PHOTOCATALYSIS -

CHALLENGES AND POTENTIALS

Prof. B. Viswanathan
Department of chemistry
Indian Institute of Technology -Madras
 catalyst
 Photocatalysis reaction assisted by photons

 Conventional redox reaction

 Oxidizing agent should have more positive potential

 Photocatalysis - simultaneous oxidation and reduction

 The redox couple capable of promoting both the

reactions can act as photocatalyst

 Metals, Semiconductors and Insulators

2
WHY SEMICONDUCTOR ?

Metals
CB
No band gap
Only reduction or oxidation CB
H+/H2
Depends on the band CB
position
VB E
H2O/O2 VB
SC
Insulators
VB
High band gap Metals Insulators

High energy requirement

3
Concepts –Why semiconductors are chosen as
photo-catalysts?
For conventional redox reactions, one is interested in either
reduction or oxidation of a substrate.

For example consider that one were interested in the

oxidation of Fe2+ ions to Fe 3+ ions then the oxidizing agent
that can carry out this oxidation is chosen from the relative
potentials of the oxidizing agent with respect to the redox
potential of Fe2+/Fe3+ redox couple.

The oxidizing agent chosen should have more positive potential

with respect to Fe3+/Fe2+ couple so as to affect the oxidation,
while the oxidizing agent undergoes reduction spontaneously.
This situation throws open a number of possible oxidizing
agents from which one of them can be easily chosen.

4
Water splitting - carry out both the redox reactions simultaneously
- reduction of hydrogen ions (2H+ + 2e- → H2) as well as (2OH-
+ 2h+ → H2O + 1/2O2 ) oxygen evolution from the hydroxyl ions.

The system that can promote both these reactions simultaneously is

essential.

Since in the case of metals the top of the valence band (measure
of the oxidizing power) and bottom of the conduction band
(measure of the reducing power) are almost identical they cannot
be expected to promote a pair redox reactions separated by a
potential of nearly 1.23 V.

where the top of the valence band and bottom of the conduction
band are separated at least by 1.23V in addition to the condition
that the potential corresponding to the bottom of the conduction
band has to be more negative with respect to be more negative
with respect to while the potential of the top of the valence band
has to be more positive to the oxidation potential of the reaction
2OH- + 2h+ → H2O + ½ O2.

5
 This situation is obtainable with semiconductors as
well as in insulators.

Insulators are not appropriate due to the high value

of the band gap which demands high energy photons
to create the appropriate excitons for promoting both
the reactions. The available photon sources for this
energy gap are expensive and again require energy
intensive methods. Hence insulators cannot be
employed for the purpose of water splitting reaction.

Therefore, it is clear that semiconductors are alone

suitable materials for the promotion of water splitting
reaction.

6
 Criterion one has to use for the selection of the
semiconductor materials and also how one can fine
tune the material thus chosen for the water
splitting reaction.

Essentially for photo-catalytic splitting of water,

the band edges (the top of valence band and
bottom of the conduction band or the oxidizing
power and reducing power respectively) have to be
sifted in opposite directions so that the reduction
reaction and the oxidation reactions are facile.

7
Ionic solids as the ionicity of the M-O bond increases, the top
of the valence band (mainly contributed by the p- orbitals of
oxide ions) becomes less and less positive (since the binding
energy of the p orbitals will be decreased due to negative
charge on the oxide ions) and the bottom of the conduction band
will be stabilized to higher binding energy values due to the
positive charge on the metal ions which is not favourable for the
hydrogen reduction reaction.

