01 25117 Magalhaes

Titanium
Rev. Adv.dioxide
Mater. Sci.
photocatalysis:
51 (2017) 91-129
fundamentals and application on photoinactivation 91
TITANIUM DIOXIDE PHOTOCATALYSIS: FUNDAMENTALS

AND APPLICATION ON PHOTOINACTIVATION
Pedro Magalhães, Luísa Andrade, Olga C. Nunes and Adélio Mendes

LEPABE, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto,
rua Dr. Roberto Frias, 4200-465 Porto, Portugal
Received: April 02, 2017
Abstract. TiO2 semiconductor is being investigated and used for different applications such as
energy production, photoinactivation, photoabatement, self-cleaning and water desalination. TiO2
has, however, a large band gap, ca. 3.2 eV, which limits its absorption to UV light range that
accounts only for ca. 5% of the solar spectrum energy. Therefore, strategies for reducing its band
gap aiming to enhance visible light harvesting and making TiO2 usable for indoors applications
are being studied; this reduction is mainly achieved by doping and decoration. More recently,
TiO2/graphene composite proved to be an interesting material for photocatalytic purposes,
presenting enhanced energy harvesting properties and an improved photocatalytic activity.
Furthermore, the micro size of the composite graphene platelets allows its use without the
potential health hazards associated to TiO2 nanoparticles. TiO2 may contribute to prevent
nosocomial infections because, similarly to the phagocytic cells of the human immune system,
it uses the cytotoxic effects of Reactive Oxygen Species (ROS) to inactivate microorganisms.
These ROS are known to be highly reactive with biological molecules and thus they are effective
for the inactivation of various types of microorganisms. The photocatalysis fundamentals and the
preparation of more efficient TiO2 photocatalysts suitable for indoor applications are reviewed
aiming their application for the photoinactivation of microorganisms. Additionally, a comparison
of the effectiveness of photoinactivation with traditionally used disinfection methods is also made.
Finally, gaps in the knowledge on the long-term effect of the utilization of TiO2 based materials are
identified.
1. INTRODUCTION Even though the environmental applications are

leading the photocatalysis, microorganism
In the past four decades photocatalysis fundamen-
photoinactivation is also catching more and more
tals and applications developed tremendously. Pres-
attention within the scientific community. In fact,
ently, there is a deeper understanding of the photo-
there is an alarming increase in the number of hos-
catalysis fundamentals and, consequently, the use
pital-acquired infections, also known as nosocomial
of photocatalysts in several emergent fields such
infections [8]. This increase was caused by an un-
as energy production (e.g. photocatalytic water split-
controlled use of substances that promote the propa-
ting [1]), environmental protection (e.g. self-clean-
gation of antibiotic resistance, strongly motivated
ing materials [2] and photo abatement of atmos-
by a lack of adequate legislation [9]. Infectious dis-
pheric pollutants such as NOx [3], volatile and halo-
eases are becoming again a real threat, with new
genated hydrocarbons [4]), water purification (e.g.
infections appearing at an alarming rate [10], and
photooxidation of micropollutants [5], volatile
the exponential movement of people across coun-
organohalide compounds, pesticides [6]) and for
microorganisms inactivation [7].
Corresponding author: O.C. Nunes, e-mail [email protected] and A. Mendes, e-mail: [email protected].
© 2017 Advanced Study Center Co. Ltd.

92 P. Magalhães, L. Andrade, O.C. Nunes and A. Mendes
tries, oceans and continents are intensively con- cies, while excited electrons normally react with
tributing to their propagation. oxygen to produce free radical O2•. These are re-
In the past decade many studies reported the sponsible for the photodecomposition of organic
photocatalysis use for disinfection purposes; espe- compounds, where adsorbed water and oxygen have
cially the antimicrobial application of titanium diox- been described to play an important role.
ide has been widely discussed in many reviews and There are, nowadays, several proposed pathways
research papers [11]. In this work, the microorgan- for the photodegradation of pollutants [17,18]. The
ism photoinactivation main issues will be reviewed, most commonly assumed photodegradation mecha-
namely regarding the development of materials with nism is based on Langmuir-Hinshelwood kinetic
enhanced visible light harvesting to foster photoca- model, as described by Ollis and Turchi [19]:
talysis for indoor applications (e.g. hospitals, health  
centres, etc.). Since the use of TiO2 for disinfection TiO 2  h   h  e (1)
purposes is being limited to its ability of absorbing
 
only UV light and by the rapid recombination of sepa- h  e  heat (2)
rated positive and negative charges, doping, deco-
h  (H2 O/ OH )s  OH (aq)

ration and the use of TiO2/graphene composites are (3)
addressed below as mechanisms for mitigating these
drawbacks.
e  O2  O2
 
(4)
2. FUNDAMENTALS OF
PHOTOCATALYSIS Reactant sol  S  Reactant (5)
The pioneer work developed by Fujishima et al. [12]

