SCIENCE CHINA

Chemistry
Science China Press and Springer-Verlag Berlin Heidelberg 2010 chem.scichina.com www.springerlink.com

*Corresponding author (email: jean-marie.herrmann@ircelyon.univ-lyon1.fr)
REVIEWS
September 2010 Vol.53 No.9: 18311843
doi: 10.1007/s11426-010-4076-y
Environmental photocatalysis: Perspectives for China
HERRMANN Jean Marie
*

Institut de Recherches sur la Catalyse et lEnvironnement de Lyon; UMR 5256 CNRS/Universit Lyon1, 2 Av.
Albert Einstein 69626 Villeurbanne Cedex, France
Received June 16, 2010; accepted July 20, 2010

Photocatalysis is based on the double aptitude of the photocatalyst (essentially titania) to simultaneously adsorb reactants and
absorb efficient photons. Heterogeneous photocatalysis is able to be efficient in Fine, Green and Environmental Chemistry.
Photocatalysis induces mild oxidations in the absence of water by generating active neutral atomic O
*
species. For instance, the
oxidation of 4-tert-butyl-toluene is 100% selective in 4-tert-butyl-benzaldehyde. In water treatment, many toxic inorganic ions
are oxidized in their harmless upper oxidized state. The elimination of organic pollutants is the main field of water photocata-
lytic decontamination. Most of aliphatic and aromatic pollutants are totally mineralized into CO
2
and innocuous inorganic ani-
ons. More complex molecules, such as pesticides (herbicides, insecticides, fungicides, etc.) or dyes, are totally destroyed. An-
other example of green chemistry is the total degradation of dyes in water, in particular for the azo-dyes, with 100% selective
degradation of N=N azo-groups into di-nitrogen. Photocatalysis is also active in the bio-world by killing bacteria (E. Coli,
streptococcus, etc.) in water without re-growth. Air pollutants can also be destroyed, especially all the VOCs (volatile organic
compounds), providing certain air humidity enabling titania to produce cracking OH

radicals. For chemical engineering rea-

sons, the photocatalyst has to be fixed on a photo-inert support. In these conditions, UV-irradiated titania-based photocatalysis
could be applied to the elimination of air pollutants, VOCs, solvents, odors, chemicals, etc. Air treatment has to be associated
with water and solid waste treatment because of odors. This is conducted by covering water treatment ponds or lagunas by rafts
on which large sheets of Ahlstrom paper are deposited, supporting titania associated with activated carbon. Eventually, virus
AH5N2, a model virus close to H5N1, responsible for the avian flu could be totally inactivated. Photocatalysis is directly con-
nected with all 12 principles of Green Chemistry defined by Anastas (1998) and possesses open perspectives for China.
photocatalysis, green chemistry, environmental chemistry, air pollutants, water pollutants, solar energy, China



1 Introduction
Photocatalysis originated from different catalysis laborato-
ries in Europe. In England, Stone et al. first studied the
photo-adsorption/desorption of oxygen on ZnO [1] before
studying the photocatalytic oxidation of CO on the same
solid [2]. They subsequently switched to titania under the
rutile phase for oxygen photo-adsorption [3] and selective
isopropanol oxidation in acetone [4]. The latter reference
was the first one, to my knowledge, to mention OH

radi-
cals as oxidizing agents formed by neutralization of surface
OH

by photo-holes h
+
. In addition, this simple and selec-
tive reaction remains a direct and simple test to demonstrate
the photo-activity of solids. Simultaneously, in Germany,
Hauffe et al. also studied the photocatalytic oxidation of CO
on ZnO [5, 6] and, actually, this reference was the first one
to include the term photocatalysis in its title. In the same
decade, Juillet and Teichner in France studied the sintering
of ultra-pure oxide powders for nuclear applications and
tested their solids through their electrical properties. The
erratic results obtained on titania anatase puzzled them till
they realized that titania was photosensitive to daylight,
especially in sunny days (Juillet F and Teichner SJ, 2003,
private communication). They subsequently used the photo-
activated oxygen species to perform mild and selective oxi-
1832 HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9
dations of alkanes [7, 8].
While photocatalysis was developed confidentially in
Europe, there was an earthquake in or from Japan, ac-
cording to Bickley [9] with the re-publication in English of
the previous work by Fujishima and Honda on the photo-
electrolysis of water using a UV-irradiated titania-based
anode [10] in the review [11]. This constituted the initial
event for the globalization of photocatalysis, which had
preferential development in Japan, as illustrated by refer-
ence [12]. Unfortunately, recent scientists in the field of
photocatalysis may have never read this article and improp-
erly cite it as the starting point of photocatalysis, which is
apparently erroneous.
With the increasing number of global publications, the
frame of photocatalysis needs to be urgently refocused, es-
pecially by senior scientists. This is the aim of this work.
Heterogeneous photocatalysis is a discipline which in-
cludes a large variety of reactions: mild or total oxidations,
dehydrogenation, hydrogen transfer, oxygen-18 and deute-
rium isotopic exchange, metal deposition, water detoxifica-
tion, gaseous pollutant removal, bactericidal action, etc. In
line with the last point, it can be considered as one of the
new Advanced Oxidation Technologies (AOT) for air and
water purification treatments. Several books and reviews
have been devoted to this problem [1224].
The review by Blake in 2001 already reported more than
1200 references on the subject [24].
2 Principles of heterogeneous photocatalysis
When a semiconductor catalyst SC of the chalcogenide type
(oxides (TiO
2
, ZnO, ZrO
2
, CeO
2
,...), or sulfides (CdS,
ZnS,...)) is illuminated with photons whose energy is equal
to or greater than their band-gap energy E
g
(hvE
g
), there
is ABsorption of these photons and creation of electron-hole
pairs within the bulk, which dissociate into free photoelec-
trons in the conduction band and photoholes in the valence
band. (Figure 1)
Simultaneously, in the presence of a fluid phase (gas or
liquid), spontaneous ADsorption occurs and according to
the redox potential (or energy level) of each adsorbate,
electron transfer proceeds towards acceptor molecules,
whereas positive photoholes are transferred to donor mole-
cules (actually the hole transfer corresponds to the cession
of an electron by the donor to the solid).
( )
+
SC e h hv

