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TiO2 Photocatalysis:
A Historical Overview and Future Prospects
Kazuhito Hashimoto*,†, Hiroshi Irie†, and Akira Fujishima‡
*Research Center for Advanced Science and Technology, The University of Tokyo
4-6-1 Komaba, Meguro-ku, Tokyo 153-8904, Japan
†Department of Applied Chemistry, The University of Tokyo
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
‡Kanagawa Academy of Science and Technology
3-2-1 Sakado, Takatsu-ku, Kawasaki, Kanagawa 213-0012, Japan
Photocatalysis has recently become a Keywords: titanium dioxide, Honda-Fu- actively, but at least in Japan, there were
common word and various products us- jishima effect, photoelectrolysis, redox a series of reports by Mashio et al., from
ing photocatalytic functions have been reaction, hydrophilic conversion, envi- 1956, entitled “Autooxidation by TiO2 as
commercialized. Among many candidates ronmental application. a photocatalyst” [3]. They dispersed TiO2
for photocatalysts, TiO2 is almost the only powders into various organic solvents
material suitable for industrial use at 1. HISTORICAL BACKGROUND such as alcohols and hydrocarbons fol-
present and also probably in the future. BEFORE HONDA-FUJISHIMA lowed by the UV irradiation with an Hg
This is because TiO2 has the most efficient EFFECT lamp. They observed the autooxidation of
photoactivity, the highest stability and TiO2 powders have been commonly used solvents and the simultaneous formation
the lowest cost. More significantly, it has as white pigments from ancient times. of H2O2 under ambient conditions. It is
been used as a white pigment from ancient They are inexpensive, chemically stable interesting to note that they had already
times, and thus, its safety to humans and and harmless, and have no absorption in compared the photocatalytic activities of
the environment is guaranteed by history. the visible region. Therefore, they have a various TiO2 powders using twelve types
There are two types of photochemical re- white color. However, the chemical stabil- of commercial anatase and three types of
action proceeding on a TiO2 surface when ity of TiO2 holds only in the dark. Instead, rutile, and concluded that the anatase ac-
irradiated with ultraviolet light. One in- it is active under UV light irradiation, tivity of the autooxidation is much higher
cludes the photo-induced redox reactions inducing some chemical reactions. Such than that of rutile, suggesting a fairly high
of adsorbed substances, and the other is activity under sunlight was known from degree of progress of the research [4]. In
the photo-induced hydrophilic conversion the flaking of paints and the degradation those days, however, the photocatalytic
of TiO2 itself. The former type has been of fabrics incorporating TiO2 [1]. Scien- power of TiO2 might have attracted only
known since the early part of the 20th tific studies on such photoactivity of TiO2 partially limited scientists’ attention in the
century, but the latter was found only at have been reported since the early part of field of either catalysis or photochemistry,
the end of the century. The combination of the 20th century. For example, there was and the study of TiO2 photocatalysis had
these two functions has opened up various a report on the photobleaching of dyes by not developed widely in either academic
novel applications of TiO2, particularly TiO2 both in vacuo and in oxygen in 1938 or industrial society.
in the field of building materials. Here, [2]. It was reported that UV absorption
we review the progress of the scientific produces active oxygen species on the 2. WATER PHOTOLYSIS WITH
research on TiO2 photocatalysis as well TiO2 surface, causing the photobleaching TiO2 ELECTRODE IN 1970S
as its industrial applications, and describe of dyes. It was also known that TiO2 itselfIn the late 1960s, one of the present
future prospects of this field mainly based does not change through the photoreaction, authors (AF) began to investigate the
on the present authors’s work. although the “photocatalyst” terminology photoelectrolysis of water, using a single
was not used for TiO2 in the report, but crystal n-type TiO2 (rutile) semiconduc-
The permission for reprinting the pres-
ent article, as published previously in called a photosensitizer. tor electrode, because it has a suffciently
Japanese Journal of Applied Physics, positive valence band edge to oxidize
Vol. 44, No. 12, 2005, pp. 8269-8285 It is equivocal when and who started water to oxygen. It is also an extremely
was granted through one of the au-
thors, Professor Kazuhito Hashimoto utilizing first such a photochemical power stable material even in the presence of
and JJAP. of TiO 2 to induce chemical reactions aqueous electrolyte solutions, much more
Fig. 1: Schematic diagram of electrochemi- Fig. 2: Schematic representation of photoelectrochemical water electrolysis using
cal photocell. (1) n-type TiO2 electrode; (2) illuminated oxide semiconductor electrode. An open circuit (or small current), pH
platinum black counter electrode; (3) ionically 2, and illuminated conditions are shown for oxides with an ECB of – 0.65 V (SHE)
conducting separator; (4) gas buret; (5) load and an EVB of 2.35 V (SHE). With the open circuit, a small excess potential (0.15
resistance; and (6) voltmeter. V) is available for H2 evolution, assuming a reversible counter electrode.