OH  Reactant  Products (6)
describing water splitting with a TiO2 photoelectrode

caught the attention of several research groups where OH• is the hydroxyl radical, O 2 is the
working on this field and rapidly TiO2 became the superoxide radical and S is an active center of the
most used semiconductor for photocatalysis. Tita- photocatalyst. This kinetic model was proposed
nium dioxide exhibits three crystalline structures: based on studies of spin trapping and electron spin
rutile, anatase and brookite. Rutile is the most ther- resonance (ESR) showing high concentrations of
modynamically stable crystal structure of titanium OH• radicals in photocatalytic systems [19]; the
dioxide but anatase is the preferred form for photo- presence of hydroxylated intermediates formed dur-
catalysis because it presents higher photocatalytic ing the photodegradation of the studied compounds
activity and it is easier to prepare. Brookite is the also supports the suggested model. However,
least stable phase and normally not used in photo- Ângelo [20] reported recently a maximum of NO
catalysis. There are studies that indicate the ben- conversion of 82.4% for a feed containing 25% of
efits of mixings different crystalline phases of TiO2 RH and of XNO = 75.7% for a feed with a dew point
for obtaining a higher photoactivity [13,14]. When of -20 °C; the same work indicates that the water-
different crystalline phases are coupled, it is mostly adsorbed monolayer is reached for a relative hu-
believed that the movement of electrons from the midity of ca. 25%. If the main intermediate oxida-
rutile phase to the anatase phase occurs, which tion species of NO is OH• the NO conversion for the
causes a more efficient e-/h+ separation and conse- dry feed should be quite smaller, see Eq. (3). This
quently an increased photocatalytic activity [15]. result along with other studies reported in literature
However, there are other studies defending that the [21] question the role of hydroxyl radicals in photo-
electron movement is from anatase to rutile [16]. catalysis or, otherwise, of the equation (3). Montoya
The anatase band gap is ca. 3.2 eV while the and co-workers [22] made a strong case against
band gap of rutile is ca. 3.0 eV. Upon excitation the direct reaction of a photogenerated hole with
with photons presenting energy higher than the band adsorbed water or OH” to form OH•, suggesting a
gap energy, an electron is injected from the valence novel direct-indirect model (D-I) – Fig. 1. The D-I
to the conduction band, generating an electron-hole model shows two different types of interfacial charge
pair in the conduction and valence bands, respec- transfer mechanisms. For strong electronic inter-
tively – Eq. (1). The photogenerated charges diffuse action, D-I model assumes that photo-oxidation is
to the surface of the semiconductor particle where mainly based in an interfacial direct transfer (DT)
they promote redox reactions; holes may generate mechanism of photogenerated valence band free
vacancies on TiO2 surface or excited reduced spe- holes to adsorbed species to TiO2 surface. On the
Titanium dioxide photocatalysis: fundamentals and application on photoinactivation 93
Fig. 1. Schematic of the Direct-Indirect Model: a) Direct Transition; b) Indirect Transition. Adapted from [13]
with permission.
other hand, for weak interactions between reactant facilitated at the traps on the surface and in the
and TiO2 surface, the D-I model assumes an inter- bulk of the particles [29]. Indeed, it is assumed that
facial indirect transfer (IT) mechanism involving two the recombination process occurs at the crystal
successive steps: at the first step, hf+ species are defects, explaining why amorphous TiO2 presents
trapped by Os2" terminal oxygen ions of the TiO2 almost negligible photocatalytic activity. Neverthe-
surface leading to generation of terminal Os•” radi- less, there are few works discussing this point since
cals; at a second step, surface trapped holes are the defects of the photocatalytic powders are very
isoenergetically transferred via tunneling to the difficult to determine. Anatase absorbs only wave-
adsorbed reactant, according to the Marcus- lengths smaller than 386 nm, which falls in the UV
Gerischer model for adiabatic electron transfer at range. Sunlight spectrum comprises only 5-7 % of
the semiconductor electrolyte interface [23]. UV light, 46% of visible light and 47% of infrared
The study conducted by Salvador and co-work- radiation [30]. So, TiO2 modifications to allow vis-
ers [24] analyze the importance of oxygen on the ible absorption are fundamental to enhance the pho-
photocatalytic phenomenon. Dillert et al. [25] and tocatalytic rate. Targeting this enhancement the
Ângelo et al. [20], also highlighted the importance research was directed for the use visible light in-
of oxygen on the photocatalytic phenomenon, show- stead of only UV radiation, and of proper immobili-
ing that without oxygen there is no NO conversion. zation of the photocatalyst. TiO2 doping and/or deco-
Thus, the photooxidation mechanisms still a mat- ration with the objective of increasing photoactivity
ter of debate. and photoabsorbance is addressed below. Doping
As previously mentioned, improving the TiO2 concerns adding foreign chemical elements (impu-
photocatalytic activity for attaining visible light ac- rities) to modify in the inner-structure of the photo-
tivity is being targeted; this improvement can be catalyst, while decoration concerns adding materi-
achieved by: i) avoiding the recombination of als to the photocatalyst surface. Both modifications
photogenerated electrons/holes; ii) narrowing the target the same objectives: preventing e-/h+ recom-
semiconductor band gap (Eg) [26]. While the first bination and red-shift of the light absorption. TiO2/
permits to efficiently generate more free radicals, graphene composite photocatalysts reduces the
the later allows the photocatalyst to absorb a larger charge recombination and originates Ti-O-C bonds
fraction of the solar spectrum. Even though the re- that promotes significant red-shift.
combination rate of e-/h+ has been neglected in
many works due to difficulties in its estimation, it 2.1. Doping and decoration
has been proved that the recombination rate has a
strong contribution for the net photocatalytic activ- Doping of TiO2 can help the improvement of photo-
ity [27,28]. The majority of the authors working on catalytic activity by enhancing the optical absorp-
this topic defend that the crystal structure of the tion of wide band gap semiconductors, increasing
photocatalyst is a dominant factor of the photocata- the minority carrier diffusion length or enhancing the
lytic activity since the recombination of e- and h+ is catalytic activity at the surface of the semiconduc-
tor [31]. However, in some cases, these dopants case of visible light activity, a less oxidative
can also promote e-/h+ recombination with the crea- superoxide radical was suggested to be formed and
tion of mid gap surface states that actually act as being the main responsible for the photocatalytic
recombination centres [31]. High values of dopant activity [54,59,60]. Renguifo-Herrera and co-work-
concentration (not above 10 6 mol·dm 3 [31]) should ers [59] developed N and S co-doped TiO2 present-
be avoided since may lead to segregation of the ing an intense visible-light absorption. However, its
dopant phase. There are two possible doping sites photocatalytic activity was low, similar to P25 un-
in TiO2: at the titanium site (cation doping) or at the der solar simulated light. These results can be as-
oxygen site (anion doping). Thus, there are two main cribed to the fact that the photogenerated holes on
types of TiO2 doping: cation-doping [32-41] and the intermediary energy levels formed by N and S
anion-doping [42-51]. Various studies have been co-doping under visible light do not present suffi-
performed to explain the band gap narrowing mecha- cient redox potential to oxidize water and thus are
nism in TiO2 doping [30,42,52]. Nitrogen doping is not able to produce OH• radicals.
the most used approach for obtaining visible light The main difference between doping and deco-
activity; [53-55] however, there is no established ration is related to which part of the TiO2 is modi-
mechanism that explains the visible light activity of fied. In the case of doping, the modifications are
N-doped TiO2. While some authors state that conducted inside the crystalline structure of TiO2,
substitutional N-doping results in band gap narrow- while in the case of decoration the modifications
ing due to the efficient mixing of orbitals 2p of N and are made on the TiO2 surface. After excitation of
O, others argue that band gap narrowing through TiO2, electrons migrate to the attached decorating
modifications in the energy levels of valence and particle where they become trapped, minimizing the
conduction bands can only occur with high concen- electron-hole recombination [61]. The migration of
trations of dopants and strong interactions among electrons to the decorating particles was confirmed
impurity energy states, valence and conduction in several studies [62-64], which showed an improved
bands [54]. Di Valentin and co-workers [56] based photocatalytic activity of the decorated TiO2 when
on the density functional theory (DFT) predicted that compared to pristine TiO2; the holes migrate then
N atoms could occupy either substitutional or inter- to the semiconductor surface without recombining
stitial sites in the TiO2 lattice and thus generate [62-64]. Few review articles analysing doping and
localized energy states. When substitutional sites decorating effects on photocatalysis have been pub-
are occupied, a higher energy level extending the lished recently [65-68].
valence band is formed, while in the case of intersti- An effect that worth to be explained and that
tial sites occupation, discrete energy levels above has been gathering interest in the scientific com-
the valence band are created. Doping with other munity is the surface plasmon resonance effect -
anions, such as carbon, can also show gap narrow- SPR effect. When a metal nanoparticle is subjected
ing [57]. Some authors suggest that the use of dop- to an oscillating electric field as the case of inci-
ing agents results in modifications of (101) TiO2 dent light, the free electrons in the nanoparticle will
surface [58]. These modifications can increase the answer to that electric field also by oscillating. This
transfer of photogenerated electrons to the outer behavior is called localized surface plasmon reso-
surface regions, facilitating the photocatalytic reac- nance and it can be adjusted by manipulating the
tions and improving the quantum efficiency of the size, shape and dielectric environment to change
photocatalytic processes. the interaction of the nanoparticles with incident light.
Another approach used for obtaining visible light Thus, it is possible to scatter the incident light with
activity is metal ion doping. Some theories explain metal nanoparticles and increase the optical path
the visible light response obtained with this type of of photons, leading to an absorption enhancement
doping such as, the occurrence of band gap nar- in certain wavelengths. SPR effect also promotes
rowing and intrinsic defects by either substitutional changes in the energy of the Fermi level caused by
or interstitial substitution in the TiO2 matrix [54]. the electron storage effects in the metal nanoparticle
Metal ion doping induces, however, recombination [54]. Localized SPR of gold and silver nanoparticles
of charge carriers lowering the overall efficiency of normally results in strong and broad absorption
photocatalysis. Additionally, some reports point to bands in the visible light region, which can be ex-
differences in the photocatalytic phenomena under ploited to attain visible light-activated photocatalysts
visible light and UV radiation. For UV radiation, as [61,69-71].
discussed in Section 2, both superoxide and hy- Important to mention that one of the possible
droxyl radicals are produced. Nevertheless, for the disadvantages of TiO2 decoration is the corrosion
and dissolution of decorating metal particles during extended light absorption range; and iii) enhanced
the photocatalytic reaction [72]. The decorative par- adsorptivity of the reactant species [79].
ticles can also act as co-catalysts, reducing the For photocatalytic indoor applications, such as
overvoltage of the redox reactions involved in pho- for photoinactivation of microorganisms, a very prom-
tocatalysis. The use of co-catalysts allow a given ising photocatalyst is Au/TiO2/graphene. The use of
electrochemical reaction to progress faster [73]. For gold nanoparticles is expected to promote increased
instance, in photoelectrochemical water splitting, values of photoactivity due to the high surface plas-
the lower level of the conduction band must be more mon resonance effect observed with these
negative than the redox potential of H+/H2 (0 V vs. nanoparticles [61,85]. The Au/TiO2/graphene, al-
NHE, at pH = 0) and the top level of the valence ready described for the H2 production [86], shows
band must be more positive than the redox poten- enhanced photocatalytic activity due to the surface
tial of O2/H2O (1.23 V, at pH = 0). Since this reac- plasmon resonance effect of the Au nanoparticles,
tion is very difficult to accomplish using TiO2 photo- that broadens the visible light response of the TiO2,
catalyst, the use of co-catalysts such as Pt, Au and the excellent electron transport properties of
and Rh for H2 evolution [74] and RuO2 for O2 evolu- graphene, which decreases the recombination of
tion [75] is essential. electron and hole pairs. Au nanoparticles, as ex-
plained before, can also reduce redox overpotentials
2.2. TiO2/graphene composite [87].
TiO2 photoactivity can also be enhanced with the

