University of Salerno

Heterogeneous photocatalysis
Department of Chemical and Food Engineering
Catalysis
A chemical reaction can be catalyzed so that the energy of the transition
state is lower than without a catalyst, and the rate can be increased.
Catalysis is the change in rate of a chemical
reaction due to the participation of a substance
called a catalyst.

Catalytic reactions have a lower rate-limiting free
energy of activation than the corresponding
uncatalyzed reaction, resulting in higher reaction
rate at the same temperature. However, the
mechanistic explanation of catalysis is complex.
Chemical reactions activation
Thermal activation: the reaction rate is increased by increasing the
temperature (Arrhenius law)

Catalytic activation: The reaction rate is increased through the action of
a catalytic substance (temperature lower than uncatalyzed reactions)

Photochemical activation: Some chemical reactions are activated by
electromagnetic radiation (light)

Radiochemical activation: o, |, and x rays, due to their high energy,
could activate chemical reactions also at very low temperature

Radiochemical activation: a, b, g and x rays, due to their high energy,
could activate chemical reactions also at very low temperature

Electrochemical processes: Electrical current flow can provide the
energy required for the activation of chemical reactions

Types of catalysis
Homogeneous catalysts: If the catalyst and reactants or their solution
form a common physical phase, then the reaction is called homogeneously
catalyzed.
Metal salts of organic acids, organometallic complexes, and carbonyls of
Co, Fe, and Rh are typical homogeneous catalysts.

Examples of homogeneously catalyzed reactions are oxidation of toluene
to benzoic acid in the presence of Co and Mn benzoates and
hydroformylation of olefins to give the corresponding aldehydes. This
reaction is catalyzed by carbonyls of Co or Rh.

Heterogeneous catalysts: Heterogeneous catalysis involves systems in
which catalyst and reactants form separate physical phases.
Typical heterogeneous catalysts are inorganic solids such as metals,
oxides, sulfides, and metal salts, but they may also be organic materials
such as organic hydroperoxides, ion exchangers, and enzymes.

An example of heterogeneously catalyzed reaction is ammonia synthesis
from the elements over promoted iron catalysts in the gas phase.

Different forms of heterogeneous
catalysts
Catalysts can be used in different forms:


Powder: mainly used in slurry reactors for the treatment of
wastewater


Pellets: mainly used in fixed-bed reactors for the treatment of gaseous
streams


Structured (monoliths): used in processes to minimize the pressure
drop- pollutants abatement in power plants (SCR for NOx abatement,
HC and NOx removal in engine exhaust after treatment device)
Advanced oxidation processes
Heterogeneous photocatalysis
Catalytic oxidation
i.e. Fenton and photofenton
H
2
O
2
+ Fe
2+
OH + OH
-
+ Fe
3+
Fe
3+
+ H
2
O
2
Fe
2+
+ HO
2

+ H
+
Fe
3+
+ H
2
O+

hv

Fe
2+
+ HO

+ H
+
AOPs (advanced oxidation processes) to be taken in consideration for
wastewater treatment
Catalysis Pulsed plasma Electrochemistry Super-critical water oxidation
Fenton Ultrasounds UV UV/H
2
O
2
Ionizing Radiation Microwaves O
3
Wet-air Oxidation


Photochemical treatment and in particular
Heterogeneous catalysis VS Photocatalysis
Classical heterogeneous catalytic process can be divided
into five independent steps
Transfer of the reactants in the fluid phase to the surface.
Adsorption of at least one of the reactants.
Reaction in the adsorbed phase.
Desorption of the product(s).
Removal of the products from the interface region.
The only difference with conventional catalysis is the way of the
catalyst activation . Thermal activation is replaced by a
photonic activation
Light wave lenght: Light frequency:
= c /
E
p
= h *c/ =h
Semiconductors
Difference in the energy arrangement between an isolated atom and the atom in a solid
Band gap, also called energy
gap, is the energy range in a
solid where no electron exist
Band gap of some semiconductors
Band gap determines if a
substance is an insulator,
semiconductor, or conductor.
Energy level diagram
s380 nm
s440 nm
Department of Chemical and Food Engineering
Heterogeneous Photocatalysis
h + SC e
-
+ p
+
A
(Ads)
+ e
-
A
-
(Ads)

