Professional Documents
Culture Documents
04 Jjap-Irp PDF
04 Jjap-Irp PDF
TiO2 Photocatalysis:
A Historical Overview and Future Prospects
Kazuhito Hashimoto1,2, Hiroshi Irie2 and Akira Fujishima3
Photocatalysis has recently become a 1. Historical Background be- compared the photocatalytic activities of
common word and various products using fore Honda–Fujishima Effect various TiO2 powders using twelve types of
photocatalytic functions have been commer- commercial anatase and three types of rutile,
cialized. Among many candidates for photo- TiO2 powders have been commonly used and concluded that the anatase activity of
catalysts, TiO 2 is almost the only material as white pigments from ancient times. They the autooxidation is much higher than that of
suitable for industrial use at present and also are inexpensive, chemically stable and harm- rutile, suggesting a fairly high degree of prog-
probably in the future. This is because TiO2 has less, and have no absorption in the visible ress of the research.4) In those days, however,
the most efficient photoactivity, the highest region. Therefore, they have a white color. the photocatalytic power of TiO2 might have
stability and the lowest cost. More signifi- However, the chemical stability of TiO2 holds attracted only partially limited scientists’ atten-
cantly, it has been used as a white pigment only in the dark. Instead, it is active under UV tion in the field of either catalysis or photo-
from ancient times, and thus, its safety to light irradiation, inducing some chemical reac- chemistry, and the study of TiO2 photocatalysis
humans and the environment is guaranteed tions. Such activity under sunlight was known had not developed widely in either academic
by history. There are two types of photo- from the flaking of paints and the degrada- or industrial society.
chemical reaction proceeding on a TiO 2 tion of fabrics incorporating TiO2.1) Scientific
surface when irradiated with ultraviolet light. studies on such photoactivity of TiO2 have 2. Water Photolysis with TiO2
One includes the photo-induced redox reac- been reported since the early part of the 20th Electrode in 1970s
tions of adsorbed substances, and the other is century. For example, there was a report on
the photo-induced hydrophilic conversion of the photobleaching of dyes by TiO2 both in In the late 1960s, one of the present
TiO2 itself. The former type has been known vacuo and in oxygen in 1938.2) It was reported authors (AF) began to investigate the photo-
since the early part of the 20th century, but that UV absorption produces active oxygen electrolysis of water, using a single crystal
the latter was found only at the end of the species on the TiO 2 surface, causing the n-type TiO2 (rutile) semiconductor electrode,
century. The combination of these two func- photobleaching of dyes. It was also known because it has a sufficiently positive valence
tions has opened up various novel applications that TiO2 itself does not change through the band edge to oxidize water to oxygen. It is
of TiO2, particularly in the field of building photoreaction, although the ``photocatalyst’’ also an extremely stable material even in the
materials. Here, we review the progress of the terminology was not used for TiO 2 in the presence of aqueous electrolyte solutions,
scientific research on TiO2 photocatalysis as report, but called a photosensitizer. much more so than other types of semicon-
well as its industrial applications, and describe ductor that have been tried. The possibility of
future prospects of this field mainly based on It is equivocal when and who started solar photoelectrolysis was demonstrated for
the present authors’ work. utilizing first such a photochemical power the first time in 1969 with the system shown
of TiO2 to induce chemical reactions actively, in Fig. 1, which was exposed to near-UV
KEYWORDS:titanium dioxide, Honda– but at least in Japan, there were a series of light, and was connected to a platinum black
Fujishima effect, photoelectrol- reports by Mashio et al., from 1956, entitled counter electrode through an electrical load.5)
ysis, redox reaction, hydrophilic ``Autooxidation by TiO2 as a photocatalyst’’.3) Then, this electrochemical photolysis of water
conversion, environmental They dispersed TiO 2 powders into various was reported in Nature by analogy with a
application organic solvents such as alcohols and hydro- natural photosynthesis in 1972. 6) In those
carbons followed by the UV irradiation with days, crude oil prices ballooned suddenly,
an Hg lamp. They observed the autooxida- and the future lack of crude oil was a serious
tion of solvents and the simultaneous forma- concern. Thus, this became known as the time
tion of H 2O 2 under ambient conditions. It of ``oil crisis’’. Therefore, this report attracted
is interesting to note that they had already the attention not only of electrochemists but
1 Research Center for Advanced Science and Technology, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8904, Japan
2 Department of Applied Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
3 Kanagawa Academy of Science and Technology, 3-2-1 Sakado, Takatsu-ku, Kawasaki, Kanagawa 213-0012, Japan
(Received August 11, 2005; accepted September 26, 2005; published December 8, 2005) ©2005 The Japan Society of Applied Physics
���� ����������������
����������������
����
� �������������������
� � � ������������������������������
��� �������������
� ����������������� ���������
��� ������
� ���
��� ���������
�������������������
�������������
���
���
�
���
� � � ��� �� �� �� �� �
�������������
Fig.1. Schematic diagram of electrochemical photocell. (1) n-type Fig.2. Schematic representation of photoelectrochemical water electrolysis using illuminated oxide semiconductor
TiO2 electrode; (2) platinum black counter electrode; (3) ionically electrode. An open circuit (or small current), pH 2, and illuminated conditions are shown for oxides with an ECB of
conducting separator; (4) gas buret; (5) load resistance; and (6) volt- -0.65V (SHE) and an EVB of 2.35V (SHE). With the open circuit, a small excess potential (0.15V) is available for H2 evolu-
meter. tion, assuming a reversible counter electrode.