3. PHOTOINACTIVATION
production of TiO2 composites. The most notable
case is the production of TiO2/graphene compos-
ites. In TiO2/graphene composites, the electron–hole 3.1. Rationale of using TiO2
pairs are generated upon TiO2 excitation under UV photocatalysis as the basis of
light irradiation. These photogenerated electrons are new disinfection methods
then injected into graphene due to the more posi-
tive Fermi level of graphene [76]. The high carrier The intensive use of antimicrobial agents, including
mobility of graphene accelerates excited electron antibiotics in human and veterinary chemo-
transport that enhances the photocatalytic perform- biotherapy, aquaculture and animal husbandry have
ance [77]. Simultaneously, Ti-O-C bonds formed in been pointed out as the main cause behind the tre-
the TiO2/graphene photocatalyst originate a red shift mendous increase of antibiotic resistance in clini-
of few dozens of nanometers in the solar spectrum, cal settings and in the environment [88]. The emer-
reducing its bandgap and making it sensitive to gence and spread of antibiotic resistant bacteria is
longer-wavelength light [78,79]. The resulted photo- not only of paramount public health concern, but it
catalyst presents then an extended photoresponse leads also to high costs for the national health serv-
of up to ca. 440 nm ices. Organic disinfectants are among the sub-
TiO 2 photooxidation is normally assigned stances that may promote antibiotic resistance dis-
intermediated free radicals OH• (oxidation potential semination, given the occurrence of co-selection due
of 2.8 V [80]) and O2•- (reduction potential of -0.137 to genetic linkage between antibiotics and biocides
V [81]), making necessary a thermodynamic mini- [89-92]. Therefore, the development of new disin-
mum band gap of 2.94 eV for generating both radi- fection techniques based on biocides naturally oc-
cals. Since most of band gap shortening approaches curring in the human immune system is very attrac-
consider the creation of intermediate energy levels, tive.
cf. section 3, making the electron energy gain a Phagocytic cells of the human immune system
stepwise process, the lowest and highest energy use the cytotoxic effects of ROS as a component
levels are still available. This means that, despite of their host defence mechanism [93-95]. When a
the band gap shortening below e.g. 2.8 eV, the pho- phagocyte encounters a microorganism, a portion
tocatalyst is still active towards OH• and O2•- gen- of the phagocyte membrane surrounds it – the first
eration [82]. Nevertheless, the visible light activity step of a phagolysosome formation. This process
of the TiO2/graphene composites is not fully under- leads to increased phagocyte oxygen consumption
stood [83,84]. When graphene is bounded to TiO2 and activates a unique membrane-associated
the overall photocatalytic performance is largely NADPH-dependent oxidase complex [96]. This
improved. This is mainly attributed to three effects: enzymatic complex univalently reduces O2 to O2•-,
i) efficient charge separation and transportation; ii) which further dismutes to H2O2 [96]. Another mecha-
nism involved in phagocyte-mediated oxidant gen- organisms in photoinactivation trials (Table 1, [103-
eration and microbial toxicity involves the iron-cata- 106]). Given the complexity of the bacterial com-
lysed intra- or extracellular reaction of O2•- and H2O2 munities in natural environments, some studies
to form OH• [94]. These ROS are known to be highly assessed the efficacy of photocatalysis in mixed
reactive with biological molecules and various au- suspensions of known composition, or in a more
thors proposed that OH• radical is the most toxic realistic way, in wastewater (Table 1). The efficacy
[97-100]. During the photocatalysis process similar of photocatalysis in the inactivation of eukaryotic
ROS are formed. Hence, photoinactivation seems microorganisms, both in axenic or mixed suspen-
a good alternative to commonly used disinfection sions has also been assessed. In fact, the differ-
methods. ences in the cellular structure of prokaryotic and
Matsunaga and co-workers in 1985 were the first eukaryotic organisms may lead to distinct toler-
authors assessing the feasibility of using UV-acti- ances to photocatalysis. Similar reasons are be-
vated TiO2 for photoinactivation [7]. This study re- hind the studies performed with prokaryotic and
ported the successful photoinactivation of both Gram eukaryotic dormant forms (spores, cysts). Indeed,
negative and Gram positive bacteria (Escherichia the inactivation of these structures, particularly the
coli and Lactobacillus acidophilus, respectively) and bacterial endospores, has been a challenge due to
yeasts (Saccharomyces cerevisiae) cells by a semi- their well-known resistance to chemical and physi-
conductor powder (platinum-doped titanium dioxide, cal antimicrobial agents [107,108].
Pt-TiO2). This pioneer work triggered numerous stud- TiO2 photoinactivation is expected to be the ba-
ies to assess the efficiency of TiO2 photocatalysis sis of different processes and materials compatible
on the inactivation of microorganisms and viruses with commercial applications for disinfection. Indeed,
(Tables 1-3) as well as microbial toxins and prions photocatalysis-based new disinfection processes
[11,101]. A representative summary of the studies can be potentially used in several fields, such as
performed up to now on photoinactivation, as well water disinfection [97,109-121], medical applications
as a comparison of this technique with traditional [119,122-125], and pharmaceutical and food indus-
disinfection methods is given below. try [124]. Given the wide variety of potential applica-
tions, assessment of photoinactivation has been
3.2. Target test organisms and TiO2 carried out in different matrices. The majority of the
matrices studies assessed the efficacy of TiO2 nanoparticles
in aqueous suspension. This happens mainly be-
Given the commercial availability of TiO 2 cause it is well known that the photoinactivation
nanoparticles, most of the studies assessing the process is favored when cells are in direct contact
efficacy of photoinactivation have been carried out with the photocatalyst. However, and primarily due
with P25 (Table 1), which shows high performance to the potential harmful effects of nanoparticles in
and stability when excited with UV radiation [102]. human health [126] and environment [127], immo-
Most of the studies used axenic suspensions of bilization of TiO2 has been studied (Tables 1-3). In-
bacteria as target organisms, being Escherichia coli, deed, TiO2 immobilization is very important for com-
the well characterized and universally used faecal mercial applications [128], also due to two main
contamination indicator, the most used. However, reasons. Firstly, it is difficult to recover the photo-
domain Bacteria accommodates an immense di- catalyst when used as powder; this requires a post-
versity of organisms, reflected in a wide variety of treatment solid-liquid separation stage, which will
phylogenetic, genotypic and phenotypic groups. add complexity and costs to the overall process
Therefore, differences in cellular structure, metabo- [109]. Secondly, when it is not possible to recover
lism, pathogenicity, or tolerance against stressful the photocatalyst, the total loss of this material
conditions, including resistance to antimicrobial implies economical losses and it becomes itself a