+ + (1)

(ads) (ads)
A e A

+ (2)

(ads) (ads)
D h D
+ +
+ (3)
Each ion formed subsequently reacts to form the interme-
diates and final products. As a consequence of eqs. (1)(3),

Figure 1 Electron energy plotted upwards as a function of the distance
from the surface to the bulk of the solid.
the photonic excitation of the catalyst appears as the initial
step of the activation of the whole catalytic system. Thence,
the efficient photon has to be considered as a reactant and
the photon flux as a special fluid phase, the electromag-
netic phase. The photon energy is adapted to the absorption
of the catalyst, not to that of the reactants. The activation of
the process goes through the excitation of the solid but not
through that of the reactants: there is no photochemical
process in the adsorbed phase but only a true heterogeneous
photocatalytic regime as demonstrated further.
The photoefficiency can be reduced by the electron-hole
recombination, shown in Figure 2, which corresponds to the
degradation of the photoelectronic energy into heat.
e h N E
+
+ + (4)
(N: neutral center; E: energy (heat))
Heterogeneous photocatalysis can be carried out in various
media: the gas phase, pure organic liquid phases or aqueous

Figure 2 Fate of electrons and holes within a spherical particle of titania
in the presence of acceptors (A) and (D) molecules (after late Dr. H. Ger-
isher, p1 in ref. [15]).
HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9 1833
solutions. As for classical heterogeneous catalysis, the overall
process can be decomposed into five independent steps: (1)
transfer of the reactants in the fluid phase to the surface; (2)
adsorption of at least one of the reactants; (3) reaction in the
adsorbed phase; (4) desorption of the product(s); (5) re-
moval of the products from the interface region.
The photocatalytic reaction occurs in the adsorbed phase
(step n 3). The only difference from conventional catalysis
is the mode of activation of the catalyst in which the ther-
mal activation is replaced by photonic activation.
Among various chalcogenides (oxides and sulfides), the
best photocatalytic performances with maximum quantum
yields are always obtained with titania. In all the systems
described in the present paper, the catalyst used was titania
(Degussa TiO
2
P-25, 50 m
2
/g, mainly anatase), unless oth-
erwise stated.
3 Influence of physical parameters governing
the kinetics
All the results are summarized in the five diagrams of Figure 3.
3.1 Mass of catalysts
Either in static or in slurry or in dynamic flow photoreactors,
the initial rates of reactions were found to be directly pro-
portional to the mass m of catalysts (Figure 3(a)). This in-
dicates a true heterogeneous catalytic regime. However,
above a certain value of m, the reaction rate levels off and
becomes independent of m. This limit depends on the ge-
ometry and the working conditions of the photoreactor. For
higher amounts of catalysts, a screening effect of excess

Figure 3 Influence of different physical parameters governing the reac-
tion rate [17]. (a) Mass of catalysts; (b) wavelength; (c) initial concentra-
tion of reactants; (d) temperature; (e) radiant flux.
particles occurs, which masks part of the photosensitive
surface. For applications, this optimum mass of catalysts
has to be chosen in order (i) to avoid an unuseful excess of
catalysts and (ii) to ensure total absorption of efficient pho-
tons. These limits range from 0.2 to 2.5 g/L of titania in
slurry batch photoreactors.
3.2 Wavelength
The variation of the reaction rate as a function of the wave-
length follows the absorption spectrum of the catalyst (Fig-
ure 3(b)), with a threshold corresponding to its band gap
energy. For TiO
2
having E
g
=

3.02 eV, this requires 400
nm, i.e., near-UV wavelength (UV-A). In addition, it needs
to be checked that the reactants do not absorb the light to
conserve the exclusive photoactivation of the catalyst for a
true heterogeneous catalytic regime (no homogeneous nor
photochemistry in the adsorbed phase).
3.3 Initial concentration
Generally, the kinetics follows a Langmuir-Hinshelwood
mechanism confirming the heterogeneous catalytic charac-
teristic of the system with the rate r varying proportionally
with the coverage u as
( ) ( )
1 r k k KC KC u = = + (5)
For diluted solutions (C

<

10
3
M), KC becomes <<1 and
the reaction is of the apparent first order, whereas for
concentrations >

5

10
3

M, (KC

>>

1), the reaction rate is
maximum and of the apparent order (Figure 3(c)).
In the gas phase similar Langmuir-Hinshelwood expres-
sions have been found including partial pressures P instead
of C.
3.4 Temperature
Because of the photonic activation, the photocatalytic sys-
tems do not require heating and operate at room temperature.
The true activation energy E
t
is nil, whereas the apparent
activation energy E
a
is often very small (a few kJ/mol) in
the medium temperature range (20 C u

80 C). How-
ever, at very low temperatures (40 Cu 0 C), the
activity decreases and the activation energy E
a
becomes
positive (Figure 3(d)).
By contrast, for various types of photocatalytic reactions
at high temperatures (u