Fig. 4: AFM images of monolayer of stearic acid on rutile (100) surface (1 mW/cm2).
substances, even though the TiO2 photo- photocatalytic anti-bacterial activity even to zero after installing the photocatalytic
catalyst is a very efficient one. under weak UV light obtained from indoor tiles in an operating room. In addition, the
lighting from fluorescent light bulbs. The bacterial count in air was also significantly
4.2. Photocatalytic Antibacterial Effect survival decay curves under irradiation in decreased. The antibacterial ceramic tile
of Copper- and/or Silver-Deposited Fig. 6 are not simple exponential curves. coated with photocatalytic TiO2 con-
TiO2 Film Initial illumination had a negligible ef- taining Cu and/or Ag started full-scale
A photocatalytic decomposition reaction fect on the survival rate, but after 2 h, a manufacturing by TOTO Ltd. in 1995, and
can be applicable to microorganisms. In marked decrease in survival was observed. its technology was exported to Western
fact, Escherichia coli (E. coli) cells can We speculate that this cell deactivation countries widely.
completely disappear on TiO2 after about proceeds as follows. The first step is that
one week under a UV irradiation of 1 the reactive species generated by the TiO2 5. PHOTO-INDUCED HYDRO-
mW/cm2. The cell deactivation can be photocatalyst attacks the outer membrane PHILICITY
achieved in a much shorter irradiation [Fig. 7b]. The second step is the effective 5.1. Water Wettability of TiO2 Surface
time, but still it takes nearly 1 h under uptake of the copper ions into the cyto- 5.1.1. What is a Photo-Induced High
outdoor UV light intensity [27]. plasmic membrane [Fig. 7c]. In this case, Hydrophilicity?
the TiO2 photocatalytic reaction assists the While investigating the novel concept
In contrast, the typical indoor UV light intrusion of the copper ions into the cell, of light-cleaning materials coated with
intensity is about several hundred nW/cm2, which is probably why the E. coli cells a TiO2 film photocatalyst under weak
which is almost about three orders of are effectively killed on a Cu/TiO2 film UV light in the 1990s, we have found
magnitude weaker than the outdoor one. even under very weak UV light [28]. It in 1995 by chance the marked change in
Therefore, the photocatalytic deactivation has been reported that the copper species the water wettability of the TiO2 surface
of microorganism requires a much longer photodeposited on the TiO2 film is a mix- before and after UV light irradiation.
time under indoor conditions than under ture of metallic copper (Cu0) and copper With the discovery of this phenomenon,
outdoor ones; thus, it cannot become a real ions (Cu+ and Cu2+). When this Cu/TiO2 the application range of TiO2 coating has
practical technology. However, the anti- film is irradiated, the copper ions can be been largely widen, as will be mentioned
bacterial function of a TiO2 photocatalyst reduced to metallic copper and metallic in detail later.
is markedly enhanced even with weak UV copper can be oxidized to copper ions
light, using a fluorescent lamp and the aid by photogenerated electrons and holes, The surface wettability is generally
of either silver or copper [28], which is respectively. Although the oxidation state evaluated by the water contact angle
harmless to the human body. Fig. 6 shows of copper might change under UV light (CA). The CA (θ) is defined as the angle
the changes in the survival of copper-resis- irradiation, copper ions (Cu2+) exist on the between the solid surface and the tangent
tant E. coli cells on a Cu-photodeposited Cu/TiO2 film [28]. The enhancement of the line of the liquid phase at the interface of
TiO2 (Cu/TiO2) film, indicating that E. antibacterial effect under weak UV light the solid-liquid-gas phases.
coli cells survived under dark conditions. was also observed on the Ag-deposited
However, when the Cu/TiO2 film is irradi- TiO2. This antibacterial technique is safe A TiO2 thin film exhibits an initial CA
ated with very weak UV light, the survival and effective. It was observed that the of several tens of degrees depending on
rate begins to decrease. This demonstrates number of bacteria on the walls decreases the surface conditions mainly surface
Fig. 6: Changes in survival rate of copper-re- Fig. 7: Schematic illustrations of bactericidal process for copper-resistant E.
sistant E. coli cells on Cu/TiO2 thin film. Error coli cells on Cu/TiO2 thin film under weak UV light irradiation.
bars: standard deviations of three replicate
experiments.
Fig. 8: Changes in CA of TiO2 surface (a) under UV irradiation and (b) in the dark.
roughness. When this surface is exposed in general, and thus, we considered that removed, reproducing the initial surface.
to UV light, water starts to exhibit a a clean TiO2 surface could be essentially For the TiO2 surface, however, the CA
decreasing CA, that is, it tends to spread hydrophilic. In fact, several reports have decreased to 0°, which was lower than
out flat instead of beading up [29, 30]. recently been published, in which the the initial value, showing that the highly
Finally, the CA reaches almost 0°, as photo-produced highly hydrophilic state hydrophilic surface of TiO2 is not simply
shown in Fig. 8a. At this stage, the surface of TiO2 is explained using a simple pho- attributed to the effect of the photocata-
becomes completely non-water-repellant tocatalytic decomposition mechanism lytic oxidation power.