agents, may influence the susceptibility of bacteria pollutant.
to photocatalysis. This explains why other bacte- TiO2 has been immobilized in different materials
ria, including Gram positive bacteria (phyla such as glass (plates, beads), polymers
Firmicutes and Actinobacteria), endospore formers (polypropylene, polycarbosilane, cellulose acetate),
(a restricted group of Firmicutes, including genera paint and quartz disks [128-142]. These materials
such as Bacillus and Clostridium), pathogens or have been employed in surface coatings (glass,
opportunistic pathogens (such as Legionella cellulose acetate sheets), paint coating and impreg-
pneumophila and Pseudomonas aeruginosa), and nated membranes. These approaches can be used
antibiotic resistant bacteria have been used as test for the inactivation of organisms in aqueous solu-
Fig. 2. Free radicals mode of action (reprinted with permission from M. Dizdaroglu, P. Jaruga, M. Birincioglu
and H. Rodriguez // Free Radical Biol. Med. 32 (2002) 1102. (c) 2002 Elsevier).
tions (e.g. reactor wall), air (e.g. air filters) and fo- ability. Consequently, ROS easily reach the cyto-
mites (e.g. paint coating). In the specific case of plasmic membrane, where peroxidation of mem-
water treatment, the advantage of using coated glass brane lipids also occurs. The consequent structural
beads is the larger specific surface area, which al- and functional disorders of the cytoplasmic mem-
lows a more efficient photoinactivation of microor- brane lead to ROS entrance in the cell, where they
ganisms. However, the use of glass beads can in- negatively interfere with DNA replication [11,145] and
crease the cost and complexity of the process. In respiratory activity [7,146] due to the direct oxida-
impregnated membranes, TiO2 is deposited in the tion of coenzyme A into its dimeric form. Ultimately,
interstices of the membrane, improving the surface ROS attack leads to the loss of cell viability and
contact area between TiO2 and the microorganisms. cell death [147-149]. The initial process of E. coli
This method seems to be useful for wastewater treat- photoinactivation by the action of TiO2 photocataly-
ment [143] but can also be used for the sis is depicted in Fig. 2. Evidences indicate that
photoinactivation of air microorganisms [136]. Paint the TiO2 photocatalytic reaction results in contin-
coating seems to be, currently, the most promising ued bactericidal activity, well after the UV illumina-
immobilization matrix for commercial applications. tion terminates [148].
Paint is a readily available material, easy to be ap- In what concerns Gram-positive bacteria, the
plied onto surfaces and does not react with the pho- majority of the studies showed that they are more
tocatalyst nor interfere with the photocatalytic effi- resistant to photocatalytic inactivation than Gram-
ciency [144]. Furthermore, paint provides a good negative [11]. However, some authors reported op-
support for the photocatalyst in a 3D arrangement posite observations [141,150,151]. Some of the dif-
and can be applied in hospitals and other buildings ferences encountered in the susceptibility to
where infections should be prevented. photoinactivation between Gram-negative and Gram-
positive bacteria may be caused by the experimen-
3.3. Photoinactivation mechanism tal conditions. For instance, van Grieken and co-
workers [152] showed that the susceptibility of E.
To better understand the effect of TiO2 photocataly- coli and Enterococcus faecalis to photocatalysis in
sis on the differential inactivation of the cells and natural waters was similar, whereas in distilled wa-
thereof dormant forms, the mechanism of action of ter the Gram-positive was more resistant. Never-
photoinactivation is summarized as follows. All the theless, the different cell wall structure of Gram-
cellular constituents, such as polysaccharides, negative and positive bacteria is actually cited as
lipids, proteins and nucleic acids can be attacked the main reason for the distinction on ROS attack
by ROS formed during photocatalysis. However, cell susceptibility. Gram-negative bacteria have a triple-
wall is the initial target for the photocatalytic attack. layer, with an inner cytoplasmic membrane, and a
Considering as example the Gram-negative bacte- cell wall composed by a thin peptidoglycan layer
ria, the oxidation of components of the outer mem- and an outer membrane. Besides the inner cyto-
brane by ROS promotes an increase in cell perme-
plasmic membrane, the Gram-positive bacteria have UV irradiance from 2 to 1000 W/m2, time of contact
a thick peptidoglycan layer. The high porosity of from 5 min up to 144 h, and cell densities ranging
peptidoglycan allows solutes, such as ROS, to per- between 103 to 107 colony forming units (CFU)/mL.
meate. Therefore, also Gram-positive cells become In addition, different strains of this species were used
susceptible to radical attack [153,154]. However, ([105,106,116,120,131,137,141,156-159], Table 1).
the thickness of the peptidoglycan layer in these Nevertheless, most of the studies performed up to
bacteria may allow a delay in the loss of cell per- now included controls and, in some cases, the in-
meability, and/or retard oxidants diffusion to vital activation of different organisms or matrices were
sites. Indeed, both mechanisms would explain the tested under the same conditions allowing a better
higher resistance of Gram-positive bacteria to TiO2 comparative assessment and thus valuable data to
photoinactivation when compared with Gram-nega- conclude on the efficacy of photoinactivation.
tive ones. On the other hand, the presence of an
outer membrane in Gram-negative cells may explain 3.4.1. UV-TiO2 photoinactivation
why under certain circumstances these bacteria are
more resistant to ROS attack than Gram-positive Photocatalytic experiments under UV radiation pro-
cells [7,141,150]. The rigid cell wall of filamentous duce high levels of photoinactivation for the majority
and unicellular fungi, composed mainly of soluble of the different microorganisms tested. As mentioned
and insoluble polysaccharide polymers, make them previously, P25 has been the most used photocata-
more resistant to ROS attack than bacterial cells lyst. However, synthetized, pristine, doped or deco-
[11,135]. Generally, dormant forms, such as fungal rated TiO2 were also reported.
spores [131], cysts [135], and bacterial endospores As referred to above, despite the difficulties en-
[131], are even more resistant than the vegetative countered on comparing the results obtained in the
cells which proves the role of cell wall thickness different studies shown in Tables 1 and 2, some
and complexity in ROS defence. conclusions can be drawn. UV-TiO2 photocatalysis
seems to be effective on the inactivation of all the
types of microorganisms. Studies carried out by
3.4. Efficiency of photoinactivation
Herrera Mélian et al. [143], Dillert et al. [118] and
In this section, a summary of the studies carried Rincón et al. [121] should be highlighted since high
out on the efficiency of photoinactivation under UV values of inactivation of total heterotrophic bacteria
and visible radiation is given. Given the high number and coliforms were reported for real wastewater sam-
of studies published up to now in this field, a selec- ples.
tion was made. The selection criteria included the But care must be taken to define the operating
