surfaces to kill or inactivate pathogens as
opposed to chemicals (e.g., chlorine, chloramines, and
chlorine dioxide) that are directly dispersed into water
[5]. Hitherto, antibacterial surfaces have been used in
medical fields to prevent infection and the formation of
biofilms on the surface of medical devices and implants
[5,9]. Recently, the antibacterial surfaces prepared on
different substrates, such as stainless steel, glass, and
ceramics, have been used for water treatment [10].
Because of its antibacterial activity, titanium dioxide
(TiO2) has been extensively studied and used to inactivate
many microorganisms [11,12,13]. Also, being environmentally suitable, it has been widely used for environmental applications, including water and air purification as well
as groundwater and soil remediation [14,15,16,17].
Therefore, in this review, we focus on the antibacterial
surfaces of TiO2 for drinking water disinfection.

Titanium dioxide
TiO2 is the most commonly used semiconducting photocatalyst and one of the most studied nanoparticles for
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Antibacterial surfaces for drinking water disinfection Han et al. 47

environmental applications. Upon UV irradiation, activated TiO2 yields photocatalytic properties applicable for
water purification techniques. Photocatalytically generated reactive oxygen species (ROS), such as hydroxyl
radicals (HO), hydrogen peroxide (H2O2), and superoxide anion (O2 ) can decompose inorganic and organic
pollutants and inactivate microorganisms, bacteria, fungi,
and viruses [11,18]. Figure 1 shows the photoexcitation
mechanism of TiO2 in detail. Economic and environmental factors make TiO2 disinfection a viable replacement
for chlorination. For example, TiO2 catalysts can be
recycled indefinitely, requiring no additional chemical
treatment, thus making its large-scale use more probable
[18].
Since photocatalysis is an interfacial phenomenon, disinfection will be optimized when the active surface-area-tovolume ratio is maximized. Therefore, maximum disinfection would occur with a mobilized mode of TiO2 (a
slurry of nanosized TiO2 powder suspended in a mixture).
The mobilized mode causes the separation between fine
TiO2 powders and the disinfected water to be a difficult
process that requires additional steps and equipment. To
accommodate for this problem, an immobilized mode for
TiO2 catalysis, though not as efficient at disinfection, is
the logical option. Immobilized TiO2 permanently
adheres to supporting materials such as soda-lime glass
and acrylic bottles.

The solar disinfection method (SODIS) was one technique explored and modified by the addition of a photocatalytic layer of TiO2 (using solvent deposition) on the
interior surface of polyethylene terephthalate (PET) and
acrylic bottles [19]. It was determined that the TiO2 coated
acrylic bottles could effectively inactivate and transform
bacteria (e.g., Escherichia coli (E. coli), organic waste (e.g.,
methyl orange), and algal toxins (e.g., microcystin-LR
(MC-LR)) after various times of solar irradiation. The
TiO2 coated acrylic bottles were found to be an effective
alternative to TiO2 coated PET bottles due to acrylics
greater UV transparency [19]. Thus, plastic bottles coated
with TiO2 and irradiated by sunlight can effectively kill
common waterborne pathogenic microorganisms and other organic pollutants, proving to be beneficial to areas with
inadequate amounts of clean water. Gelover et al. [20]
immobilized TiO2 on glass cylinders by the solgel method [21] to enhance the efficiency of SODIS. The TiO2
coated glass cylinders were placed in a homemade solar
collector (Figure 2). The collector was then exposed to
solar light with an average radiation of 1037 W m 2. With
the TiO2 coating, complete inactivation of E. coli without
bacteria regrowth was obtained after 15 min of solar irradiation. However, for SODIS without TiO2, regrowth
occurred and it took 30 min to inactivate E. coli.
Bonetta et al. [22] and Alrousan et al. [23] studied the
inactivation of pathogens by immobilizing TiO2 on petri

Figure 1

Ox
Conduction Band

Ox

Substrate

Reduction

UV or visible light
Bandgap (3.2 or < 3.2eV)

h+
Valence Band

Red
+

Oxidation
Red+

Conventional or modified TiO2 (anatase)

Immobilized TiO2
Current Opinion in Chemical Engineering

Photoexcitation mechanism of titanium dioxide photocatalyst.