and is termed “highly hydrophilic”. The [32-34]. However, it is important to note
surface retains a CA of a few degrees for that a completely clean surface cannot be (ii) Relationship between amount of
a day or two under the ambient condition obtained by the photocatalytic reaction stains and contact angle
without being exposed to UV light. Then, because the surface is easily contami- Figure 10 shows the representative the C
the CA slowly increases, and the surface nated by airborne stains under the ambi- 1s spectra of the TiO2 surface detected by
becomes the initial less hydrophilic state ent condition. We have obtained many X-ray photoemission spectroscopy (XPS)
again, as shown in Fig. 8b. At this point, experimental results showing that this before and after UV light irradiations (60
the high hydrophilicity can be recovered highly hydrophilic state is not a simple min and 12 h). Before UV light irradiation,
simply by exposing the surface again to clean surface but is a structurally changedthe carbon peak derived from the stains
UV light. In short, this type of TiO2-coated metastable one. Some of these results will was detected and the CA on such surface
material is the only known practical highly be described below. was found to be 56°. After 60 min UV
hydrophilic one that shows stable and semi light irradiation, the CA was confirmed to
permanent properties. (i) Comparison of hydrophilic proper- be 0° when the distinct carbon peak was
ties of TiO2 and SrTiO3 surfaces detected, although the amount of stains
How can we explain this phenomenon? Figure 9 shows the changes in CA under decreased compared to that before UV
We have vigorously attempted to find UV light irradiation after applying oleic
the answer by analyzing it from various acid to the surfaces of TiO2 and SrTiO3
points of view [29-31, 35-37, 39, 44, 45, [35]. Just after applying oleic acid, both
48-50, 53, 54]. TiO2 and SrTiO3 surfaces were converted
to the hydrophobic state with CAs of
5.1.2. Characteristics of Photo-Induced around 70° due to the hydrophobic prop-
Highly Hydrophilic State erty of the oleic acid adsorbed on the
First, we considered that this highly hy- surfaces. When UV light was irradiated
drophilic conversion originates from the on the SrTiO3 surface, the CA decreased
clean surface produced by the decompo- to 20°, which was almost the same as that
sition of staining compounds adsorbed observed before applying oleic acid. As
on the surface through the conventional a result of conventional photocatalytic
Fig. 10: Change in XPS spectrum of TiO2 in C
photocatalytic oxidation. This is because oxidation processes, surface-adsorbed 1s peak region before and after UV illumination
metal oxides have large surface energies oleic acid was decomposed and almost with an intensity of 2.0 mW/cm2.
Fig. 11: Change in XPS spectrum of TiO2 in C Fig. 12: Changes in water contact angle for Fig. 13: Ambient temperature dependence
1s peak region before and after rinsing in warm TiO2 film subjected to alternate ultrasonic on less hydrophilic conversion for TiO2 film
4M NaOH solution (50 ℃). treatment in pure water (•) and UV light ir- maintained in the dark.
radiation (∆).
γSL = γS + γL – Φ(γS / γL)1/2. (10) Fig. 15: FFM images of rutile TiO2(110) single crystal surface before
(left) and after (right) UV light irradiation.
Here, Φ is a constant parameter ranging
from 0.6 to 1.1, depending on the solid.
In addition, γL is the water surface free in the dark. In this study, we concluded
energy, which has a constant value of 74 that the nanoscale separation between
mJ/m2. Therefore, by combining Eqs. (9) the hydrophilic and hydrophobic phases
and (10), the CA can be simply expressed accounts for the highly hydrophilic char-
as acteristic on the TiO2 surface.
cos θ = cγS1/2 – 1 (c: constant). (11) (ii) Surface hardness change after UV
light irradiation
This final equation shows that the CA Hardness changes before and after irradia-
Fig. 16: Relationship between changes in water
decreases simply with increasing γS. tion with UV light on the surface of the contact angle and hardness at surface of TiO2
Therefore, it can be considered that the rutile TiO2(110) single crystal were also film (within 50 nm) and inside (300 nm).
highly hydrophilic state with a CA of 0° observed. Fig. 16 shows the repetition of
is achieved by the generation of some UV light on and off dependence of surface
states with large surface energies when hardness (within 50 nm from the surface), was fitted with two bands, which are as-
irradiated with UV light. As previously inner hardness (300 nm from the surface), sociated with the dissociatively adsorbed
mentioned, the highly hydrophilic state and CAs [44]. When irradiated with UV water on the TiO2 surface as well as the
generated by UV light gradually returns light, CAs decreased to 0°, accompanied physically adsorbed molecular water on
to the initial less hydrophilic state in the by an increase in surface hardness. In the dissociatively adsorbed OH groups.
dark. Moreover, we showed that some contrast, the inner hardness remained The shoulder gradually decreased in size
external stimuli and a higher ambient constant. These findings suggested that the during storage in the dark. Therefore,
temperature increase the rate of the back highly hydrophilic surface is subjected to these photogenerated surface OH groups
reaction. All these suggest that the photo- compressive stress caused by the expan- were considered to be thermodynamically
produced state with a large surface energy sion of the surface volume. metastable.
is metastable.