D
(Ads)
+ p
+
D
+
(Ads)

e
-
+ p
+
Energy
h > E
bg
A
-
and D
+
are highly reactive species which oxidize or reduce the
compounds adsorbed on the catalyst surface .
E
bg=
Band gap Energy

Semiconductors in photocatalysis
The most used semiconductor in
photocatalytic processes is TiO
2
TiO
2
crystallographic forms:
Anatase (important in photocatalysis).
Rutile
Brookite



Ti
O
OH
Ti Ti
OH
O
H
On TiO
2
surface
O O
Reactions in photocatalytic process
with TiO
2
+
+ h e hv
Light Absorption
Bulk Reactions
heat h e +
+

Recombination
- +
+
OH OH h
Hole Conversion
Surface Electron
Transfer Reactions

+
2 2
O O e Electron Conversion
2 2
HO H O +
+
-

+
2 2
HO e HO -
2 2 2
O H H HO +
+
-
Surface Reactions
(Acid Conditions)

+ OH O HO 2 2
2 2
-

+ + OH HO O H O
2 2 2
-

+
2 2
HO e HO -
Surface Reactions
(Basic Conditions)

+ OH O HO 2 2
2 2
-

Main factors affecting kinetics of a
photocatalytic process

Catalyst weight.
Light wavelength.
Initial concentration of reactants.
Reaction temperature.
Photonic flux.
Influence of photocatalyst weight

The reaction rate of a photocatalytic reaction increases with
catalyst weight.
Above a certain value of m the reaction rate becomes
independent of the mass.
Influence of photocatalyst weight

The reaction rate of a photocatalytic reaction increases with
catalyst weight.
Above a certain value of m the reaction rate becomes
independent of the mass.
All particles of photocatalyst
are fully illuminated
Part of the photosensitive
area is masked
Influence of light wavelength

The trend of reaction rate as a function of wavelength follows
the absorption spectrum of the catalyst, with a threshold that
corresponds to the energy of Band-Gap.

It 'worth checking that there is no absorption by the reagent,
so as to ensure that all the photons hitting the photocatalyst,
activating it.

Influence of initial reactant
concentration

Generally, the kinetics follows the Langmuir-Hinshelwood
mechanism.

The reaction rate r varies proportionally with the coverage
degree according to:

KC << 1

First order
kinetics

KC >> 1

Order zero
kinetics

1
KC
r k k
KC
u
| |
= =
|
+
\ .
Influence of reaction temperature

Initially, the reaction rate increases with temperature (Arrhenius-type
dependency).
There is also a temperature range within the reaction rate is almost
constant or increases slightly as there are other limiting factors such
as the photon flux.
Further increasing the temperature, the reaction rate decreases
markedly, as in this state the desorption of reagents is favored
decreasing the reaction rate.

Effect of photonic flux

The reaction rate is proportional to the photon flux .
Above a threshold value, the reaction rate becomes proportional to

1/2
: the rate of formation of electron-hole pairs is higher than the
rate of photocatalytic reaction, and this promotes the phenomenon of
recombination.


Cyclohexane total oxidation:
thermodynamic evaluation
80
85
90
95
100
0 200 400 600 800 1000 1200 1400
T, C
C
6
H
1
2

c
o
n
v
e
r
s
i
o
n
,

%
C
6
H
12
+9O
2
6CO
2
+6H
2
O
Photocatalysis applications
Environmental
Wastewater treatment
Air purification
Disinfection
Self cleaning materials


Novel syntheses
Selective synthesis of organic chemicals
Hydrogen production by direct pthotocatalytic water splitting

Photocatalysis and Environment
Wastewater treatment.