7080 C), the activity de-
creases and the apparent activation energy becomes nega-
tive (Figure 3(c)). This behavior can be easily explained
within the frame of the Langmuir-Hinshelwood mechanism
described above. The decrease in temperature favors ad-
sorption (which is a spontaneous exothermic phenomenon)
with in particular that of the final product, which becomes
the inhibitor of the reaction. By contrast, when u increases
1834 HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9
above 80 C and tends to the boiling point of water, the
exothermic adsorption of reactant A becomes disfavored
and tends to become the rate limiting step of the whole re-
action.
As a consequence, the optimum temperature is generally
between 20 and 80 C. This explains why solar devices
which use light concentrators instead of light collectors re-
quire coolers [25]. This absence of heating is attractive for
photocatalytic reactions carried out in aqueous media and in
particular for environmental purposes (photocatalytic water
purification). There is no need to waste energy in heating
water, which possesses a high heat capacity. This explains
why photocatalysis was estimated cheaper than incineration.
3.5 Radiant flux
It has been shown that for all types of photocatalytic reac-
tions, the reaction rate r is proportional to the radiant flux u
(Figure 3(e)). This confirms the photo-induced nature of the
activation of the catalytic process, with the participation of
photo-induced electrical charges (electrons and holes) to the
reaction mechanism. However, above a certain value de-
pending on the photoreactor, the reaction rate r becomes
proportional to u
1/2
, indicating strong electron-hole recom-
bination. These two regimes have been independently
demonstrated by Egerton et al. [26] and the author [27, 28].
3.6 Quantum yield
By definition, it is equal to the ratio of the reaction rate in
molecules converted per second (or in mols per second) to
the incident efficient photonic flux in photons per second
(or in Einstein per second (an Einstein is a mol of photons)).
This is a kinetic definition, which is directly related to the
instantaneous efficiency of a photocatalytic system. Its
theoretical maximum value is equal to 1. It may vary in a
wide range according to (i) the nature of the catalyst, (ii) the
experimental conditions used (m
cat
, concentrations, T, u, ...)
and especially (iii) the nature of the reaction considered. We
have found values between 10
2
% and 70%. The knowledge
of this parameter is fundamental. It enables one (i) to com-
pare the activity of different catalysts for the same reaction,
(ii) to estimate the relative feasibility of different reactions,
and (iii) to calculate the energetic yield of the process and
the corresponding cost.
4 Main types of photocatalytic reactions
4.1 Mild oxidation reactions
The gas phase oxidations using dry air as the oxidizing
agent mainly concern the mild oxidation of alkanes, alkenes
and alcohols into carbonyl-containing molecules (aldehydes
and ketones) [4, 8, 9, 29]. Liquid phase reactions concern
the selective mild oxidation of liquid hydrocarbons (alkanes,
alkenes, cycloalkanes, aromatics) into aldehydes and ke-
tones [30, 31]. For instance, cyclohexane and decaline were
oxidized into cyclohexanone and 2-decalone, respectively,
with an identical selectivity (86%) [30]. Aromatic hydro-
carbons [31] such as alkyltoluenes or o-xylenes were 100%
selectively oxidized on the methyl group into alkylbenzal-
dehyde:

6 4 3 2 6 4 2
R C H CH O R C H CHO H O + + (6)
Pure liquid alcohols were also oxidized into their corre-
sponding aldehydes or ketones. In particular, the oxidation
of isopropanol into acetone, first mentioned in reference [4],
was later chosen as a photocatalytic test for measuring the
efficiency of passivation of TiO
2
or ZnO-based pigments in
paintings against weathering.
The high selectivity was ascribed to a photoactive neutral,
atomic oxygen species [29].
( )
*
O ads h O
+
+ (7)
4.2 Photocatalytic reactions involving hydrogen
In photocatalytic reactions involving hydrogen, either as a
reactant (deuterium-alcane isotopic exchange [32]) or as a
product (alcohol dehydrogenation [33]), the system requires
the presence of a metal acting as a co-catalyst necessary (i)
to dissociate the reactant (D
2
) and (ii) to recombine H and D
into dihydrogen (or HD). Additionally, the metal (i) attracts
electrons by photoinduced metal-support interaction (PMSI),
(ii) decreases the electron-hole recombination and (iii)
makes the reaction run catalytically.
4.3 Total oxidation reaction in aqueous phase
The selective mild oxidation reaction could be obtained in
gaseous or liquid organic phases. By contrast, as soon as
water is present, the selectivity turns in favor of total oxida-
tive degradation. This was ascribed to the photogeneration
of stronger, unselective, oxidizing species, namely OH

radicals originating from water via the OH

groups of tita-
nia's surface:

2 ads
(H O H OH ) h H OH
+ + +
+ + + (8)

( )

2 2
OH reactants Intermediates
Final Products CO , H O, X , A ...

+
(9)
OH

radicals are known as the second best oxidizing entity

after fluorine. This system is the most promising issue for
an application of heterogeneous photocatalysis, because it is
directly connected to water detoxification and pollutant re-
moval in aqueous effluents. The oxidative degradation is
based on the production of OH

radicals which is described

in Table 1.
HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9 1835
Table 1 Electronic processes for OH

