University of Salerno

Department of Chemical and Food Engineering

Heterogeneous photocatalysis

Catalysis
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.

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.

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: , , 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

AOPs (advanced oxidation processes) to be taken in consideration for
wastewater treatment
Catalysis
Pulsed plasma
Electrochemistry Super-critical water oxidation
Fenton
Ultrasounds
UV
UV/H2O2

Ionizing Radiation

Microwaves

O3

Wet-air Oxidation

Photochemical treatment and in particular

Heterogeneous photocatalysis

H2O2 + Fe2+

Catalytic oxidation
i.e. Fenton and photofenton

OH + OH- + Fe3+

Fe3+ + H2O2
Fe2+ + HO2 + H+
Fe3+ + H2O+ h
Fe2+ + HO + H+

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
= c /
E
=
h
*c/
=h
p

Light wave lenght:

Light frequency:

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 determines if a
substance is an insulator,
semiconductor, or conductor.
Energy level diagram

Band gap of some semiconductors

440 nm

380 nm

Heterogeneous Photocatalysis
Ebg=Band gap Energy

h > Ebg
h + SC
A(Ads)+ eD(Ads) + p+

e- + p +

e - + p+
A-(Ads)
D+(Ads)

Energy

A- and D+ are highly reactive species which oxidize or reduce the

compounds adsorbed on the catalyst surface .
Department of Chemical and Food Engineering

Semiconductors in photocatalysis
The most used semiconductor in
photocatalytic processes is TiO2
TiO2 crystallographic forms:
Anatase (important in photocatalysis).
Rutile
Brookite
On TiO2 surface
OH

OH

Ti O Ti
O

H
O Ti
O

Reactions in photocatalytic process

with TiO2

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.

Part of the photosensitive

area is masked
All particles of photocatalyst
are fully illuminated

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
r k k

KC

KC
First order
kinetics

KC
Order zero
kinetics

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
C6H12+9O2

6CO2+6H2O

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 CNion (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 TiO2
E. Coli destruction by irradiated TiO2

Photocatalytic treatment of gaseous

streams
PHOTOCATALYST: TiO2 anatase
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)]

Department of Chemical and Food Engineering

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 CO2 and H2O, without undesired
products (CO and NOx)
Use of cheap and non-toxic catalysts (TiO2).

Main odorous compounds and their origin

Volatile organic acids

Ammonia and amines
Aromatic and other ring structures
Sulfur compounds (H2S, 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 m3/h) to ventilation systems for tunnels
(1,500,000 m3/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
TiO2)

Photocatalytic materials
Self-cleaning materials (cement, glass) coated with TiO 2 films
Photo-induced super-hydrophilicity

Slow, no light

NOx decomposition promoted by ecocoatings

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 TiO2, contained in the materials, and the
subsequent degradation of pollutants such as NO and NO2, which are first
adsorbed on the particles and then converted into nitric acid (HNO3).

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)

Self-cleaning coatings: applications(2/3)

Dives in Misericordia (Roma)

Self-cleaning coatings: applications(3/3)

Facade and structural detail of the of the City of Music and Fine
Arts in Chambery (France)

Photocatalysis for green chemistry

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

Advantages

Possibility to operate at ambient temperature and pressure

Catalysts relatively inexpensive (mainly TiO2 based)

Photocatalysis can lead to more sustainable processes by :

Increasing process selectivity to the required products

Different chemistry

Decreasing energy consumption of the process

Department of Chemical and Food Engineering

Hydrocarbons selective Photo-oxidation Reactions

Reactants

Cataysts

Products

References

Olephins
(Prophilene)

TiO2, MoO3,
WO3, CdS

epoxides,
alcohols,
aldehydes, and
ketones

Ward, M. D.; Brazdill, J. F., Jr.; Grasselli, R. K. U.S. Patent 4,571,290,

1986

Toluene

TiO2

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

TiO2

2formylcinnamald
ehydes,
naphthoquinone

Linear olephins

TiO2

epoxides

Ohno, T.; Nakabeya, K.; Mutsumura, M. J. Catal. 1998, 176, 76.

