INTRODUCTION TO ENVIRONMENTAL

PHOTOCATALYSIS
(fundamental and applications)

Dr. Didier ROBERT

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 Contents

1- Advanced oxidation technologies (AOT)

2- Background of photocatalysis

3- Photoactivity of TiO2 nanoparticles and reactions

4- Fundamental parameters

5- Solar heterogeneous photocatalysis

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 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

1. Advanced oxidation technologies (AOT)

Advanced Oxidation technology is a method that uses a range of technologies to

the increase oxidation power.

Oxidizing agent Oxidation Relative oxidation

AOT produces OH° RADICAL which
Potential (V) power *
has stronger oxidation power than
Chlorine 1.36 1 ordinary oxidants normally used in
oxygen 1.23 0.88 the oxidation process in water

permanganate ion 1.67 1.24

HO2° (perhydroxyl 1.70 1.25

radical)
Hydrogen peroxide 1.77 1.3
OH° decomposes the organic
Ozone 2.07 1.52 compounds into relatively harmless
OH° radical 2.80 2.06 compounds, such as CO2, H2O or
HCl.
Table 1: Redox potential of major oxidizing agents that are used in water treatment
technology

* Relative oxidizing power when chlorine’s oxidation power is 1

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 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
A variety of AOTs exist according to the methods to generate Hydroxyl radicals :

Ozone treatment Electrochemical process

High pH
H2O2 Electro Fenton
UV-Vis Anodic Fenton

OH° Photocatalysis

Direct decomposition of The advanced technology that

water Semiconductive metal uses TiO2 photocatalysis is
and metal oxides attracting the most attention for
(TiO2, ZnO, Fe2O3, WO3, CdS, ZnS, etc…)
- Radiolysis generating OH° using only
Ultrasound photoenergy without additional
Microwave chemicals.

Figure 1 : Hydroxyl radicals formed according to advanced oxidation technologies

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 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
Table 2 : Advantages and disadvantages of photocatalytic system and existing water treatment methods

AOTs Advantage Disadvantage

- High reliability of the method - Efficiency of processing difficulty securing

stable
Biological treatment technique
- High load operation can be processed - high level of sludge,
- Operating management requires
expective

Coagulation/precipitation - High efficiency of processing - Excessive sludge

- Difficulty to maintain
- Low sites

- Wide coverage - High operating cost over the use of the

-Treatment process is simple and easy to Fenton’ s reagent
Fenton technology
manage - Remove the equipment needing iron salts
- Effective colored dicsoloration of
wastewater

- Non-biodegradable waste water - Limited lamp life when UV-Lamp is used

treatment is possible - Photocatalyst recovery facility when
Heterogeneous Photocatalysis
- Low operational and installation cost using powder
- Unprofessional and unmannd operation
is possible
- Less area is linked with the existing
treatment facilities
- Sludge treatment costs do not occur, no
burden of costs

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 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
2. Background of photocatalysis

- 1970 : Two research teams, (French and Japanese) revealed the possibility of hydrogen production through
water decomposition by photocatalysis and solar energy
-Formenti et al, Physics in technology, 1(1971) 680

An explosive research began! - Fujishima, Honda, Nature 238(1972)37

- Afterwards, the interest in TiO2 photocatalysis has been growing in the academic and industrial fields, and
has been applied actively to :

 Hydrogen production
 Air cleaning
 Metal anti-corrosion Some of these technologies have been
 Self-purification released on the market
 Water treatment
Antibacterial activity…
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

ENVIRONMENTAL
Water purification Residence
Removal of hazardous Painting/Tile
Air purification Substances/Disinfection Glass/Tent
Deodorizing
Removal of air pollutants
Car Agriculture
Side mirror Removal of residual pesticide
Electric appliance Hydroponic culture
Refrigerator deodorization
Fluorescent light
TiO2 + Light
Road Medical
Tunnel lighting - Oxidation or Cancer treatment
Removal NOx, Self cleaning reduction Catheter/Operating room
- Superhydrophilicity

Energy concersion Water splitting

Solar battery Hydrogen production

ENERGY
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Figure 2 : Various applications of TiO2 photocatalyst
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
2. Background of photocatalysis

- 1970 : Two research teams, (French and Japanese) revealed the possibility of hydrogen production through
water decomposition by photocatalysis and solar energy
-Formenti et al, Physics in technology, 1(1971) 680

An explosive research began! - Fujishima, Honda, Nature 238(1972)37

- Afterwards, the interest in TiO2 photocatalysis has been growing in the academic and industrial fields, and
has been applied actively to :

 Hydrogen production
 Air cleaning
 Metal anti-corrosion Some of these technologies have been
 Self-purification released on the market
 Water treatment
Antibacterial activity…

- Since then, fundamental processes of TiO 2 photocatalysis have been

studied intensively.