type of tested microorganism, light sources and conditions since organisms with different cellular
testing conditions, and the utilization of novel TiO2 structure and complexity, such as E. coli, Bacillus
based photocatalysts. A more extensive literature subtilis endospores and the yeast Candida albicans,
review on this topic can be found elsewhere [11]. have very different susceptibility to photoinactivation.
The factors affecting cell death, caused by an Total inactivation of E. coli cellular at a density of
antimicrobial agent, include the agent concentra- 106 CFU/mL was achieved within 40 minutes of con-
tion, time of exposure, and type and density of cells. tact in suspension, with a photocatalyst concentra-
Therefore, for a rigorous comparison of efficiency tion of 0.1 g/L and irradiance of 55 W/m2 [116]. How-
among antimicrobial agents and/or type of target ever, to completely inactivate Bacillus subtilis
organisms, standardized methods should be used. endospores at a similar initial spore density (106
Even though there is already a standard for testing spore/mL), a photocatalyst concentration of 0.25
photocatalytic materials [155], most studies does g/L, an irradiance of 70 W/m2 and 540 minutes were
not follow this standard, probably because this needed [160]. Despite of shorter time of contact (30
standard is referred to surfaces and most of studies minutes) and photocatalyst concentration (0.02
are based on the use of suspensions, as previously g/L) a very high irradiance value (330 W/m 2)
mentioned. Hence, it is very difficult to compare the was necessary to achieve 96% inactivation of
photoinactivation efficiency against different target Candida albicans at and initial cellular density of
organisms in different conditions, even when the 103 CFU/mL [161]. On the contrary, pathogenicity
same photocatalyst (e.g., P25) is used (Tables 1- seems to have less influence on bacterial suscepti-
3). For example, studies reporting the inactivation bility against photoinactivation. For example, Cheng
of E. coli in suspension used photocatalyst con- et al. [162] reported that total inactivation of patho-
centrations ranging from 50 to 1000 mg/L, values of genic Legionella pneumophila serotype 1 at an ini-
tial cellular density of 107 CFU/mL was attained af- irradiance of 4 W/m2 for 20 minutes were sufficient
ter 105 minutes with a photocatalyst concentration to inactivate 93 % of S. aureus viable cells at an
of 0.2 g/L and an irradiance of 1.65 W/m2, condi- initial higher concentration (109 CFU/mL).
tions comparable to the ones used by Ibañez et al.
[116] for the photoinactivation of E. coli. 3.5. Visible light-TiO2
Some antibiotic resistant bacteria are also sus- photoinactivation
ceptible to TiO 2 photocatalytic inactivation.
Photoinactivation values of susceptible and antibi- Despite the success of UV-photocatalysis in disin-
otic resistant strains of E. coli [105] and S. aureus fection, the mutagenic action of this type of radia-
(MRSA) [106] were not significantly different (Table tion hampers its use in the majority of the indoor
1). However, differences between antibiotic resist- spaces [113]. On the other hand, the negligible UV
ant and sensitive counterparts have also been re- irradiancy under common internal lighting conditions
ported [106]. A multidrug-resistant Acinetobacter prevents the use of pure photocatalytic TiO2 in in-
baumannii (MDRAB) was ca. 2 times more sus- door spaces. Even in outdoor events, the low frac-
ceptible to photoinactivation than the antibiotic sen- tion of solar UV compared to the total solar irradia-
sitive Acinetobacter baumannii control strain. Op- tion advises the use of visible light photocatalysts.
posite results were obtained for Enterococcus To overcome this major drawback, several studies
faecalis, where the vancomycin resistant strain focused on the development of modified titanium
(VRE) showed ca. 2 times less susceptibility against dioxide with enhanced visible light photoactivity have
photoinactivation than the susceptible strain [106]. been conducted, as mentioned in Section 3.
Indeed, different susceptibility against oxidative Among the modified photocatalysts tested up
stress was already reported among strains of the to now, carbon doped TiO2, decorated [184] or not
same microbial species [163,164]. Hence, despite [185] with silver nanoparticles was shown to respec-
the utmost importance of comparing the response tively fully inactivate E. coli and S. aureus under
of a wide variety of these organisms against visible light. Also manganese-, cobalt doped or co-
photoinactivation, to the best of our knowledge, such doped Mn/Co-TiO2 was shown to fully inactivate
studies were not reported yet. Klebsiella pneumonia [100]. As mentioned in Sec-
Even though efficient, high photocatalyst con- tion 4, the use of graphene for photocatalytic appli-
centrations, powerful light sources or high contact cations by Akhavan et al. [186] resulted in a novel
times are needed when P25 or other synthetized graphene oxide/TiO2 composite with an increased
pristine TiO2 are used. Thus, in order to achieve antibacterial activity under solar light irradiation when
higher photoinactivation performances with less compared to bare TiO2 (roughly 7.5 times more).
severe conditions, modified titanium dioxide (doped Nevertheless, the disinfection performance of
and/or decorated) has been studied (Table 2). As modified TiO2 under visible light is still lower than
discussed in detail in Section 3, these TiO2 modifi- under UV radiation. Indeed, the inactivation fraction
cations enhance the photocatalytic activity of the of vegetative cells of a wide variety of microorgan-
photocatalyst. Much lower irradiance (0.5 versus isms under UV irradiation varies between 96% and
55 W/m2, respectively) and lower contact times (35 100% (Table 1), while under visible light ranges from
versus 40 minutes) were necessary to achieve total 65% to 90% (Table 3). Moreover, to attain these
inactivation of E. coli at a higher cellular density inactivation values extreme conditions were neces-
(109 versus 106 CFU/mL, respectively) with a TiO2 sary, i.e, very high values of irradiance (up to 15 000
decorated with silver nanoparticles [181] compared lux), photocatalyst concentration (1 g/L) and/or con-
with pristine TiO2 [116]. However, a final conclusion tact time (1440 minutes). Finally, inactivation of
concerning the performance of the modified photo- dormant forms such as spores of Aspergillus niger
catalyst cannot be retrieved because a 10 times under visible light was also not attained yet (Table
higher concentration of TiO2 decorated with Ag (1 3).
g/L) [181] than of pristine TiO2 [116] was used. Nev- Thus, optimization of photoinactivation under vis-
ertheless, other studies suggest that modification ible light envisaging a future commercial applica-
of the photocatalyst improve, in fact, their inactivation of this technique is still needed.
tion performance. For the complete inactivation of
S. aureus at an initial cellular density of 10 6 3.6. Traditional disinfection methods
CFU/mL, 10 g/L of synthetized pristine TiO2 and ir- Traditional disinfection methods are based on the
radiance of 8 W/m2 for 60 minutes were necessary utilization of heat, radiation or chemical compounds.
[165], while 2.5 g/L of Fe3O4 decorated TiO2 and an
Chlorine, hydrogen peroxide, ozone, and UV radia-