5.1.5. What is the Metastable State? Fourier transformation infrared (FTIR)
5.1.4. Structural Changes on TiO2 Sur- We have shown that the surface structure spectroscopy provides another method of
faces Irradiated with UV Light of TiO2 changes after UV irradiation, investigating the relationship between hy-
(i) Domain formation after UV light forming a metastable state. Then, what drophilicity and the amount of OH groups
irradiation is this state? Thus far, we have not yet [45]. TiO2 shows IR bands positioned at
To gain information about surface changes obtained a definite answer. However, 3695 cm–1, assigned to the stretching of
at the microscopic level, friction force several experimental data indicate that OH groups chemisorbed on the surface,
microscopy (FEM) was utilized. A rutile the metastable state could be caused by an 3,300 cm–1, assigned to hydroxyls for
TiO2(110) single crystal was used. Be- increase in the number of hydroxyl (OH) both dissociated water and molecularly
fore UV light irradiation, no difference groups on the TiO2 surface [31]. adsorbed water, and 1,623 cm–1, pertaining
in contrast was observed, indicating mi- to H-O-H bending for molecular water.
croscopically homogeneous wettability. This increase could be detected by X- This observation denotes the coexistence
After irradiation, the hydrophilic (bright) ray photoemission spectroscopy (XPS) of dissociated water and molecular water
and hydrophobic (dark) areas of 30-80 nm [36]. The O 1s spectrum for the highly on the TiO2 surface. Storage in the dark
were clearly observed [Fig. 15] [29]. A hydrophilic TiO2 surface exhibited a broad for one week resulted in the decrease of
gradual reversion to a smaller contrast was shoulder to the higher binding energy all the bands, correlated with both disso-
observed during the storage of the crystal side of the main O 1s peak. The shoulder ciated and molecular water desorptions.
Thus, the TiO2-coated materials used however, surprising that a research study observed by comparing their surface atom
outdoors where they are exposed to on TiO2 photocatalysis is still carried alignments. In fact, the (100) and (110)
rainfall show a very effective self-clean- out for developing both its science and faces of a rutile single crystal exhibited
ing function, i.e., stains are decomposed technology after the 21st century. In the a higher hydrophilicity than the (001)
partially by the conventional photo- following, some of the recent development face, as the former faces have two-fold
catalytic reaction as well as washed by will be introduced. oxygens, which are higher in position
rainwater. Such materials, which we call and energetically more reactive than
“photocatalytic building materials”, e.g., 6.1. Design of Nanostructure of TiO2 their surrounding atoms and are so-called
exterior tiles, glass, aluminum walls, and Surface for Highly Sensitive Hy- the “bridging site oxygens”, whereas the
PVC fabric [Fig. 18], have already begun drophilicity latter has three-fold oxygens, which are
to be commercialized. For example, the When utilizing the photooxidative decom- lower in position and energetically more
photocatalytic exterior glass with an area position properties,TiO2 has already been inactive [50]. Therefore, the (100) and
of 20,000 m2 was installed in the terminal applied to indoor use with the aid of either (110) faces are favorable for increasing
building of Chubu International Airport copper or silver for anti-bacterial purpose, the number of OH groups. This finding
opened in 2005. as mentioned in Sec. 4.2. However, as for could serve as a guideline for selecting
neither the decomposition of VOC nor the appropriate faces of the TiO2 crystal
5.2.2. Anti-Fogging Function the utilization of hydrophilic properties, for surface exposure.
Another function blessed with the photo- TiO2 has yet to be applied to indoor use.
induced hydrophilicity is the anti-fogging For example, the TiO2 surface does not To obtain the appropriate faces, the
function. The fogging of the surfaces of undergo the highly hydrophilic conver- photoetching technique was applied to
mirrors and glasses occurs when steam sion when the UV light has an intensity of the (001) face of a rutile single crystal. As
cools down on these surfaces to form 1 μW/cm2, available in an ordinary living shown in the inset of Fig. 20, a large num-
many water droplets. On a highly hydro- environment. Thus, a highly sensitive ber of rectangular porous holes shaped like
philic surface, no water drops are formed. TiO2 that undergoes highly hydrophilic wells, with a size of 50-100 nm, emerged
Instead, a uniform thin film of water is conversion has been required. We have with a fairly regular arrangement. Accord-
formed on the surface. This uniform water intensively investigated this on the ing to Sugiura et al. [51] and Nakato et al.
film prevents the fogging. Once the surface basis of the mechanism for the highly [52], rectangular holes proceed toward the
turns into the highly hydrophilic state, it hydrophilic conversion, as described in <001> direction (c-axis direction), and
remains unchanged for several days or Sec. 5.1.6. the (100) face or equivalents are exposed
one week. Thus, we expect that various selectively on the walls. This rectangular
glass products, mirrors and eyeglasses, for As the reconstruction of surface OH porous surface increased the sensitivity of
example, can be imparted with antifogging groups is responsible for the hydrophilic the photoinduced hydrophilic reaction and
functions using this technology, with sim- conversion, different types of hydrophilic achieved a high hydrophilicity under UV
ple processing and at a low cost. In fact, conversion behavior among the various light irradiation of 1 μW/cm2, whereas the
Japanese-made cars are being equipped single crystal faces are expected to be surface without a photoetching treatment
with antifogging highly hydrophilic side-
view mirrors, as shown in Fig. 19.