The publication number increases exponentially with publication

years. Over 10,000 papers have been published each year on TiO 2
since 2000.

Fig. 3 shows the publication in the past 100 publication years.

 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

 Several semiconductors (oxides and sulfides) have been developed to exhibit

photocatalytic behaviour. The most commonly referenced semiconductors for wastewater
degradation are TiO2, ZnO, CdS, Fe2O3....

 Titanium dioxide has been demonstrated to be an excellent catalyst because of its

photooxidation efficiency and stability under illumination in aqueous environments.

 The best photocatalytic performances with maximum quantum yields are always obtained
with titania. Anatase is the most active allotropic form.

SOME REFERENCES IN THE FIELD OF PHOTOCATALYSIS

- Pichat P. in Handbook of heterogeneous photocatalysis, eds G. Ert, H. Knözinger and J.

Weitkamp, VCH-Wiley, Weiheim, 1997, p. 2111.

-K. Hashimoto, H. Irie, A. Fujishima, Japanese Journal of Applied Physics, 44(2005) 8269–
8285

- J.M. Herrmann, Topics in Catalysis Vol. 34, Nos. 1–4, May 2005.

-Bahnemann D. Photocatalytic water treatment: solar energy applications, Solar Energy

77(2004)445-459.

- S. Malato et al, Decontamination and disinfection of water by solar photocatalysis: Recent

overview and trends Review Article Catalysis Today, 147(2009)1-59
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 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

According to EPA, more than 1200 compounds can be eliminated by this process
(Blake NREL 2001).

USES COMPOUNDS

Chloroform, CCl4, dichloromethane,

Chlorinated Solvents trichlorethylene, chlorobenzene...

Acetone, acetonitrile, benzene, cyclohexane,

Other Solvents formaldehyde, phenol, toluene...

aldrin, dichlorvos, lindane, parathion,

Pesticides monocrotophos,...

Herbicides atrazine, diuron, monuron, ...

Dyes Acid orange 7, malachite green, naphtol blue

black...

Detergents Octoxynol (triton X-100)...

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 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

Water disinfection : mechanism of bacteria degradation by TiO2

photocatalysis

- Close contact between the bacteria

and the catalyst

- Destruction of the cell wall

- Degradation of internal components TiO2

of the cell ?
H2O2
O2°- OH°
Bacteria
Photocatalysis has proven its
effectiveness to degrade :

- Bacteria (coliform, E. coli,

Figure 1: Dispersion of TiO2 in contact with the E. coli
- Virus (A/H5N2…),
bacteria, observed by TEM
- Pathogen fungi (fusarium…)
By Rincón A.G., Pulgarin C., Solar Energy, 2004, 77, p. 635
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 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
3. Photoactivity of TiO2 nanoparticles and reactions

A. Photogeneration of holes and electrons :

h
TiO2 h+ + e-

This excited electrons and holes can either be used directly to create electricity in
photovoltaic solar cells or drive a chemical reaction, which is called photocatalysis

The oxidation potential of the photo-induced holes is up to 3.0 eV much higher than that of hydrogen (1.36 eV) and ozone
(2.07 eV).

Therefore the formed electron-hole pairs are strong redox systems.