radical generation used in organic

degradation
Processes Entry
TiO
2
+

hv

+

h
+
(1)
O
2
+

e

O
2
- (2)
H
2
O OH

+

H
+
(3)
OH

+

h
+

OH

(4)
O
2

+

H
+

HOO

(5)
2 HOO

O
2
+

H
2
O
2
(6)
H
2
O
2

2 OH

(7)
H
2
O
2
+

e

OH

+

OH

(7)
RH

+

OH

+

H
2
O (8)
R

OH

+

H
2
O (9)
ROH

+

OH

Intermediates

CO
2
(10)
Loss of one carbon atom via the photo-Kolbe reaction:
RCOO

+

h
+

COO

R

+

CO
2


5 Photocatalytic water decontamination
Besides the main field of organic pollutant removal, the
photocatalytic water decontamination can also be employed
for the recovery or the detoxification of inorganic pollut-
ants.
5.1 Inorganic pollutants
Various toxic anions can be oxidized into harmless or less
toxic compounds by using TiO
2
as a photocatalyst. For in-
stance, nitrite is oxidized into nitrate, sulfide, sulfite and
thiosulfate are converted into sulfate, whereas cyanide is
converted either into isocyanate or nitrogen or nitrate.
5.2 Organic pollutants
The aim of our studies was to establish correlations between
the molecular structure of the pollutants and their photo-
catalytic degradability. The analysis of the various interme-
diates was carried out both to have an idea of the degrada-
tion pathways and to determine whether toxic and stable
intermediate compounds are generated.
The dearomatization is rapid even in the case of deacti-
vating substituents on the aromatic ring, such as Cl, NO
2
,
CONH
2
, CO
2
H and OCH
3
. If an aliphatic chain is bound to
the aromatic ring, the breaking of the bond is easy as was
observed in the photocatalytic decomposition of pesticides.
The oxidation of carbon atoms into CO
2
is relatively easy.
It is, however, in general markedly slower than the dearo-
matization of the molecule. Until now, the absence of total
mineralization has only been observed in the case of
s-triazines herbicides, for which the final product obtained
was essentially 1,3,5-triazine-2,4,6, trihydroxy (cyanuric
acid) [34], which is, fortunately, not toxic. This is due to the
high stability of the triazine nucleus, which resists most
oxidation methods.
6 Photocatalytic air treatment
All pollutants degraded in the aqueous phase can also be
destroyed in air, provided the presence of certain air humid-
ity enabling titania to produce cracking OH

radicals at the
surface and/or in the adsorbed phase. This concerns the
degradation of volatile organic compounds (VOCs) and
odors. This is mostly applied to clean air in confined at-
mospheres (workshops, submarines, clean rooms, refrigera-
tors, hospitals) on fixed catalytic beds. For chemical engi-
neering reasons, the photocatalyst has to be used in a fixed
bed, deposited on a photo-inert support. This has been done
using special AHLSTROM papers on which titania can also
be associated with activated carbon to absorb pollution
peaks. In these conditions, UV-irradiated titania-based
photocatalysis could be applied to the elimination of air
pollutants, VOCs, solvents, odors, chemicals, etc.
Some air purification devices are envisaged for the elec-
tronics industry, which requires molecular purity of the
ambient atmosphere for better performances of their nano-
scale components. It can be noted that silicon-containing
VOCs are destroyed, the organic part being mineralized as
CO
2
and H
2
O, whereas Si is converted in silica, which re-
mains at the surface of titania, but without troubles for
photocatalysis as it is transparent to UV-light.
7 Misconceptions in photocatalysis to be avoided
There are common erroneous features in previous reports
which need to be listed to avoid them.
7.1 Use of over-powered UV-lamps
It is not necessary to use overpowered electrical lamps, i.e.,
with an electrical power P

>

100W. It is just necessary to
know the number of UV-photons emitted per second and
adapt it to the optimum quantum yield. Visible photons are
inactive, whereas IR-ones, responsible for heat, can be det-
rimental for the initial (exothermic) adsorption of the reac-
tants.
7.2 Confusion between reaction rate and conversion
Very often it can be read, in published or submitted articles,
that reaction rate r is of the (apparent) first order:
d d r C t kC = =
However, a few lines further in the text, it is written that
the rate decreases when the concentration is increased. This
surprising contradiction is due to the confusion between
reaction rate r and conversion t which is defined as:
1836 HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9
( )
0 0 0
1 C C C C C t = =
From the derivatives of r and t (dr/dC

=

+k and d t

/dC

=

1/C
0
), it is apparent that rate r always increases with C,
whereas conversion t decreases with C. This misconception
is due to the ignorance of definitions in catalysis of new
comers in the field.
7.3 Non-respect to thermodynamics
The attempt to decrease the photon energy towards the visi-
ble to harvest the abundant visible energy spectrum of the
sun needs to take into account the necessity of passing over
a minimum energy threshold because, otherwise, the energy
supply for the activation and the generation of such highly
cracking and degrading species that are OH

radicals would
become thermodynamically detrimental.
+
2
h H O H +OH
+
+


7.4 Conversions lower than the Stoichiometric
Threshold
For demonstrating the true catalytic nature of a photocata-
lytic reaction, the conversion has to be carried out beyond a
certain percentage corresponding to the catalytic threshold.
It is defined as the minimum number of molecules that have
to be converted to be greater than the maximum number of
potential active sites initially present at the surface of a
mass m of titania photocatalyst used in the reaction. If we
admit that for titania the maximum surface site density is
equal to 5

10
18
sites/m
2
according to Boehm [35], a mini-
mum number n
min
of molecules converted equal to n
min
=

(5

10
18
)

S
BET
is obtained. For example, if a photoreactor
contains 1 g of titania Degussa P-25 (with S
BET
=

50 m
2
/g),
which is fully illuminated and respects the laws mentioned
above, a given photocatalytic reaction could be declared
truly catalytic only if the number of converted molecules
is larger than n
min
=

(5

10
18
)

S
BET
=

2.5

10
20
mole-
cules/g
cat
, i.e., 4.2

10
4
mol/g
cat
. Actually, a true catalytic
system works with ratios n/n
min
of several orders of magni-
tude. For example, ratios n/n
min
much higher than 10
3
could
be obtained in alcohol dehydrogenation [21].
7.5 Absence of mass balance determination
All the studies in photocatalysis should include an exhaus-
tive overall mass balance analysis, especially (i) for carbon
based on Total Organic Carbon analysis (TOC) and (ii) for
organic nitrogen. In the latter case, in the photocatalytic
degradation of azo-dyes, the nitrogen mass balance estab-
lished on the final aqueous contents in NH
4
+
and NO
3