technology. We came to the conclusion that such as water or air. In this case, the absolute the daytime. This is low from the viewpoint of
it is fundamentally inadequate to utilize TiO2 amounts of the substances decrease, and thus, energy density, but corresponds to about 1015
photocatalysis for either energy acquisition the rather weak UV light existing in an ordi- of photons/cm2 per second, which is a huge
or the treatment of huge amounts of water nary environment could be a sufficient light amount compared to the number of mole-
and/or air, because light energy density is source for maintaining the TiO2 surface clean. cules adsorbed on the surface. Let us consider,
primarily low, and in addition, TiO2 can utilize We thus obtained the novel concept of light- for example, a highly packed organic mole-
only the small amount of UV light contained in cleaning materials, which would be coated cule monolayer. Figure 4 shows the atomic
solar light. Based on such understanding, we with TiO2 film photocatalysts.20,21) force micrograph (AFM) images of mono-
conceived the idea of applying photocatalysis layer stearic acid prepared on a TiO2 rutile
targeting only the substances adsorbed origi- 4.1 Photocatalytic cleaning effect (110) single crystal by the Langmuir–Blodgett
nally on surfaces. In other words, we could of TiO2-coated materials method. 22,23) The thickness of the organic
take the substances existing on two-dimen- substance was about 2nm, and the number of
sional surfaces as the object of decomposition There exists typically several hundred stearic molecules was roughly estimated to be
instead of those in three-dimensional spaces µW/cm2 of UV light even in outdoor shade in 1016–1017/cm2. When this was exposed to UV
Fig.4. AFM images of monolayer of stearic acid on rutile (100) surface (1mW/cm2).
light of about 2.5mW/cm2, surface morpho- in the original purpose of the lighting, but is completely disappear on TiO2 after about one
logical changes were clearly observed, i.e., sufficient to keep the surface clean when the week under a UV irradiation of 1mW/cm2. The
the inhomogeneous pitting of the film was cover glass is coated with the TiO2 photocata- cell deactivation can be achieved in a much
very distinct. Further irradiation merged the lyst (Fig. 5).26) This light cleaning based on the shorter irradiation time, but still it takes nearly
pits, producing a mosaic that eventually disap- photocatalytic decomposition effect is used 1h under outdoor UV light intensity.27)
peared with the progress of the reaction. After now in other various commercial products
20min, the island structure of the LB film was such as window blinds. However, it is impor- In contrast, the typical indoor UV light
no longer discernible, suggesting the complete tant to note that this function is effective only intensity is about several hundred nW/cm2,
decomposition of stearic acid to CO2. when the number of incident photons is much which is almost about three orders of magni-
greater than that of filming mole-
This observation suggests a potential utili- cules arriving on the surface per
zation of the photocatalysis of TiO2-coated unit time. In other words, the func-
materials, i.e., the surface coated with TiO2 tion is not effective when the flux
could be kept clean. We first reported this of photons is insufficient compared
type of photocatalytic cleaning material with to that of the organic substances,
a ceramic tile in 1992.24) Heller et al. also even though the TiO2 photocata-
conceived a similar idea independently.25) One lyst is a very efficient one.
of the first commercialized products using
this effect was the self-cleaning cover glass 4.2 Photocatalytic anti-
for tunnel light. In most tunnels in Japan, bacterial effect of copper-
sodium lamps emitting yellow light are used and/or silver-deposited
for lighting, and the decrease in light inten- TiO2 film
sity due to filming with exhaust compounds
is one of the most serious problems. A high A p h o t o c a t al y t i c d e c o m -
pressure sodium lamp also emits UV light of position reaction can be appli-
about 3mW/cm 2 at a position of its cover cable to microorganisms. In fact,
Fig.5. Glass covers on highway tunnel lighting fixtures darkened by
glass. This UV light had not been considered Escherichia coli (E. coli ) cells can automobile exhaust without TiO2 and maintained clean with TiO2.
� ������������
����������
�����������
�� �������������
����������
���� �������� �����������
��������
��
� � � � � � ��� ��� ���
�������������������
Fig.6. Changes in survival rate of copper-resistant E. coli cells on Fig.7. Schematic illustrations of bactericidal process for copper-resistant E. coli cells on Cu / TiO2 thin film
Cu / TiO2 thin film. Error bars: standard deviations of three replicate exper- under weak UV light irradiation.
iments.
tude weaker than the outdoor one. Therefore, species photodeposited on the TiO2 film is a TiO2 surface before and after UV light irradia-
the photocatalytic deactivation of microor- mixture of metallic copper (Cu0) and copper tion. With the discovery of this phenomenon,
ganism requires a much longer time under ions (Cu+ and Cu2+). When this Cu / TiO2 film the application range of TiO2 coating has been
indoor conditions than under outdoor ones; is irradiated, the copper ions can be reduced largely widen, as will be mentioned in detail
thus, it cannot become a real practical tech- to metallic copper and metallic copper can be later.
nology. However, the anti-bacterial function oxidized to copper ions by photogenerated
of a TiO2 photocatalyst is markedly enhanced electrons and holes, respectively. Although the The surface wettability is generally evalu-
even with weak UV light, using a fluorescent oxidation state of copper might change under ated by the water contact angle (CA). The
lamp and the aid of either silver or copper,28) UV light irradiation, copper ions (Cu2+) exist on CA (θ ) is defined as the angle between the
which is harmless to the human body. Figure the Cu / TiO2 film.28) The enhancement of the solid surface and the tangent line of the liquid
6 shows the changes in the survival of copper- antibacterial effect under weak UV light was phase at the interface of the solid–liquid–gas
resistant E. coli cells on a Cu-photodeposited also observed on the Ag-deposited TiO2. This phases.