B. Holes on nanoparticles surfaces can oxidize OH - and H2O molecules absorbed on TiO2 surface into hydroxyl
radicals
h+ + H2O OH° + H+

h+ + OH- OH°

C. e- reacts with an electron acceptor such as O 2 to form superoxide radical :

O2
e -
O 2 -°
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
D - Attack of pollutants by OH° radicals or holes

Hydroxyl and peroxy radicals : OH°, O2-° are atomic species with a free unpaired electron,
possessing strong ability to degrade organic pollutants

OH°, h+, O2-°…

Organic pollutants (ads) intermediates H 2O + CO2 + ions

For exemple : photocatalytic

degradation of phenol

FINAL STEP : Mineralization

 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

Figure 4: Schematic illustration on removal of pollutants by the formation of photoinduced charge carriers
(e-/h+) in a semiconductor TiO2 particle surface

O2°-, HO2°

h >3.2 eV O2
Conduction band
<400 nm e- e- e-

Eg = 3.2 eV
h

OH-, H2O, pollutant

h+ h+ h+
Valence band

CO2, H2O… OH°, pollutant°+

TiO2 14
INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
PHOTOCATALYTIC PROCESSES

HETEROGENEOUS CATALYSIS
PHOTO CATALYSIS

1) Transfer of the reactants in the fluid phase

2) Adsorption of the reactants at the surface of the catalyst

3) Reaction in the adsorbed phase

3.1 Absorption of photons by the solid (no photochemistry)

3.2 Creation of photo-induced electrons and holes

3.3 Electron Transfer Reactions (Ionosorption, charge neutralization,

radical formation, surface reactions...)

4) Desorption of the final products

5) Removal of the final products in the fluid phase

 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
4. Fundamental parameters

The rate and efficiency of a photocatalytic reaction depends on a number of factors which govern
the kinetics of photocatalysis such as :

Initial concentration of Mass of photocatalyst

reactant,

Semi-conductor
photocatalysis
pH
Radiant flux

Concentration of oxygen

Figure 5 : Factors which govern the kinetics of photocatalysis

 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
- Initial concentration of reactant
Generally, the kinetics follows a Langmuir–Hinshelwood (L-H) mechanism confirming the heterogeneous catalytic
character of the system. According L-H, the reaction rate r is proportional to the fraction of surface covered by the
substrate θx, kr the reaction rate constant, C the concentration of reactant and K is the reactant adsorption constant :

For diluted solutions (C < 10−3M), KC becomes <<1 and the reaction is of the
kr KC
r = - dC = krθx = apparent first order,
dt 1 + KC whereas for concentrations >5.10−3M, (KC1), the reaction rate is maximum
and of the zero order

Due to the saturation produced on the TiO 2

surface as the concentration of the reactant
increase,

it reaches a point at which the

rate becomes steady.

Figure 6 : Effect of the initial concentration on the degradation rate

 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
- Mass of photocatalyst
TiO2 is often used as suspension and the rate of photomineralization is generally found to increase with catalyst concentration
towards a limiting value at high TiO2 concentration.

This limit depends on the geometry and working conditions of the photoreactor and is for a definite
amount of TiO2 in which all the particles are totally illuminated.

When catalyst concentration is very high, after

travelling a certain distance on an optical path,
turbidity impedes further penetration of light in the
reactor

This optimum catalyst mass has to be found

in order to avoid excess catalyst and ensure
total absorption of efficient photons.

Figure 7: Effect of the catalyst concentration on the degradation rate

carbamazepine
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
- pH (in the case of water treatment) The pH of the aqueous solution significantly affects TiO 2 :
- the charge on the particles,
- the size of the aggregates and it forms
- the positions of the conductance and valence bands).

The pH at which the surface of an oxide is uncharged is defined as the Zero Point Charge (pHZPC), which for TiO2 depends on the
production method (for exemple pHZPC = 6.3 for TiO2-P25).

-TiOH2+ TiOH + H+ pK TiOH2+ = 2.4

-TiOH TiO- + H+ pK TiOH = 8.0

3 pH 10

TiOH2+ > 20% TiOH > 80% TiO- > 20%

-Under these conditions, the photocatalytic degradation of the ionizable organic compounds is affected by
the pH.

- For pollutants for which pKa is outside the range of 1 to 13, a very acidic solution appears to be detrimental
and very basic solution to be favourable, since the variations are modest or non-existent around neutrality.
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

Exemple : pH effect on the degradation of 4-hydroxybenzoic acid.

For acidic organic molecule (acids or phenols), two phenomena have to be taken in account:

1- the adsorption, via surface carboxylate or phenolate formation: at pH lower than the pHzpc of TiO 2,
the higher the adsorption, the higher is the degradation;

2- at basic pH values, the change in the surface charge of the TiO 2 phenomenon leads to additional
repulsion, leading to a decrease in the degradation of 4-HBZ.