6. PHOTOCATALYSIS IN 21ST
CENTURY
As was described above, TiO2 photocataly- UV irradiation time / h
sis has become a real practical technology
Fig. 20: Changes in water contact angles on rutile (001) surface with and without
after the middle of the 1990s, particularly photoetching treatments. The inset shows a SEM image of rectangular holes
in the field of building materials. It is, emerged by photoetching treatment on a (001) surface.
did not, as shown in Fig. 20 [53]. Be- influencing the highly sensitive photoin- lysts sensitive to visible light have already
cause the surface roughness enhances the duced hydrophilicity of a film. been reported in 1986 [65, 66].
hydrophilicity, the high sensitization for
hydrophilic conversion by the photoetch- The other highly sensitive system we Yellow and transparent nitrogen-doped
ing treatment was caused by the exposure produced is the heterogeneous TiO2/WO3 TiO2 thin films can be fabricated by sput-
of faces with bridging site oxygens and the one [55]. As photogenerated holes are tering a Ti or TiO2 target in a gas flow
increase in surface roughness. This high effectively accumulated on TiO2 without that contains N2O or N2 [61]. The N 1s
sensitization was also observed on the ru- recombining with electrons, and as WO3 XPS peak at 396 eV indicates that the
tile polycrystal by the photoetching treat- could absorb visible light contained in dopant nitrogen is located at an oxygen
ment, which suggested that this technique the fluorescent light up to a wavelength site [60, 61].
is applicable to anatase thin films. of around 440 nm due to its bandgap of
2.8 eV, the reaction responsible for the Figure 22a shows the hydrophilic con-
The introduction of residual tensile increased hydrophilicity was greatly en- version behaviors of the nitrogen-doped
stress to anatase thin films is also a can- hanced, and the high hydrophilicity was TiO 2 thin film irradiated with visible
didate method to increase the sensitivity. achieved on this system irradiated with light (400-530 nm). The nitrogen-doped
As the hydrophilic conversion is caused extremely weak UV light with an intensity TiO2 thin film underwent hydrophilic
by the increase in the number of surface of 1 μW/cm2 from a fluorescent lamp. As conversion; however, irradiating only
OH groups, the Ti–O bond length should such, the high sensitization of TiO2 under with visible light did not achieve the high
be larger in the highly hydrophilic surface weak UV light is expected to increase the hydrophilicity. Irradiating with UV light
than in the less hydrophilic surface. In fact, application areas to indoor conditions. (300-400 nm), the nitrogen-doped TiO2
as previously mentioned, the surface vol- thin film underwent highly hydrophilic
ume increased after UV light irradiation. 6.2. Visible-Light-Sensitive TiO2 conversion, as shown in Fig. 22b. The
Therefore, it can be expected that the TiO2 The current area of interest in this field photocatalytic activities (both oxidative
surface in the presence of tensile stress is has been the modification of TiO2 sensi- decomposition and hydrophilic conversion
favorable for hydrophilic conversion. The tive to visible light. One approach was to activities) generated by visible light-in-
residual tensile stress in the anatase thin substitute Cr, Fe or Ni for a Ti site [56, duced holes are inferior to those generated
film fabricated by the sputtering technique 57]. Another approach was to form Ti3+ by UV light-induced ones [67].
greatly enhanced the hydrophilic behavior, sites by introducing an oxygen vacancy
compared to a thin film without residual in TiO2 [58]. However, these approaches Before discussing the reason for this,
stress, as shown in Fig. 21 [54]. In con- were not widely accepted due to the lack of let us discuss the origin of visible light
trast, the compressive stress degraded the reproducibility and chemical stability. sensitivity. When the N atoms are substi-
hydrophilic behavior. The photocatalytic tuted as N3– ions at O2– sites, the impurity
oxidation activities were identical regard- In 2001, several groups reported visible- (accepter) level, composed of 2p orbitals
less of the residual stresses. The surface light-sensitive TiO2-based powders and of N (N 2p), is formed above the valence
morphologies of the four films were thin films [59-61]. Subsequently, nitrogen- band. Electron vacancies exist at the ac-
controlled to be the same, and therefore, doped TiO2 has attracted considerable at- ceptor level. Therefore, nitrogen-doped
the residual stress is an important factor tention [62-64]. In fact, similar photocata- TiO2 should be a p-type semiconductor
Fig. 21: Changes in water contact angles on Fig. 22: Changes in water contact angles on TiO2 and nitrogen-doped TiO2 thin
TiO2 films when irradiated with UV light, with- films irradiated with (a) vis and (b) UV lights.
out residual stress and with residual tensile/
compressive stresses.