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Current Opinion in Chemical Engineering 2016, 11:4651

48 Materials engineering

Figure 2

60

and chemical water contaminants. Platinum deposition is

ideal to use in hospitals, swimming pools, and water
theme parks, but it can also be used for industrious water
purification [24]. Additionally, Fisher et al. [25] developed
a photoreactor coated with nitrogen and copper-doped
TiO2 to inactivate E. coli K12 (MG1655) and Enterococcus
faecalis (29181) and to decompose methylene blue (MB)
under natural solar light illumination. The thin films of
Cu-doped and Cu/N-doped TiO2 effectively inactivated
bacteria and degraded MB under their experimental
conditions. Fisher et al. [25] demonstrated the potential
of antibacterial films for environmental decontamination
under solar irradiation.

19
Current Opinion in Chemical Engineering

Solar collector for solar disinfection.

Copyright from Ref. [20].

dishes, ceramic tiles, and borosilicate glass sheets. For

their experiments, commercially available Degussa P25
TiO2 was coated on the surface of the substrates. Bonetta
et al. [22] used TiO2 coated petri dishes and tiles to
inactivate four different bacteria: E. coli, Staphylococcus
aureus, Pseudomonas putida, and Listeria innocua. All bacteria were effectively inactivated by the TiO2 coated
surfaces under UV with irradiance of 9 W m 2. Listeria
innocua inactivated the easiest with comparison to other
bacteria. However, there was no difference of the antibacterial activity between petri dishes and ceramic tiles.
Alrousan et al. [23] investigated the effects of catalyst
loading and solution pH on water disinfection. The
antibacterial activity of the TiO2 coated surface for surface water was also evaluated. The optimal catalyst loading was 0.5 mg cm 2, yet no significant effect of solution
pH was observed from 5.5 to 8.5. The inactivation rate for
the surface water decreased due to the presence of NOM
and inorganic ions such as sulphate and nitrate.
Recently, much effort has been made to use visible light,
which is a larger portion (about 45%) of the solar spectrum
compared to UV (only 45%) [14,15,24]. The preparation of platinum-deposited TiO2 (PtTiO2) catalysts and
its immobilization on ordinary ceramic tiles have also
been studied to inactivate bacteria and purify contaminated water [24]. The PtTiO2 compounds were characterized by X-ray diffraction, scanning electron
microscopy, energy dispersive X-ray spectroscopy, and
diffuse reflectance spectroscopy. By extending the TiO2
optical absorbance to the visible spectrum, platinum
deposition enhanced solar photocatalytic pollution remediation. After determining the optimal Pt loading (0.5%),
the Pt/TiO2 particles were immobilized on ceramic tiles.
This catalyst proved to effectively remediate bacterial
Current Opinion in Chemical Engineering 2016, 11:4651

The versatility of TiO2s application is an advantageous

property. Park et al. [26] used TiO2 to enhance water
disinfection with the knowledge that an increase in
surface area would result in an increase in antibacterial
activity. Park et al. used aerosol deposition, which was
quick and conducted at room temperature, making it
simple and economical. During aerosol deposition,
TiO2 particles accelerated to supersonic speeds collided
with a glass surface, forming a functional thin film. After
particle deposition, tests were conducted to count the
colonies of bacteria and to evaluate the films antibacterial
activity through MB decolorization tests. It was determined that the structure of the films contributed to
enhance bacterial remediation. The aerosol-deposited
films had a unique, honeycomb-like structure, resulting
in a rough texture, which increased the surface area. Nonannealed films, for example, exhibit optimal photocatalytic activity due to their small crystalline size and large
surface area [26]. Ochiai et al. [27] investigated a unit
which could not only purify water, but simultaneously
assist in air purification. The unit, a versatile photocatalyst-excimer-lamp hybrid, consisted of a xenon filled
quartz tube and TiO2 nanoparticles-modified titaniummesh sheet. Emissions (at 172 nm from a Xenon excimer)
produced ROS (e.g., HO) by direct photolysis to excite
TiO2 nanoparticles on the surface. The emissions also
decomposed organic contaminants (by synergy of photocatalysis and photolysis) as well as inactivated waterborne
pathogenic microorganisms.

Problems or possible difficulties with

proposed method
Employing a photocatalyst as a slurry or in a mobilized
mode makes pilot testing difficult due to scale-up issues,
such as removal from purified waters. Gumy et al. [28]
investigated the disinfection action of different samples
of TiO2 (Degussa P-25, Millennium PC-100 and PC-50,
Tayca AMT-100 and AMT-600) coated on fibrous webs
using E. coli as the model microorganism for disinfection
experiments [28]. Although TiO2 is a proven alternative
for water disinfection, there are some drawbacks to using
it alone. For example, TiO2 photocatalysis will not occur
without a light source since TiO2 composites must absorb
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Antibacterial surfaces for drinking water disinfection Han et al. 49