TiO 2 (Cu / TiO 2) film, indicating that E. coli antibacterial technique is safe and effective.
cells survived under dark conditions. However, It was observed that the number of bacteria A TiO2 thin film exhibits an initial CA of
when the Cu / TiO2 film is irradiated with very on the walls decreases to zero after installing several tens of degrees depending on the
weak UV light, the survival rate begins to the photocatalytic tiles in an operating room. surface conditions mainly surface roughness.
decrease. This demonstrates photocatalytic In addition, the bacterial count in air was When this surface is exposed to UV light,
anti-bacterial activity even under weak UV also significantly decreased. The antibacterial water starts to exhibit a decreasing CA, that is,
light obtained from indoor lighting from fluo- ceramic tile coated with photocatalytic TiO2 it tends to spread out flat instead of beading
rescent light bulbs. The survival decay curves containing Cu and/or Ag started full-scale up.29,30) Finally, the CA reaches almost 0°, as
under irradiation in Fig. 6 are not simple manufacturing by TOTO Ltd. in 1995, and its shown in Fig. 8(a). At this stage, the surface
exponential curves. Initial illumination had technology was exported to Western countries becomes completely non-water-repellant and
a negligible effect on the survival rate, but widely. is termed ``highly hydrophilic’’. The surface
after 2 h, a marked decrease in survival was retains a CA of a few degrees for a day or two
observed. We speculate that this cell deactiva- 5. Photo-induced Hydrophilicity under the ambient condition without being
tion proceeds as follows. The first step is that 5.1 Water wettability of TiO2 sur- exposed to UV light. Then, the CA slowly
the reactive species generated by the TiO2 face increases, and the surface becomes the initial
photocatalyst attacks the outer membrane less hydrophilic state again, as shown in Fig.
[Fig. 7(b)]. The second step is the effective 5.1.1 What is a photo-induced high hydro- 8(b). At this point, the high hydrophilicity can
uptake of the copper ions into the cytoplasmic philicity? be recovered simply by exposing the surface
membrane [Fig. 7(c)]. In this case, the TiO2 again to UV light. In short, this type of TiO2-
photocatalytic reaction assists the intrusion of While investigating the novel concept of coated material is the only known practical
the copper ions into the cell, which is prob- light-cleaning materials coated with a TiO2 highly hydrophilic one that shows stable and
ably why the E. coli cells are effectively killed film photocatalyst under weak UV light in the semi permanent properties.
on a Cu / TiO2 film even under very weak UV 1990s, we have found in 1995 by chance the
light.28) It has been reported that the copper marked change in the water wettability of the How can we explain this phenomenon?
��������
�� ��
was decomposed and almost removed, repro-
�� ��
ducing the initial surface. For the TiO2 surface,
�� ��
however, the CA decreased to 0°, which was
� � ��������������
lower than the initial value, showing that the
� �
� �� �� ��� � ��� ���� ����
highly hydrophilic surface of TiO2 is not simply
UV Irradiation Time/min Dark Storage Time/hour attributed to the effect of the photocatalytic
oxidation power.
Fig.8. Changes in CA of TiO2 surface (a) under UV irradiation and (b) in the dark.
��
Water contact angle / deg
���
����������������������
�� �������������
����
�� ��������
���������� ������ �����������������������
��
�� ���������������������
��
��
��
�
� �� ��� ��� ��� ��� ��� ��� ��� ���
Time / hour �������������������
Fig.9. Changes in water contact angle after applying oleic acid to surfaces of Fig.10. Change in XPS spectrum of TiO2 in C 1s peak region before and after
TiO2 and SrTiO3. UV illumination with an intensity of 2.0mW/cm2.
������ ��
��������
�����
�
Figure 11 shows the changes in the C Subjected to cycles of alternating ultrasonic surface increases gradually toward the initial
1s XPS spectra before and after the treat- treatment and UV light irradiation, the water value in the dark even without any external
ment of the TiO2 surface in a warm concen- contact angles switched between 0 and 10° stimuli. However, the rate of this back reac-
trated NaOH solution. No distinct carbon reversibly. It is hardly believed that the ultra- tion strongly depends on the ambient temper-
peak was detected within the experimental sonic treatment makes the surface fouler. ature. Figure 13 shows the result. Because
error. Although the surface stains were nearly this measurement was carried out in a vessel
completely removed by this treatment, we Similarly, the highly hydrophilic state is filled with synthetic air under the same condi-
found that such a ``nearly clean’’ surface does turned to a less hydrophilic one by a ``wet tions other than temperature, even if the
the CA of 20°, which is much higher than rubbing’’ method, which is a type of mechano- surfaces were adsorbed with stains, their influ-
that of 0° induced by UV light.36) By consid- chemical surface treatment with clean lint-free ence could be ignored. It is obvious that the
ering these findings, only the removal of stains paper. Kamei and Mitsuhashi reported that the apparent rate was enhanced by increasing the
cannot lead to the highly hydrophilic state CA increases drastically from 3 to 80° by the temperature. To estimate the activation energy
under the ambient condition. wet rubbing method.38) These results indicate for this transformation, we used the rate (kb)
that the photo-produced highly hydrophilic obtained by the reciprocal plot of CA against
(iii) Stability of photo-produced highly hy- state is broken by external stimuli. the logarithm of the dark storage time.31,40)
drophilic TiO2 surface
(iv) Temperature dependence of back reac- Figure 14 shows the natural logarithm of
When the highly hydrophilic TiO 2 film tion in the dark39) kb obtained at CA of 20° versus the reciprocal
prepared by UV light irradiation was soni- of the absolute temperature. According to Fig.
cated in pure water, the CA was found to As was described previously, the CA of 14, the activation energy was calculated to be
increase to around 10°, as shown in Fig. 12.37) the photo-produced highly hydrophilic TiO2 62.4kJmol–1.