Fig. 24: SEM images for polycrystalline TiO2 surfaces (a) before and Fig. 25: Back reactions on etched and non-
(b) after etching treatments. etched polycrystalline TiO2 surfaces as a func-
tion of storage time in the dark.
of solid as described in Eqs. (9) and (11). phobic TiO2 requires surface roughness light and dark storage [75]. At present, the
As for a non-flat surface, however, surface where air can intrude between the water hydrophobic conversion takes much time,
roughness affects the wettability. Wenzel droplet and the TiO2 surface. and must be further enhanced.
modified Young’s equation by considering
the surface roughness to obtain [73] To achieve such a rough surface, we ap- In addition, the surface with a CA above
plied a photoetching technique to a rutile 150° is called the super-hydrophobic
cos θ' = r cos θ, (12) pellet. Before the etching treatment, grains surface, and such a surface is attracting
and grain boundaries were observed, considerable attention at present [76-84],
where θ' is the apparent contact angle and which is typical of a polycrystalline pel- because the limited contact area between
r is the surface roughness ratio between let, as shown in Fig. 24a. After etching, the solid surface and the water could
the actual surface area and the apparent the surface structure changed and was change chemical reactions and/or bond
surface area. This equation indicates that accompanied by an increase in surface formation through water, introducing
the surface roughness enhances the hydro- roughness. Random directions of dig- novel properties on the surface. Therefore,
philicity of hydrophilic surfaces (θ < 90°) ging “ditches” as shown in Fig. 24b were if one succeeds in the preparation of the
and also enhances the hydrophobicity of plausible, considering the polycrystalline TiO2 surface with a CA of more than 150°,
hydrophobic surfaces (θ > 90°) since the pellet. The pellets with the etched and non- it indicates that the surface property of
r value is always larger than 1. Because etched surfaces were stored in the dark at TiO2 can be markedly controlled.
the CA of a flat TiO2 surface is always less room temperature in a clean vessel filled
than 90°, the hydrophobic TiO2 surface with synthetic air. Maintaining the samples 6.4. New Environmental Applications
cannot be obtained by considering only in the dark for 15 days caused the CA to TiO2-coated materials practically used
the Wenzel equation. To realize the hy- reach approximately 120° on the etched thus far have been provided with self-
drophobic TiO2 surface, we must introduce surface, whereas the CA was around 80° cleaning, anti-bacterial and/or anti-fog-
a different concept to describe the CA on the nonetched surface, indicating that ging functions based on the photo-induced
(θ') on a rough surface. Cassie proposed we could obtain the hydrophobic TiO2 sur- decomposition reaction and photo-induced
an equation for a surface composed of face, on which Cassie’s mode dominates, hydrophilicity. It is important to note that
solid and gas [74]. When a unit area of by the photoetching process [Fig. 25]. these functions are obtained without using
the surface has an area friction, f, where any chemicals, but with only sunlight and
a water droplet contacts the solid surface The UV irradiation of this hydrophobic rainwater. Therefore, these TiO2-coated
with a CA of θ, the θ' on the surface can TiO2 markedly changed the surface wet- materials can be classified as being envi-
be expressed as follows, called Cassie’s tability, i.e., the CA decreased to 0°. In ad- ronmentally friendly. In this section, we
equation, in which the CA for air is as- dition, storing the samples in the dark for a will show further applications of TiO2
sumed to be 180°: long time caused the CA on the etched sur- photocatalysis, which can actively contrib-
face to further increase to approximately ute to environmental preservation and/or
cos θ' = f cos θ + (1 – f) cos 180° 140°, whereas the CA on the nonetched improvement technologies.
= f cos θ + f – 1. (13) surface remained constant at around 80°.
We can thus control the surface wettability 6.4.1. Photocatalytic Decomposition of
Considering Eq. (13), the θ' increases from highly hydrophilic to hydrophobic Pollutants
with decreasing f value. Thus, the hydro- repeatedly by alternating between UV Environment pollution, including water,
air and soil is becoming an increasingly We developed a glass wool mat with cally illustrated in Fig. 26. The wastewater
serious problem today. There have been a large surface area deposited with very from the hydroponic tomato culture with
many reports aiming at applying TiO2 photoactive TiO2 nanoparticles; we were a planting area of about 80 m2 was intro-
photocatalysis to pollution clean-up since able to show that the wastewater solution duced into a shallow vessel with a bottom
the 1970s. However, the purification of the is easily purified using the photocatalytic area of 4 m2 and a depth of 10 cm in which
three-dimensional spaces by photocataly- mat under only solar light. The treatment porous ceramic plates coated with TiO2
sis is much more difficult than that of the method is very simple, i.e., the wastewater photocatalyst nanoparticles were placed.
