China-US Workshop’ 2009—Session 5 Environment B

Modification and oxygen storage properties

of CeO2-ZrO2 mixed oxides used for
automotive emission purification
Rui RAN
Dept. Mater. Sci. & Eng., Tsinghua University, Beijing 100084
ranrui@mails.thu.edu.cn

 Introduction;
 Oxygen storage material design;
 Modification mechanism;
 Application in catalysts;
 Summary.
 Automotive emission pollution becomes one of the
biggest environmental problems

Emission:

 CO~ 33562 104t/y

 HC~ 331 104t/y
 NOx~4188 104t/y
 PM10~895 104t/y

Auto productions of China in the recent

decade
 Catalytic convertor and the key materials
 Oxygen storage materials: CeO2-ZrO2 mixed oxides

NO
,x O
2
CO
, HC

CO2, H2O
N2

Three-way catalytic convertor

Zr  increase the thermal stability and

oxygen mobility.
  Oxygen storage material design: Doping by RE

Static OSC: CZP2~CZN2~CZ;

Dynamic OSC: CZP5>CZP2>CZP8>CZN2>CZ;

OSC results of the aged Pr, Nd doped samples (500℃)

XD Wu, D Weng, R Ran. Solid States Science 2007, 9 (7): 636-643

 Oxygen storage material design: impregnation
Promotion of Pr
(a) (b)

Promotion of Pr

OSC results of the aged (a) Pr-doped; (b) Pr-loaded samples (500℃).
CZ: CeO2-ZrO2; CZPx: Pr-doped CZ: PCZx: Pr-loaded CZ

3wt.% Pr6O11 loaded CZ

  Oxygen storage material design: impregnation
 Sr can effectively promote the dynamic OSC of CeO2-ZrO2.
 The results suggested that the impregnated Sr should affect the
surface/ interface structure.

OSCsurf * OSCC
Samples
(μmol CO2 gcat‑1) (μmol CO2 gcat‑1)

CZa 39.9 466.6

CZSa 52.8 536.6

SCZa 60.0 601.9

*
OSCsurf (μmol CO2 gcat–1) = SBET×3.8 μmol CO2 m–2

Dynamic OSC of aged Sr-modified samples

Ageing condition ： 1050℃ ， 6h

J Fan, XD Wu, R RAN, D Weng. J Catal, 2008, 258: 177–186

 Modification mechanism: Oxygen mobility
Ce reduction peak
Ce reduction peak
(a) (b)
PdO
reduction peak

Adsorbed
oxygen

CO-TPR curve for aged samples: (a) supports; (b) Pd catalysts

Pr can be considered as an inert species under 500°C in reduction process.

The Pr ions affect the properties only by influencing the structure and the
status of Ce, Pd species which are directly related to the OSC of catalysts.
  Modification mechanism: ionic valence

Pr3+

Pr4+

XPS patterns for aged CZP XANES spectra at Ce L3-edge for Pr6O11
w and w” derive from Pr3+; and aged CZP7a
w’ and w’’’ derive from Pr4+

 Pr mainly exists in Pr3+ over aged CZP samples.

XD Wu, D Weng, R Ran. Solid States Science 2007, 9 (7): 636-643

 Modification mechanism: bulk structure

c Tetragonality (c/a) of aged samples (XRD results)

c’ Samples c/a Samples c/a
CZa 1.013
b CZP2a 1.011 CZN2a 1.013
b’ CZP5a 1.008 CZN5a 1.012
a’
CZP8a 1 CZN8a 1
a
tetragonal structure
Vacancy formation:
3 3 Ce4
Pr / Nd 
 PrCe
'
 2Vo
3 3 Zr 4
 PrZr'  2Vo
Pr / Nd 

Pr3+ cation has larger ion radius than Nd3+.

Its insertion should lead more lattice distortion
t’’: pseudo-cubic structure in the bulk.
 Modification mechanism: crystallite size

Lattice constants and crystal sizes of the Pr-contained samples

Lattice constants (Ǻ) SBET Crystallite

(m2/g) size (Ǻ)
Fresh Aged Aged Aged
Samples a a c c/a
CZ 5.215(2) 5.172(2) 5.254(3) 1.016 22 196
CZP2 5.227(1) 5.189(1) 5.248(1) 1.011 16 196
CZP5 5.235(1) 5.210(1) 5.250(2) 1.008 13 197
CZP8 5.241(1) 5.238(1) / 1 9 182
PCZ1 5.212(3) 5.180(1) 5.259(2) 1.015 22 153
PCZ3 5.216(1) 5.185(1) 5.246(1) 1.012 30 129
PCZ5 5.212(1) 5.200(1) 5.250(1) 1.010 24 127

Pr is mainly dispersed Pr is partially inserted

on the surface. into the ceria lattice
  Modification mechanism: model
Take Sr for an
example:

Doping

Loading

J Fan, XD Wu, R RAN, D Weng. J Catal, 2008, 258: 177–186

 Summary

 Appropriate Pr/Nd/Sr doping or loading can promote the OSC of

CeO2-ZrO2 mixed oxides. It is found that 3wt% of Pr-loaded CZ by
impregnation is an optimized route to improve the oxygen storage
capacity (OSC) and thermal stability of CZ.

 The promotion of Pr/Nd/Sr is related to their more oxygen vacancies

and larger surface Ce3+ content, which are benefit to the oxygen
migration and surface reaction. Larger Pr3+/Nd3+/Sr2+ cations doping
leads more lattice distortion to accelerate oxygen migration.

 Surfacial modification can also promote the oxygen storage velocity

by creating structure defects at grain boundaries and suppress the
crystallite growing during the ageing process.
 Acknowledgement

 This work was supported by the National Natural Science

Foundation of China, Project No. 50972069.

 I would like to acknowledge my team colleagues: Prof. Duan

Weng, Dr. Xiaodong Wu, Dr. Jun Fan, Miss Xiaodi Wu, Miss Lei
Wang, and those who made great efforts on this work.
 谢 谢！
Thank You for Your Attention!