Abatement of pollutants in gas streams (VOC, NO
x
,
sulfur compounds and chlorinated hydrocarbons)

Disinfection
Reactions of photocatalysis for water
purification: advantages
The photocatalytic reactions are non-specific, able
to degrade a wide range of organic compounds
(hydrocarbons, halogenated solvents, pesticides
and toxic organic compounds).

The process is able to completely mineralize organic
substances

The process is suitable for degradation of xenobiotic
toxic compounds
Commercial applications of photocatalysis (1/4)
Photo-Cat water treatment systems (Purifics) is able
to treat wastewaters having high turbidity, high levels
of dissolved solids and high concentrations of metals.
Commercial applications of photocatalysis:
depuration of aquariums (2/4)
Commercial applications of photocatalysis:
(3/4)
Depuration of aquariums
Commercial applications of photocatalysis:
(4/4)
Depuration of aquariums
Examples of photoreactors for the treatment of
wastewater: double layer sheet solar
photoreactor
The reactor consists of a series of channels through which
circulates water
The photoreactor is made of Plexiglas (polymethyl meta
acrylate) which is very transparent to UV radiation.
Examples of photoreactors: photoreactor for the
degradation of the CN- ion
A catalytic photoreactor is currently used for the degradation of the CN-
ion (Plataforma Solar de Almera, Spain)

Solar photoreactor and scheme of the pilot plant : A) sampling
valves, B) thermocouples, C) reservoirs containing reagents, D)
pumps, PFP) plug flow photoreactor
Examples of photoreactors: photoreactor for the
cyanide degradation
A photocatalytic reactor that uses UV lamps is currently the heart
of a pilot plant used to degrade cyanide, contained inside an in
industrial waste at Puertollano, Spain.
Schematic and photograph of the pilot reactor tank
containing reagents
Photocatalysis for disinfection
Its possible to consider photocatalytic disinfection
processes using suspended TiO
2

E. Coli destruction by irradiated TiO
2
Department of Chemical and Food Engineering
Benzene
[X. Fu, W. A. Zeltner, M. A. Anderson ;(1995). N. N. Lichtin, M. Sadeghi;(1998)]
Trichloroethane
[L. A. Dibble, G. B. Raupp; (1988). D. M. Blake, W. A. Jacoby and M. R. Nimlos; (1992)]
Acetone
[Jun Lin, Jimmy C. Yu; (1998)]
Methanol [C. S. Turchi, R. Rabago; (1995)]
Acetaldehyde
[I. Sopyan, M. Watanabe, S. Murasawa, K. Hashimoto, A. Fujishima; (1996). E. Obuchi, T.
Sakamoto and K. Nakano; (1999)]
Toluene
[ O. dHennezel, P. Pichat, D. F. Ollis; (1998)]
Cyclohexane
[ H. Einaga, S. Futamura, T. Ibusuki; (2002)]
Photocatalytic treatment of gaseous
streams
PHOTOCATALYST: TiO
2
anatase
Photocatalytic oxidation systems: advantages
Room temperature
High efficiency for substance degradation also
when using low-power radiation sources.
Complete oxidation of hydrocarbons, with the
formation of CO
2
and H
2
O, without undesired
products (CO and NOx)
Use of cheap and non-toxic catalysts (TiO
2
).

Main odorous compounds and their origin
Volatile organic acids
Ammonia and amines
Aromatic and other ring structures
Sulfur compounds (H
2
S, mercaptans, etc.).
Peculiar activities able to origin disturbing smells:

Wastewater treatment plants
Composting plants
Tanneries
Petrochemical planes
Food industries
Typical stinking compounds degraded by
means of catalytic processes
Photocatalytic Purification Systems