More ionic the M-O bond of the semiconductor is, the less
suitable the material is for the photo-catalytic splitting of
water. The bond polarity can be estimated from the
expression
(  A   B )2
Percentage ionic character (%) = 
(1  e 4
) 100

8
The percentage ionic character of the M-O bond
for some of the semiconductors
Semiconductor M-O Percentage ionic
character
TiO2 Ti-O 59.5
SrTiO3 Ti-O-Sr 68.5
Fe2­O3 Fe-O 47.3
Zn-O 55.5
ZnO
W-O 57.5
WO3
Cd-S 17.6
CdS Cd-S 16.5
CdSe La-O-Rh 53.0
LaRhO3 La-O-Ru 53.5
LaRuO3 Pb-O 26.5
PbO Zn-Te 5.0
ZnTe Zn-As 6.8
ZnAs Zn-Se 18.4
ZnSe Zn-S 19.5
ZnS Ga-P 3.5
GaP Cu-Se 10.0
CuSe Ba-O-Ti 70.8
BaTiO3 Mo-S 4.3
MoS2 Fe-O-Ti 53.5
K-O-Ti 72.7
FeTiO3­
Mn-O-Ti 59.0
KTaO3 Sn-O 42.2
MnTiO3 Bi-O 39.6
SnO2
9
The oxide semiconductors though - suitable for the
photo-catalytic water splitting reaction in terms of
the band gap value which is greater than the water
decomposition potential of 1.23 V.

Most of these semiconductors have bond character

more than 50-60 % and hence modulating them will
only lead to increased ionic character and hence the
photo-catalytic efficiency of the system may not be
increased as per the postulates developed

Therefore from the model developed in this

presentation the following postulates have been
evolved.

10
The photo-catalytic semiconductors are often
used with addition of metals or with other hole
trapping agents so that the life time of the
excitons created can be increased.

This situation is to increase the life time of the

excited electron and holes at suitable traps so that
the recombination is effectively reduced.

In this mode, the positions of the energy bands

of the semiconductor and that of the metal overlap
appropriately and hence the alteration can be either
way and also in this sense only the electrons are
trapped at the metal sites and only reduction
reaction is enhanced.

11
•Hence we need stoichiometrically both oxidation
and reduction for the water splitting and this
reaction will not be achieved by one of the
trapping agents namely that is used for electrons
or holes.

•Even if one were to use the trapping agents for

both holes and electrons, the relative positions of
the edge of the valence band and bottom of the
conducting band may not be adjusted in such a way
to promote both the reactions simultaneously

12
Normally the semiconductors used in photo-catalytic
processes are substituted in the cationic positions so as
to alter the band gap value.

Even though it may be suitable for using the available

solar radiation in the low energy region, it is not possible
to use semiconductors whose band gap is less than 1.23 V
and any thing higher than this may be favourable if both
the valence band is depressed and the conduction band is
destabilized with respect to the unsubstituted system.

 Since this situation is not obtainable in many of the

available semiconductors by substitution at the cationic
positions, this method has not also been successful.

13
In addition the dissolution potential of the
substituted systems may be more favourbale than
the water oxidation reaction and hence this will be
the preferred path way.

These substituted systems or even the bare

semiconductors which favour the dissolution
reaction will undergo only preferential photo-
corrosion and hence cannot be exploited for photo-
catalytic pathway. In this case ZnO is a typical
example.

14
Very low value of the ionic character also is not
suitable since these semiconductors do not have
the necessary band gap value of 1.23 V. - the
search for utilizing lower end of the visible region
is not possible for direct water splitting reaction.

If one were to use visible region of the

spectrum, then only one of the photo-redox
reactions in water splitting may be preferentially
promoted and probably this accounts for the
frequent observation that non-stiochiometric
amounts of oxygen and hydrogen were evolved in
the photo-assisted splitting of water.

15
Therefore it is deduced that the systems which
has ionic bond character of about 20-30% with
suitable positions of the valence and conduction
band edges may be appropriate for the water
splitting reaction.

This rationalization has given one a handle to

select the appropriate systems for examining as
photo-catalysts for water splitting reaction.

16
There are some other aspects of photo-
catalysts on which some remarks may be
appropriate.

Though they have been derived from the solid

state point of view like flat band potential , band
bending, Fermi level pinning, these parameters
also can be understood in terms of the bond
character and the redox chemical aspects by
which the water splitting reaction is dealt.