�� �
�
���� �����������������
���� ��
��
����
�
��� � ��
�����
�������������������
�
��� �
���������
��
��
��
���
�� ���
����� ������ ����� ������
� ���������
� ��� ���� ���� ���� ����
�����������������������
Fig.13. Ambient temperature dependence on less hydrophilic Fig.14. Activation energy of less hydrophilic conversion for TiO2 film kept in
conversion for TiO2 film maintained in the dark. the dark.
Taking all the above experimental results has a constant value of 74mJ/m2. Therefore, phobic phases accounts for the highly hydro-
into consideration, we are certain that the by combining eqs. (9) and (10), the CA can be philic characteristic on the TiO2 surface.
photo-produced TiO2 surface is not completely simply expressed as
clean but contains some stains, although it is (ii) Surface hardness change after UV light
cosθ = cγ S1/2–1 (c: constant). (11)
highly hydrophilic with a CA of almost 0°. In irradiation
other words, the removal of stains by oxida- This final equation shows that the CA
tive decomposition can make the surface decreases simply with increasing γ S. Therefore, Hardness changes before and after irradia-
only moderately hydrophilic, with a CA of it can be considered that the highly hydrophilic tion with UV light on the surface of the rutile
10–20° under the ambient condition. In addi- state with a CA of 0° is achieved by the gener- TiO2(110) single crystal were also observed.
tion, it seems that the highly hydrophilic state ation of some states with large surface ener- Figure 16 shows the repetition of UV light
is not the most stable state but forms some gies when irradiated with UV light. As previ- on and off dependence of surface hardness
metastable one. In fact, evidence has been ously mentioned, the highly hydrophilic state (within 50nm from the surface), inner hard-
obtained, showing that the surface structure generated by UV light gradually returns to the ness (300nm from the surface), and CAs.44)
of TiO2 is changed by UV light irradiation, initial less hydrophilic state in the dark. More- When irradiated with UV light, CAs decreased
which will be shown below. over, we showed that some external stimuli to 0°, accompanied by an increase in surface
and a higher ambient temperature increase hardness. In contrast, the inner hardness
5.1.3 Wettability of solid surface the rate of the back reaction. All these suggest remained constant. These findings suggested
that the photo-produced state with a large that the highly hydrophilic surface is subjected
Before examining some evidence for surface energy is metastable. to compressive stress caused by the expansion
surface structural changes accompanying the of the surface volume.
highly hydrophilic conversion, let us briefly 5.1.4 Structural changes on TiO2 surfaces ir-
review a classical theoretical treatment for radiated with UV light 5.1.5 What is the metastable state?
the wettability of the flat solid surface. It is
commonly evaluated in terms of the CA, (i) Domain formation after UV light irradia- We have shown that the surface structure
which is given by Young’s equation:41) tion of TiO2 changes after UV irradiation, forming
a metastable state. Then, what is this state?
γ S =γ SL +γ L · cosθ , (9)
To gain information about surface changes Thus far, we have not yet obtained a defi-
where γ S and γ L are the surface free energies at the microscopic level, friction force micros- nite answer. However, several experimental
per unit area of the solid and liquid, respec- copy (FEM) was utilized. A rutile TiO2(110) data indicate that the metastable state could
tively, and where γ SL is the interfacial free single crystal was used. Before UV light irra- be caused by an increase in the number of
energy per unit area of the solid–liquid inter- diation, no difference in contrast was observed, hydroxyl (OH) groups on the TiO2 surface.31)
face. In addition, γ SL can be approximated indicating microscopically homogeneous wetta-
using the Girifalco–Good equation,42,43) with γ S bility. After irradiation, the hydrophilic (bright) This increase could be detected by X-ray
and γ L, as and hydrophobic (dark) areas of 30–80nm were photoemission spectroscopy (XPS).36) The O
clearly observed (Fig. 15).29) A gradual rever- 1s spectrum for the highly hydrophilic TiO2
γ SL =γ S +γ L − Φ (γ S /γ L ) 1/2. (10)
sion to a smaller contrast was observed during surface exhibited a broad shoulder to the
Here, Φ is a constant parameter ranging from the storage of the crystal in the dark. In this higher binding energy side of the main O 1s
0.6 to 1.1, depending on the solid. In addi- study, we concluded that the nanoscale sepa- peak. The shoulder was fitted with two bands,
tion, γ L is the water surface free energy, which ration between the hydrophilic and hydro- which are associated with the dissociatively
���� ��
�����������������������������
���� ��
����������������
���� ��
���� ��
��� ��
��� ��
��� ��
��� ��
� �
Fig.15. FFM images of rutile TiO2(110) single crystal surface before (left) and after (right) �� ���� �� ���� �� ����
UV light irradiation.
� ������������������� ���������� ��������������������
Fig.16. Relationship between changes in water contact angle and hardness at surface of
TiO2 film (within 50nm) and inside (300nm).
� � � �
� � ����������
�������
� �
�� ��
� � ����
�
���� � � � �
� ��
� � �
�
�� ��
+ � �
� �H
��� � � �� Unstable OH
� H2O
�� � (metastable state)
�� � �� hydrophilic
�� �� ��
� �
Fig.17. Schematic illustrations of reversible changes in amount of hydroxyl groups on TiO2 Fig.18. Conventional tent material (left) and TiO2-coated tent material (right).
film under UV light irradiation and in the dark.
