Catalysis Today 340 (2020) 334–346

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Review

Can the photocatalyst TiO2 be incorporated into a wastewater treatment T

method? Background and prospects
⁎
Satoshi Horikoshia,b, , Nick Serponec
a
Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyodaku, Tokyo 102-8554, Japan
b
Microwave Science Research Center (MSRC), Sophia University, 7-1 Kioicho, Chiyodaku, Tokyo 102-8554, Japan
c
PhotoGreen Laboratory, Dipartimento di Chimica, Università di Pavia, Via Taramelli 12, Pavia 27100, Italy

A R T I C LE I N FO A B S T R A C T

Keywords: This brief non-exhaustive review article aims to highlight first and foremost, what we consider to be, some of the
Photocatalysis milestones of photocatalysis and of titanium dioxide as the workhorse among metal-oxide photocatalysts, in
Titanium dioxide particular, and metal chalcogenides, in general, together with some of the attempts at using titania in waste-
Reactor designs water treatment systems. In this regard, over half a century has passed since the initial research on water
Wastewater treatment
treatment using TiO2 as the preferred photocatalyst. During that period, the decomposition of water pollutants,
the mechanisms of photocatalytic reactions, the development of a method to immobilize TiO2 on suitable
support substrates, reactor designs, and engineering scale-ups have all been addressed worldwide.
Unfortunately, the use of titania as the photocatalyst in current water treatment methods appears to have little
consequences in Advanced Oxidation Technologies (AOT), although its prospects are not to be discounted.
Consequently, first we briefly examine the historical background of what was achieved in the first 50 years of the
20th century with regard to photocatalysis, and then the second 50 years of the 20th century and beyond about
implementing photocatalysis and TiO2 as a photocatalyst in the treatment of wastewaters contaminated with
organics, followed by probing some of the features of various reactor designs in scale-ups to treat large volumes
of wastewaters.

1. Background: the first 50 years of the 20th century of
photocatalysis and photocatalyst
A search of the Internet with the keyword photocatalyst reveals
about 1,750,000 hits, which demonstrate the interest and perhaps even
the popularity of photocatalysts and the associated science photo-
catalysis. This keyword is by no means new as an examination of its
historical background reveals that the oxidation of organic acids with
light energy in the presence of uranyl salts as the photoresponsive
substrates was reported long ago in the late 1800s by Fay [1]. However,
it was only in 1910 that the words Photokatalyse and photokatalytisch
were coined for the first time by Johann Plotnikow in the book "Pho-
tochemie" [2], subsequently to be followed by the word photocatalyst
coined by Bruner and Kozak a year later [3]. The latter was also used
soon thereafter by Landau [4] in his report on the electron-accepting
photosensitization of oxalic acid by uranyl salts. While the term pho-
tocatalyst began to be used in many published articles to describe cer-
tain phenomena, it differed from the meaning and current use of the
word photocatalyst. Research on photocatalysts that can be associated
with the present usage were initiated in 1911 by a study conducted by
Eibner [5] on the effect of ZnO on organic and inorganic coloring
materials exposed to light irradiation; he showed that addition of ZnO
to a dye enhanced the rate of fading of the dye’s color by light irra-
diation. Similar research reports using zinc compounds appeared in the
literature subsequently. For instance, Baur and Perret [6] reported that
suspending ZnO powder in an aqueous solution of AgNO3 that had
previously been thoroughly boiled and air removed, followed by stir-
ring and irradiating with sunlight, caused the initially white mixture to
turn black after a certain period, after which silver was liberated
yielding a yellowish suspension. An analysis of the progress of the re-
action was traced to the transformation of Ag+ ions to silver oxide and
silver peroxide intermediates, ultimately yielding silver metal (reaction
1) and oxygen (reaction 2); no nitrite ions were formed in the process.
They concluded that formation of silver resulted from the reduction of
Ag+ ions by ZnO subjected to light irradiation, while oxygen was
generated by the oxidation of hydroxyl ions of water also by the ZnO

⁎
Corresponding author at: Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyodaku, Tokyo 102-
8554, Japan.
E-mail address: horikosi@sophia.ac.jp (S. Horikoshi).

https://doi.org/10.1016/j.cattod.2018.10.020
Received 9 August 2018; Received in revised form 11 October 2018; Accepted 12 October 2018
Available online 23 November 2018
0920-5861/ © 2018 Published by Elsevier B.V.
S. Horikoshi, N. Serpone
Fig. 1. Outline of the history of solar cells and photocatalysts represented by the reported milestones selected for this review. Reproduced from Nosaka [23];
Copyright 2011 by Elsevier B.V.
exposed to light irradiation; the following mechanism was proposed
[6]:
ZnO(–) + Ag+ → Ag
−
ZnO(+) + OH → (1/4) O2 + (1/2) H2O
where ZnO(–) and ZnO(+) indicate, respectively, that ZnO possessed
both a cathodic function and an anodic function under light irradiation.
The overall reaction occurring in aqueous media was (reaction 3):
2AgNO3 + ZnO → 2Ag + (1/2)O2 + Zn(NO3)2
Several research studies began to appear in the 1920s in attempts to
elucidate those two functions of ZnO; those various efforts may well
have triggered the foundation of photocatalysis and photocatalysts.
2. Background: the second 50 years of the 20th century and
beyond
In the early 1950s and early 1960s, Markham and coworkers [7,8]
confirmed that organic matter could be oxidized on the ZnO surface
upon irradiation with UV light in the presence of oxygen. For example,
the photocatalytic oxidation of various alcohols was examined from the
viewpoint of kinetics with free radicals being generated at the metal-
oxide semiconductor surface. These authors [9] also attempted to
polymerize methyl methacrylate with photoactivated ZnO and noted
that polymerization was a non-starter when surface oxygen was com-
pletely removed, which demonstrated that dissolved oxygen was a ne-
cessary mediator for the photocatalytic polymerization to occur. For the
first time, this called attention to the presence of oxygen as an im-
portant factor in the application of photocatalysis in wastewater
Catalysis Today 340 (2020) 334–346
treatment methods. Yamamoto and Oster [10] further noted that since
polymerization could not be started unless water was added to the re-
action system, they inferred that the generation of hydroxyl radicals by
(1)
photooxidation of water by light-irradiated ZnO was a significant factor
(2) in the polymerization.
Current understandings indicate that whenever researchers think of
a photocatalyst, the first thing that comes to mind is TiO2 rather than
ZnO. The first report of TiO2 as a photocatalyst was from a study by
Keidel in 1929 [11] who described that if TiO2 powder was added as a
(3) white pigment to colored paint to improve the coloring, the color
quickly faded under sunlight. In the same year, Wagner [12] showed
that TiO2 had a greater effect on this discoloration than did ZnO; he
attributed this greater effect, albeit erroneously, to the presence of
sulfuric acid as an impurity in the TiO2 sample. However, it is now well
known that the photocatalytic activity of TiO2 is greater than ZnO and
thus was responsible for the greater extent of color fading.
In the era when synthetic ammonium salts were widely used as
chemical fertilizers, it was pointed out that when the chemical fertilizer
was used for a long time, the nitrite concentration in the soil increased
with sunlight, which was attributed to the photocatalytic action of TiO2
and ZnO present as minerals in the soil [13]. At that time (1931), it was
alleged that ammonia was photodecomposed by sunlight, although no
research was done to demonstrate this allegation. Later on, Osugi and
Aoki [14] quantitatively confirmed that HONO acid and NO3− ions are
generated when a TiO2 powder suspended in an ammonium carbonate
aqueous solution was irradiated with sunlight; evidently, TiO2 and ZnO
in the soil caused the photocatalytic decomposition of ammonia. Ad-
ditionally, Horio [15] recounted that when TiO2 powder was mixed
with artificial silk fibers to whiten the artificial silk threads (rayon) it
caused a photolytic action under light irradiation.
335
S. Horikoshi, N. Serpone Catalysis Today 340 (2020) 334–346