17
PROCESSES ON THE PHOTO-EXCITED SEMICONDUCTOR
SURFACE AND BULK

A. Millis and S. L. Hunte J. Photochem. Photobiol. A: Chem 180 (1997) 1

18
 TYPICAL PHOTOCATALYTIC PROCESS

 Photodecomposition of water

 Photocatalytic formation of fuel

 Photocatalysis in pollution abatement

19
 HYDROGEN PRODUCTION
There are various methods and technologies that have
been developed and a few of them have already been
practiced. These technologies can be broadly classified
as:
 Thermo-chemical routes for hydrogen production

 Electrolytic generation of hydrogen

 Photolytic means of hydrogen formation

 Biochemical pathways for hydrogen evolution and

 Chemical (steam ) reformation of naphtha

20
Photo electrolysis of Water-Holy Grail of
Electrochemistry

Historically, the discovery of photo-electrolysis

of water directly into oxygen at a TiO2 electrode
and hydrogen at a Pt electrode by the illumination
of light greater than the band gap of TiO2 [3.1
eV] is attributed to Fujishima and Honda though
photo catalysis by ZnO and TiO2 has been
reported much earlier by Markham in 1955

21
CHALLENGES IN PHOTODECOMPOSITION OF WATER

2H + + 2e- H2 0.00V
O2 + 4e- + 4H+ 2H2O 1.229V

 The band edges of the electrode must overlap with the

acceptor and donor states – Minimum band gap 1.23 eV

 Charge transfer from the surface of the semiconductor

must be fast - prevent photo corrosion

 Shift of the band edges resulting in loss of photon

energy

22
PHOTO-ELECTROCHEMICAL CELL FOR THE
PHOTO CLEAVAGE OF WATER

23
 TYPES OF SEMICONDUCTORS BASED ON WATER
ELECTOLYSIS – CHOICE OF MATERIALS
NH
OR Type – Oxidation & Reduction E
H+/H2 0.00
R Type – Reduction
eV
O Type – Oxidation
H2O/O2 1.23
X type - None

 Semiconductor materials that satisfy the band gap

requirement (~1.4 eV) - susceptible for photo corrosion.

 Stable materials with a wider band gap absorb light only in

the UV region.
24
 Conditions for photo electrolysis of water
For the direct photo electrochemical decomposition of
water to occur, several key criteria have to be met with.
These can be stated at the first level as follows:

 The band edges of the electrode must overlap with the

acceptor and donor states of water decomposition reaction,
thus necessitating that the electrodes should at least have
a band gap of 1.23 V, the reversible thermodynamic
decomposition potential of water. This situation necessarily
means that appropriate semiconductors alone are
acceptable as electrode materials for water decomposition.

 The charge transfer from the surface of the

semiconductor must be fast enough to prevent photo
corrosion and shift of the band edges resulting in loss of
photon energy.

25
 What modifications?
 various conceptual principles have been incorporated into
typical TiO2 system so as to make this system responsive
to longer wavelength radiations. These efforts can be
classified as follows:
 Dye sensitization
 Surface modification of the semiconductor to improve the
stability
 Multi layer systems (coupled semiconductors)
 Doping of wide band gap semiconductors like TiO2 by
nitrogen, carbon and Sulphur
 New semiconductors with metal 3d valence band instead of
Oxide 2p contribution
 Sensitization by doping.
 All these attempts can be understood in terms of some
kind sensitization and hence the route of charge transfer
has been extended and hence the efficiency could not be
increased considerably. In spite of these options being
elucidated, success appears to be eluding the researchers.