tion are amongst the most used agents currently
used to disinfect water, air or fomites. The disinfec-
tion methods based on each of these antimicrobial
agents will be briefly overviewed next.
3.6.1. Chlorination
Chlorination as a disinfection technique is mainly
based on the use of gaseous chlorine and/or hy- Fig. 3. Equilibrium of chlorine and its derivatives in
pochlorite. Chlorine gas (Cl2) is the elemental form solution at 25 °C (adapted from [196]).
of chlorine at standard temperature and pressure.
Chlorine gas is approximately 2.5 times heavier than
air and is highly toxic. Hypochlorite (ClO-) is usu- The precise mechanism by which microorgan-
ally obtained from sodium hypochlorite and calcium isms are inactivated by chlorine has not yet been
hypochlorite [199]. fully explained. However, some studies show that
Chlorine gas hydrolyzes in water according to the bacterial cell membrane changes its permeabil-
the following reaction (Eq. (7)): ity in the presence of chlorine [205,206]. The pres-
ence of suspended solids influences the action of
 
Cl2  H2 O  HOCl Cl  H (7) chlorine because the particles and organic com-
pounds usually provide protection to microorgan-
while hypochlorous acid, resulting from the previ-
isms. This protection usually comes from
ous reaction, is a weak acid, which dissociates in
stabilization of the cell membranes, which reduces
aqueous solution:
the access of chlorine to key cellular components
HOCl  ClO  H
 