two-dimensional surface of building mate- is poured onto mats that are spread over a The organic contaminants in the wastewa-
rials due to the following two reasons. One wide area on the ground. The agricultural ter were easily decomposed under solar
is that photocatalytic reactions are surface chemicals were completely decomposed light, but the nutrient compounds contain-
reactions and thus the reactants must be under sunlight in a few days. It is surpris- ing nitrogen, phosphorous and potassium
captured by the photocatalyst surface. The ing that the initial total organic carbon were not, because these components ex-
other is that the total amount of reactant (TOC) values of several hundred to one isted in their most oxidized forms, NO3–,
is, in general, higher in three-dimensional thousand ppm decreased to nearly zero PO43– and K+, in the nutrient solution.
spaces than on a two-dimensional surface, in one week. This could be one of the Therefore, this system is also expected
indicating that much more light energy is simplest and easiest environmental tech- to serve as a nutrient-saving technology.
necessary for the purification of the three- nologies.
dimensional space. Therefore, practical (iii) Treatment of VOC-polluted soil
technologies have not been obtained in (ii) Water treatment of hydroponic Volatile chlorinated organic compounds
this field. However, we have recently culture system (VOCs), such as trichloroethylene and
succeeded in the construction of practical Most of the hydroponic culture installa- tetrachloroethylene, have been widely
purification systems for wastewater from tions are adopting run-to-waste systems used as solvents for the dry cleaning of
agriculture and soil polluted by volatile or- (as opposed to recirculating). The nutri- clothes and washing of semiconductors.
ganic compounds (VOCs). These systems ent solution contains highly concentrated They had been indiscriminately disposed
are based on TiO2 photocatalysts and use nitrogen and phosphorus compounds, and by the middle of the 1980s, causing soil
only solar light. thus, the wastewater causes soil pollution. and groundwater pollution. These types of
From the viewpoint of environmental pollution are serious environmental prob-
Important keys for these successes are problems, the recycling of nutrient so- lems, because the carcinogenic and toxic
(1) the utilization of nanosized TiO2 pho- lutions is desirable. However, organic chemicals had been widely disposed. The
tocatalyst powders dispersed on substrates contaminants accumulate in the solution, most common method of treating the pol-
with extremely large surface areas, and (2) inhibiting plant growth. luted soil is either the simple replacement
spreading them on the ground widely to with clean soil or the heating of the soil to
collect sunlight. Because the concentra- We succeeded in constructing a recy- volatilize the VOCs into air. It is obvious
tions of environmental pollutants are low cling system in a tomato hydroponic cul- that these methods do not truly purify the
in general, the UV light contained in sun- ture system using the TiO2 photocatalyst environment.
light is sufficiently strong to decompose and solar light. The system is schemati-
them by TiO2 photocatalysis, if we can
collect the light from a broad area.
7. CONCLUSIONS
In this paper, an overview of the devel-
opment of TiO2 photocatalysis and its
Fig. 28: Energy-saving system using solar light and stored rainwater. future prospects from both scientific and
technological viewpoints are given. It tionality of Molecular Systems” in Chem. B 101, 11000 (1997).
is interesting to note that this field has Photoelectrochemical Conversion, [23] P. Sawunyama, A. Fujishima, and
experienced major developments every ed. K. Honda (Springer, Tokyo, K. Hashimoto, Langmuir 15, 3551
ten years for the last thirty years, namely, 1999), Vol. 2, p. 196. (1999).
water photoelectrolysis (Honda-Fujishima [10] N. Sato, Electrochemistry at Metal [24] T. Watanabe, K. Hashimoto, and
effect) in the early 1970s, photocatalytic and Semiconductor Electrodes (Else- A. Fujishima, Proc. 1st Int. Conf.
H2 production in the 1980s, and the pho- vier, Amsterdam, 1998). TiO2 Photocatalyst, ed. H. Al-Ekabi
tocatalysis and hydrophilicity of TiO 2 [11] L. M. Peter, “Applications of Kinetic (1992).
films in the 1990s. Based on the basic re- Modeling” in Photoelectrochemical [25] A. Heller, Acc. Chem. Res. 28, 503
search results, real industrial applications Kinetics at Semiconductor Elec- (1995).
have been achieved since the end of the trodes, eds. R. G. Compton and G. [26] H. Honda, A. Ishizaki, R. Soma, K.
1990s. In addition, this field is still being Hancock (Elsevier, Amsterdam, Hashimoto, and A. Fujishima, J. Il-
developed further in the 21st century. We 1999), Vol. 37, p. 223. lum. Eng. Soc. 27(1), 42 (1998).
believe that TiO2 photocatalysis is one of [12] M. K. Nazeeruddin, A. Kay, I. Rodi- [27] K. Sunada, Y. Kikuchi, K. Hashi-
the best examples how, on the time scale cio, R. Humphry-Baker, E. Mueller, moto, and A. Fujishima, Environ. Sci.
of tens of years, basic scientific knowledge P. Liska, N. Vlachopoulos, and M. Technol. 32, 726 (1998).
can be developed into a technological field Gräzel, J. Am. Chem. Soc. 115, 6382 [28] K. Sunada, T. Watanabe, and K.
and can produce a new industry. (1993). Hashimoto, Environ. Sci. Technol.