could
only reach ca. 30%35% [3638]. A thorough complete
analysis indicates an unsuspected evolution of gaseous ni-
trogen in the air. Actually, this amount of N
2
(g) corresponds
to a 100 % selective conversion of the N=N azo-groups.
Such a result underlines the environmentally friendly char-
acteristic of the degradation of azo-dyes, which represents
45% of the global industrial dye production.
7.6 Erroneous photocatalysis normalized tests
In line with the applications and commercialization of
photocatalytic devices (air purifiers, domestic refrigerators,
self-cleaning materials, etc.), photocatalytic normalized
tests have to be clearly defined and disseminated. In addi-
tion to the above recommendations, a real photocatalytic
activity test can be erroneously claimed if a non-catalytic
side reaction or an artifact does occur. Many tests are based
on dye decolorization, which is easy to perform with a
UV-visible spectrophotometer. However, these tests can
represent the most subtle pseudo-photocatalytic systems,
hiding the actual non-catalytic nature of the reaction in-
volved. This was quantitatively demonstrated with the ap-
parent photocatalytic disappearance of indigo carmine
dye [39]. Whereas indigo carmine IC was totally destroyed
by UV-irradiated titania, its color also disappeared when
only visible light was used. Actually, IC was decolorized
but its corresponding Total Organic Carbon (TOC) re-
mained intact. The loss of color actually corresponded to a
limited stoichiometric transfer to titania of electrons origi-
nating from indigo molecules, photo-excited in the visible
as IC
*
. This is quite possible because the electronic energy
level of IC
*
is higher than that of the conduction band of
titania.
This electron transfer destroys the regular distribution of
conjugated bonds within the dye molecule and causes its
decolorization. Once transferred to titania, the electron par-
ticipates in an additional ionosorption of molecular oxygen
as O
2

.
This is described by the following equations and illus-
trated by Figure 4.

Figure 4 Degradation of Indigo Carmine dye under UV-irradiation (a)
and electron transfer from excited IC
*
molecules without hole formation
under visible light (b) [39].
HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9 1837
( )
( ) ( )
*
ads ads
vis IC IC hv + (10)

( )
( )
*
2 ads
IC IC e TiO
+
+ (11)
( )
( ) 2 2(ads) 2 ads
e TiO O O

+ (12)
When the same reaction was performed with a higher
concentration of IC providing an initial number of mole-
cules larger than the stoichiometric threshold described
above, the solution remained totally colored with the same
constant initial TOC value.
As a consequence, all standardization tests, exclusively
based on dye decolorization, should be banished.
.
7.7 Failure of improvement of the activity by modifica-
tions of the catalysts
This has been done by (i) noble metal deposit and (ii)
ion-doping
7.7.1 Noble metal deposit
The beneficial effects of metal deposits were only observed
for hydrogen-involving reactions. By contrast, these deposits
become detrimental for total oxidation reactions [40]. This
was accounted for by the electron transfer to metal
nano-crystallites, which becomes concurrent to dioxygen
ionosorption.
( )
e Pt e Pt

+ (13)
( )
2 2(ads)
O g e O

+ (14)
In addition, once negatively charged, platinum particles
become attractive for holes which recombine with electrons
into inefficient thermal energy. This is why efficient titania
oxidation photocatalysts do not contain noble metals, which
is of a great advantage for environmental (solar) photocata-
lytic applications.
7.7.2 Ion doping
The other modification aimed at extending the photosensi-
tivity of titania to the visible region to harvest cheaper and
more abundant solar efficient photons. The best expected
case would have been Cr
3+
-doping, because its absorption
spectrum gives a significant shoulder in the visible. Unfor-
tunately, Cr
3+
-doping was found to strongly inhibit the reac-
tions and to decrease the quantum yield [41]. This detri-
mental behavior was confirmed by ion doping, either of the
n-type (by dissolving pentavalent heterocations such as
Nb
5+
, Sb
5+
, Mo
6+

and

Ta
5+
in the lattice of titania)

or of the
p-type (by dissolving trivalent heterocations such as Ga
3+

and Al
3+
).
Actually, it is noteworthy that doping consists of dis-
solving controlled and moderate amounts of heterovalent
cations in lattice sites of Ti
4+
host cations to apply the in-
duction valence law defined in electronics [42] and illus-
trated in Figure 5.
As shown in Figure 5, n-type doping creates additional
conduction electrons, which increases the rate R of electron-
hole recombination:
R
e h . R k
+
( ( =


By contrast, p-type doping creates acceptor center A,
which was once charged as A

, attracts holes h
+
. As a con-
sequence, both pentavalent donor impurities and trivalent
acceptor impurities behave as electron-hole recombination
centers.
Photocatalytic studies on doping have been numerous,
even too numerous. Improvement in catalysis requires a
benefit by at least a factor of two, or even by one order of
magnitude. This was never observed in previous reports.
Our group have personally only observed detrimental ef-
fects since 1982 [30, 41].
Anionic doping has been a new innovative concept with
the narrowing of the band gap energy [43]. For nitrogen
doping (N-doping) which must not be confunded with
n-type doping (see above), it must be demonstrated that (i)
nitrogen is present in a nitride state N
3
, (ii) N
3
anions are
in O
2
lattice bulk positions and (iii) in oxidizing working
conditions, titania has no tendency to self-clean by reoxi-
dizing and expulsing N
3
anions with a favorable decrease
of the ionic radius of element N from 1.71 to 0.55, 0.25,
0.16 and 0.13 for 3, 0, +1, +3 and +5 oxidation number
of N, respectively. My personal position is Wait and see.
8 Environmental photocatalysis: Perspectives
for China
Photocatalysis is particularly attractive for environmental
applications, in line with the rules of Green Chemistry.