(8) for inactivation [206]. Indeed, microbial aggregates
or microorganisms attached to or embedded in par-
Under typical water treatment conditions in the ticles have been shown to have increased resist-
pH range 6–9, hypochlorous acid and hypochlorite ance to inactivation by chlorine, when compared to
are the main chlorine species. Depending on the non-attached, free-swimming microorganisms.
temperature and pH level, different distributions of Dietrich and co-workers [206]reported, however, that
aqueous chlorine species (Cl2, HOCl, and ClO-) are chlorine is capable of penetrating particles in
observed [200]. In addition to these major chlorine wastewater by radial diffusion. Greater chlorine pen-
species, other chlorine intermediates including etration into wastewater particles was observed with
trichloride (Cl3") and chlorine hemioxide (Cl2O) can increasing initial chlorine concentration, indicating
also be formed – Fig. 3. In solution, ratios of these that chlorine application could be tailored to pen-
intermediates are a function of temperature, pH and etrate particles of known size in order to achieve
chloride concentration. Under typical water treat- inactivation [206].
ment conditions, the concentrations of Cl3- and Cl2O Some of the studies reported in the literature on
are very low, accounting, at most, to 20% of all the the efficiency of chlorination on disinfection are sum-
chlorine species in solution [200,201]. marized in Table 4. Koivunen and co-workers [207]
Chlorination as a water disinfection method was studied the chlorination of Enterococcus faecalis,
first introduced in 1902 in Middlekerke, Belgium Escherichia coli, and Salmonella enteritidis in aque-
[202]. Chlorination is mainly used in water disinfec- ous solution. In this work, concentrations of chlo-
tion, however, hypochlorite is also used for the dis- rine of 12 mg/L with a contact time of 10 minutes
infection of some surfaces (mostly for countertops were used in order to achieve a log reduction value
and floors), mainly in health care facilities [203]. A of around 3 for Enterococcus faecalis. But, even
leading advantage of chlorination is that it is effec- with a higher chlorine concentration (18 mg/L), lower
tive against a wide variety of bacteria and viruses. reduction values were registered for Escherichia coli
However, it cannot inactivate all microbes, being and Salmonella enteritidis (0.3 and 0.44, respec-
some protozoan cysts resistant to the effects of tively) for the same contact time, demonstrating that
chlorine [204]. In cases where protozoan cysts are microorganisms have distinct tolerance against chlo-
not a major concern, chlorination seems to be a rination. In wastewater samples, Hassen and co-
good water disinfection method because it is inex- workers [208] registered log reduction values up to
pensive. 3.7 and 4.4 for fecal coliforms and enterococci, re-
Fig. 4. Mechanisms involved in the ozonation process. In the figure, M is referred to the solute, Moxid to the
oxidized solute, Si to the free radical scavenger, Ø to products that do not catalyze the ozone decomposi-
tion and R to the free radicals that catalyze the ozone decomposition. (Reprinted with permission from J.
Koivunen and H. Heinonen-Tanski // Water Res. 39 (2005) 1519. (c) 2005 Elsevier).
spectively, when using chlorine concentrations rang- compound present in the peptidoglycan of bacterial
ing from 6.5 and 13.6 mg/L and contact times up to cell walls, was resistant to the action of ozone in
40 minutes. aqueous solution at pH 3 to 7. This explains the
higher resistance of Gram-positive bacteria com-
3.6.2. Ozonation pared to Gram negative ones, because the former
contains higher amounts of peptidoglycan in their
Ozone is produced when oxygen molecules are dis- cell walls than the later. Ozone can react signifi-
sociated by an energy source into oxygen atoms cantly with amino acids and peptides, especially at
and subsequently collide with the non-dissociated neutral and basic pH. Furthermore, ozone reacts
oxygen molecules. Ozone is one of the most pow- quickly with nucleobases, especially thymine,
erful oxidizing agents (E0 = 2.07 V) and it is mostly guanine, and uracil. Reaction of ozone with the
used to destroy organic compounds [215]. nucleotides releases the carbohydrate and phos-
The oxidation of the target compounds can oc- phate ions [217].
cur through two different mechanisms: i) direct re- Ozone is mainly used for water treatment, how-
action with molecular ozone or ii) indirect reaction ever the use of ozone for surface disinfection was
with secondary oxidants formed upon the decom- already reported [218]. Water disinfection by
position of ozone in water. Such decomposition is ozonation has been extensively reported, and some
catalyzed by hydroxide ions (OH-) and other sol- of the works are summarized in Table 5. Low ozone
utes. Highly reactive secondary oxidants, such as concentrations (0.15-0.20 mg/L) and contact time
hydroxyl radicals (OH•), are thereby formed. These (180 s) were sufficient to inactivate several Gram
radicals and their reaction products can cause the negative bacteria in suspension to values up to
decomposition of ozone. Consequently, radical-type 99.99% [219]. Nebel and co-workers [220] reported
chain reactions may occur, which consume ozone one of the first works describing the treatment of
concurrently with the direct reaction of ozone with wastewater by ozonation. In this work, with an ozone
dissolved organic material and contributing to the dose of 14 mg/L and a contact time of 5 minutes it
formation of additional hydroxyl radicals – Fig. 4 was possible to achieve log reduction values of up
[216]. to 3 log for enterococci, total coliforms and fecal
Ozone reacts with polysaccharides slowly, lead- coliforms.
ing to breakage of glycosidic bonds and formation
of aliphatic acids and aldehydes. The reaction of
3.6.3. UV
ozone with primary and secondary aliphatic alcohols
may lead to formation of hydroxy-hydroperoxides, Ultraviolet processing involves the use of radiation
precursors to hydroxyl radicals, which in turn react from the ultraviolet region of the electromagnetic
strongly with the hydrocarbons [217]. However, it spectrum for purposes of disinfection. Usually, the
was already shown that N-acetyl glucosamine, a range of UV refers to wavelengths between 100 and
400 nm. This range can be further subdivided. UVA was possible to achieve high values of inactivation
corresponds to wavelengths between 315 and 400 of different microorganisms in wastewater samples.
nm and it is normally responsible for change in hu- A contact time of 50 seconds permitted to achieve
man skin that cause tanning; UVB refers to wave- log reductions of 4 to 5 for methicillin-resistant Sta-
lengths between 280 and 315 nm and is the main phylococcus aureus (MRSA), E. coli, and Pseu-
responsible for skin burning and can also lead ulti- domonas aeruginosa. A higher contact time (100 s)
mately to skin cancer. UVC – 200 to 280 nm – is was needed to reach similar log reduction values
called the germicidal range, because it is consid- for vancomycin resistant Enterococcus faecium
ered to be the most effective towards the inactiva- (VRE) [242]. In a study assessing the effectiveness
tion of bacteria and viruses. Finally, the vacuum UV of UV radiation on the inactivation of several vegeta-
range (100 to 200 nm), can be absorbed by almost tive bacteria (Staphylococcus aureus, Enterococ-
all substance and can only be transmitted in the cus faecalis, E. coli, Salmonella enterica, Shigella
vacuum [228]. sonnei) Bacillus subtilis spores, Acanthamoeba
Among the above mentioned disinfection meth- castellanii cysts and viruses (poliovirus type 1 and
ods, UV light has been adopted as the most appro- simian rotavirus SAil), Chang and co-workers [243]
priate treatment process for drinking water because reported that viruses, spores and cysts were 3-4, 9
it is simple to use, highly effective for inactivating and 15 times more resistant than the vegetative
microbes and it does not introduce chemicals or bacteria, respectively.
cause the production of harmful disinfection by-prod-
ucts in the water [229]. This method promotes ad- 3.6.4. Hydrogen peroxide
ditional security after traditional treatment processes
[230,231]. UV radiation is responsible for a wide Hydrogen peroxide is a metastable molecule – it
range of biological effects [232-234], including modi- easily decomposes into water and oxygen - with
fications in the protein structure and in the DNA high redox potential (1.77 V) [244]. Even though the
[235]. Regarding DNA damage, it may result on in- mechanism of hydrogen peroxide inactivation to-
hibition of cell replication and, in case of lethal doses, wards cells is usually attributed to the production of
on the loss of ability to reproduce. Although the UV- highly reactive hydroxyl radical, hydrogen peroxide
A wavelengths bordering on visible light are not suf- itself presents some cytotoxicity towards cells. H2O2
ficiently energetic to directly modify DNA bases, can directly oxidize the catalytic iron atom of dehy-
cellular membrane damage can be induced through dratase clusters, precipitating iron loss and enzyme
the production of ROS, such as singlet oxygen, inactivation. H2O2 poisons the Isc system, which is
superoxide, hydrogen peroxide and hydroxyl radi- responsible for the transfer of [4Fe-4S] clusters to
cal, generated via excitation of dissolved oxygen in newly synthesized apoenzymes. However, the
water [177,236]. Furthermore, according to several mechanism of cytotoxic activity of H2O2 is generally
authors, the damage induced by UV radiation con- reported as based on the production of highly reac-
tinues even after the end of the irradiation period tive hydroxyl radicals from the interaction of the
[236,237]. Bacterial DNA is a critical target of UV superoxide (O2•-) radical and H2O2, a reaction first
radiation and its effects depend on several param- proposed by Haber and Weiss [245] (Eq. (9)):
eters, such as UV spectrum, dissolved oxygen con- 
O 2  H2 O 2  O 2  OH OH