�������������
6. Photocatalysis in 21st Cen- ��
tury
�� � � �� �� �� ��
As was described above, TiO2 photoca-
talysis has become a real practical technology �����������������������
after the middle of the 1990s, particularly in
the field of building materials. It is, however, Fig.20. Changes in water contact angles on rutile (001) surface with and without
photoetching treatments. The inset shows a SEM image of rectangular holes emerged by
surprising that a research study on TiO2 photo- photoetching treatment on a (001) surface.
�� ��
These anion-doped TiO 2 are candidate
��������
��������
��������
�������� photocatalysts in terms of reproducibility and
�� �� �������� chemical stability. Therefore, further research
�������� and practical applications are desirable.
�� �������� �� ��������
6.3 Hydrophobic TiO2 surface
��� �
� �
� �� �� �� �� ��� � �� �� �� ��� ��� ��� As the discovery of the photo-induced
�������������������� ���������������������� hydrophilicity has markedly widened the appli-
cation field of TiO2-coated materials, a highly
Fig.22. Changes in water contact angles on TiO2 and nitrogen-doped TiO2 thin films irradiated with (a) vis and (b) UV lights.
hydrophobic TiO2 surface could open a new
application field. In addition, if it is realized,
we will be able to control the wettability on
a TiO2 surface using external stimuli, such as
UV light, which we believe is both scientifically
and practically very important.
tial titanium is clearly not possible, an oxygen Compared with the conventional TiO2,
vacancy is simultaneously produced. There- the advantage of nitrogen-doped TiO2 is the Let us try to design the hydrophobic TiO2
fore, the schematic illustration in Fig. 23 is the increased absorbed photon number, but the surface. As previously mentioned, the wetta-
essential procedure when oxygen is replaced disadvantage is the decreased photocatalytic bility of a flat solid surface is determined
by nitrogen. activity. Therefore, whether to use nitrogen- simply by the surface free energy of solid as
doped TiO2 or conventional TiO2 depends on described in eqs. (9) and (11). As for a non-flat
The Ti 3d impurity (donor) level, derived the light source. surface, however, surface roughness affects
from oxygen vacancies, is known to be nonvis- the wettability. Wenzel modified Young’s
ible light sensitive. In fact, hydrogen-reduced In addition to nitrogen, the sulfur-doped equation by considering the surface roughness
TiO2 (TiO2-x) powders, which have a gray color, and carbon-doped TiO2 systems are reported to obtain73)
do not show visible light sensitivity. The N 2p to be visible-light-sensitive photocatalysts.68–71)
cosθ ’ = r cosθ , (12)
level exists much deeper than the Ti 3d donor However, the visible-light-induced photocata-
level, from which we can consider that the N lytic activities of these anion-doped TiO2 are where θ ’ is the apparent contact angle and
2p level has a much more oxidation power insufficient and should be further enhanced. r is the surface roughness ratio between the
than the Ti 3d level. Therefore, the origin of This is because the introduced 3p
visible light sensitivity of nitrogen-doped TiO2 orbitals of S (S 3p) and 2p orbitals
is considered to be the N 2p narrow band. of C (C 2p), similar to N 2p, also
formed the localized narrow band �� �� ��
�� � �� � �� � ��
Thus, the reason that irradiating the in the forbidden band, by not �� �� ��
�� � �� ��
nitrogen-doped TiO2 with UV light resulted in mixing with the valence band � �� � �
higher photocatalytic activities than irradiating composed of O 2p. Thus, it can ��
with visible light is as follows. Irradiating with be speculated that mixing the
��
UV light excites electrons in both the valence introduced anion 2p (or 3p) with � ����������������������
��
band composed of O 2p and the narrow band O 2p, leading to the bandgap
composed of N 2p, but irradiating with visible narrowing, is the key method of �� �� �� ��
�� � �� � �� �� ��
light only excites electrons in the narrow band enhancing the visible-light-induced
�� ��
�� �� ��
��
of N 2p. In addition, the hole mobility in the photocatalytic activities. We have ��
� �� �
isolated narrow band should be low. There- found using the DOS calculations ��
fore, the hydrophilic properties when irradi- that the simultaneous doping ��
ating with UV light were higher than when of nitrogen and sulfur into TiO2
�– �– ��
irradiating with visible light. Although the could narrow the bandgap of TiO2 �� � �� � �� �� ��
nitrogen concentration increases, it is not by mixing N 2p and S 3p with the �� �–
�� �� �–
��
suggested by the density of states (DOS) calcu- valence band composed of O 2p. � �� �
��
lations that the bandgap narrowing by mixing It can be expected that the broad ��
N 2p with O 2p occurs. expanse of the electronic state,
compared with the isolated one, Fig.23. Schematic illustration of nitrogen doping into oxygen site.
6.4.1 Photocatalytic decomposition of pol- large surface area deposited with very photo- in Fig. 26. The wastewater from the hydro-
lutants active TiO2 nanoparticles; we were able to ponic tomato culture with a planting area of
show that the wastewater solution is easily about 80m2 was introduced into a shallow
Environment pollution, including water, purified using the photocatalytic mat under vessel with a bottom area of 4m2 and a depth
air and soil is becoming an increasingly serious only solar light. The treatment method is of 10cm in which porous ceramic plates
problem today. There have been many reports very simple, i.e., the wastewater is poured coated with TiO 2 photocatalyst nanopar-
aiming at applying TiO2 photocatalysis to pollu- onto mats that are spread over a wide area ticles were placed. The organic contaminants
tion clean-up since the 1970s. However, the on the ground. The agricultural chemicals in the wastewater were easily decomposed
purification of the three-dimensional spaces by were completely decomposed under sunlight under solar light, but the nutrient compounds
photocatalysis is much more difficult than that in a few days. It is surprising that the initial containing nitrogen, phosphorous and potas-
of the two-dimensional surface of building total organic carbon (TOC) values of several sium were not, because these components
materials due to the following two reasons. hundred to one thousand ppm decreased to existed in their most oxidized forms, NO3–,
One is that photocatalytic reactions are nearly zero in one week. This could be one of PO43– and K+, in the nutrient solution. There-
surface reactions and thus the reactants must the simplest and easiest environmental tech- fore, this system is also expected to serve as a
be captured by the photocatalyst surface. The nologies. nutrient-saving technology.