The 1930s also witnessed the description of the formation of ex-
citons in a photocatalyst by Frenkel [16], while Goodeve [17] eluci-
dated the mechanism of the chalking of paints by the TiO2 pigment.
Furthermore, it became possible to measure the absorption spectrum of
the solid; the quantum efficiency of a photosensitized process occurring
on the surface sharply increased when irradiating with UV rays of a
lower wavelength [18]. The thinking in the 1930s was that irradiation
of a metal-oxide pigment, such as TiO2 and ZnO, with UV light caused
some problems when in contact with dyes and other organic matter;
this was the first hint of the decomposition of pollutants with such
pigments. However, we had to await nearly 30 years before the notion
that such pigments as TiO2 could be actively used as a photocatalyst in
wastewater treatment methods.
3. Discovery of phenomena and increased applications
Attempts to actively utilize TiO2 as a photocatalyst started in the
1970s with one of the first examples being the detoxification of HCN
[19], the synthesis of ammonia from N2 and water [20], the reduction
of CO2 [21], and the generation of H2 from carbohydrates and water
[22] among others. Moreover, various phenomena of the photocatalyst
were discovered and the range of applications expanded such as, for
example, the photodecomposition of water, environmental purification,
and the fabrication of dye-sensitized solar cells. Nosaka [23] has nicely
summarized some of the milestones of photoinduced phenomena (see
e.g., Fig. 1).
Discoveries of completely new photocatalyst phenomena and ap-
proaches to applications have also been reported. One such phenom-
enon discovered by chance in the mid-1990s by Hashimoto and cow-
orkers [24] originated from photoinduced redox reactions of adsorbed
substances, for which marked changes appeared in the water wett-
ability of the TiO2 surface before and after UV-light irradiation. The
discovery of this phenomenon significantly widened the application
range of TiO2 coatings.
A TiO2 thin film exhibits an initial water contact angle (WCA) of
several tens of degrees depending on the surface conditions, mainly
surface roughness. When this surface is exposed to UV light, water
starts to exhibit a decreasing WCA as it tends to spread out rather than
beading up [24], with the final WCA reaching nearly 0° (see Fig. 2a)
[25]. At this stage, the surface becomes completely non-water-repellent
and is said to be highly hydrophilic. The surface retains a contact angle of
a few degrees for a day or two under ambient conditions without UV
light. Subsequently, the WCA slowly increases as the surface returns to
its initial less hydrophilic state (see Fig. 2b) At this point, the highly
hydrophilic character can be recovered by exposing the surface to UV
light again. In short, this type of TiO2 coating is the only known prac-
tical highly hydrophilic material that shows stable and semi-permanent
properties. The combination of these functions has opened various
novel applications for TiO2, particularly in the field of building mate-
rials. In this regard, the photogeneration of a highly amphiphilic (both
hydrophilic and oleophilic) TiO2 surface was credited to the micro-
structured composition of the hydrophilic and oleophilic phases pro-
duced by UV irradiation. In terms of applications, the resulting TiO2-
coated glass was both antifogging and self-cleaning [24].
4. Photocatalytic applications in environmental protection
An early study on the photocatalytic decomposition of a pollutant
such as tetralin in aqueous media was reported in 1964 by Kato and
Masuo [26], followed over a decade later (1977) by a study from Frank
and Bard [19] who described the decomposition of CN− ions in UV-
irradiated aqueous TiO2 suspensions. With the coming of the 1980s,
detoxifications of various harmful compounds in both aquatic and at-
mospheric environments became the subject of extensive demonstrated
decontamination of wastewaters and air polluted by Volatile Organic
Compounds (VOCs) using powdered TiO2 as the metal-oxide photo-
catalyst of choice [27,28]. The photocatalytic destruction of pollutants
in aqueous media with TiO2 is facilitated mostly by a series of hydro-
xylation reactions initiated by reactive oxygen radicals. Both reduction
and oxidation sites are located on the TiO2 surface; reduction of ad-
sorbed O2 takes place on the TiO2 surface mediated by photogenerated
conduction band electrons. The photoholes (h+) generated in TiO2 are
highly oxidizing such that most organic-based compounds undergo
complete mineralization to final products H2O and CO2. Various forms
of reactive oxygen species (e.g., O2−%, %OH, HO2% and O% radicals) are
produced by events summarized in reactions 4–7 and are the principal
oxidants responsible for the decomposition reactions in Advanced
Oxidation Technologies.

Fig. 2. Changes in CA of TiO2 surface (a) under UV irradiation and (b) in the dark. Reproduced from Wang et al. [25]; Copyright 2005 by The Japan Society of
Applied Physics.

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S. Horikoshi, N. Serpone Catalysis Today 340 (2020) 334–346