Cumene

TiO2

acetophenone

Ermolenko, L. P.; Giannotti, C. J. Chem. Soc., Perkins Trans. 2 1996,

1205.

Butadienes

TiO2

acetaldehyde

OShea, K. E.; Jannach, S. H.; Garcia, I. J. Photochem. Photobiol., A

1999, 122, 127.

Propene

TiO2 SnO2,
WO3, Sb2O4

Acetaldehyde,
acetone, acroelin

Cyclohexane

V2O5/ZrO2

cyclohexanol,
cyclohexanone

K. Teramura, T. Tanaka, T. Yamamoto, T. Funabiki, J. Mol. Catal. 165

(2001) 299

Cyclohexane

MoO3/TiO2

Benzene,
cyclohexene

P. Ciambelli, D. Sannino, V. Palma, V.Vaiano , Catal. Today 99 (2005)

143

Ethylbenzene

MoO3/ -Al2O3

Styrene

P. Ciambelli, D. Sannino, V. Palma, V. Vaiano, Italian patent Application

SAA2008000012

Soana, F.; Sturini, M.; Cermenati L.; Albini, A. J. Chem. Soc.,Perkins

Trans. 2 2000, 649.

Pichat, P.; Herrmann, J. M.; Didier, J.; Mozzanega, M. N. J.Phys. Chem.

1979, 83, 3122.

Department of Chemical and Food Engineering

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

Photocatalytic system

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.

Department of Chemical and Food Engineering

Experimental Apparatus

Hydrocarbons

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-CO2 analyzer

Fluidized bed photoreactor

Gas OUT

-Al2O3, SiO2

Particles expand uniformly

and gas bubbles form

Gas IN
PHYSICAL MIXTURES WITH - AL2O3 OR
SILICA WITH TITANIA BASED CATALYSTS
WERE REALIZED

Cohesive tendencies
The gas opens channels

TiO2

Illumination systems
Traditional

Microscale
INTERNAL HEATING

EXTERNAL HEATING

Hg LAMPS Light intensity: 30 mW/cm2

UV LEDs Light Intensity: 10-122 mW /cm2

Department of Chemical and Food Engineering

Effect of UV source
Cyclohexane conversion (X) and benzene production (P)

Ligth intensity: 30mW/cm2

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
Department of Chemical and Food Engineering

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

monolite

EFFECTIVE IN:
Removal of acetic acid, ethanol,
methanol
P. Ciambelli, D. Sannino, M.
Ricciardi, L. Isupova; (2007).

Removal of MTBE
Wine wastewater treatment

Homogeneous Photo-Fenton vs.

Heterogenous Photo-Fenton
Acetic acid solution

LaFeO3

60

Initial TOC : 500 ppm

LaMnO3

50

T O C re m o v a l, %

LaNiO3

40

Ln2O3 -Pd

Catalyst: monilite

Ln2O3 - Pt

V tot.: 100 ml

LaCoO3

H2O2/CH3COOH= 4
(stoichiometric ratio)

LaCuO3

30

C0H2O2= 0.083 mol/l

Fe 2(C2O4 )3

20

C0Fe3+= 0.0296 M
(homogeneous)

omogenea

10

P=1 atm
T=25C

0
0

t, h

Qair=250 Ncc/min
pH=3.9

The most promising catalyst are LaFeO3 e LaMnO3

Catalysts were supplied by Boreskov Insitute of
Catalysis

Heterogeneous photo-Fenton process:

mechanism
O2(g)

O2(g)

CxHyOz(l)

H2O2(l)

H2O2(l)
O2(g)

H 2O2 2 HO

OH. +H2O2
HOO. + H2O2
HO2. +HO2 .

O2(g)

H2O2ads

O2(g)

CO2(g)

1
H 2O2 (l ) H 2O(l ) O2 ( g )
2

H 2O2 2 HO

H2O2(l)

CxHyOz(l)
O2(g)

H2O2ads
CxHyOz(ads) H O ads
2 2

CxHyOz(ads)
CO2(g)

HO2.+H2O
OH. +H2O+O2
H2O2+ O2

Synergic Effect