other is that the total amount of reactant is,
in general, higher in three-dimensional spaces (ii) Water treatment of hydroponic culture (iii) Treatment of VOC-polluted soil
than on a two-dimensional surface, indicating system
that much more light energy is necessary Volatile chlorinated organic compounds
for the purification of the three-dimensional Most of the hydroponic culture installa- (VOCs), such as trichloroethylene and tetra-
space. Therefore, practical technologies have tions are adopting run-to-waste systems (as chloroethylene, have been widely used as
not been obtained in this field. However, we opposed to recirculating). The nutrient solu- solvents for the dry cleaning of clothes and
have recently succeeded in the construction of tion contains highly concentrated nitrogen and washing of semiconductors. They had been
practical purification systems for wastewater phosphorus compounds, and thus, the waste- indiscriminately disposed by the middle of the
from agriculture and soil polluted by volatile water causes soil pollution. From the view- 1980s, causing soil and groundwater pollu-
organic compounds (VOCs). These systems point of environmental problems, the recycling tion. These types of pollution are serious envi-
are based on TiO2 photocatalysts and use only of nutrient solutions is desirable. However, ronmental problems, because the carcinogenic
solar light. organic contaminants accumulate in the solu- and toxic chemicals had been widely disposed.
tion, inhibiting plant growth. The most common method of treating the
Important keys for these successes are polluted soil is either the simple replacement
(1) the utilization of nanosized TiO2 photo- We succeeded in constructing a recy- with clean soil or the heating of the soil to
catalyst powders dispersed on substrates cling system in a tomato hydroponic culture volatilize the VOCs into air. It is obvious that
with extremely large surface areas, and (2) system using the TiO2 photocatalyst and solar these methods do not truly purify the environ-
spreading them on the ground widely to light. The system is schematically illustrated ment.
collect sunlight. Because the concentrations of
environmental pollutants are low in general,
the UV light contained in sunlight is sufficiently
strong to decompose them by TiO2 photoca-
talysis, if we can collect the light from a broad
area.
6.4.2 Efficient water evaporation from hy- It is important to emphasize that the In this paper, an overview of the devel-
drophilic surfaces buildings and surroundings are not cooled by opment of TiO2 photocatalysis and its future
water itself, but by the latent heat flux when prospects from both scientific and techno-
Rapid increases in the absorption of solar water evaporates. In fact, it is often observed logical viewpoints are given. It is interesting
energy and increases in energy consumption that the temperature of a wall surface is lower to note that this field has experienced major
in large cities cause a temperature increase, than that of sprinkling water. The thinner developments every ten years for the last
the so-called heat island phenomenon. The the water layer is, the more effectively the thirty years, namely, water photoelectrolysis
former is due to the coverage of the ground building surface temperature and surrounding (Honda–Fujishima effect) in the early 1970s,
surface by artificial structures, such as build- air temperature decrease as the amount photocatalytic H2 production in the 1980s, and
ings and paved roads, and the latter is due of latent heat flux decreases to cool down the photocatalysis and hydrophilicity of TiO2
to the heat emissions from automobile traffic the thin water film. Although the margin of films in the 1990s. Based on the basic research
and air conditioners. An effective method of the temperature drop depends on the color results, real industrial applications have been
preventing the heat island phenomenon is and / or type of building material, as well as achieved since the end of the 1990s. In addi-
increasing the area of green tract land or the the atmosphere temperature and humidity, it tion, this field is still being developed further in
the 21st century. We believe that TiO2 photo-
catalysis is one of the best examples how, on
the time scale of tens of years, basic scientific
knowledge can be developed into a techno-
logical field and can produce a new industry.
Acknowledgment
�������������������
The authors gratefully thank many collab-
� ��������� ����� orators in both academia and industry who
����� have been involved in the present research.
�������������� We also thank Dr. D. A. Tryk for carefully
����� ����������� reading the manuscript.
���� ��������
�������������
Fig.27. Purification system for polluted soil utilizing solar energy and photocatalyst sheets.
1 ) E. Keidel: Farben-Zeitung. 34 (1929) 1242. 14 ) This field remains active, with novel layered 28 ) K. Sunada, T. Watanabe and K. Hashimoto: En-
2 ) C. F. Doodeve and J. A. Kitchener: Trans. Fara- metal oxides being the favored materials. For viron. Sci. Technol. 37 (2003) 4785.
day Soc. 34 (1938) 902. example, a very efficient production of H2 and 29 ) R. Wang, K. Hashimoto, A. Fujishima, M. Chiku-
3 ) For example, S. Kato and F. Mashio: Abtr. Book O2 using deep UV light of around 290nm has ni, E. Kojima, A. Kitamura, M. Shimohigoshi and
Annu. Meet. Chemical Society of Japan, 1956, been reported. T. Watanabe: Nature 388 (1997) 431.
p.223. 15 ) T. Kawai and T. Sakata: Nature 286 (1980) 474. 30 ) R. Wang, K. Hashimoto, A. Fujishima, M. Chiku-
4 ) S. Kat and F. Masuo: Kogyo Kagaku Zasshi 67 16 ) L. Kavan, M. Gräzel, S. E. Gilbert, C. Klemenz ni, E. Kojima, A. Kitamura, M. Shimohigoshi and
(1964) 1136 [in Japanese]. and H. J. Scheel: J. Am. Chem. Soc. 118 (1996) T. Watanabe: Adv. Mater. 10 (1998) 135.