26
 Conditions to be satisfied?
 The band edges of the electrode must overlap with the
acceptor and donor states of water decomposition
reaction, thus necessitating that the electrodes should
at least have a band gap of 1.23 V, the reversible
thermodynamic decomposition potential of water. This
situation necessarily means that appropriate
semiconductors alone are acceptable as electrode
materials for water

 The charge transfer from the surface of the

semiconductor must be fast enough to prevent photo
corrosion and shift of the band edges resulting in loss
of photon energy.

27
 ENGINEERING THE SEMICONDUCTOR
ELECTRONIC STRUCTURES

 without deterioration of the stability

 should increase charge transfer processes at

the interface

 should improvements in the efficiency

28
Positions of bands of semiconductors relative to the
standard potentials of several redox couples

29
 THE AVAILABLE OPPORTUNITIES
 Identifying and designing new semiconductor materials
with considerable conversion efficiency and stability

 Constructing multilayer systems or using sensitizing

dyes - increase absorption of solar radiation

 Formulating multi-junction systems or coupled systems

- optimize and utilize the possible regions of solar
radiation

 Developing nanosize systems - efficiently dissociate

water

30
 ADVANTAGES OF SEMICONDUCTOR NANOPARTICLES
 high surface area

 morphology

 presence of surface states

eV
 wide band gap

 position of the VB & CB edge

CdS – appropriate choice for

the hydrogen production

31
 The opportunities

 The opportunities that are obviously available

as such now include the following:

 Identifying and designing new semiconductor materials

with considerable conversion efficiency and stability
 Constructing multilayer systems or using sensitizing
dyes so as to increase absorption of solar radiation.
 Formulating multi-junction systems or coupled
systems so as to optimize and utilize the possible
regions of solar radiation.
 Developing catalytic systems which can efficiently
dissociate water.

32
 Opportunities evolved
 Deposition techniques have been considerably perfected
and hence can be exploited in various other applications
like in thin film technology especially for various devices
and sensory applications.
 The knowledge of the defect chemistry has been
considerably improved and developed.
 Optical collectors, mirrors and all optical analysis
capability have increased which can be exploited in many
other future optical devices.
 The understanding of the electronic structure of
materials has been advanced and this has helped to our
background in materials chemistry.
 Many electrodes have been developed, which can be a
useful for all other kinds of electrochemical devices.

33
 Limited success – Why?
The main reasons for this limited success in all these directions
are due to:
 The electronic structure of the semiconductor controls the
reaction and engineering these electronic structures without
deterioration of the stability of the resulting system appears to
be a difficult proposition.
 The most obvious thermodynamic barriers to the reaction and
the thermodynamic balances that can be achieved in these
processes give little scope for remarkable improvements in the
efficiency of the systems as they have been conceived and
operated. Totally new formulations which can still satisfy the
existing thermodynamic barriers have to be devised.
 The charge transfer processes at the interface, even though a
well studied subject in electrochemistry has to be understood
more explicitly, in terms of interfacial energetics as well as
kinetics. Till such an explicit knowledge is available, designing
systems will have to be based on trial and error rather than
based on sound logical scientific reasoning.

34
 Nanocrystalline (mainly oxides like TiO2, ZnO, SnO and Nb2O5 or
chalcogenides like CdSe) mesoscopic semiconductor materials with
high internal surface area If a dye were to be adsorbed as a
monolayer, enough can be retained on a given area of the
electrode so as to absorb the entire incident light.

 Since the particle sizes involved are small, there is no significant

local electric field and hence the photo-response is mainly
contributed by the charge transfer with the redox couple.

 Two factors essentially contribute to the photo-voltage observed,

namely, the contact between the nano crystalline oxide and the
back contact of these materials as well as the Fermi level shift
of the semiconductor as a result of electron injection from the
semiconductor.

35
Another aspect of thee nano crystalline state is
the alteration of the band gap to larger values as
compared to the bulk material which may facilitate
both the oxidation/reduction reactions that cannot
normally proceed on bulk semiconductors.

The response of a single crystal anatase can be

compared with that of the meso-porous TiO2 film
sensitized by ruthenium complex (cis RuL2 (SCN)2,
where L is 2-2’bipyridyl-4-4’dicarboxlate).