A typical application of photocatalytic materials is for air
purification using UV lamps
Air purifiers are designed in different sizes, ranging from
household (100 m
3
/h) to ventilation systems for tunnels
(1,500,000 m
3
/h).
Many of these systems work in combination with filters
or electrostatic precipitators which remove some of the
dangerous gases and airborne particles
Photocatalytic materials
Cementitious materials, containing titanium dioxide (within 1 - 5%)
and irradiated with sunlight, have a high efficiency in the oxidation of
the organic substances which settle on them, keeping their colour
unchanged in the time
Antibacterial materials (glass and ceramics containing TiO
2
, for
hospitals information from literature confirms the possibility to
destroy bacteria and viruses thanks to the photocatalytic activity of
TiO
2
)
Photocatalytic materials
Self-cleaning materials (cement, glass) coated with
TiO
2
films
Photo-induced super-hydrophilicity
Slow, no light
NOx decomposition promoted by eco-
coatings
A photocatalytic application, still under study but already tested in laboratory
and in situ, deals with the possibility to reduce the nitrogen oxides (NOx),
currently produced by the exhaust of cars and vehicles, by using cementitious
materials (paints, floorings or self-locking blocks)
UV light promotes the activation of the TiO
2
, contained in the materials, and the
subsequent degradation of pollutants such as NO and NO
2
, which are first
adsorbed on the particles and then converted into nitric acid (HNO
3
).
Rain washes away the nitric acid as harmless nitrate ions, which may be used to
fertilize the soil, or the acid can be neutralized by the alkaline calcium carbonate
contained in the materials.
Self-cleaning coatings: applications(1/3)
Dives in Misericordia (Roma)
Self-cleaning coatings: applications(2/3)
Facade and structural detail of the of the City of Music and Fine
Arts in Chambery (France)
Self-cleaning coatings: applications(3/3)
Department of Chemical and Food Engineering
Photocatalysis for green chemistry
Advantages
Possibility to operate at ambient temperature and pressure
Catalysts relatively inexpensive (mainly TiO
2
based)
Photocatalysis can lead to more sustainable processes by :
Increasing process selectivity to the required products
Different chemistry
Decreasing energy consumption of the process
Heterogeneous photocatalysis is a promising technology for a wide range of
applications, such as organic synthesis, photo-destruction of volatile organic
compounds and purification of waste water
Department of Chemical and Food Engineering
Hydrocarbons selective Photo-oxidation Reactions
Reactants Cataysts Products References
Olephins
(Prophilene)
TiO
2
, MoO
3
,
WO
3
, CdS
epoxides,
alcohols,
aldehydes, and
ketones
Ward, M. D.; Brazdill, J. F., Jr.; Grasselli, R. K. U.S. Patent 4,571,290,
1986
Toluene TiO
2
Benzaldehyde
Gonzalez, M. A.; Howell S. G. and Sikdar, S. K. J. Catal. 1999, 183, 159.
Fujihira, M.; Satoh, J.; Osa, T. Nature 1981, 293, 206
Naphthalene TiO
2
2-
formylcinnamald
ehydes,
naphthoquinone
Soana, F.; Sturini, M.; Cermenati L.; Albini, A. J. Chem. Soc.,Perkins
Trans. 2 2000, 649.

Linear olephins TiO
2
epoxides Ohno, T.; Nakabeya, K.; Mutsumura, M. J. Catal. 1998, 176, 76.
Cumene TiO
2
acetophenone
Ermolenko, L. P.; Giannotti, C. J. Chem. Soc., Perkins Trans. 2 1996,
1205.

Butadienes TiO
2
acetaldehyde
OShea, K. E.; Jannach, S. H.; Garcia, I. J. Photochem. Photobiol., A
1999, 122, 127.

Propene
TiO
2
SnO
2
,
WO
3
, Sb
2
O
4
Acetaldehyde,
acetone, acroelin
Pichat, P.; Herrmann, J. M.; Didier, J.; Mozzanega, M. N. J.Phys. Chem.
1979, 83, 3122.