UV and visible light for photocatalytic bacterial inactivation. Because of the necessity of light, research in metal or
nonmetal-doped TiO2 compounds (e.g., silver and copper-doped TiO2, and nitrogen-doped TiO2) has been
conducted. Results showed antibacterial activity occurring with limited or no light irradiation in both cases
[23,29,24,3042]. In addition, the use of Ag enhanced
TiO2 disinfection is considerably interesting. Investigations have been performed on the use of Ag enhanced
TiO2 surfaces and their wide range of potential uses from
the photodegradation of estrogen to E. coli inactivation
[29,24,3042].
Moreover, a significant drawback of TiO2 photocatalysis
is the rapid charge recombination of the electronhole
pairs, which reduces the efficiency of the photocatalytic
processes, for its practical applications. Therefore, the
improvement of charge separation during the TiO2
photocatalysis became a significant strategy to enhance
the efficiency of the process. The formation of heterojunction of TiO2 with other semiconductors and/or noble
metals has been widely studied to achieve high photocatalytic efficiency of the processes by decreasing the
recombination rate of photoinduced electronhole pair
[43].

TiO2 efficiency of cleaning out algal toxins

The degradation of cylindrospermopsin (CYN) and MCLR under TiO2 irradiation has been investigated [14,44
47]. CYN and MC-LR are dangerous cyanotoxins commonly formed by harmful cyanobacteria in various water
bodies [14,4447]. Because of their high toxicity (including hepatotoxicity and nephrotoxicity), CYN and MC-LR
have received great public attention in recent years.
However, information is limited due to its relatively
recent discovery. Nonetheless, the U.S. EPA considers
CYN and MC-LR contaminants of high priority [48].
Several techniques have proven effective at treating
CYN and MC-LR, such as activated carbon and chlorination. However, these techniques are typically expensive and form byproducts. Thus, a low cost disinfectant
that forms minimal byproducts, such as TiO2 has been
considered. TiO2 nanoparticles and films were synthesized through an ambient condition sol process and a dipcoating process. Then, the prepared catalysts were characterized by X-ray diffraction, Micro-Raman spectra, UV
vis diffuse reflectance, scanning electron microscopy, and
transmission electron microscopy. According to a study by
Zhang et al. [44], it was determined that an increase in the
concentration of TiO2 nanoparticles correlated to an
increase in CYN removal up to a concentration of
0.5 g/L. The scattering effect of the white TiO2 nanoparticles from the incident light was a probable cause for
the stop of CYN removal. The pH, NOM levels, and
alkalinity were also investigated as these water quality
parameters are directly associated with the efficiency of
TiO2 photocatalysis to decompose CYN. Higher pH and
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NOM concentrations corresponded to lower reaction

rates. It was determined that both CYN and TiO2 were
negatively charged, resulting in a lower degradation rate.
It was also determined, with respect to the effects of
alkalinity, that CO32 had a positive effect on CYN
degradation while HCO3 had a negative effect [44].
MC-LR, a cyanotoxin, also effectively decomposed by
visible light-induced sulfur-doped TiO2 photocatalysis
[14,45,47]. On the basis of the results of a study by
Andersen et al. [49], the produced ROS effectively
and
destroyed
the
amino
acids,
attacked
2S,3S,8S,9S,4E,6E)-3-amino-9-methoxy-2,6,8-trimethyl10-phenyldeca-4,6-dienoic acid (Adda), associated with
the biological toxicity of MC-LR.

Conclusion
The field of water disinfection is gaining interest with
immobilized bactericidal agents on surfaces. Though
used for years in medical and food processing industries,
antibacterial surfaces are now considered a new and
environmentally efficient technique for water disinfection to reduce the amount of carcinogenic byproducts
formed through chlorine and NOM reactions. ROS produced at the surfaces composed of TiO2 demonstrate
reliable antibacterial properties to inactivate various pathogenic microorganisms such as E. coli, Enterococcus faecalis,
Staphylococcus aureus, Pseudomonas putida, and Listeria
innocua. Moreover, algal toxins were effectively decomposed by TiO2 photocatalysis. Therefore, these antibacterial surfaces may be used in many applications,
including hospital and food industry, ceramic and building industry, and environmental remediation.

Disclosure
The U.S. Environmental Protection Agency, through its
Office of Research and Development, funded and managed, or partially funded and collaborated in, the research
described herein. It has been subjected to the Agencys
administrative review and has been approved for external
publication. Any opinions expressed in this paper are
those of the author(s) and do not necessarily reflect the
views of the Agency, therefore, no official endorsement
should be inferred. Any mention of trade names or
commercial products does not constitute endorsement
or recommendation for use.

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