The incident photon to current conversion

efficiency (IPCE) is only 0.13% at 530 nm ( the
absorption maximum for the sensitizer) for the
single crystal electrode while in the nano crystalline
state the value is 88% showing nearly 600-700
times higher value.

36
This increase is due to better light harvesting
capacity of the dye sensitized nano crystalline
material but also due to mesoscpic film texture
favouring photo-generation and collection of
charge carriers .

It is clear therefore that the nano crystalline

state in combination with suitable sensitization is
one another alternative which is worth
investigating.

37
 The second option is to promote water splitting in the visible range
using Tandem ells. In this a thin film of a nanocrystalline WO3 or
Fe2O3 may serve as top electrode absorbing blue part of the solar
spectrum. The positive holes generated oxidize water to oxygen
 4h+ + 2H2O --- O2 + 4 H+

 The electrons in the conduction band are fed to the second photo
system consisting of the dye sensitized nano crystalline TiO2 and
since this is placed below the top layer it absorbs the green or
red part of the solar spectrum that is transmitted through the
top electrode. The photo voltage generated in the second photo
system favours hydrogen generation by the reaction
 4H+ + 4e-­­ --- 2H2

 The overall reaction is the splitting of water utilizing visible light.

The situation is similar to what is obtained in photosynthesis

38
 Dye sensitized solid hetero-junctions and extremely
thin absorber solar cells have also been designed
with light absorber and charge transport material
being selected independently so as to optimize solar
energy harvesting and high photovoltaic output.
However, the conversion efficiencies of these
configurations have not been remarkably high.

 Soft junctions, especially organic solar cells, based

on interpenetrating polymer networks,
polymer/fullerene blends, halogen doped organic
crystals and a variety of conducting polymers have
been examined. Though the conversion efficiency
of incident photons is high, the performance of the
cell declined rapidly. Long term stability will be a
stumbling block for large scale application of
polymer solar cells.

39
 New Opportunities

1. New semi-conducting materials with conversion

efficiencies and stability have been identified.
These are not only simple oxides, sulphides but
also multi-component oxides based on perovskites
and spinels.

2. Multilayer configurations have been proposed for

absorption of different wavelength regions. In
these systems the control of the thickness of
each layer has been mainly focused on.

40
 New Opportunities

3. Sensitization by dyes and other anchored

molecular species has been suggested as an
alternative to extend the wavelength region of
absorption.

4. The coupled systems, thus giving rise to multi-

junctions is another approach which is being
pursued in recent times with some success

5. Activation of semiconductors by suitable catalysts

for water decomposition has always fascinated
scientists and this has resulted in various metal or
metal oxide (catalysts) loaded semi conductors
being used as photo-anodes

41
 New opportunities (Contd)
 Recently a combinatorial electrochemical synthesis and
characterization route has been considered for
developing tungsten based mixed metal oxides and this
has thrown open yet another opportunity to quickly
screen and evaluate the performances of a variety of
systems and to evolve suitable composition-function
relationships which can be used to predict appropriate
compositions for the desired manifestations of the
functions.
 It has been shown that each of these concepts, though
has its own merits and innovations, has not yielded the
desired levels of efficiency. The main reason for this
failure appears to be that it is still not yet possible to
modulate the electronic structure of the semiconductor
in the required directions as well as control the electron
transfer process in the desired direction.