5 ) A. Fujishima, K. Honda and S. Kikuchi: Kogyo 6716. 31 ) N. Sakai, A. Fujishima, T. Watanabe and K.
Kagaku Zasshi 72 (1969) 108 [in Japanese]. 17 ) S. N. Frank and A. J. Bard: J. Am. Chem. Soc. 99 Hashimoto: J. Phys. Chem. B 107 (2003) 1028.
6 ) A. Fujishima and K. Honda: Nature 238 (1972) (1977) 303. 32 ) J. M. White, J. Szanyi and M. A. Henderson: J.
37. 18 ) Many reviews have been published. For ex- Phys. Chem. B 107 (2003) 9029.
7 ) W. Jaegermann: in The Semiconductor/ ample, M. A. Fox and M. T. Dulay: Chem. Rev. 33 ) C. Wang, H. Groenzin and M. J. Schltz: Lang-
Electrolyte Interface: A Surface Science Ap- 93 (1993) 341; M. R. Hoffman, S. T. Martin, W. muir 19 (2003) 7330.
proach, eds. R. E. White, B. E. Conway, J. O’M. Choi and D. W. Bahnemann: Chem. Rev. 95 34 ) T. Zubkov, D. Stahl, T. L. Thompson, D. Panayo-
Bochris (Plenum Press, New York, 1996) Mod- (1995) 69. tov, O. Diwald and J. T. Yates, Jr.: J. Phys. Chem.
ern Aspects of Electrochemistry, Vol.30, p.1. 19 ) R. W. Matthews: J. Phys. Chem. 91 (1987) B 109 (2005) 15454.
8 ) A. J. Nozik and R. Memming: J. Phys. Chem. 3328. 35 ) M. Miyauchi, A. Nakajima, A. Fujishima, K.
100 (1996) 13061. 20 ) T. Watanabe, K. Hashimoto and A. Fujishima: Hashimoto and T. Watanabe: Chem. Mater. 12
9 ) A. Fujishima and D. A. Tryk: in Photoelectro- in Photocatalytic Purification and Treatment of (2000) 3.
chemical Conversion, ed. K. Honda (Springer, Water and Air, eds. D. F. Ollis and H. Al-Ekabi 36 ) R. D. Sun, A. Nakajima, A. Fujishim, T. Wata-
Tokyo, 1999) Functionality of Molecular Sys- (Elsevier, Amsterdam, 1993). nabe and K. Hashimoto: J. Phys. Chem. B 105
tems, Vol.2, p.196. 21 ) A. Fujishima, K. Hashimoto and T. Watanabe: (2001) 1984.
10 ) N. Sato: Electrochemistry at Metal and Semi- TiO2 Photocatalysis: Fundamentals and Appli- 37 ) N. Sakai, R. Wang, A. Fujishima, T. Watanabe
conductor Electrodes (Elsevier, Amsterdam, cations (BKC, Tokyo, 1999). and K. Hashimoto: Langmuir 14 (1998) 5918.
1998). 22 ) P. Sawunyama, L. Jiang, A. Fujishima and K. 38 ) M. Kamei and T. Mitsuhashi: Surf. Sci. 463
11 ) L. M. Peter: in Photoelectrochemical Kinetics at Hashimoto: J. Phys. Chem. B 101 (1997) 11000. (2000) L609.
Semiconductor Electrodes, eds. R. G. Compton 23 ) P. Sawunyama, A. Fujishima and K. Hashimoto: 39 ) H. Irie, M. S. Utami, T. Shibata and K. Hashimo-
and G. Hancock (Elsevier, Amsterdam, 1999) Langmuir 15 (1999) 3551. to: submitted to Chem. Commun.
Applications of Kinetic Modeling, Vol.37, p.223. 24 ) T. Watanabe, K. Hashimoto and A. Fujishima: 40) kb was obtained using θ and t described as the
12 ) M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Proc. 1st Int. Conf. TiO2 Photocatalyst, ed. H. Al- CA and dark storage time (min), respectively.
Humphry-Baker, E. Mueller, P. Liska, N. Vlacho- Ekabi, 1992.
1/θ = a – b×ln(t)
poulos and M. Gräzel: J. Am. Chem. Soc. 115 25 ) A. Heller: Acc. Chem. Res. 28 (1995) 503.
d(1/θ ) / dt = –b×(1/t)
(1993) 6382. 26 ) H. Honda, A. Ishizaki, R. Soma, K. Hashimoto
13 ) M. K. Nazeeruddin, P. Pechy and M. Gräzel: and A. Fujishima: J. Illum. Eng. Soc. (1998) 42. Combining these equations, kb can be
Chem. Commun. 18 (1997) 1705. 27 ) K. Sunada, Y. Kikuchi, K. Hashimoto and A. Fu- described as a function of 1/θ :
jishima: Environ. Sci. Technol. 32 (1998) 726.
kb(deg–1·min–1) = –d (1/θ ) /dt = b ×exp ( (1/θ –a)/b).
41 ) Principles of Colloid and Surface Chemistry, ed. 56 ) E. Borgarello, J. Kiwi, M. Gratzel, E. Pelizzetti 70 ) T. Ohno, T. Mitsui and M. Matsumura: Chem.
