CHINA-US Workshop’ 2009

Studies of Ceria-based Materials in

Automotive Exhaust Control Catalysis

Meiqing Shen
mqshen@tju.edu.cn
School of Chemical Engineering and Technology,
Tianjin University
 Automotive Catalysis at Stoichiometric and Lean conditions
Oxidation catalysts

Selective Catalytic Reduction

HC+CO+PM+NOx
Emission limit raised by engine and catalysts optimization.

NOx Storage Reduction

Besides TWC, novel catalysts required for lean-burn exhaust control.

*Gandhi H S et al. Journal of Catalysis, 2003, 216, 433. 2
* Burch R. Catalysis Reviews, 2004, 46, 271.
Ceria-based Materials in Automotive Catalysts

Rare-earth materials can be utilized in automotive catalysts with

multiple functions
Challenges:
Mechanisms of specific catalytic process;
Know-how materials’ design and synthesis;
Sustainable high activity;
TWC Systematic approach to the development of after-treatment

LNT/ SCR

Gasoline Engine

3
 Ceria Catalysis

Oxygen Storage Capacity;

1
x
2CeCe + OO ↔ 2CeCe
'
+ VO.. + O2
2

Enhancement for WGS and SR; 100 (a) 100

CO Conversion (%)
80 80

C3H8 Conversion (%)

60 60

40 40

20 20

0 0

0 100 200 300 400 500 600

Temperature (oC)

Disperse and activate active sites;

Modifications of Ceria-based materials

*Kašpar J et al. Catalysis Today, 2003, 77(4),419. 4

Controllable Synthesis of Ceria-zirconia Solid Solutions

Synthesizing nanospherical CeO2-ZrO2 by two-phase approach

The TEM image of Ce0.7Zr0.3O2 after calcination at 300 ºC for 4h in air.

Homogeneous bulk phases and meso-poresize distributions after calcination at 300 ºC for 4h in air.
5
 Studies of Dynamic Reactions

Developing cycling pulse tests for kinetics study and real practice

Flow chart of dynamic OSC measurement.

CO inlet

CO outlet
Concentration(a.u)

CO2(1)

O2 inlet
CO2 outlet

CO2(2) O2 outlet CO-O2 pulses pass through catalysts’ bed almost as

plug flows (catalysts are mixed with quartz sand).

0 5 10 15 20
Time(s)
CO, O2 and CO2 responding curves in dynamic OSC measurement.
6
 Experimental Studies on Oxygen Mobility

Developing cycling pulse tests for kinetics study and real practice

In-situ EPR/ Isotopic exchange:

DRIFTS: Oxygen
Local Superoxides storage/release
environment mechanism
around O2-

Flow chart of the combined vacuum system for the Schematic system of the isotopic exchange .
in-situ analysis of oxygen species.
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Simulation Studies on Lattice Oxygen Mobility

Oxygen vacancies and Ce 4f electrons

Substitute site of Ni Interstitial site of Ni

Ni-doping enhances the O buffering effect of ceria;

Substitutional system: O vacancy formation in the leads to the
reduction of Ni atoms;
Insterstitial system: Reduction of the determines the reduction of
two Ce atoms.

8
O Backspillover Controlled Oxidation Capability
Different states of Pd can be observed Increasing gap of activation energies for
on oxidized (A) and reduced (B) CZ deep oxidation by Pd catalysts

9
 Oxidation Capability Determined by Lattice Oxygen

Lean Rich

Temperature/ Oxygen
Reducibility Vacancy
Dependence Dependence

OSC activity of Pd supported samples at EPR Ce3+ related signal of CZ samples.

increasing temperatures. 10
O Transfer Controlled Selective Redox Activities

NOx conversion shows negative order to OSC performance.

11
Modified Reaction Networks
Competitions of different reactions
WGS SR WGS and SR
compete with
each other
along the
increasing
temperatures
…

Evolution of gases along the catalysts bed in dynamic reactions

Evolution of multiple gases (left) and surface adsorbates on catalysts (right) in the complete lean-rich cycles. 12
Interactions among Standard Components

Ceria related interactions with main active sites

Effect of ceria
HA-SA
in hindering
PGM sintering
Pd/SA-Pd/SAA
is essential…

10 % H2O
Pd/HA-Pd/SA hydrothermal
aging at 1073 K

Ceria related interactions with promoters and support oxides

Ceria is
sensitive to
aging
atmosphere
in modifying
components
distributions
10 % H2O +10 %
CO2 hydrothermal
aging at 1073 K 13
Dopants Induced Interactions

Effects of dopants (Fe) for ceria lattice (Rietveld Analysis)

24

Oxygen vacancy (%)

5.412
20
Lattice Constant

Solubility of
5.410 16
dopants controls
12 lattice
5.408
8
relaxation…

5.406 4
0.00 0.02 0.04 0.06 0.08 0.00 0.02 0.04 0.06 0.08
[Fe]/[(Fe)+(Ce)] (%)
[Fe]/[(Fe)+(Ce)] (%)
Effects of dopants (Sr) for catalytic activity at varying A/F windows

Effects of
dopants for CO,
HCs and NOx
conversion may
not always go in
the same
direction… 14
 Optimizations of the Catalysts Formulations

Ceria-alumina support oxides with different mixing ways

CZAMO-A CZAMO-P CZAMO-M

2 Al 3+
2CeO2 ←→ 2 AlCe
'
+ Vo•• + 3Oo×
CZ
A

Al3+

Ce4+ VO

O2-

Activation energies of CO oxidations.