e− + O2 → O2−% (ads) (4) Table 2

−%
Redox potentials of major oxidizing agents that are used in wastewater treat-
O2 (ads) + H +
→ HO2% (ads) (5) ment technologies.
%
h +
+ H2O → OH(ads) + H +
(6) Oxidizing agent Oxidation potential (V) Relative oxidation
power
h +
+ O2−% (ads) → 2 O (ads)%
(7)
OH radical (%OH) 2.8 1.00
Many elementary mechanistic processes have been described in the Ozone (O3) 2.07 0.74
photocatalytic degradation of organic compounds over the TiO2 parti- Hydrogen peroxide (H2O2) 1.77 0.63
culate surface; in many cases, a scavenger is used to unravel the me- Potassium permanganate (KMnO4) 1.7 0.61
chanistic details. In this regard, the { > TiIV‒%OH+} and { > TiIII‒OH} Chlorine dioxide (ClO2) 1.57 0.56
Iodine (I2) 0.54 0.19
species represent surface-trapped valence band holes and surface- Oxygen gas (O2) 1.2 0.43
trapped conduction band electrons, respectively [29]. The surface-
bound •OH radical represented by { > TiIV‒%OH+} is chemically
equivalent to a surface-trapped hole, which has allowed several re- reaction did not proceed in the absence of water [39]. The stages in the
searchers to use the former and the latter terms interchangeably. In photoinduced processes of the photomineralisation of organic con-
other words, the trapped hole and the surface-bound •OH radical are taminant in presence of TiO2 are displayed in Fig. 3 [40].
indistinguishable species [30]. A good correlation exists between From what has been said so far, what then might be the advantage
charge carrier dynamics, surface densities of charge carriers, and effi- (or perhaps disadvantage) of TiO2 as a photocatalyst in AOTs? A re-
ciencies of photocatalytic degradations carried out over TiO2. In the last sponse might be had from a 2013 review article by Lee and Park [41]
two decades, aqueous suspensions of TiO2 have been probed by pico- who summarized some of the technologies with a focus on TiO2, as well
second and more recently by femtosecond absorption spectroscopies as on latest modifications of TiO2 to improve its photocataytic activity
[31]. In this regard, Gaya and Abdullah [32] have summarized the by introduction of metals or heteroatoms in the bulk lattice and on the
characteristic times of each elementary event (see Table 1). The fem- surface of TiO2 particulates, by physical modifications of TiO2 into
tosecond spectroscopic study by Colombo and Bowman [31] of a TiO2/ various morphologies, and by fabrication of hybrid TiO2/nanocarbon
SCN− aqueous system indicated a dramatic increase in the population composites. The basic tenets of TiO2 photocatalysis is the photoinduced
of trapped charge carriers within the first few picoseconds. Their results generation of charge carriers (conduction band electrons and valence
confirmed that for species adsorbed onto TiO2, hole transfer can suc- band holes) that ultimately, through various stages, migrate/drift to the
cessfully compete with the picosecond electron/hole recombination metal-oxide surface depending on the surface potential; the highly re-
process. active oxygen species form subsequently that can lead to microbial
Advanced Oxidation Technologies (AOTs) represent a range of inactivation and mineralization of organics without secondary pollution
technologies that employ agents of increasingly oxidative power. For [42,43]. Decomposition reactions of pollutants are mostly oxidative
effective wastewater treatments, a range of pollutants needs to be re- reactions that are highly dependent on the flatband potential of the
moved economically at ambient temperature and atmospheric pressure valence band (VB) of the photocatalyst. Consequently, an oxidation
[33]. Table 2 summarizes some of the reactive oxygen species (and reaction is enhanced when the VB holes have a higher redox potential
others) used in AOTs together with their oxidation potentials. Clearly, relative to the potential of the normal hydrogen electrode (NHE). The
the •OH radical has the strongest oxidative power relative to ordinary bandgap of TiO2 generally ranges from 3.0 eV for rutile (absorption
oxidants normally used in oxidation processes in aqueous media often edge, 400 nm) to 3.2 eV for anatase (absorption edge, 387 nm), which
involved in the mineralization of organic compounds. The various implies that UV-light radiation below 400 nm initiates the photo-
technologies that make up the AOTs and implicate •OH radicals are: (i) induced events [44]. A significant characteristic of TiO2 is that the
the use of O3 [34]; (ii) the Fenton process [35]; (iii) the direct de- photoholes are more oxidative than the photoelectrons are reductive,
composition of water with such external energy sources as electro- and since the redox potential of H2O is 1.23 eV sandwiched within the
magnetic beams [36] and ultrasounds [37]; and (iv) metal-oxide (and bandgap, water splitting becomes a thermodynamically possible pro-
others) semiconductor photocatalysts [38]. cess [45].
In most applications, photocatalytic degradation reactions are car- Titanium dioxide is an industrially mass-produced material that is
ried out in the presence of water, air, the target contaminant and the easily obtained, is relatively inexpensive, and can easily be synthesized
photocatalyst. The presence of water is indispensable in TiO2 photo- in a laboratory environment, either as a white TiO2 powder, or as a
catalysis. Earlier work on 2-propanol photooxidation indicated that the colloidal dispersion in a liquid phase, or as a thin film deposited on a
suitable support substrate. Hence, the ease of applying these various
forms of TiO2 highlights its potential applications in photocatalytic
Table 1
Primary processes and time domains in TiO2-catalyzed mineralization of or-
technologies [46]. Titania is a very stable product both chemically
ganic pollutants [32]. (resistance to acids and alkalis) and photochemically (photocorrosion)
and is relatively safe and non-toxic – so much so that in addition to the
Primary process Characteristic time
photocatalytic purification of the environment, it finds applications as
Charge carrier generation fs (very fast) additives in foodstuffs and medicinals [47]. By contrast, other semi-
TiO2 + hv → e− + h+ conductors such as CdS, GaP and ZnO are not very useful for environ-
Charge carrier trapping 10 ns (fast) mental purification as well as in foods and medicinals because they can
h+ + { > TiIV‒OH} → { > TiIV‒•OH+} 100 ps (shallow trap; dynamic dissolve and produce toxic by-products in aqueous media during the
e− + { > TiIV‒OH} ↔ {TiIII‒OH} equilibrium)
e− + > TiIV → TiIII 10 ns (deep trap)
photocatalytic events [40]. Therefore, TiO2-based photocatalysis bears
Charge carrier recombination 100 ns (slow) much potential as a technology toward the degradation of organic
e− + { > TiIV‒%OH+} → { > TiIV‒OH} 10 ns (fast) pollutants in groundwaters and industrial wastewaters. In its applica-
h+ + { > TiIII‒OH} → {TiIV‒OH} tions as a photocatalyst in AOTs for water treatments, TiO2 displays fast
Interfacial charge transfer 100 ns (slow)
response to irradiation and a non-negligible photonic efficiency, even
{ > TiIV‒%OH+} + organic molecule ms (very slow)
→ { > TiIV‒OH} + oxidized molecule under weak light conditions.
{ > TiIII‒OH} + O2 → { > TiIV‒OH} + Though titania displays interesting features as a photocatalyst, it
O2−% also exhibits some disadvantages, among which is its photo-inactivity

