Applications in

Catalysis
1
4.1 Catalytic NO Decomposition
The direct decomposition of NO into N
2
and O
2
has large negative Gibb's free
energy and is regarded as one of the most ideal way of NO removal.
Perovskite oxides with an oxygen defect act as promising catalysts for NO removal.
Oxygen vacancy provide space for NO adsorption.
The redox ability of B-site cation .
are two major factors influencing NO adsorption and activation.
NO-TPD experiment shows that
La
2
NiO
4
with excess oxygen showed no adsorption capacity at low
temperatures but showed at a temperature above 100
o
C.
LaSrNiO
4
possesses an oxygen vacancy and showed good adsorption capacity
even at room temperature and max. value observed at 200-250
o
C .


2
From the nature of the reaction, it is known that NO decomposition is a
self-redox reaction as no oxidizing or reducing agent is added.
The catalyst should account for oxidation and reduction process and
hence the redox properties of the catalyst should be crucial
parameter.
By measuring the redox potential of two series of Perovskite oxides:
La
2-x
Sr
x
CuO
4
(x=0,0.5,1) and LaSrMO
4
(M= Co,Ni,Cu)
it was observed that the redox potentials is the most crucial
parameter and number of oxygen vacancy is the next influencing
parameter.

3
Reaction Mechanism of NO decomposition over Perovskite oxides
have been widely studied, yet no conclusion has been drawn.
Based on theoretical calculations and the NO decomposition activity
of LaSrNi
1-x
Al
x
O
4
and La
2-x
Sr
x
CuO
4
, it was found that structure with one
lattice oxygen situated between two B-site cations and two oxygen
vacancies linked to the B-site cation is more favorable for the reaction.

4
4.2 Catalytic NO Reduction
Although NO direct decomposition is an ideal way of NO removal, Its operation in
practice however encounters problems due to
kinetics limit as well as inhibition by oxygen
Poisoning by other coexisting gases such as CO
2
, SO
2
, and H
2
O .
For practical application, catalytic NO reduction is preferred.
Perovskite oxides are also good catalysts for catalytic NO reduction, using either CO,
NH
3
, hydrocarbons or H
2
as reducing agent.
The presence of reducing agent compensates for the inadequacy of reducing
capacity and mitigates dependence of activity on redox potentials of Perovskite oxide
catalysts.
The type of B-site cation also is a crucial parameter .The redox property of B-site cation
has a significant effect on the NO adsorption and the oxygen mobilization by
generating electrons.
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Using CO and C
x
H
y

Significant achievements were obtained by using
LaFe
0.57
Co
0.38
Pd
0.05
O
3
as catalyst for removal of NO using CO
and C
x
H
y
as reducing agents.
When the catalyst was used in oxidative and reductive
atmospheres, the Pd reversibly moves into and out of the
Perovskite lattice .
The growth of metallic Pd particles can be suppressed
because of this movement, maintaining its high activity
during long-term use.
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Using NH
3

Catalytic reduction of NO or NO
2


by NH
3
is currently the most effective
technology for NO
x
removal .
One of the main advantages of using NH
3
as a reducing agent is that it can
reduce NO
x
with high selectivity even in oxygen-rich atmosphere.
The commercial catalyst V
2
O
5
-WO
3
/TiO
2
although shows satisfactory performance
for the reaction but problem is the toxicity of vanadia.
Using H
2
The reduction of NO by H
2
is also a promising route for NO removal.
As Hydrogen being a clean reducing agent will not produce secondary pollution.
The reduction occurs at lower temperatures than using CO,C
x
H
y
and NH
3

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4.3 Catalytic NO oxidation
For removing NO ,NO is oxidized to NO
2
before reacting with reducing agents like
C
x
H
y
or NH
3
.
The ability to oxidize NO into NO
2
could be a prerequisite in optimizing catalyst.
Traditional precious metals like platinum are active for NO oxidation but are
expensive and prone to aggregate.

Investigation of catalytic performance of LaMeO
3
(Me = Mn,Fe,Co) Perovskites
prepared by sol-gel method found that LaCoO
3
with stronger reducibility was more
efficient.
Further studies showed that the nonstoichiometry of Perovskite oxide LaMnO
3
also
influenced the NO oxidation activity.
For e.g. La
0.9
MnO
3
with richer Mn atoms and higher Mn
4+
/Mn
3+
ratio showed better
catalytic performances at lower temperature due to easily regenerated oxygen
associated with Mn
4+
.
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Besides these, the synthesis conditions are also important in preparing Perovskite
oxides for NO oxidation.
Samples prepared with faster heating rate during the calcination process produced
various impurities, lowered the surface oxygen and caused particle aggregation
leading to lower activity.
Consequently, the synthesis with low heating rate conditions is suggested.