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Optimizations of the Catalysts Formulations

Ceria-barium-alumina
with stepwise changing
core-shell distributions
Texture

Chemistry

Performance

Storage Promoter Support

Components oxides
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Sustainable Activity of Ceria-based Catalysts

500 ppm NO, 7.5 % O2, GHSV: 30,000 h-1, 800 ℃, 12 h hydrothermal + 10 % CO2 aging.

FeCrAl foils and washcoat on γ-alumina based ceramic materials (left), and the change of E10catalysts
morphology along the radial wall of monolith after being used.
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Summary and Final Words

O transfer ability in ceria (or other RE elements) lattice is essential

for the activity of automotive catalysts, but different catalysis and
technical issues appear in different situations…

Kinetics study of O mobility based on the precise measurement of

active sites needs further addressing…

Novel catalysts with nanostructured design and synthesis are

demanded for the study of fundamental issues and the
development of advanced material …

A system approach is required to develop and optimize

aftertreament catalysis technologies (Materials, Reactions, and
Simulations)…
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Related Recent Publications

1. Yang M, Shen M, Wang J at al. Pd-Support interaction defined selective redox activities in Pd−Ce0.7Zr0.3O2−Al2O3 model
three-way catalysts. Journal of Physical Chemistry C, 2009, 113, 12778-12789.
2. Shen M, Yang M, Wang J et al. Pd/support interface-promoted Pd−Ce0.7Zr0.3O2−Al2O3 automobile three-way catalysts:
studying the dynamic oxygen storage capacity and CO, C3H8, and NO conversion. Journal of Physical Chemistry C, 2009,
113(8) 3212-3221.
3. Shen M, Wang J, Shang J et al. Modification ceria-zirconia mixed oxides by doping Sr using the reversed microemulsion for
improved Pd-Only three-way catalytic performance. Journal of Physical Chemistry C, 2009, 113(4): 1543-1551.
4. Wang Y, Wang J, Shen M et al. Synthesis and properties of thermostable γ-alumina prepared by hydrolysis of phosphide
aluminum. Journal of Alloys and Compounds, 2009, 467(1-2): 405-412.
5. Wang J, Wen J, Shen M. Effect of interaction between Ce0.7Zr0.3O2 and Al2O3 on structural characteristics, thermal stability,
and oxygen storage capacity. Journal of Physical Chemistry C 2008, 112(13): 5113-5122.
6. Jia L, Shen M, Hao J et al. Dynamic oxygen storage and release over Mn0.1Ce0.9Ox and Mn0.1Ce0.6 Zr0.3Ox complex
compounds and structural characterization. Journal of Alloys and Compounds, 2008, 454(1-2): 321-326.
7. Zhao M, Shen M, Wen X et al. Ce–Zr–Sr ternary mixed oxides structural characteristics and oxygen storage capacity.
Journal of Alloys and Compounds, 2008, 457(1-2): 578-586.
8. Jia L, Shen M, Hao J et al. Dynamic oxygen storage and release over Mn0.1Ce0.9Ox and Mn0.1Ce0.6 Zr0.3Ox complex
compounds and structural characterization. Journal of Alloys and Compounds, 2008, 454(1-2): 321-326.
9. Zhao M, Shen M, Wang J et al. Influence of Pd morphology and support surface area on redox ability of Pd/Ce0.67Zr0.33O2
under CO-He pulse and transient CO-O2 measurements. Industrial & Engineering Chemistry Research, 2007, 46(24): 7883-
7890.
10. Jia L, Shen M, Wang J. Preparation and characterization of dip-coated γ-alumina based ceramic materials on FeCrAl foils.
Surface & Coatings Technology, 2007, 201(16-17): 7159-7165.
11. Zhao M, Shen M, Wang J. Effect of surface area and bulk structure on oxygen storage capacity of Ce0.67Zr0.33O2. Journal of
Catalysis, 2007, 248(2): 258-267.

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Acknowledgements

Collaborators:
 Natural Science Foundation of China;
 BASF Catalysts LLC, USA;
 General Motors R&D Center, USA;
 CNR-INFM DEMOCRITOS National Simulation Center, Italy

Current Students:
 Xinquan Wang
 Jianqiang Wang
 Yuewei Zhang
 Jing Wen
 Ming Yang
 Anju Shi
 Chao Lei
 Jiahao Chen

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