337
S. Horikoshi, N. Serpone
Fig. 3. Energy band diagram and fate of electrons and holes in a semiconductor particle in the presence of water containing a pollutant (P). Reproduced from ref.
[40]. Copyright 2009 by Elsevier B.V.
under visible light irradiation and is unsuitable for a mass processing
system [48]. Other consequences have to do with additional recovery/
separation of TiO2 from suspensions after the water treatment process,
and with having to use artificial light sources to initiate TiO2 photo-
catalysis. The reason is that the bandgaps (3.0 eV and 3.2 eV for rutile
and anatase, respectively) of the TiO2 semiconductor, which absorbs
from the UV region of the solar spectrum, are some of the downsides in
photocatalysis because about only 5% of the sunlight is UV radiation.
Until recently, applications of visible-light-responsive photocatalysts
have been witnessed over a wide research area [see e.g. ref. [49]).
Modification of the bandgap in TiO2 has therefore been a topic that has
received much attention in the last two decades. Modifications of TiO2
to bring it to absorb some of the solar visible light can be effected either
in the bulk or on the surface of TiO2 particulates Surface modifications
are usually achieved by anchoring either colored inorganic semi-
conductors (e.g. CdS or CdSe as quantum dots) [50] or organic dyes on
the TiO2 surface [51], where they act as sensitizers. However, most of
these sensitizers are susceptible to photocorrosion or degradation in
aqueous media and are thus not suitable for photocatalytic water-
treatment applications. Instead, they are good candidates for solar cell
devices. On the other hand, doping metals or non-metals in the bulk of
the TiO2 lattice mainly effect bulk modification. The modified catalysts
appear to be photo-stable in aqueous media and so can be used in
photocatalytic water purification. In this regard, recent studies have
reported the successful doping of TiO2 with vanadium [52], iron [53],
rhodium [54], palladium [55], and silver [56] metals, and carbon [57],
nitrogen [58], sulfur [59], fluorine [60], and iodine [61]. However, this
crucial material is not being used in the water treatment field at an
industrial scale; there are other reasons for that.
In current reactor designs, either TiO2 slurries or immobilized films
are used. In slurry reactors, suspended commercially available nano-
size photocatalytic TiO2 particles display a high surface to volume ratio.
However, the suspended particles need to be removed at the end of the
exercise. This is more difficult for smaller particles as they easily stay
suspended in water, clog filter membranes, and penetrate filter mate-
rials. The filtering of the slurry is not practical and comes at a non-
insignificant economic cost. Nonetheless, one of the few advantages of
TiO2 particles is the increasing quantity of adsorbed contaminants. The
limiting rate of water treatment by photocatalytic TiO2 is an active
oxygen species generated by oxidation-reduction of water in the pho-
tocatalytic reaction. Therefore, if contaminants are adsorbed on the
TiO2 surface, generation of these active radical species could be in-
hibited, thereby causing the decomposition efficiency to be lowered.
That is, in the decomposition of contaminants with photocatalysts, rates
of adsorption and desorption of contaminants on the photocatalyst
surfaces are important, as in the case of existing organic contaminants
338
Catalysis Today 340 (2020) 334–346
when using solid catalysts. Accordingly, if a photocatalyst such as TiO2
with a high specific surface area were used, the rate of adsorption may
be improved but the rate of decomposition not always follows.
In the latter case, various methods have been developed to im-
mobilize TiO2 nanoparticles in such supports as silica and apatite upon
which organic materials can also be deposited [62]. Germane to this,
Table 3 [62] summarizes some basic features of immobilization of TiO2
developed for the photocatalytic decomposition of VOCs, which can
also be used in water treatment. With respect to the latter, the TiO2-
coated materials should have a large specific surface area, the photo-
catalytic film should be thick and porous, and the quantity of TiO2 used
should be flexible as per the requirements of the treatment [63]. Zeo-
lites [64], ceramics [65], glasses [66], and fibers [67] have been widely
contemplated as suitable supports for anchoring TiO2 nanoparticles and
hybrid TiO2 composites with carbonaceous materials. Important prop-
erties of the substrate are a good adhesion of the TiO2 particles, re-
sistance against sintering temperatures, a high specific surface area and
strong adsorption affinity towards the pollutants. Glass and silica sub-
strates may be desirable because they are transparent. Activated carbon
is very porous and has a very high specific surface area, and has been
shown to increase the activity of the catalyst [68]. TiO2-based catalysts
can be deposited on structured substrates through aqueous or gaseous
routes. Some examples of aqueous methods include sol-gel and elec-
trophoretic deposition, while gas phase methods include spray pyrolysis
deposition, chemical vapor deposition, and physical vapor deposition.
Table 4 highlights the advantages and disadvantages of different
methods used for immobilising TiO2 catalysts [69]. To deposit the ti-
tanium dioxide on the substrate, different techniques may be utilized.
The sol-gel method has been reported extensively as being low cost and
easy to use [68]. This method involves a colloidal suspension of TiO2
particles. In the process, the suspension is converted to a viscous gel and
finally to a solid material. Sol-gel shows good adherence to the sub-
strate because of oxygen bridges that are formed during the heating of
the precursor (such as TiCl4 for example). Dip or spread coating can be
used to coat the substrate [68]. Dip coating results in a thin and con-
trollable layer while spread coating may be used to attain a thicker
layer. Another facile and reproducible technique is the use of previously
made titania powder (PMTP) [70]. Unlike the sol-gel method which
uses a precursor, commercially available titania powder is used and
mixed with a solvent. Coating may be done by different methods such
as pipetting and spin coating. After sintering at high temperature
(400 − 600 °C), the film will adhere to the substrate. Chemical vapor
deposition (CVD) covers several different processes that differ by type
of precursor, type of support, uniformity of the film and reaction con-
ditions. The method generally involves exposing the substrate to a vo-
latile gaseous phase precursor in an inert, high temperature and
S. Horikoshi, N. Serpone Catalysis Today 340 (2020) 334–346

pressure environment. The precursor will decompose at the surface,

Generally lower activity/surface area; higher cost

forming the TiO2 film. This method can coat a substrate of any shape.
Loss of activity due to binder; powder dropout; Other deposition techniques include sputtering, thermal treatment, and
electrophorectic deposition [68].

Calcination usually at high temperature

Engineered nanoparticles (NPs) have found applications in several
commercial products and industrial processes or materials, including
cosmetics, drug delivery, electronics, energy technology, agricultural
Smaller specific surface area

and environmental sciences [71]. There are evidences that during their
usage and disposal, these nanoparticles are released into aquatic eco-
degradation of binder

systems [72]. If wastewater treatment processes are unable to remove

nanoparticles from water, NPs will enter in drinking water sources and
(400–600 °C)

natural aquatic environments, increasing the risk of exposure to plants,

Demerits

animals and humans [73]. NPs properties, such as large surface area-to-
volume ratios and small sizes, provide unique materials with new ap-
plications compared to the corresponding bulk materials. However,
Transparent films can be prepared. Surface area increased by

these same properties may also result in the enhancement of the bioa-
vailability, thereby increasing their toxicity. TiO2 is the most widely
used nanomaterial owing to its application as a pigment, in cosmetics,
in paints, in coatings, and in materials for environmental and energy
Precise control of thickness; composition; etc…

technologies [74]. The annual production of this nanomaterial is

around 40,000 tonnes in the U.S.A [75] and 10,000 tonnes in Europe
[76]. About 54% of the globally produced amount is expected to enter
wastewater treatment plants [77]. TiO2 nanoparticles have already
Thick films can be easily prepared

Thick films can easily be prepared

been detected in biosolids and wastewater treatment effluents, which

mixing template compounds

suggest that it may ultimately end up in surface water bodies [77].