Figure 5 Illustration of the doping of titania, either n-type by penta- or
hexavalent heterocations or p-type by trivalent cations.
1838 HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9
8.1 Definition of Green Chemistry
Green Chemistry is not the chemistry of agricultural
products and/or residues. It is that directly connected with
all 12 principles of Green Chemistry [44], which are
listed below:
(1) Prevention
(2) Atom Economy
(3) Less Hazardous Chemical Syntheses
(4) Designing Safer Chemicals
(5) Safer Solvents and Auxiliaries
(6) Design for Energy Efficiency
(7) Use of Renewable Feedstocks
(8) Reduce Derivatives
(9) Use of Catalysis
(10) Design for degradation
(11) Real-time Analysis for Pollution Prevention
(12) Safer Chemistry for Accident Prevention
It can be easily demonstrated that photocatalysis is in line
with at least the nine first principles.
8.2 Green selective mild oxidations in Fine Chemicals
In dry media, photocatalysis is able to induce mild and (regio-)
selective oxidations owing to the creation of a neutral
atomic O
*
species, generated by the neutralization of disso-
ciatively adsorbed oxygen by photo-induced holes
( )
2
TiO hn e h
+
+ +
*
(ads)
O h O
+
+
which are able to insert in a CH bond forming a hot
molecule of alcohol subsequently easily oxidizable in alde-
hyde or ketone.
*
3 2
R CH O R CH OH
+
+
( )
*
2 2
2
R CH OH O R CH OH R CHO H O
+
+ +
For example, a significant intermediate in industrial fine
(perfume) chemistry (4-tert-butyl-benzaldehyde) is envi-
ronmentally-hostilely prepared in industry by a stoichiomet-
ric oxidation of 4-tert-butyl-toluene by permanganate in a
strongly acidic aqueous medium with a lot of (in)organic
by-products:
4 9 6 4 3 4 2 4
4 9 6 4 2 4 4 2
5C H C H CH 4KMnO 6H SO
5C H C H CHO 2K SO 4MnSO 11H O
+ +
+ + +

By contrast, the oxidation of 4-TBT is 100% selective in
4-tert-butyl-benzaldehyde by mere irradiation of titania at
room temperature in pure organic phase (both gas or liquid)
without using water [31]:
( ) | |
4 9 6 4 3 2 2
4 9 6 4 2
C H C H CH O air TiO h
C H C H CHO H O
+ + + v
+

The photocatalytic oxidation of 4-TBT is a typical exam-
ple of Green Chemistry with the use of air and a cheap,
stable and recyclable titania catalyst which does not need
solvents nor heating but only UV-A light provided by lamps
whose technology permanently improves.
8.3 Environmental photocatalysis
As mentioned above, titania becomes a total oxidation cata-
lyst once in water or in humid air because of the photogen-
eration of OH

radicals (2nd best oxidant after fluorine)

resulting from the neutralization of OH

surface groups by
positive holes h
+
.
( )

OH ads h OH
+
+
8.3.1 Water treatment
Many toxic inorganic ions are oxidized in their harmless
upper oxidized state. For example, SO
3
2
, HSO
3

, S
2
O
3
2
, S
2
and HS

are oxidized into innocuous SO

4
2
ions, whereas
PO
3
3
is oxidized into PO
4
3
. NO
2
and NH
4
+
ions are oxidized
into NO
3

, whereas CN

is oxidized into OCN

-
and subse-
quently hydrolyzed into NH
4
+
and CO
3
2
.
The main field of water photocatalytic decontamination
concerns the mineralization of organic pollutants. Most of
aliphatic and aromatic pollutants are totally mineralized into
CO
2
and H
2
O. More complex molecules such as pesticides
(herbicides, insecticides, fungicides, etc.) or dyes are totally
destroyed. The detoxification is total because all hetero-
atoms contained in the initial molecule are converted into
innocuous inorganic anions. In particular, the dangerous
organophosphorous compounds are completely eliminated,
for example, phenitrothion.
It completely disappeared [45] according to the stoich-
iometry:
( ) ( ) ( )
3 6 3 2 3 2
2
2
2 2 2 4 4 3
CH P S O C H NO CH 13 2O
9CO 3H O 4H H PO SO NO
+
+
+ + + + +

In the long degradation chain of this insecticide, the first
intermediate formed is fenitrooxon (see the formula below)
which is used as homicide in warfare gas composition.

fenitrooxon
Another example of green chemistry is the total degrada-
tion of dyes present in used water of textile industries. In
particular, the azo-dyes, which represent 45% of the global
world market, are heavily released in the environment. An
example is given with reactive Red-4 in Figure 6.
HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9 1839

Figure 6 Reactive Red-4 (Cibacron Brilliant Red 3B-A) [38].
max
= 517 nm.
Interestingly, 100% selective degradation of the N=N
azo-groups into di-nitrogen N
2
was observed. This is valid
for all azo-dyes tested and this constitutes a very environ-
mentally-friendly reaction.
Concerning water treatment, photocatalysis is unable to
compete with biological treatments, which are adapted to
large amounts of wastes, while being cheaper and more
friendly to the environment. However, it can be used as a
complementary initial partial treatment by eliminating pol-
lutants which are toxic for bio-organisms. In addition, this
photocatalytic pretreatment should be done upstream, close
to the emission source of pollutants, before dilution or, sig-
nificantly, before mixing with other aqueous pollutants.
8.3.2 Photocatalytic potabilization of water
This is a significant point because photocatalysis can be
efficient for producing moderate amounts of drink water.
Potabilization requires (i) detoxification and (ii) disinfection.
Detoxification was commented in the above paragraph. For
disinfection, photocatalysis is also active in the bio-world
by killing several micro-organisms such as bacteria (E. coli,
streptococcus faecalis, etc.) in water without re-growth.
This is illustrated in Figure 7.
8.3.3 Air treatment
This mainly concerns the degradation of VOCs and odors.
This is mostly applied to clean air in confined atmospheres
(workshops, submarines, clean rooms, refrigerators, hospi-
tals) on fixed catalytic beds. All pollutants degraded in the
aqueous phase can also be destroyed when they are in the