42
PREPARATION OF CdS NANOPARTICLES
1 g of Zeolite (HY, H, HZSM-5)

1 M Cd(NO3)2 , stirred for

24 h, washed with water

Cd / Zeolite

1 M Na2S solution, stirred for

12 h, washed with water

CdS / Zeolite

48 % HF, washed with water

CdS Nanoparticles

43
 XRD PATTERN OF CdS

M. Sathish, B. Viswanathan, R. P. Viswanath Int. J. Hydrogen Energy (In press)

44
d SPACING AND CRYSTALLITE SIZE

Debye Scherrer Equation

0.89  = diffraction angle T = Crystallite size
T  = wave length  = FWHM
 cos 
d-spacing (Å) Crystallite
(0 0 2) (1 0 1) (1 1 2)
Catalyst Size(nm)
CdS (bulk) 1.52 1.79 2.97 21.7

CdS (bulk) 1.52 1.79 2.93 21.7

(HF treated)
CdS-Y 1.53 1.79 2.96 8.8

CdS- 1.52 1.78 2.93 8.6

CdS-Z 1.52 1.79 2.97 7.2

45
UV –VISIBLE SPECTRA OF CdS SAMPLES

Samples Band Gap

(eV)
CdS – Z 2.38

CdS – Y 2.27

CdS -  2.21

Bulk CdS 2.13

M. Sathish, B. Viswanathan, R. P. Viswanath Int. J. Hydrogen Energy (In press)

46
PHOTOCATALYTIC PRODUCTION OF HYDROGEN

35ml of 0.24 M Na2S and

0.35 M Na2SO3 in Quartz cell

N2 gas purged before the 0.1 g CdS

reaction and constant stirring 400 W Hg lamp

Hydrogen gas was collected over

water in the gas burette

47
AMOUNT OF HYDROGEN EVOLVED BY CdS
PHOTOCATALYST

48
TEM IMAGE OF CdS NANOPARTICLES
Surface Rate of hydrogen CdS-Z
Particle Size
Catalyst area production
(nm)
(m2/g) (  moles /h)
CdS - Y 8.8 36 102

CdS - Z 6 46 68

CdS -  11 26 67

CdS - Bulk 23 14 45

CdS-Z CdS- 

100 nm 100 nm
49
SCANNING ELECTRON MICROGRAPHS
CdS-Z CdS-Y

CdS- CdS- bulk

50
PHOTOCATALYSIS ON Pt/TiO2 INTERFACE

Vacuum level
 Electrons are transferred
to metal surface
 Reduction of H+ ions Aq. Sol Pt TiO2 Aq. Sol
takes place at the metal
surface pH = 7 C.B
H+/H2
 The holes move into pH=0
EF
the other side of
semiconductor
 The oxidation takes
place at the V.B
semiconductor surface

T.Sakata, et al Chem. Phys.Lett. 88 (1982) 50

51
MECHANISM OF RECOMBINATION REDUCTION BY
METAL DOPING

Conduction Band
e-(M) <-- M+e-e- e- e- e- e- e- e- e- e- e- e- e-

Eg Electron/hole pair Electron/hole pair

recombination generation

Valence Band
h+ h+ h+ h+ h+ h+ h+ h+ h+ h+

Metallic promoter attracts electrons from TiO2 conduction

band and slows recombination reaction

52
PHOTOCATALYTIC
HYDROGEN EVOLUTION
OVER METAL LOADED
CdS NANOPARTICLES

Activity of the catalyst is directly

proportional to work function of the
metal and M-H bond strength.

53
HYDROGEN PRODUCTION ACTIVITY OF METAL
LOADED CdS PREPARED FROM H-ZSM-5

Redox Metal- hydrogen Work Hydrogen

Metal potential bond energy function evolution rate*
(E0) (K cal mol-1) (eV) (µmol h-1 0.1g-1)
Pt 1.188 62.8 5.65 600
Pd 0.951 64.5 5.12 144
Rh 0.758 65.1 4.98 114
Ru 0.455 66.6 4.71 54

*1 wt% metal loaded on CdS-Z sample. The reaction data is presented

after 6 h under reaction condition.