It was observed that the activity of LaCoO
3
can be significantly improved when Sr
was doped for La (La
0.9
Sr
0.1
CoO
3
) but there was no improvement in La
0.9
MnO
3
.
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4.4 Catalytic N
2
O Decomposition
Catalytic N
2
O removal is also essential in the application of catalyst for NO-NO
2

elimination.
Because of the problem such as high cost, low thermal and hydro-thermal stability
encountered by precious metals ,application of Perovskite oxides for N
2
O removal is
of great importance.
Screening tests on Perovskite catalysts LaBO
3
(B=Cr, Mn,Fe and Co) indicated cobalt
as the best transition metal for N
2
O decomposition.
For Sr doped materials, the N
2
O decomposition activity decreased in the order
La
0.8
Sr
0.2
CoO
3
> La
0.8
Sr
0.2
FeO
3
> La
0.8
Sr
0.2
MnO
3
>La
0.8
Sr
0.2
CrO
3

the good catalytic activity of LaCoO
3
was due to its better reducibility.
Surface composition of the catalyst also influenced the activity. Sample with La
deficiency or surface Co enrichment was favorable for the reaction at medium and
high temperature, likely due to the improvement of oxygen mobility.
10
Besides the B-site transition metal , the substitution at A-site cation has also
significant effect on the catalytic performances.
The substitution of Ba
2+
for La
3+
or Pr
3+
in LaMnO
3
or PrMnO
3
showed effect for N
2
O
decomposition.
Substitution by Ba
2+
leads to increase of Mn
4+
/Mn
3+
ratio and enhanced redox
property, which are responsible for the improved catalytic activity.
11
It is well-known that the oxygenoxygen recombination (2O* = O
2
+ 2*) is the rate-
limiting step in N
2
O decomposition, it is therefore essential to remove the surface
adsorbed oxygen immediately after its formation to allow the reaction to proceed.
Surface adsorbed oxygen can be separated using Perovskite membrane, which
ensures removal of surface adsorbed oxygen by reducing agent such as methane
The active site can be rapidly regenerated because of this removal resulting in
improved activity.

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4.5 Catalytic Complete Oxidation
of CO and CH
4

The oxidation of CO and CH
4
represents two surface interactive processes
conducted on Perovskite oxides.
The former is suprafacial, in which the catalyst surface provides a set of electronic
orbitals of proper symmetry and energy for bonding of reactant and intermediate.
The latter is intrafacial process, in which the catalyst participates as a reagent that is
purely consumed and regenerated.
From the molecular formula, it is known that the oxidation of CO into CO
2
needs to
capture one external atomic oxygen without rupturing the C-O bond.
Oxygen vacancy of the Perovskite oxides has the capability of splitting the
molecular oxygen into atomic oxygen and CO is good reducing agent that can
react with atomic oxygen.
The material with more oxygen vacancy should benefit the reaction.
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The substitution of Sr
2+
for La
3+
in La
2x
Sr
x
CuO
4
could lead to a significant increase in
the number of oxygen vacancy and hence increases the CO oxidation activity at
high temperatures.
Besides the number of oxygen vacancy, the redox properties of B-site cation also
have significant influence on the activity.
the Fe containing samples were substantially more active than LaAlO
3
, thus pointing
to the essential role of the redox properties of transition metal ion in developing
highly active catalysts.
It was found that there existed a dilution effect and concluded that isolated iron
ions are more active than iron species surrounded by oxygen bound to other iron
ions.
Optimization of B-site transition metals, based on the series LaCo
0.5
M
0.5
O
3
(M = Mn,
Cr, Fe, Ni, Cu), suggested that the composition LaCo
0.5
Mn
0.5
O
3
is the most
favorable.
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In addition to the natural properties of catalyst such as oxygen vacancy and redox
properties of B-site cation, the surface crystallinity was also reported to be important for
the reaction.
It was found that LaCoO
3
prepared using ethylene glycol and citric acid, although
possessing low surface area, showed better activity to that prepared using ethylene
glycol only, as a result of its better surface crystallinity.

Relative to CO oxidation, the dependence of CH
4
oxidation
on the oxygen vacancy is weak, as it belongs to different
types of reactions (suprafacial vs intrafacial).
For CH
4
oxidation the CH bond was ruptured before reacting
with the adsorbed oxygen, which required the catalyst to
participate in as a reagent that was partly consumed and
regenerated in a series of continuous redox cycles.
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