The document describes a study that synthesized three-dimensionally ordered macroporous (3DOM) perovskites using a dual-templating method to produce nanohybrid catalysts for methane combustion. The 3DOM La1-xCexCoO3 catalysts exhibited higher catalytic activity than conventional 1D nanowire structures due to their larger surface areas, higher oxygen species concentrations, better low-temperature reducibility, and unique nanovoid structure. Optimization of cerium content in the La1-xCexCoO3 solid solutions improved the materials' thermal stability and high catalytic activity, with 3DOM La0.7Ce0.3CoO3 demonstrating the best performance.

1. ACS Appl. Mater. Interfaces, 2016, 8 (4), pp 2457–2463
DOI: 10.1021/acsami.5b11050
Meso-Molding Three-Dimensional Macroporous Perovskites: A New
Approach to Generate High-Performance Nanohybrid Catalysts
Hamidreza Arandiyan†
, Jason Scott†
, Yuan Wang†
, Hongxing Dai‡
, Hongyu Sun§
, and Rose Amal†
†
Particles and Catalysis Research Group, School of Chemical Engineering, The University of New South Wales, Sydney, New South Wales
2052, Australia
‡
Beijing Key Laboratory for Green Catalysis and Separation, and Laboratory of Catalysis Chemistry and Nanoscience, College of Environmental and
Energy Engineering, Beijing University of Technology, Beijing 100124, China
§
Department of Micro- and Nanotechnology, Technical University of Denmark, 2800 Kongens Lyngby, Denmark
Key Contact
Scientia Prof. Rose Amal
School of Chemical Engineering
University of New South Wales
Tel: +61 2 93854361
Email: r.amal@unsw.edu.au

2. CH4 2O2 CO2 2H2O
+ +
Research Purpose: Design
Promising Heterogeneous Catalyst

3.  Excellent Activity
x High Price
x Low Stability
x Catalyst Poisoning
x Moderate Activity
Comparing with Noble Metal
 Low Price
 High Thermal-Stability
 High Hydrothermal Stability
 Resist Sulphur Poisoning
Background
Hamidreza Arandiyan et al. Catal Surv Asia, 19 (2015), 140-171
Hamidreza Arandiyan et al. ACS Catal., 5 (2015), 1781-1793

4. To design and synthesize 3DOM-m oxides with the
facile synthesis method.
To optimize Ce into La-Co-O solid solutions to
improve their thermal stability and high catalytic
activity for methane combustion.
Motivation of this work
Dual-templating synthesis of
3DOM-m La0.7Ce0.3CoO3

5. 100 nm
(a) PMMA Colloidal Crystal
(d) 3DOM-m La0.1Ce0.9CoO3 (e) 3DOM-m La0.3Ce0.7CoO3
(g) 3DOM-m La0.7Ce0.3CoO3 (h) 3DOM-m La0.9Ce0.1CoO3
100 nm 100 nm
100 nm 100 nm
(b) Hard template
PMMA
Wall thickness
Void size
Windows size
1st
Layer
2nd
Layer
3rd
Layer
0.1 mm
1 µm
100 nm
(c) 3DOM-m La0.5Ce0.5CoO3
(f) 3DOM-m La0.5Ce0.5CoO3
(i) 3DOM-m La0.5Ce0.5CoO3
S
E
M
A
F
M

6. a c e
db f h
g
5 nm5 nm10 nm 10 nm
50nm 50nm50nm 50nm
Windows between
macropores
Interconnected
macropores
Windows size
Mesostructre in wall
84 nm
68 nm
24 nm
23 nm
18 nm
0.277 nm
(110)
Mesostructured
hybrid network
51 nm
43 nm
High-resolution TEM images and the SAED pattern (inset) of a, b) 3DOM-m
La0.1Ce0.9CoO3, c, d) 3DOM-m La0.3Ce0.7CoO3, e, f) 3DOM-m La0.7Ce0.3CoO3 and g,
h) 3DOM-m La0.9Ce0.1CoO3.
TEM / SAED

