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Multi-scale catalyst design
Wei Liu
C, respectively.
The Cu-ceria catalytic activity was found comparable or supe-
rior to the Pt catalyst. Although Au/FeO
x
or Au/TiO
2
system
was reported for low-temperature CO oxidation in the earlier
research (Haruta et al., 1993), Au-ceria has simple crystalline
structure and high stability, presenting a nice model system
clearly demonstrating synergistic effect of a composite catalyst.
It is noteworthy that active catalyst conguration comprises
nano-sized copper or Au particles/clusters embedded in ce-
ria matrix (Liu and Flytzani-Stephanopoulos, 1995b). Small
amounts of Cu or Au (a few wt% or less) are sufcient to make
an active composite catalyst (Liu and Flytzani-Stephanopoulos,
1996; Fu et al., 2003), which is consistent with the model pro-
jection. Large interfacial area resulting from nano-sized Cu or
Au clusters enables electronic and chemical interactions be-
tween the two kinds of materials to occur to a large extent. As
illustrated in Fig. 11, such interactions are postulated to extend
3510 W. Liu / Chemical Engineering Science 62 (2007) 35023512
Table 2
Kinetic parameters of CuCeO
2
composite catalyst for CO oxidation (data
from Liu and Flytzani-Stephanopoulos, 1995b)
Catalyst Relative k A E
a
Q
at 150
C (kJ/mol) (kJ/mol)
Cu
0.15
[Ce(La)]
0.85
O
x
9.4 10
4
7.0 10
8
78 28
Cu
0.01
[Ce(La)]
0.99
O
x
As prepared
a
7.8 10
3
1.4 10
7
73 37
+3 h in air at 860
C 1.7 10
4
1.6 10
9
87 61
CuOCrO
x
/-Al
2
O
3
1 3.0 10
5
91 5
a
This catalyst was prepared by 4-h calcination in N
2
gas at 650
C, while
the other composite catalyst was typically calcined in air at 650
C.
beyond the interface and may decline exponentially with dis-
tance away from the interface. Degree of the interaction is
clearly reected in the reaction kinetics.
CO oxidation over the Cu-ceria composite catalyst shows the
following reaction kinetics:
rate
CO
2
=
k
s
K
CO
P
CO
P
0.1
O
2
1 +K
CO
P
CO
Table 2 lists the kinetic parameters of three CuCuO
composite catalysts in comparison to the CuOCrO
x
/alumina
catalyst. The CuOCrO
x
catalyst was regarded as the most
active base metal catalyst for CO oxidation at high temper-
atures prior to discovery of the present composite catalyst.
The heat of adsorption of CO on the CuCeO composite
catalysts, derived from K
CO
, is substantially higher than that
on the CuOCrO
x
/alumina. Relative reaction rate constants
at 150
2
e
O
2
2
O
e
O
2
lattice
.
For example, oxidation of methane may involve lattice oxy-
gen, while CO oxidation uses super oxide species (O
2
). The
oxidation/reduction cycle involves both electron transfer and
oxygen atom transfer. Cerium oxide has little electronic con-
ductivity. Addition of transition metal species, such as Cu, Au,
W. Liu / Chemical Engineering Science 62 (2007) 35023512 3511
Reducing molecule
(CO) reacts with surface
oxygen specie
Surface capping
oxygen vacancy
Oxidizing molecule
transfers oxygen to
vacancy (O
2
)
Fig. 12. Unied reaction mechanism for (Cu, Au, Ni)/ceria nano-composite catalyst.
and Ni, facilitates the electron transfer and also provides surface
sites for reducing molecules to adsorb. As a result, synergistic
effects are displayed for enhancement of the catalytic activity.
5. Summary
Multi-scale analysis and approach is effective to elucidate
impacts of design perspective at different scales to a catalytic
reaction process performance and open up new design dimen-
sions to break up the compromise that often needs to be made
with the conventional approach. A few promising catalyst de-
sign directions at catalyst bed level, catalyst particle level, and
intrinsic catalyst structure level are proposed and elaborated
with specic examples.
In the catalyst bed scale, micro- or mini-structured catalyst
designs enable decoupling of hydrodynamics and external mass
transfer from internal mass transfer and catalytic reactions. As
a result, all mass transfer resistance can potentially be mini-
mized and intrinsic catalytic performance is realized. It is par-
ticularly promising to gas/liquid multiphase catalytic reactions
that involve complex mass transfer steps and ow hydrody-
namics. The micro-structured bed design also provides a good
platform for integration with catalyst-particle level designs.
In the catalyst particle scale, design of bulk uid/catalyst
boundary condition is proposed to control mass transfer rate of
individual molecules into and out of the catalyst, which could
not be realized by catalyst bed level designs. For example, ad-
dition of a membrane coating layer onto external surface of
a catalyst unit enables dramatic improvement in reaction se-
lectivity that can be as important as the conversion rate for a
practical process. Commercial process of selective dispropor-
tionation of toluene to paraxylene over a modied zeolite cat-
alyst and recent research progress for other reactions are used
to show feasibility of this design strategy.
At the level of intrinsic catalyst structures, 3-D catalyst de-
sign approaches are outlined to outweigh limitations or con-
straints associated with the conventional 2-D catalyst model.
The 3-D catalyst design is illustrated by (i) optimizing size
and/or shape of a catalyst material at nano-scale to enhance den-
sity of active catalysis sites, (ii) integrating catalyst materials of
different functions in vertical direction, and (iii) incorporating
different kinds of catalyst material to form nano-composite cat-
alysts. Exceptional catalysis properties of the nano-composite
catalyst made of common catalyst materials are clearly demon-
strated with (Cu, Au, or Ni)/ceria catalyst system for a range
of reactions in hydrogen processing and air pollution control
application.
Acknowledgments
The author would like to thank Institute of Process En-
gineering, Chinese Academy of Sciences for promoting and
supporting studies of multi-scale science and technology.
Scientic discussion with Dr. Jinghai Li in the institute there
about understanding uidization and particle clustering from
1st principles was inspiring. The author is grateful to Profs.
Flytzani-Stephanopoulos and Adel Sarom for their mentorship,
and his colleagues in the industry for technical discussion and
cooperation on various catalyst and reactor technologies.
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