Emissions to aquatic environments via wastewater treatment plant
(WWTP) effluents are estimated to be around 1100 to 29,000 tonnes per
year globally [75]. Currently, there is not data on measured environ-
mental concentrations of TiO2 nanoparticles in surface waters; how-
ever, several researchers have estimated values between 21 and
10,000 ng L–1 [78]. Canesi and coworkers [79] have recently demon-
Merits

strated that suspensions of selected nano-TiO2 photoinduced oxyradical

production and lysosomal enzyme release in the hemocytes of the
Sheet glass; glassware; ceramics; metal; plastic
TiO2 electrode (heat in air); building material
Paint; paper; nonwoven fabric; fluoro- carbon

marine mussel Mytilus in vitro, while Long and coworkers [80] showed
adverse effects of these NPs, such nanoparticles stress in human cells.
Immobilization of TiO2 nanoparticles may also be effective from this
viewpoint.
There have been a few cases where success has been had in pro-
moting water treatment with immobilized TiO2. An example of success,
albeit limited, is the novel flow-type photoreactor (Fig. 4) considered
sheet; hardened cement

relatively efficient in water treatment using photocatalytic TiO2 as es-

(anodic oxidation)

tablished by Hofstadtler and coworkers [81]. The reactor was composed

Sheet glass; etc.

of TiO2-coated fused-silica glass fibers specifically designed for treat-

Characteristics and methodologies of immobilized TiO2 photocatalyst [62].

ment of a wastewater contaminated with 4-chlorophenol. Since the si-

Example

lica fibers had a large surface area and high light permeability, the
coated TiO2 was distributed sufficiently to be activated by light. Com-
parison of degradation rates and quantum efficiencies using this reactor
Metallic titanium; titanium alloy

design in degrading the chlorophenol showed that the degradation rate

Organic titanium compounds;

of the chlorophenol was 1.6 times greater and loss of total organic
carbon was 2.8 times faster relative to the use of a Degussa P25 TiO2-
TiO2; metallic titanium

slurry wastewater treatment method.

Another non-negligible characteristic of pondered products regards
Raw material

the photocatalytic activity of TiO2 when using sunlight to activate TiO2

TiO2 sols

as only 3–5% of the solar radiation reaches the Earth [82]. Accordingly,
Powder

increasing the photo-activity of TiO2 under visible light irradiation has

been the subject of numerous investigations through doping the TiO2
with metals or non-metals in the bulk lattice and on the surface, with
Vacuum evaporation; sputtering

the dopant either substituting one of the atoms in the lattice or being
Immobilization with binder

located at interstitial sites. The non-metallic heteroatoms included,

among others, boron [83], nitrogen [59], fluorine [84], phosphorous
[85], and sulfur [86] all of which have red-shifted the absorption of
Surface oxidation

light by the doped photocatalyst. Nonetheless, we must point out that

any notion of scale-up will necessitate (i) the operation to be performed
Coating
Method

at ambient temperature and pressure, (ii) complete mineralization must

Table 3

be achieved without secondary pollution, (iii) the process must undergo

repetitive cycles, and (iv) the costs of the operations must be low.