P. C. Hiemenz (Dekker, New York, 1986) p.307. and M. Visca: J. Am. Chem. Soc. 104 (1982) Lett. 32 (2003) 364.
42) L. A. Girifalco and R. J. Good: J. Phys. Chem. 61 2996. 71 ) H. Irie, Y. Watanabe and K. Hashimoto: Chem.
(1957) 904. 57 ) H. Yamashita, Y. Ichihashi, M. Takeuchi, S. Kishi- Lett. 32 (2003) 772.
43) R. J. Good and E. Elbing: Ind. Eng. Chem. 62 guchi and M. Anpo: J. Synchrotron Radiat. 6 72 ) H. Irie and K. Hashimoto: Photocatalysis 15
(1970) 54. (1999) 451. (2004) 78 [in Japanese].
44) T. Shibata, H. Irie and K. Hashimoto: submitted 58 ) I. Nakamura, N. Negishi, S. Kutsuna, T. Ihara, 73 ) R. N. Wenzel: J. Phys. Colloid Chem. 53 (1949)
to J. Phys. Chem. B. S. Sugihara and K. Takeuchi: J. Mol. Catal. 161 1466.
45) K. Hashimoto and T. Watanabe: Hyomen (2000) 205. 74 ) A. B. D. Cassie: Discuss. Faraday Soc. 3 (1948)
Kagaku 20 (1999) 27 [in Japanese]. 59 ) Y. Sakatani, K. Okusako, H. Koike and H. Ando: 11.
46) R. Nakamura, K. Ueda and S. Sato: Langmuir 17 Photocatalysis 4 (2001) 51 [in Japanese]. 75 ) H. Irie, T. S. Ping, T. Shibata and K. Hashimoto:
(2001) 2298. 60 ) T. Ihara, M. Ando and S. Sugihara: Photocataly- Electrochem. Solid-State Lett. 8 (2005) D23.
47) K. Uosaki, T. Yano and S. Nihonyanagi: J. Phys. sis 5 (2001) 19 [in Japanese]. 76 ) A. Nakajima, K. Hashimoto and T. Watanabe:
Chem. B 108 (2004) 19086. 61 ) R. Asahi, T. Ohwaki, K. Aoki and Y. Taga: Sci- Monatsh. Chem. 132 (2001) 31.
48) N. Sakai, A. Fujishima, T. Watanabe and K. ence 293 (2001) 269. 77 ) A. Nakajima, A. Fujishima, K. Hashimoto and T.
Hashimoto: J. Phys. Chem. B 105 (2001) 3023. 62 ) H. Irie, Y. Watanabe and K. Hashimoto: J. Phys. Watanabe: Adv. Mater. 11 (1999) 1365.
49) A. Fujishima, K. Hashimoto and T. Watanabe: Chem. B 107 (2003) 5483. 78 ) A. Nakajima, K. Abe, K. Hashimoto and T.
TiO2 Photocatalysis, Fundamentals and Appli- 63 ) H. Irie, S. Washizuka, N. Yoshino and K. Hashi- Watanabe: Thin Solid Films 376 (2000) 140.
cations (BKC, Tokyo, 1999). moto: Chem. Commun. 11 (2003) 1298. 79 ) A. Nakajima, K. Hashimoto, T. Watanabe, K.
50 ) R. Wang, N. Sakai, A. Fujishima, T. Watanabe 64) S. Sakthivel and H. Kisch: Chem. Phys. Chem. 4 Takai, G. Yamauchi and A. Fujishima: Langmuir
and K. Hashimoto: J. Phys. Chem. B 103 (1999) (2003) 487. 16 (2000) 7044.
2188. 65 ) S. Sato: Chem. Phys. Lett. 123 (1986) 126. 80 ) N. Ogawa, M. Soga, Y. Takada and I. Nakaya-
51 ) T. Sugiura, T. Yoshida and H. Minoura: Electro- 66 ) H. Noda, K. Oikawa, T. Ogata, K. Matsuki and H. ma: Jpn. J. Appl. Phys. 32 (1993) L614.
chemistry 67 (1999) 1234. Kamada: Nippon Kagaku Kaishi (1986) 1084 [in 81 ) K. Tadanaga, N. Katata and T. Minami: J. Am.
52 ) A. Tsujiko, T. Kisumi, Y. Magari, K. Murakoshi and Japanese]. Ceram. Soc. 80 (1997) 1040.
Y. Nakato: J. Phys. Chem. B 104 (2000) 4873. 67 ) H. Irie, S. Washizuka, Y. Watanabe, T. Kako and 82 ) K. Tadanaga, N. Katata and T. Minami: J. Am.
53 ) T. Shibata, T. Watanabe, K. Hashimoto and A. K. Hashimoto: J. Electrochem. Soc. 152 (2005) Ceram. Soc. 80 (1997) 3213.
Nakajima: Photocatalysis 4 (2001) 45 [in Japa- E351. 83 ) A. Hozumi and O. Takai: Thin Solid Films 303
nese]. 68 ) T. Umebayashi, T. Yamaki, H. Itoh and K. Asai: (1997) 222.
54 ) T. Shibata, H. Irie and K. Hashimoto: J. Phys. Appl. Phys. Lett. 81 (2002) 454. 84) A. Hozumi and O. Takai: Thin Solid Films 334
Chem. B 107 (2003) 10696. 69 ) T. Umebayashi, T. Yamaki, S. Tanaka and K. Asai: (1997) 54.
55 ) M. Miyauchi, A. Nakajima, K. Hashimoto and T. Chem. Lett. 32 (2003) 330.
Watanabe: Adv. Mater. 12 (2000) 1923.