Figure 7 Killing of E. coli before (left) and during the adsorption before
attack by UV-irradiated titania particles (right). (This Figure is from final
report of European Project AQACAT headed by the author.)

air, especially all the VOCs, provided the presence of cer-
tain air humidity enabling titania to produce cracking OH

radicals at the surface to react in the adsorbed phase.
In addition, it has been previously shown that the addi-
tion of activated carbon to titania in the aqueous phase cre-
ated a strong interaction between both solid phases, with a
kind of synergy: activated carbon adsorbs a great amount of
pollutants which are subsequently transferred to titania un-
der the action of a driving force corresponding to an intense
concentration gradient between activated carbon and
self-cleaning titania. Such synergy exists in (humid) air
treatment and enables one to absorb pollution peaks. In
these conditions, UV-irradiated titania-based photocatalysis
could be applied to the elimination of air pollutants, VOCs,
solvents, odors, chemicals, etc.
Concerning odors, air purification has been recently ap-
plied to the removal of odors in confined atmospheres, in
particular in domestic refrigerators (Figure 8) [46]. An
anti-odor domestic refrigerator prototype has been validated,
patented and industrially produced in a first series at 40000
examplaries followed by a second one of 70000 units.
Air treatment also has to be associated to water and solid
waste treatment because of odors. This is done by covering
water treatment ponds or lagunas by rafts on which large
sheets of special strong papers, named as media and pro-
duced by Finnish firm Ahlstrom, whose R&D center is lo-
cated close to Lyon, are deposited, supporting associated
titania-activated carbon catalysts which destroy odors with
solar UV-photons in the daytime, whereas activated carbon
traps odors during the night before their transfer to titania
the next day, the driving force being the very strong con-
centration gradient between AC and self-cleaning titania
(Figures 9 and 10).
The same system for odor removal was also applied to
solid wastes. For example, the sludge of paper mills has to
be stored in warehouses before disposal on agricultural
fields before plowing, which happens only twice a year.
During storage, fermentation occurs with emission of bad
odors, in particular those containing sulfur. These sludges
are stored in special warehouses, whose covers and win-
dows are made of Ahlstrom paper covered with titania as-
sociated with activated carbon.
As for water treatment, titania-based photocatalysis is

Figure 8 Photocatalytic elimination of odors in domestic refrigerators.
1840 HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9
active for disinfection by killing bacteria (E. coli, streptococ-
cus faecalis, etc.) without re-growth. Virus H5N2, a model
virus close to H5N1, responsible for the avian flu, was inac-
tivated in a contaminated air flow of 40 m
3
/h with 99.93%
efficiency for a total air disinfection in a single pass [47].
8.4 Solar photocatalysis or heliophotocatalysis
The UV-A solar spectrum can be advantageously used for

Figure 9 Elimination of strong odors emitted by biological treatment
basins in food industry (presently mustardery close to Dijon) (by courtesy
of Mr. J. Dussaud, Ahlstrom Co., 2007).

Figure 10 (Top): Drying sludge of paper mills stored in a warehouse
whose walls and windows are constituted of special Ahlstrom paper sup-
porting titania. (Bottom): Outside view with sunlight activation) (by cour-
tesy of Mr. J. Dussaud, Ahlstrom Co., 2007).
outside applications as demonstrated by solar prototypes in
agricultural, water and food industries, especially for re-
moval of odors and self-cleaning properties of outdoor ma-
terials. The present challenge is the development of the
photocatalytic engineering for optimization of the reactions,
which are performed in a wide range of media and condi-
tions. The polyphasic nature of the systems has to be taken
into account, including UV-light, the electromagnetic
phase. Different types of photoreactors have been built
with the catalyst used under various shapes: fixed beds,
magnetically or mechanically agitated slurries, catalyst par-
ticles anchored on the walls of the photoreactor or in mem-
branes or on glass beads, or on glass-wool sleeves, small
spherical pellets, etc. The main purpose is to have easy
separation of the catalyst from the fluid medium, thence it is
necessary to support titania and to avoid the final ultrafine
particle filtration.
8.4.1 Solar photocatalytic reactors using slurries of titania
Solar photocatalysis has been baptized Heliophotocataly-
sis by the author, who had the opportunity to intensively
study it at Plataforma Solar de Almeria (PSA) in Spain
within the frame of European cooperation programs [48].
The principle of the CPC photoreactor used is described in
references [49] and [50]. The CPC collector which is the
irradiated part of the system corresponds to a plug flow re-
actor, but as it is connected to a tank via a recirculation
pump, the ensemble corresponds to a batch reactor.
The photocatalytic degradation of various pollutants,
previously studied on the lab scale, was successfully per-
formed in CPC photoreactors at PSA using solar energy, as
exemplified by the total mineralization of 2,4-D (2,4-
dichlorophenoxyacetic acid) [43], a well known herbicide.
Figure 11 shows the temporal variations of 2,4-D, 2,4-

Figure 11 Purification of water containing herbicide 2,4-D. Kinetics of (i)
2,4-D and TOC disappearance, (ii) Cl

anion formation and (iii) 2,4-DCP

appearance and disappearance. (This Figure is from final report of Euro-
pean Project AQACAT headed by the author.)
HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9 1841
dichlorophenol (2,4-DCP), the main intermediate formed,
Cl

anions produced and the total organic carbon (TOC).