339
S. Horikoshi, N. Serpone
Table 4
Advantages and disadvantages of different methods used for immobilizing TiO2 photocatalysts [69].
Catalyst preparation method Advantages
Sol-gel 1. High purity of materials
2. Homogeneity
3. Versatile means of processing and control of parameters
4. Large surface area
5. Chemical bonding results in strong adherence of coating to the
substrate
Physical vapor deposition 1. Does not require complex chemical reactions
2. Low to medium deposition temperature
Chemical vapor deposition 1. Suitable for uniform and pure films with high deposition rate
2. Short processing time
5. Wastewater treatments with photocatalytic TiO2
The viability of the photocatalytic degradation of organic com-
pounds in aqueous media using TiO2 was demonstrated in the mid-
1960s. Since then, research on the use of TiO2 for the photo-oxidation
of organic compounds, for the removal of inorganic compounds and
(toxic and precious) metal ions, and for the disinfection of waters has
witnessed considerable activity. More than 1000 substances have been
tested by advanced oxidation using TiO2; this has offered potential
opportunities for the tertiary treatment of municipal wastewaters
[87,88], for the removal of endocrine disrupting chemicals [89], for the
disinfection of waters [89], especially effluents containing pathogens
resistant to chlorination [90], and for the mineralization of halocarbons
[91], polychlorinated biphenyls [92], dioxins [93], and pesticides [94],
for the treatment of hazardous effluents from hospitals [95], for the
industrial effluents from pulp and paper mills [96], the dairy manu-
facturing [97], the textile dyeing [98], pollutants from agricultural oil
mills and distilleries [99], chemicals from the pharmaceutical industry
[100], wastewater effluents containing phenols [101] and chlor-
ophenols [102], herbicides and pesticides [103], ammonia [104],
plasticizers [105] and surfactants [106], drinking water disinfection
[107] and purification of micro-pollutants [108], cyanide [109] and
arsenic [110] from wastewaters. Beginning in the late 1980s, scale-up
experiments began assertively for water treatment using TiO2 as the
photocatalyst of choice.
6. Sterilization of drinking water
Applications of photocatalytic processes are widely recognized as
viable solutions to environmental problems [111]. Disinfection of
bacteria is of particular importance, because traditional methods such
as chlorination are chemical intensive and have many associated dis-
advantages. For example, in water treatment applications, chlorine
used for disinfection can react with organic materials to generate
chloro-organic compounds that may be highly carcinogenic [112].
Fig. 4. (a) Titanium dioxide-coated optical fiber: schematic drawing of concept, (b) Photocatalytic reactor with cooling jacket, light window, and liquid flow.
Reproduced from Hofstadtler and coworkers [81]; Copyright 1994 by the American Chemical Society.
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Catalysis Today 340 (2020) 334–346
Disadvantages
1. Hydrolysis rate is difficult to control
2. Longer processing time compared to CVD and PVD
3. Calcination at high temperatures results in the decomposition of substrates
4. Multiple coating cycles is required depending on the sol viscosity
1. Expensive as vacuum systems are used
2. Difficulty in deposition of multiple source precursors due to various
evaporation times
1. Could be expensive if vacuum systems are used
2. Difficulty in deposition of multiple source precursors due to various
evaporation times
3. High deposition temperature (> 600 °C) is required
Furthermore, some pathogens such as viruses, certain bacteria such as
Legionella, and protozoans such as Cryptosporidium and Giardia lamblia
cysts are known to be resistant to chlorine disinfection [113]. Other
treatment alternatives such as ozonation and irradiation using germi-
cidal lamps (254 nm) have their own problems and limitations, such as
the lack of residual effect [114] and generation of small colony variants
for the latter [115], and production of toxic disinfection by-products for
the former [116]. In comparison, the TiO2 semiconductor commonly
used in photocatalytic processes is nontoxic, chemically stable, avail-
able at a reasonable cost, and capable of repeated use without sub-
stantial loss of photocatalytic ability [117]. Heterogeneous photo-
catalysis using titanium dioxide is typically regarded as being a safe,
nonhazardous, and ecofriendly process that does not produce harmful
by-products. Extensive research in this field has been done in the area of
photocatalytic removal of organic, inorganic, and microbial pollutants
[118]. The mechanism of bactericidal action of TiO2 photocatalysis, as
reported by Sunada et al. [119], is attributed to the combination of cell
membrane damage and further oxidative attack of internal cellular
components, ultimately resulting in cell death. Since the breakthrough
work of Matsunaga et al. in 1985 [123] reporting the application of
TiO2 photocatalysis for the destruction of Lactobacillus acidophilus,
Saccharomyces cerevisiae, and Escherichia coli using platinum-loaded
TiO2, there has been much interest in the biological applications of this
process. A very comprehensive review of the application of TiO2 pho-
tocatalysis for disinfection of water is given by Mccullagh et al. [93],
with many others available in the literature [see e.g., ref. [121]). Re-
search in the field of photocatalytic disinfection has been very diverse,
with the UV/TiO2 process being shown to successfully inactivate many
microorganisms including bacteria such as E. coli [see e.g. ref. [122]), L.
acidophilus [120], Serratia domonas stutzeri [123], Bacillus pumilus
[124], Poliovirus I [125], Cryptosporidium parvum [126], and Giardia
intestinalis [127].
Cyanobacteria and their secondary metabolites, in particular their
toxins, pose a serious health hazard to both humans and animals.
Failure to control the propagation of cyanobacteria can result in the
S. Horikoshi, N. Serpone
Fig. 5. Schematic of the possible reaction mechanism of photocatalytic procedure. Reproduced from ref. [129]. Copyright 2017 by Elsevier B.V.
production of potent toxic secondary metabolites in aquatic systems.
The management of cyanotoxins is important when considering water
safety, especially for potable use. Consequently, the removal of these
toxins during water treatment is a key concern. The photocatalytic
destruction of cyanotoxins using TiO2, particularly microcystin-LR, has
been studied in detail and is a very effective process for the removal of
these toxins from water. The implementation of this technology by the
water treatment sector, however, has been limited due to the difficulties
encountered in overcoming post-treatment catalyst removal [128].
Wang and coworkers [129] reported the solar light-driven photo-
catalytic destruction of cyanobacteria by F-Ce-TiO2/expanded perlite
floating composites. Among the F-Ce-TiO2/EP photocatalysts, F-Ce-
TiO2/EP450 had the highest photocatalytic activity and achieved the
algal cells removal rate of 98.1% following a 9-hr reaction. During the
photocatalytic process, the algal cells were damaged as a result of
photocatalytic oxidation, whether in the solution or on the photo-
catalyst surface. These authors proposed a possible mechanism invol-
ving the F-Ce-TiO2/EP floating photocatalyst; it is illustrated in Fig. 5
[129]. The as-prepared photocatalyst possessed a honeycomb-like
structure with F-Ce co-doped TiO2 distributed on the EP surface. The F-
Ce co-doping facilitated the activation of TiO2 by visible light. Under
solar light irradiation, the electrons (e−) in the mid-gap levels formed
from mixing the O 2p orbitals of TiO2 with the F 1 s orbital in anatase
are excited up to the conduction band (CB) causing the generation of
holes (h+) in the valence band (VB). The latter charge carriers can
convert surface-bound H2O into %OH radicals. Meanwhile, the photo-
generated electrons are trapped by Ce4+ reducing to Ce3+. Subse-
quently, the Ce3+ can be re-oxidized to Ce4+ by the adsorbed oxygen in
this system, resulting in the production of O2‒% radical anions. The %OH,
h+ and O2‒% are the primary reactive oxygen species (ROS) in the
photocatalytic process, which can be divided into three stages. The first
stage involves the photocatalytic destruction of cell walls and mem-
branes through the ROS generated by the photocatalyst resulting in
irreversible damages to membrane proteins and in electrolyte leaking,
thereby increasing solution conductivity [130]. The second stage in-
volves the photocatalytic enhanced photoinhibition and the oxidation
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Catalysis Today 340 (2020) 334–346
of pigments; after the cell walls are damaged, cell organelles become
exposed to the highly oxidative stress environment caused by the
photocatalytic process with excessive photon intensity [131]. The
photogenerated ROS attack the pigments and active proteins, thus in-
hibiting the electron transfer in the W-W cycle, which accelerates the
death of algal cells. The third and final stage implicates the photo-
catalytic degradation of metabolic products. During the dying of algal
cells, these metabolic products, considered as secondary pollutants, are
then released into water. The floating photocatalyst can adsorb these
products through the porous structure and degrade them into H2O and
CO2 by the powerful oxidizability of the ROS species.
7. Scale-up attempts and types of reactor designs
Attempts to utilize sunlight in relation to cost have been made to
treat large volumes of water using TiO2 in many cases. A parabolic
trough concentrator was used in the late-1980s for the first field de-
monstration of solar heterogeneous photocatalytic water treatment
[132], subsequently followed by several other studies. Despite the ex-
tensive research on photocatalytic oxidation with TiO2, during the last
four decades pilot and demonstration plants have been few and far
between (see Table 5) [133–142].
Currently used large-scale water treatment infrastructures that have
been highly reported are displayed in Fig. 6, while their main features
are briefly described (see ref. [133] for a fuller discussion). Note that
many of these are benchtop-scale reactors awaiting further scale-up.
Fig. 6a shows an image of the parabolic trough reactor (PTR), which
consists of a transparent pipe through which contaminated water flows.
The pipe is located at the focal line of a radiation collector consisting of
a parabolic light-reflecting surface. The collector is mounted on a mo-
bile platform equipped with a solar tracking system [144]. PTRs con-
centrate the solar light at ratios from 10 to 50 [145], based on calcu-
lations of the collector width and half the circumference of the glass
pipe, while concomitantly taking into consideration reflective and
transmissive losses [134]. PTRs are operated at high flow rates; tur-
bulent flow ensures high mass transfer rates between the pollutants and
S. Horikoshi, N. Serpone Catalysis Today 340 (2020) 334–346

Table 5
Solar TiO2 pilot and demonstration plants.
Reactor Type Treated Water Pollutant Treated Volume Ref.