[13] M. K. Nazeeruddin, P. Pechy, and M. 37, 4785 (2003).
ACKNOWLEDGEMENT Gräzel, Chem. Commun. 18, 1705 [29] R. Wang, K. Hashimoto, A. Fu-
The authors gratefully thank many col- (1997). jishima, M. Chikuni, E. Kojima, A.
laborators in both academia and industry [14] This field remains active, with novel Kitamura, M. Shimohigoshi, and T.
who have been involved in the present layered metal oxides being the fa- Watanabe, Nature 388, 431 (1997).
research. We also thank Dr. D. A. Tryk for vored materials. For example, a very [30] R. Wang, K. Hashimoto, A. Fu-
carefully reading the manuscript. efficient production of H2 and O2 us- jishima, M. Chikuni, E. Kojima, A.
ing deep UV light of around 290 nm Kitamura, M. Shimohigoshi, and
REFERENCES has been reported. T. Watanabe, Adv. Mater. 10, 135
[1] E. Keidel, Farben-Zeitung 34, 1242 [15] T. Kawai and T. Sakata. Nature 286, (1998).
(1929). 474 (1980). [31] N. Sakai, A. Fujishima, T. Watanabe,
[2] C. F. Doodeve and J. A. Kitch- [16] L. Kavan, M. Gräzel, S. E. Gilbert, and K. Hashimoto, J. Phys. Chem. B
ener, Trans. Faraday Soc. 34, 902 C. Klemenz, and H. J. Scheel, J. Am. 107, 1028 (2003).
(1938). Chem. Soc. 118, 6716 (1996). [32] J. M. White, J. Szanyi, and M. A.
[3] For example, S. Kato and F. Mashio, [17] S. N. Frank and A. J. Bard, J. Am. Henderson, J. Phys. Chem. B 107,
Abtr. Book Annu. Meet. Chemical Chem. Soc. 99, 303 (1977). 9029 (2003).
Society of Japan (1956), p. 223. [18] Many reviews have been published. [33] C. Wang, H. Groenzin, and M. J.
[4] S. Kat and F. Masuo, Kogyo Kagaku For example, M. A. Fox, and M. T. Schltz, Langmuir 19, 7330 (2003).
Zasshi 67, 1136 (1964) [in Japa- Dulay, Chem. Rev. 93, 341 (1993); [34] T. Zubkov, D. Stahl, T. L. Thompson,
nese]. M. R. Hoffman, S. T. Martin, W. D. Panayotov, O. Diwald, and J. T.
[5] A. Fujishima, K. Honda, and S. Ki- Choi, and D. W. Bahnemann, Chem. Yates, Jr., J. Phys. Chem. B 109,
kuchi, Kogyo Kagaku Zasshi 72, 108 Rev. 95, 69 (1995). 15454 (2005).
(1969) [in Japanese]. [19] R. W. Matthews, J. Phys. Chem. 91, [35] M. Miyauchi, A. Nakajima, A. Fu-
[6] A. Fujishima and K. Honda, Nature 3328 (1987). jishima, K. Hashimoto, and T. Wata-
238, 37 (1972). [20] T. Watanabe, K. Hashimoto, and A. nabe, Chem. Mater. 12, 3 (2000).
[7] W. Jaegermann, “Modern Aspects Fujishima, in Photocatalytic Purifi- [36] R. D. Sun, A. Nakajima, A. Fujishim,
of Electrochemistry” in The Semi- cation and Treatment of Water and T. Watanabe, and K. Hashimoto, J.
conductor/Electrolyte Interface: A Air, eds. D. F. Ollis and H. Al-Ekabi Phys. Chem. B 105, 1984 (2001).
Surface Science Approach, eds. R. (Elsevier, Amsterdam, 1993). [37] N. Sakai, R. Wang, A. Fujishima,
E. White, B. E. Conway, and J. O’M. [21] A. Fujishima, K. Hashimoto, and T. T. Watanabe, and K. Hashimoto,
Bochris (Plenum Press, New York, Watanabe, TiO2 Photocatalysis: Fun- Langmuir 14, 5918 (1998).
1996), Vol. 30, p. 1. damentals and Applications (BKC, [38] M. Kamei and T. Mitsuhashi, Surf.
[8] A. J. Nozik and R. Memming, J. Phys. Tokyo, 1999). Sci. 463, L609 (2000).
Chem. 100, 13061 (1996). [22] P. Sawunyama, L. Jiang, A. Fu- [39] H. Irie, M. S. Utami, T. Shibata, and
[9] A. Fujishima and D. A. Tryk, “Func- jishima, and K. Hashimoto, J. Phys. K. Hashimoto, submitted to Chem.