Cyclohexane V
2
O
5
/ZrO
2
cyclohexanol,
cyclohexanone
K. Teramura, T. Tanaka, T. Yamamoto, T. Funabiki, J. Mol. Catal. 165
(2001) 299
Cyclohexane MoO
3
/TiO
2
Benzene,
cyclohexene
P. Ciambelli, D. Sannino, V. Palma, V.Vaiano , Catal. Today 99 (2005)
143
Ethylbenzene MoO
3
/-Al
2
O
3
Styrene
P. Ciambelli, D. Sannino, V. Palma, V. Vaiano, Italian patent Application
SAA2008000012
Aroma green synthesis
Aldehydes are widely applicated as aromas to enrich the flavor of different types
of products.
If we consider the case of vanillin, its extensive utilization (more than 12
thousand tons per year) makes it the most important aroma. Currently, more
than 99% of vanillin is produced by chemical synthesis and is sold at a much
lower price (typically less than 1%) than the natural vanilla extract, which
requires very long, complex and expensive procedures of cultivation of the plant,
induced production of the beans, curing of the pods and extraction of the
aromas.
In spite of the high price, the demand of the natural product remains noteworthy.
On the other hand, the processes of chemical synthesis are not environmentally
safe and the "bouquet" of the obtained "artificial" vanillin is usually considered to
be of lower quality due to the lack of many trace components which substantially
contribute to the flavor of the "natural" product.
In the last decades many researchers investigated also the possibility of
producing vanillin through a "green" biotechnological route. But, till now, only
one commercial biotech product is present on the market. In fact, even if future
improvements are hoped, the proposed biotechnology methods show some
limitations such as relatively high costs, low yields, long production times,
difficult purification and necessity of selected strains of microorganisms.

Photocatalytic synthesis of vanillin

ferulic acid was chosen since it can be of natural origin,


Advantages
A substantial improvement of the yield and of the selectivity;
A satisfactory purification of the product, that is in some case does not need any
further separation. Note also that the product stream is in any case free from the
photocatalytic powders, which are preferably used instead of the photocatalytic
films, due to their higher photocatalytic activity, but are usually problematic to
separate without the integrated process;
Low energy demand for the separation step;
Green process (mild conditions, that is low harmless temperatures and
atmospheric pressure, reagent in aqueous solution without any chemical additive,
possibility of using natural precursors, possibility of a complementary utilization
of the solar radiation to satisfy the energy requirements);
modularity (both the capacity of the photocatalytic and of the membrane
separation apparatuses can be varied by adding or removing modules);
possibility of choice between continuous or discontinuous (batch) processing;
very simple control so that qualified technicians are not required and the actions
of operators are minimized.

Main reactions
The membrane PEBAX
2533 (polyether block amide by Arkema)
It has been observed that the life of the membrane is significantly shortened when it is exposed to the
UVA radiation in presence of the photocatalyst, so the pervaporation membrane has been kept
separated from the reactor.
Photocatalytic system

Department of Chemical and Food Engineering
Experimental Apparatus

Experimental set up apparatus: (1) rotameter; (2) mass flow controllers; (3) MFC control unit;
(4) hydrocarbons saturator; (5) manometer; (6) photoreactor; (7) thermocouple; (8) GC-MS;
(9) CO-CO
2
analyzer
Hydrocarbons
Cohesive tendencies
The gas opens channels
PHYSICAL MIXTURES WITH - AL
2
O
3
OR
SILICA WITH TITANIA BASED CATALYSTS
WERE REALIZED
Particles expand uniformly
and gas bubbles form
Gas OUT
Gas IN
-Al
2
O
3
, SiO
2
TiO
2
Fluidized bed photoreactor