The higher the adsorption,

The higher is the degradation

TiOH2+ TiO-
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

- Oxygen concentration

In semiconductor photocatalysis for water purification, the pollutants are usually organic and, therefore, the overall process
can be summarized by the following equation :

TiO2 + light
Organic pollutant + O2 CO2 + H2O + Mineral acids

 Oxygen is necessary for complete mineralization and does not seem to be competitive with other reactives during the
adsorption on TiO2 since oxidation takes place at a different location from where reduction occurs .

 The concentration of oxygen also affects the reaction rate but it seems that the difference between using air or pure
oxygen is not drastic.
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

- Radiant flux

The rate of reaction r is proportional to the radiant flux Φ.

 This confirms the photo-induced nature of the activation of the Φ1/2

catalytic process, with the participation of photo-induced electrical

rate
charges (electrons and holes) to the reaction mechanism.

 The optimal light power utilization corresponds to the domain where r

is proportional to Φ.
Φ

 However, above a certain value, the reaction rate r becomes

proportional to Φ1/2.

radiant flux Φ

- Wavelength
TiO2 having EG = 3.02 eV,
this requires: λ ≤ 400 nm
The variations of the reaction rate as a function of the
wavelength follows the absorption spectrum of the catalyst
with a threshold corresponding to its band gap energy.

 It must 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).
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS

Table : Summary of factors which govern the kinetics of photocatalysis and their effect on the rate of the
photocatalytic reactions
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
5. Solar heterogeneous photocatalysis
TiO2 is actually the most popular photocatalyst….HOWEVER, the main problems of TiO 2 are:

- The rapid recombination of photoproduced holes and electrons significantly decreases the efficiency of
the photocatalytic reactions.
- Titanium dioxide absorbs only a small fraction of solar light (Eg = 3.2 eV   < 380nm)

LIMITATION OF PRACTICAL
APPLICATIONS

TiO2
A.U

Particularly with
SOLAR ENERGY Solar spectrum

250 300 350 400 450 500

Wavelenght (nm)

Photocatalysis
Only 5% of the solar spectrum at the
area
earth surface can be utilized
 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
- How to enhances solar TiO2 heterogeneous photocatalysis?

Firstly, it is possible to replace TiO2 by another semiconductor better adapted to solar spectrum (with a smaller
bandgap), eg CdS or WO3.

Table 3 : Band position (water pH 1) for some common semiconductor

photocatalysis.
Valence Band Conduction Band Band gap Band gap
Semiconducto (V vs NHE) (V vs NHE) energy wavelength
(eV) (nm)
r
TiO2 +3.1 -0.1 3.2 387

SnO2 +4.1 +0.3 3.9 318

ZnO +3.0 -0.2 3.2 387

ZnS + 1.4 -2.3 3.7 335
However, CdS is photooxidizable and it will
WO3 + 3.0 +0.4 2.8 443 release Cd2+ ions in water and WO3 is much
CdS + 2.1 -0.4 2.5 496 less effective as a photocatalyst than TiO 2.

CdSe + 1.6 -0.1 1.7 729

Fe2O3 2.2 565

New composites for solar photocatalysts actually studied in

research laboratories :

- Bi2O3, Cu2WS4, BiOCl, ZnFe2O4, Ag/AG3PO4

Ref: M.A. Fox, in Photocatalysis and environment, Kluwer A.C. 1988.

 INTRODUCTION TO ENVIRONMENTAL PHOTOCATALYSIS
- How to enhances solar TiO2 heterogeneous photocatalysis?
SECONDLY: Coupling titanium dioxide with narrow bandgap semiconductor : When a large band gap semiconductor is
coupled with a small band gap semiconductor with a more negative conduction band level, conduction electron can be
injected from the small band gap semiconductor to the large band gap semiconductor.

Bi2S3 is a good candidate for a preparation

Small bandgap SC Large bandgap SC of an efficiency heterojunction with TiO2.
e- e-
e -
e-
e -
e- Because, its conduction band is less
anodic than the corresponding band
of TiO2 and the valence band of this
sensitizer is more cathodic than the
valence band of TiO2.

Under visible (solar) irradiation, a

photoelectron generated on Bi2S3
can be injected into the (inactivated)
TiO2 conduction band while the
photoholes remains on Bi2S3.

Fig. . Energetic diagrams of Bi2S3/TiO2 heterojunction at pH 7.