After an adsorption period of 1 h in the dark, 2,4-D disap-
pears following a first order kinetics. Cl

anions follow a
sigma shaped curve in agreement with the consecutive reac-
tion scheme:
1 2
2
2, 4-D 4-DCP 2 Cl 8 CO
k k
+
giving
( ) ( ) ( ) ( )
0 2 1 1 1 2 1 2
Cl 2 exp exp C k k k k t k k k k t

( = + (


The TOC decreases linearly to zero within 1 h with an
apparent zero kinetic order. That could be interpreted by
assuming a saturation of surface sites by all the intermedi-
ates.
| |
( )
2
i i i i sat
d TOC d d[CO d
1
i
t t k
k K C K C kq k
u = + = _
= _ + ~ ~

where u
i
represents the surface coverage of the i
th
interme-
diate and u
sat
represents the overall coverage at saturation.
These experiments were compared with initial studies
performed in a laboratory microphotoreactor working with
artificial light. Despite a volume extrapolation factor of
12500, the same first order was found for 2,4-D disappear-
ance; the quantum yields and the intermediates were the
same, indicating an identical reaction pathway.
8.4.2 Solar photocatalytic reactors using deposited titania
Although slurry photoreactors can be estimated as the most
efficient, they exhibit a significant drawback: the final tedi-
ous filtration of titania particles. To overcome this obstacle,
titania can be deposited on photo-inert supports. A success-
ful attempt was made by depositing titania on special Ahl-
strom paper using amorphous silica as a binder to anchor
the photocatalyst particles on inorganic fibers. Such a
photocatalytic material has been used in an adapted solar
photoreactor named Cascade Falling Films Photoreactor
(CFFP) described in Figures 12 and 13.
The photocatalytic activity is based on the rate of the

Figure 12 Comparative schemes of CPC and Cascade Falling Films
Photoreactors.

Figure 13 Comparison of the activities of titania photocatalysts used (i)
in a CPC slurry photoreactor (bottom right) and (ii) in a Cascade Falling
Films photoreactor using a titania fixed bed deposited on Ahlstrom paper
(bottom left).
Total Organic Carbon (TOC) removal from a solution con-
taining 50 ppm of 4-chlorophenol chosen as a model pol-
lutant. To test the efficiency of the CFFP solar reactor,
photocatalytic reactions were calibrated against a slurry
CPC photoreactor having the same surface of a sun collec-
tor as shown in photographs in Figure 13. Surprisingly, the
results were similar in the total degradation of 4-chlroro-
phenol as indicated by the Total Organic Carbon (TOC)
disappearance (Figure 13).
These fixed bed photoreactors were used to produce drink
water for remote isolated human communities in arid coun-
tries either in North Africa (European AQUACAT Program)
or in Latin America (European SOLWATER Program).
8.4.3 Solar photocatalytic for self-cleaning materials
Besides fixation of titania on a support, used in various
types of photoreactors, material science is developing to
prepare thin and invisible layers of titania on self-cleaning
objects, such as glass, concrete walls, ceramics, and tools.
Solar photocatalysis is actually an efficient process,
which makes self-cleaning glass work. Fouling of glass is
mainly due to dust and/or atmospheric particles stuck at the
surface on greasy stains mainly constituted of fatty acids.
Self-cleaning glass is coated with an invisible thin layer of
titania, which, in the simultaneous presence of oxygen (air),
atmospheric water vapor and solar UV-light, is able to de-
compose fatty acids by successive photodecarboxylation
reactions named photo-Kolbe [51] and make coated glass
recover its initial cleanness.
9 Conclusions
An overview has been presented on the various aspects and
potentials of heterogeneous photocatalysis. The potential
applications strongly depend on the future development of
photocatalytic engineering.
1842 HERRMANN Jean Marie Sci China Chem September (2010) Vol.53 No.9
Water pollutant removal appears as the most promising
potential application as many toxic water pollutants, either
organic or inorganic, are totally mineralized or oxidized at
their higher degrees into harmless final compounds. Despite
some drawbacks (use of UV-photons and necessity for the
treated waters to be transparent in the spectral region; slow
complete mineralization in cases where heteroatoms are at a
very low oxidation degree; photocatalytic engineering to be
developed), room-temperature heterogeneous photocatalysis
offers interesting advantages: (i) chemical stability of TiO
2

in aqueous media and in a large range of pH (0 pH 14),
(ii) low cost of titania, (iii) cheap chemicals in use, (iv) no
additives required (only oxygen from the air), (v) systems
applicable at low concentrations, (vi) total mineralization
achieved for many organic pollutants, (vii) efficiency of
photocatalysis with halogenated compounds sometimes
very toxic for bacteria in biological water treatment, and
(viii) possible combination with other decontamination
methods (in particular biological).
As the number of publications on photocatalysis has in-
creased exponentially, photocatalysis has to be urgently
refocused concerning the following challenges:
(1) Are we condemned to exclusively work with tita-
nia?
(2) Can TiO
2
be photosensitized in the visible by doping?
(It is already known that cationic doping is not efficient and
rather detrimental, whereas anionic doping, still under in-
vestigation, has to be more clearly defined.)
(3) Can we find a new photocatalyst, different from TiO
2

and directly active in the visible?
(4) Can invisible titania thin layers be efficient enough
when deposited on self-cleaning objects?
(5) Is photocatalysis suitable for preparative Fine Chem-
istry as exemplified in 8.2?
(6) Is photocatalysis bactericidal enough in water and in
air?
(7) Can photocatalysis be employed as a new medical
tool in medicine (cancericide effect) [52]?
(8) Are we able to define a few standardized and globally
accepted tests for each photocatalytic application?
(9) Are we able to adapt to Chemical Engineering culture
to promote environmental and green applications of
photocatalysis?
This listing may constitute serious objectives for future
research in photocatalysis.
The author is indebted to Mrs. C. Delbecque for her help in editing this
paper and to M. J. Dussaud from Ahlstrom Co.,/ for the communication on
his performing industrial devices. The author also thanks Drs. J. Blanco
and S. Malato for their initiation to solar photocatalytic engineering.
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