Department of Chemical and Food Engineering
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
250 300 350 400 450
wavelenght, nm
s
p
e
c
t
r
a
l

i
r
r
a
d
i
a
n
c
e
,

W
/
m
2

-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
250 300 350 400 450
wavelenght, nm
s
p
e
c
t
r
a
l

i
r
r
a
d
i
a
n
c
e
,

W
/
m
2

Illumination systems
EXTERNAL HEATING
Hg LAMPS Light intensity: 30 mW/cm
2
INTERNAL HEATING
UV LEDs Light Intensity: 10-122 mW /cm2
Traditional Microscale
Department of Chemical and Food Engineering
Effect of UV source
Cyclohexane conversion (X) and benzene production (P)
Ligth intensity:
30mW/cm
2

Catalyst : 10MoPCAl, 28g
Temperature: 120C
Flow rate: 830 Ncc/min
Carrier: He
Cyclohexane : 0.1%
Oxygen/Cyclohexane ratio: 1.5
Water/Cyclohexane : 1.6
These results indicate that
UVA-LEDs allow
better performances in
terms of catalyst
illumination avoiding
photons dispersion
Homogeneous vs. Heterogeneous catalysis
Homogeneous Fenton process
Advantages
Room pressure and temperature
Cheap and non-toxic catalysts
High process efficiency
Disadvantages
Handling of chemical reactants
Working pH range (pH=2-4)
High cost of chemical reagents
Catalyst recovery
Formation of sludge
Heterogeneous Fenton process
pH working range (2-5)
Separation and catalyst recovery
Potentially, lower catalytic
activity compared to
homogeneous catalytic process
Photo-Fenton apparatus which does not
require a separation system of the catalyst
EFFECTIVE IN:
Removal of acetic acid, ethanol,
methanol
Removal of MTBE
Wine wastewater treatment
Distributore daria
Aria IN
H
2
O Out H
2
O Out
H
2
O IN H
2
O IN
Termocoppia
Lampada 8 W a vapori di Hg: emissione 254 nm Lampada 8 W a vapori di Hg: emissione 254 nm
Analisi gas
raffreddamento raffreddamento
Pompa Pompa
Valutazione TOC Valutazione TOC Valutazione TOC Valutazione TOC
monolite

P. Ciambelli, D. Sannino, M.
Ricciardi, L. Isupova; (2007).
Homogeneous Photo-Fenton vs.
Heterogenous Photo-Fenton
0
10
20
30
40
50
60
0 1 2 3 4 5 6
t, h
T
O
C

r
e
m
o
v
a
l
,

%
Fe
2
(C
2
O
4
)
3
LaCoO
3
LaMnO
3
LaFeO
3
Ln
2
O
3
- Pt
Ln
2
O
3
-Pd
LaNiO
3
LaCuO
3
omogenea
The most promising catalyst are LaFeO
3
e LaMnO
3
Catalysts were supplied by Boreskov Insitute of
Catalysis
Acetic acid solution
Initial TOC : 500 ppm
Catalyst: monilite
V tot.: 100 ml
H
2
O
2
/CH
3
COOH= 4
(stoichiometric ratio)
C
0
H2O2
= 0.083 mol/l
C
0
Fe3+
= 0.0296 M
(homogeneous)

P=1 atm
T=25C
Q
air
=250 Ncc/min
pH=3.9
Heterogeneous photo-Fenton process:
mechanism
O
2
(g)

H
2
O
2
(l)
H
2
O
2
ads
O
2
(g)
O
2
(g)

H
2
O
2
(l)
H
2
O
2
ads
C
x
H
y
O
z
(l)
C
x
H
y
O
z
(ads)
HO O H 2
2 2

CO
2
(g)
C
x
H
y
O
z
(l)
C
x
H
y
O
z
(ads)

) (
2
1
) ( ) (
2 2 2 2
g O l O H l O H +
CO
2
(g)
H
2
O
2
(l)
H
2
O
2
ads
O
2
(g)
O
2
(g)
HO O H 2
2 2

O
2
(g)
OH
.
+H
2
O
2
HO
2
.
+H
2
O
HOO
.
+ H
2
O
2
OH
.
+H
2
O+O
2
HO
2
.
+HO
2
.

H
2
O
2
+ O
2
Synergic Effect