(9)
centration, salt concentration and post-irradiation
growth conditions [236]. Different microorganisms Further, it is believed that the production of extremely
respond differently to the lethal effects of UV. It is short-lived hydroxyl radicals within the cell by the
known that the effectiveness of a UV disinfection Haber–Weiss cycle is catalyzed in vivo by the pres-
system depends on the sensitivity of the target mi- ence of transition metal ions (particularly iron-II)
croorganisms to UV, microbial content, antibiotic according to Fenton chemistry [246] (Eq. (10)):
resistance phenotypes, light source, UV radiation 2 3 
Fe  H2 O 2  Fe  OH (10)
intensity, exposure time of microorganisms to ra-
diation and their ability to re-growth [120,223,236- The iron released from oxidized metalloproteins
238]. UV treatment can be used for the inhibition of enlarges its intracellular pool, favoring the produc-
microorganisms in surfaces, in the air or in water tion of hydroxyl radical through the Fenton reaction
[239-241]. [247]. The production of hydroxyl radical is, as de-
Some works reporting the use of UV radiation scribed before, of utmost importance in the inacti-
on the inactivation of microorganisms are presented vation of microorganisms, accelerating the process
in Table 6. When using a light intensity of 2 W/m2, it of DNA damaging [217].
H2O2 can be used in both liquid and vapor commercialized by companies such as Pilkington,
phases. Hence, it is used in water disinfection (liq- Italcementi Group and Taiheiyou Cement. Coatings
uid phase) or in the disinfection of surfaces (vapor and ceramics with antimicrobial activity are also
phase). Indeed, it is believed that the vapor phase commercialized by several companies. Deutsche
has higher kinetic energies and is uncharged, so it Steinzeug company, which commercializes flags,
can surround and penetrate the three-dimensional tiles and sanitary ceramics and, company Kurare,
protein structures more easily, oxidizing buried which commercializes textile fibers containing TiO2
cysteine residues and breaking vulnerable bonds photocatalysts, should be highlighted. Japanese
between subunits [248]. Thus, an enhanced antimi- Arc-Flash, the first company commercializing pho-
crobial activity of hydrogen peroxide vapor when tocatalyst-based materials in 1992, uses a photo-
compared to its liquid state is usually reported [249- catalyst fixation technology that allows spraying the
252]. photocatalytic product directly on surfaces. The
Some studies reporting the utilization of hydro- photocatalytic coating produced by Arc-Flash uses
gen peroxide as a disinfectant are summarized in titania nanoparticles as main ingredient and is used
Table 7. Otter and co-workers [251] studied the ef- to sterilize mildew, sanitize environments such as
fectiveness of hydrogen peroxide on the inactiva- hospitals, residential kitchens, schools, and floors,
tion of nosocomial bacteria and spores on surfaces. killing bacteria with over 98% efficiency [257].
After 90 minutes of contact with hydrogen peroxide The versatility mentioned for photocatalysis is
vapor, all of the tested microorganisms were com- also reported for UV radiation. Advances in the opti-
pletely inactivated (Log reduction of 6). However, mization of UV reactors permitted to inactivate a
differences on the resistance against the hydrogen high variety of waterborne microorganisms in few
peroxide vapor treatment were observed. seconds [242]. However, there are still some limita-
Acinetobacter showed the highest resistance to this tions on the use of this technique. Very high values
treatment, while vancomycin-resistant enterococci of irradiation (in most cases over 50 W/m2) must be
were the first to be completely inactivated, after only used to inactivate some microorganisms (Table 6),
10 minutes of treatment. Hydrogen peroxide is also and even under these harsh conditions, inactivation
suitable to disinfect wastewater. Indeed, the den- of some microbial forms, such as Clostridium
sity of total coliforms in wastewater was reduced 4 difficile spores, is not possible. Several studies
fold when using H2O2 up to 2.5 mL/L and a contact where the effectiveness of UV treatment was directly
time of 3 h [253]. compared with photocatalysis demonstrated that,
as expected, UV treatment was less efficient than
3.7. Comparison between TiO2-UV [105,116,118]. The use of a photocatalyst,
photoinactivation and traditional in most cases decreases the need of high irradia-
disinfection methods tion intensity and promotes the decrease of con-
tact times. Ibanez and co-workers [116] verified that
In contrast with the traditional disinfection methods it was not possible to inactivate Enterobacter
described above, TiO2-UV photocatalysis is not yet cloacae, E. coli, P. aeruginosa and Salmonella
considered as an established water disinfection tech- typhimurium with an UV irradiance of 55 W/m2. How-
nology [255]. However, until this date, several re- ever, when coupling UV irradiation with 0.1 g/L TiO2,
ports showed the potential of this technique for dis- log reduction values around 6 were achieved for all
infecting. Indeed, photocatalysis is a versatile and the tested strains for the same time of contact. The
effective process that can be adapted for use in decrease of contact time from 360 to 50 minutes to
many applications for disinfection in both air and achieve 3 log reduction of the total heterotrophic
water matrices. Additionally, improved photocata- bacteria of wastewater was also reported [118], when
lytic coatings are being developed, tested and even using a photon flux of approximately 390 mmol/h
commercialized for use in the context of “self-disin- and 5 g/L of photocatalyst. More recently, Lin and
fecting” materials. In this sense, the strength of co-workers [180] showed that it was possible to
photocatalytic disinfection lies in its versatility for reduce the load of the total coliforms in wastewater
use in many different applications [256]. Indeed, 4 fold, when irradiance of 1.5 W/m2 and a contact
photocatalytic-based products already reached a time of 120 s was coupled with the presence of a
global volume of US$848 Million in 2009 of which TiO2 coated reactor, while a 3 fold reduction was
over 87% were related to products with self-clean- obtained in the absence of the photocatalyst.
ing activity used for construction [257]. Among these Ozonation is a technique that can promote total
are glass coatings, cements and textile fibers [257], inactivation of most types of microorganisms under
low contact times, in most cases under 20 min- these dangerous by-products leads to the neces-
utes, and with low O3 doses, at most 4 mg/L – Ta- sity of coming up with suitable alternatives to chlo-
ble 5. However, it is important to note that ozonation rination. The main advantages and disadvantages
may cause the formation of very harmful by prod- of each of these techniques are summarized in Ta-
ucts, specially bromide and other brominated com- ble 8.
pounds [258]. Rizzo and co-workers [259] compared Although promising, photocatalysis still faces
the efficiency of ozonation and photocatalysis for some drawbacks when imposing itself as a refer-
the treatment of urban wastewaters. In this work, it ence disinfection technique. As for other disinfec-
was shown that it was possible to obtain increased tion methods, re-growth after photocatalytic treat-
degradation of organic matter with the photocata- ment may occur [223,261]. In addition, one of the
lytic oxidation process, even at low TiO2 concentra- main problems, usually disregarded by most of
tions. Furthermore, a 30 min photocatalytic treat- works conducted up to now in this field, is the ab-
ment was found to produce an effluent complying sence of knowledge on the long time effect of
with the trihalomethanes limit set by Italian regula- photoinactivation. Little is known on the type of or-
tion for wastewater reuse. Furthermore, the cost ganisms able to tolerate the oxidative stress im-
associated to the use of ozonation is still very high posed by photocatalysis; however, increased toler-
[260]. Additionally, the coupling of ozonation with ance of antibiotic resistant bacteria when compared
photocatalysis was already studied. Moreira and co- with the susceptible counterpart is reported [106].
workers [261] reported the use of photocatalytic This observation points out for the need of further
ozonation for the disinfection of urban treated studies on the type and fate of the organisms sur-
wastewaters. In this study, a photocatalytic viving the treatment. This is particularly important,
ozonation system using TiO2-coated glass Raschig because under real conditions it may be not eco-
rings with LEDs irradiation - two 10 W UV high in- nomically feasible to use conditions guaranteeing
tensity LEDs with dominant emission line at 382 the inactivation without regrowth of potentially dan-
nm - was tested in continuous mode. This study gerous microorganisms [267]. Furthermore, and in
reported the reduction of enterococci, enterobacte- order to be applied in full scale, the optimization of
ria, and fungi from 105 - 106 CFU/100 mL to values the photocatalyst to fully take advantage of the vis-
around or below 101 CFU/100 mL; total heterotrophs ible light spectrum should be achieved. This optimi-
presented lower reductions, but still reaching val- zation should be focused in the future either by the
ues of around 102 CFU/100 mL after the treatment. optimization of the photocatalytic material (TiO2) or
The use of hydrogen peroxide to disinfect water by the use of suitable supports (for example
requires, usually, high contact times (up to 240 min- graphene).
utes) or concentrations (up 150 mL/L) (Table 7). Although being a very promising disinfection tech-
Lower contact times (90 minutes) are required to nology, the massive use of TiO2 nanoparticles with-
inactivate the microorganisms when the vapor phase out a proper evaluation concerning of their antimi-
is used (Table 7), suggesting that hydrogen perox- crobial potential can produce negative drawbacks.
ide is a good technique to disinfect surfaces. How- Indeed, using TiO2 nanoparticles, even in those prod-
ever, the toxic effects of H2O2, require the interdic- ucts not directly designed for disinfection, may cause
tion of the site to be disinfected [262] for periods up the propagation of the aforementioned antibiotic and
to 1 hour and 40 minutes. Also chlorination requires oxidative stress resistant microorganism in a worri-
high contact times (up to 120 minutes) to be effec- some scale. Thus, the definition of new standards
tive on the inactivation of microorganisms (Table 4). to test the efficacy of photocatalytic systems, in-
Additionally, some microorganisms are resistant to cluding organisms with high tolerance to oxidative
chlorination treatments [263,264]. Nevertheless, it stress and antibiotics, is a subject of utmost impor-
is important to note that nowadays chlorination re- tance in nowadays society.
mains as the most used disinfection method [265].
This is mainly due to the fact that the new alterna- 4. CONCLUSIONS
tive processes require expensive chemicals or
costly equipment to generate the disinfectant onsite. TiO2-anataseis presently the most used photocata-
However, chlorination causes the formation of sev- lyst for environmental applications due to its high
eral highly toxic by-products. Among these, it is stability, good location of the band edges, low charge
important to highlight the formation of transport resistance, high photocatalytic activity,
trihalomethanes and dichloroacetic acid that are high chemical and thermal stability, low toxicity and
believed to be carcinogenic 266]. The existence of low price. However, to increase the usefulness of
titanium dioxide, it is necessary to increase its n 321315). This work was financially supported by
photoactivity and ability to absorb visible light. This the projects POCI-01-0145-FEDER-006939 - Labo-
review article presents an overview of the fundamen- ratory for Process Engineering, Environment, Bio-
tals of photocatalysis and briefly reviews the most technology and Energy – LEPABE and NORTE 01
relevant strategies to enhance the photocatalytic 0145 FEDER 000005 – LEPABE-2-ECO-INNOVA-
activity of TiO 2, aiming ultimately the indoor TION, funded by FEDER funds through COM-
photoinactivation of harmful biological agents. Since PETE2020 - Programa Operacional Competitividade
TiO2 may contribute to prevent nosocomial infec- e Internacionalização (POCI) and Programa
tions, its practical application in this field is strongly Operacional Regional do Norte (NORTE2020) and
envisaged. TiO2 photocatalysis, similarly to the by national funds through FCT - Fundac’aÞo para a
phagocytic cells of the human immune system, use Ciencia e a Tecnologia and was also partially funded
the cytotoxic effects of Reactive Oxygen Species by the project “Synthesis and characterization of
(ROS) to inactivate microorganisms. These ROS new TiO2-graphene composite photocatalysts: ap-
are known to be highly reactive with biological mol- plication to NOx photoabatement and water split-
ecules and thus they are effective for the inactivating for hydrogen production.” (Reference: PTDC/
tion various different types of microorganisms. EQU-EQU/115614/2009).
Photoinactivation of microorganisms under UV
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