PTR Deionized water Salycilic acid 1100 L [134]

PTR Contaminated groundwater Trichloroethylene 15 L min–1 [135]
PTR Industrial platform Pentachlorophenol 837 L [136]
Tubular Pre-treated groundwater BTEX 530 L [137]
CPC Deionized water Cyanide 247 L [138]
Fixed-bed thin-film Textile wastewater TOC 1000 L [139]
DSSR Biologically pre-treated industrial wastewater TOC 500 L [140]
CPC Raw water Cyanide 1000 L [141]
Packed Tubular City water Aromatic organics 1000 L day–1 [111]
Shallow tank Tap water Phenol 1350 L [142]
Open tank Oil and gas wastewater Oil, phenol and ammonia 4000 L [143]

the photocatalyst surface [146].
Compound parabolic concentrator (CPC) reactors are static reactors
that consist of transparent pipes mounted on a reflector (Fig. 6b), which
espouses the shape of two half parabolas intersecting beneath each
tube; this shape allows any incident light to be concentrated on the
transparent pipe with no need for sun tracking systems. CPCs use direct
as well as diffuse solar radiation while exhibiting a small concentration
factor (< 1.2) [147]. A demonstration plant using CPC reactors was
erected in HIDROCEN, Madrid; it is a fully automated plant that can
treat 1000 L of water. The plant consists of two rows of 21 CPC col-
lectors (made of anodized aluminium; total aperture area: 100 m2)
connected in series; each collector has dimensions 1.5 m × 1.5 m en-
compassing 16 parallel glass tubes (inner diameter, 29.2 mm). The
plant was operated in a recirculating batch mode. After the treatment,
the pH in the sedimentation tank was adjusted to enhance the ag-
glomeration of TiO2 into bigger particles for quick settling. The su-
pernatant from the sedimentation tank containing < 7 mg L–1 TiO2 was
passed through a microfiltration system for final catalyst removal

Fig. 6. Schematic drawings of (a) parabolic trough reactor (PTR) system, (b) slurry compound parabolic concentrator (CPC) system, (c) shallow pond employing
slurry TiO2, (d) fluidized bed shallow pond reactor, (e) thin-film fixed-bed reactor (TFFBR) system, (f) step reactor system, (g) fountain reactor, (h) non-concentrating
slurry bubble column reactor, (i) flat plate column reactor, (j) packed bed reactor system. Adapted from Abdel-Maksoud and coworkers [133].