7. 300 400 500 600 700 800
0
20
40
60
80
100
.
.
.
479
o
C
Half Conversion
Temperature (T50
)
Methaneconversion(%)
Temperature (
o
C)
1DDN La0.7
Ce0.3
CoO3
3DOM-m La0.1
Ce0.9
CoO3
3DOM-m La0.3
Ce0.7
CoO3
3DOM-m La0.5
Ce0.5
CoO3
3DOM-m La0.9
Ce0.1
CoO3
3DOM-m La0.7
Ce0.3
CoO3
564
o
C
532
o
C
525
o
C
494
o
C
512
o
C
(a)
1.3 1.4 1.5 1.6 1.7 1.8
-6
-5
-4
-3
-2
-1
0
53.3 kJ/mol
62.4 kJ/mol
60.4 kJ/mol
59.1 kJ/mol
66.7 kJ/mol
ln(k)/mLg
-1
S
-1
10
3
/T(K
-1
)
1DDN La0.7
Ce0.3
CoO3
3DOM-m La0.1
Ce0.9
CoO3
3DOM-m La0.3
Ce0.7
CoO3
3DOM-m La0.5
Ce0.5
CoO3
3DOM-m La0.7
Ce0.3
CoO3
3DOM-m La0.9
Ce0.1
CoO3
89.2 kJ/mol
(b)
a) Activity profiles and b) Arrhenius plots for methane combustion over the as-prepared
catalysts.
TOFLCCO (4.07×10-6
) of 3DOM-m
La0.7Ce0.3CoO3 was approximately 11.1
times as much as that (3.67×10-7
) of 1DDN
La0.7Ce0.3CoO3 for methane combustion at
300 °C.
Mixture
Furnace
GC
Micro-TCD
Mass Flow Controller
Catalytic Activity

8. 0.00.20.40.60.81.0
0
5
10
15
20
25
30
35
0.0 0.2 0.4 0.6 0.8 1.0
15
20
25
30
35
3DOM-m La1-x
Cex
CoO3
1DDN La1-x
Cex
CoO3
Ce (molar fraction)
BETSurfacearea(m
2
/g)
(A)
2.0
2.5
3.0
3.5
BETSurfacearea(m2
/g)
1DDN
La 1-x
Ce x
CoO 3
3DOM
-m
La 1-x
Ce x
CoO 3
BETSurfacearea(m2
/g)Ce (molar fraction)
0.0 0.2 0.4 0.6 0.8 1.0
50
60
70
80
90
100
3DOM-m - Activation energy
3DOM-m - T50%
1DDN - Activation energy
1DNN - T50%
Activationenergy(kj/mol)
480
500
520
540
560
580
T50%
(°C)
Lanthanum content
31.535.422.320.9
BET surface area (m
2
/g)
3DOM-m - BET (m
2
/g)
17.1
Catalytic Performance Evaluation
The 3DOM-m La1-xCexCoO3 catalyst showed enhanced catalytic activity for methane
combustion, which is attributed to its
1.Larger surface areas;
2.Higher concentration of chemisorbed oxygens species;
3.Better low-temperature reducibility
4.Higher surface-to-volume ratio;
5.Unique nanovoid 3DOM structure.
The 3DOM-m La1-xCexCoO3 catalyst showed enhanced catalytic activity for methane
combustion, which is attributed to its
1.Larger surface areas;
2.Higher concentration of chemisorbed oxygens species;
3.Better low-temperature reducibility
4.Higher surface-to-volume ratio;
5.Unique nanovoid 3DOM structure.

9. This work can be found in the
ACS Appl. Mater. Interfaces, 8 (2016) 2457–2463
DOI: 10.1021/acsami.5b11050
More information on the
Particle Catalysis Research Group at:
http://www.pcrg.unsw.edu.au/
Th A N K SThorium Adamantium Nitrogen Potassium Sulpher
90 124 7 1619
Cover Journal Page

10. This work can be found in the
ACS Appl. Mater. Interfaces, 8 (2016) 2457–2463
DOI: 10.1021/acsami.5b11050
More information on the
Particle Catalysis Research Group at:
http://www.pcrg.unsw.edu.au/
Th A N K SThorium Adamantium Nitrogen Potassium Sulpher
90 124 7 1619
Cover Journal Page