M. Sathish, B. Viswanathan, R. P. Viswanath Int. J. Hydrogen Energy (In press)

54
EFFECT OF METALS ON HYDROGEN EVOLUTION RATE

Pt
Pd
1000
 Pt, Pd & Rh show higher Rh
Au
activity
Cu
100
 High reduction potential.
Ag
 Hydrogen over voltage
Ni
is less for Pt, Pd & Rh
10
Fe

Ru

3%
55
EFFECT OF SUPPORT ON THE CdS PHOTOCATLYTIC
ACTIVITY
2, 5,10 and 20 wt % CdS on support - by dry impregnation method

Alumina & Magnesia

supports enhance
photocatalytic activity

MgO support has higher

photocatalytic activity -
favourable band position

56
 Pb2+/ ZnS
 Absorption at 530nm (calcinations at 623-673K)
 Formation of extra energy levels between the band gap by Pb
6s orbital
 Low activity at 873K is due to PbS formation on the surface
(Zinc blende to wurtzite)

Eg

(a) 573 K, (b) 623 K, (c) 673 K, (d) 773 K, and (e) 873K Band structure of ZnS doped with Pb.

I. Tsuji, et al J. Photochem. Photobiol. A. Chem 622 (2003) 1 57

PREPARATION OF MESOPOROUS CdS NANOPARTICLE
BY ULTRASONIC MEDIATED PRECIPITATION

250 ml of 1 mM
Cd(NO3)2

Rate of addition
20 ml / h

Ultrasonic waves
 = 20 kHz

250 ml of 5 mM The resulting precipitate was

Na2S solution washed with distilled water until
the filtrate was free from S2-
ions

58
N2 ADSORPTION - DESORPTION ISOTHERM

 The specific surface area and pore volume are 94 m2/g and
0.157 cm3/g respectively
 The adsorption - desorption isotherm – Type IV (mesoporous nature)

 Mesopores are in the

range of 30 to 80 Å size

 The maximum pore

volume is contributed by
45 Å size pores

59
 X- RAY DIFFRACTION PATTERN
 XRD pattern of as-prepared CdS -U shows the presence of cubic
phase

 The observed “d” values are 1.75, 2.04 and 3.32 Å corresponding
to the (3 1 1) (2 2 0) and (1 1 1) planes respectively - cubic

 The peak broadening shows the

formation of nanoparticles

The particle size is calculated

using Debye Scherrer Equation

 The average particle size of as-

prepared CdS is 3.5 nm

M. Sathish and R. P. Viswanath Mater. Res. Bull (Communicated)

60
 ELECTRON MICROGRAPHS
 The growth of fine spongy particles of CdS-U is observed on the
surface of the CdS-U

 The CdS-bulk surface is found with large outgrowth of CdS particles

 The fine mesoporous CdS particles are in the nanosize range

 The dispersed and agglomerated forms are clearly observed for

the as-prepared CdS-U
TEM SEM
CdS-U CdS-U CdS - Bulk

100 nm
61
PHOTOCATALYTIC HYDROGEN PRODUCTION

Na2S and Na2SO3 mixture

used as sacrificial agent

Amount of hydrogen (µM/0.1 g)

Metal CdS-U CdS-Z CdS

bulk
- 73 68 45

Rh 320 114 102 1 wt % Metal loaded CdS – U

is 2-3 times more active than
Pd 726 144 109 the CdS-Z

Pt 1415 600 275

62
LIMITED SUCCESS – WHY?

 Difficulties on controlling the semiconductor electronic

structure without deterioration of the stability

 Little scope on the thermodynamic barriers and the

thermodynamic balances for remarkable improvements in the
efficiency

 Incomplete understanding in the interfacial energetic as well

as in the kinetics

63
THE OTHER OPPORTUNITIES EVOLVED

 Deposition techniques -thin film technology, for various devices

and sensory applications.

 Knowledge of the defect chemistry has been considerably

improved and developed.

 Optical collectors, mirrors and all optical analysis capability

have increased

 Understanding of the electronic structure of materials

 Many electrodes have been developed- useful for all other

kinds of electrochemical devices.

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your kind attention