342
S. Horikoshi, N. Serpone
[141].
The CPC reactor has the merits of maintaining a turbulent flow that
guarantees good mixing and negligible mass transfer limitations.
However, long exposures to solar radiation severely reduce the tubes’
UV transmittance [149], thereby impairing the treatment efficiency and
incurring additional costs to replace the tubes. Another CPC limitation
is the need to purge continuously the wastewater with oxygen gas, or
alternatively the need to add suitable oxidants to act as electron sca-
vengers. Where a supported photocatalyst is used, problems of reactor
clogging and catalyst fouling add to operational concerns, not least of
which are pressure drop and high pumping costs. A slurry CPC system
operating in a recirculating batch mode is illustrated in Fig. 6b. The
demonstration plant at the Plataforma Solar Almeria (PSA) used TiO2
slurries to treat 1000 L of contaminated water; it involved 672 pipes
(pipe length, 1.5 m). If a supported photocatalyst were to be used, ease
of operation regarding regular inspection and replacement of the sup-
ported photocatalyst becomes questionable.
The shallow pond reactor is a non-concentrating reactor that utilizes
both direct and diffuse radiation, thus operating in sunny as well as in
cloudy and overcast days (Fig. 6c). A solar pond (dimensions:
106.5 cm × 53.3 cm; surface area: 0.57 m2; depth: 5 cm) fabricated
from plywood and lined with polyethylene sheets was used to degrade a
chlorophenol in tap water; it worked in a recirculating batch mode
employing a TiO2 slurry with vigorous achieved using a recirculating
pump and a submerged spray bar. After the treatment ended and the
mixing facility stopped, the TiO2 particulates settled to the bottom of
the pond, following which the treated effluents were decanted from the
pond surface [148]. Shallow ponds have the potential to treat industrial
wastewaters, especially in industries that already use holding ponds –
these include pulp and paper mills, as well as the pharmaceutical and
textile industries [132]. Sparging the pond/tank with air might not be
needed given that the pond/tank depth does not limit a continuous
oxygen supply from the atmosphere and does not impede light pene-
tration. However, finding an efficient immobilized photocatalyst re-
mains a necessity. Shallow pond systems working in a batch mode are
illustrated in Figs. 6c and d.
The falling film reactor – often referred to as thin-film fixed-bed
reactor (TFFBRs) – is a variation of the flat-plate collector where the
surface of the reactor is left open to the atmosphere; an image of this
type of reactor with immobilized TiO2 working in a recirculating batch
mode is depicted in Fig. 6e [149]. Falling film reactors can also be used
with both direct and diffuse solar radiation. Laminar flow conditions
prevail resulting in a film thickness of 1 mm [149]. Eliminating the
reactor cover has two advantages: (1) purging the reaction solution
with air/oxygen is unnecessary since oxygen is exchanged rapidly be-
tween air and water [150]; (2) falling film reactors have higher optical
efficiency and eliminate transmissive losses that might otherwise be
caused by the cover material and its thickness [155]. However, such
falling film reactors suffer during strong winds as they lose homo-
geneity of the falling film [102]. During cross winds, parts of the cat-
alyst film dry up which impacts the treatment efficiency [151]. Another
profound limitation is the difficulty of immobilizing TiO2 on large flat
surfaces without stripping off the photocatalyst during the water flow.
A step reactor with immobilized TiO2 working in a recirculating
batch mode is illustrated in Fig. 6f. This photoreactor is based on the
cascade thin-film principle and consists of a stainless-steel staircase
(2 m × 0.5 m) with 21 steps covered with a Pyrex glass sheet. The TiO2
is immobilized on a flexible Ahlstrom paper support impregnated with a
silica-based inorganic binder; subsequently, the paper is pressed by
cylindrical rolls under constant speed and pressure [152]. Neither the
quantity of TiO2 loading nor the coating stability have been reported.
Like flat-plate reactors, enclosing a large-scale reactor with a UV
transparent material is a limitation against scale-up and commerciali-
zation because of increased capital costs associated with cover material,
film problems that decrease reactor efficiency, increased operational
cost associated with the need for purging the solution with oxygen or
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Catalysis Today 340 (2020) 334–346
addition of oxidants, not least of which is the need for regular cleaning.
The photocatalytic fountain reactor is a slurry-type reactor in which
a thin film of polluted water containing dispersed TiO2 is continuously
generated by pumping water through a specially designed nozzle
(Fig. 6g) [153]. Water treatment via an unsupported thin film offers
two advantages: (i) a high oxygen exchange rate between air and water
eliminates the need for an additional aeration system, and (ii) light
penetration for excitation of the photocatalyst allows for the use of
higher catalyst loading [154]. Use of a reflecting surface mounted be-
neath the lower side of the fountain allows the water thin film to be
irradiated from both sides. Fountain photoreactors are operated in
continuous mode with very high recycle ratios, with nearly all the water
being recirculated through the nozzle with a minimum effluent flow
rate under good mixture conditions with dispersed TiO2.
A schematic drawing of a non-concentrating slurry bubble column
photoreactor is illustrated in Fig. 6h. The concept of the slurry bubble
column reactor is not attractive for scale-up and commercialization for
the following reasons: (i) the presence of moving solar tracking parts in
the case of a concentrating column adds to investment and operational
costs, and (ii) reactors with transparent walls for radiation transmit-
tance experience film problems, and are prone to breakage, to loss of
UV transmittance and to aging following long exposures to sunlight.
These types of reactors are composed of a borosilicate glass column
(inner diameter, 10 cm; length, 3 m) supported by steel rods [155].
Water to be treated enters the column at the top, while air supplied to
the reaction medium enters from the column bottom. Sieve plates are
used to reduce back-mixing throughout the column. A parabolic re-
flector (total surface area, 6 m2) has been used to concentrate the solar
radiation on the reactor. The collector position is typically changed
every 15 min to continuously track the sun. The TiO2 particulates are
separated from the treated waters using a candle filter placed before the
effluent outlet.
A schematic drawing of a flat-plate column reactor is shown in
Fig. 6i. Since the reactor is closed, aeration or addition of oxidants is a
must. For scale-up purposes, channelling can be avoided using multiple
liquid distributors throughout the column; however, pressure drop
across the column associated with excessive pumping remains a con-
cern. The reactor has been tested for degrading methylene blue
(10 mg L–1) in aqueous media; about 65% degradation was reported
within 6.5 h of visible-light irradiation but reached 90% when using UV
light [156].
A packed bed reactor (Fig. 6j) working in a recirculating batch mode
uses TiO2 immobilized on sand as a photocatalyst; the packed bed
(length, 35 cm; width, 2 cm) consisted of 40 g of sand. Naturally oc-
curring sand enables the manufacture of an inexpensive photocatalyst;
the sol gel method was used to immobilize TiO2 on quartz sand
(average grain size, 250 μm) followed by calcination at 850 °C. Al-
though unsupported anatase generally transforms into rutile at tem-
peratures around 600 °C, Ahmadi and coworkers [161] found that dif-
fusion of Si from the sand to the TiO2 coating restricted atomic
rearrangement, thereby causing the anatase phase to be stable.
Two other interesting reactor types are the (i) rotating drum pho-
toreactor and the (ii) rotating disc photoreactor for wastewater treat-
ments, both of which are displayed in Fig. 7 [157] and Fig. 8 [158],
respectively.
The design of the rotating drum photoreactor incorporates periodic
illumination and increased agitation through the introduction of rota-
tion; the effects ofrent degrees and flat fins increase the surface area and
the rotational speed can be varied, which allow initial pollutant con-
centration and illumination intensities to be investigated. According to
the report of Meunier and coworkers [157], the corrugated and finned
drums exhibited no critical rotational speed, so that there was excellent
mass transfer in the system investigated, which showed that the overall
reaction rate increased with increasing surface area from 0.046 mg
L–1 min–1 for the annular drum to 0.16 mg L–1 min–1 for the 40-fin drum;
the apparent photonic efficiency increased with increasing surface area
S. Horikoshi, N. Serpone
Fig. 7. (a) Illustration of a rotating drum photoreactor, and (b) the different drum configurations. Reproduced from ref. [157]. Copyright 2010 by Sarah M. Meunier
et al.
Fig. 8. Illustration of a rotating disc photoreactor. Reproduced from ref. [158].
Copyright 2006 by Elsevier B.V.
at a faster rate for the corrugations than for the fin additions, while the
energy efficiency (EE/O; electrical energy per order) for the drums
varied from 380 to 550 kW h m−3, up to 490% more energy-efficient
than the annular drum.
A model rotating disc photoreactor, also designed for wastewater
treatment, was reported by Zhang and coworkers [158] who, based on
experiments and simulation of the radiation field, analysed it kineti-
cally using a model that implicated the thickness of the water film and
the irradiance, the most important factors for such a photoreactor.
Their experimental results and mathematical simulations revealed (1)
that the configuration using discs had a larger illuminated area, but the
photon flow rate onto the disc was similar to that of the drum; (2) that
the thickness of the water film on the surface of disc/drum was a crucial
factor for the rotating reactor, determined by both rotation speed and
disc diameter; (3) that although deeper valleys in the disc reactor can
increase the capture of reflected photons, it had little influence on the
photonic efficiency compared with the influence of the illumination
area, from which they recommended a shallow valley and small angle;
and finally (4) that under low radiation intensities gave rise to higher
photonic efficiencies – the radiation distribution was sensitive to the
layout of the lamps.
An important point to emphasize in designing any photoreactor is
that one must consider the following components: (i) the hydrodynamic
field, (ii) the radiation source and the associated field, (iii) the mass
balance, and (iv) the reaction kinetics [159].
8. Epilog
The late 1960s saw Fujishima and Honda begin their investigation
into the photoassisted electrolysis of water for which they used a single
crystal of TiO2 (n-type, rutile) as the light harvesting electrode, as it
possessed a sufficiently positive valence band edge to oxidize water to
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Catalysis Today 340 (2020) 334–346
oxygen. This metal-oxide electrode was very stable even in the presence
of aqueous electrolytes, more so than other types of semiconductor
electrodes that were also examined. For the first time in 1969 they
demonstrated the possibility of solar photoelectrolysis of water by ex-
posing the electrochemical system to near-UV light; the counter elec-
trode consisted of platinum black connected through an electrical load
[160]. Their 1972 seminal paper in Nature [161] established the elec-
trochemical photolysis of water that mimicked natural photosynthesis
at a time when crude oil prices ballooned, and the likelihood of future
lack of crude oil was a serious concern (so-called oil crisis). Their study
[161] attracted much attention, not only from electrochemists but also
from photochemists because of two main reasons: (i) the potential for
water splitting photoelectrochemically to produce a solar fuel (H2), and
(ii) that electron transfer between photoexcited donors and acceptors
was possible. Several studies were rapidly undertaken worldwide in the
fields of photoelectrochemistry and photochemistry with the principal
focus of producing H2 from a reliable source: water – this was to lead to
the so-called Hydrogen Economy. Unfortunately, reaction efficiency
and the recognition that TiO2 can only absorb the 3 to 5% of UV light
that reaches the Earth’s surface from the solar spectrum have dampened
the attractive perspective of a H2 production technology based on TiO2
photocatalysis. Although various other semiconductors with smaller
bandgaps (e.g., CdS and CdSe) have been explored, their lower effi-
ciency and poor stability vis-à-vis TiO2 caused the enthusiasm in H2
research to fizzle out by the mid-1980s [25]. What message should we
then take away from this historical background? The message is rather
simple: Don’t give up, period! Researchers need to take up the challenge
and work on the technical restrictions that appear to limit significant
water splitting, as evidenced by the yields of solar H2 from thousands of
studies of the last three decades that have proven rather disappointing
[162].
Designs of suitable photocatalytic reactors that embody TiO2 as the
photocatalyst for wastewater treatments present significant challenges
because of the need to consider the reaction solution, the solid photo-
catalyst, the oxygen gas stream and the ultra-bandgap visible light.
Although a few reports have appeared recently, they have not demon-
strated that the novel reactor technology might prove useful in waste-
water treatments. Nonetheless, we hasten to note that water treatment
is positioned as the 6th technology in the United Nations' 17 Sustainable
Development Goals (SDGs) of its 2030 Agenda for Sustainable
Development [163].
In summary, at the present infancy stage of the 21st century, future
S. Horikoshi, N. Serpone Catalysis Today 340 (2020) 334–346

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