NSFC-NSF Workshop’ 2009

Synergetic effect between copper oxide and

ceria for soot catalytic oxidation

Xiaodong Wu
Department of Materials Science and Engineering, Tsinghua
University, Beijing 100084, China

Changzhou, China
2009-10-17

1
 Beijing

EcoMaterials Group

Essential research field: automobile exhaust catalysts

 Three-way catalysts
 Soot oxidation catalysts
 Oxidation catalysts
 deNOx catalysts (NH3-SCR, LNT)
 Supports and coating technologies
2
Outline
Background

Studies on Cu-Ce mixed oxide catalysts

 Choice of support material;
 Optimization of the Cu/Ce ratio;
 Modification of Cu-Ce catalysts.

Challenges

3
 Schematic of Diesel Particulate Matters (PM)
PM ： important pollutant to human health and environment

Vapor Phase
Solids (Soot) Solid Carbon Spheres (0.01
Hydrocarbons -0.08 m diameter) from to
make Solid Particle
Agglomerates (0.05-1.0 m
diameter) With Adsorbed
Hydrocarbons

Adsorbed
Soluble Organic Hydrocarbons
Fraction (SOF)
/Particle Phase Liquid Condensed
Hydrocarbon Particles
Hydrocarbons
Sulfate with Hydration

Adsorbed Sulfate (SO4)

Hydrocarbons

Vuk and Johnson, SAE 760131 (1976)

Background
Most promising method ： DPF or POC
Key techniques:
(catalyst, fuel additive, external heater…)

regeneration
regeneration

Reg
n
tio

ener
l tra
Fi

ation
p

time
Diesel particulate filter Exhaust back pressure vs. time
5
Reported work
NOx-assisted
NOx storage
soot oxidation

Modern diesel engines

• Low NOx emission
• Low exhaust temperature

Comparison of the soot-TPO profiles on Mn25Ce75 (■)

and a commercial platinum catalyst (▲).
Reactant gas: 10% O2 + 1000 ppm NO + 3% H2O in N2.

K. Tikhomirov, et al, Appl. Catal. B 64 (2006) 72. 6

Objective

CuOx
• Cheap
• Redox activity

To form Cu-Ce
mixed oxides
• Activity and selectivity
CeO2 • Hydrothermal resistance
• Cheap • Resistance to SO2
• Oxygen storage capacity • …

• In the presence of NO+O2

Experimental • Fast heating rate: 10-20℃/min;
conditions: • High flow rate: 500ml/min;
F. E. López-Suárez, et al, Appl. Catal. B 84 (2008) 651. • Loose catalyst-soot contact
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A. Setiabudi, et al, Appl. Catal. B 51 (2004) 9. conditions.
 Choice of support: CeO2 or Ce-Zr?
Demonstrating the importance
of the Cu-Ce interactions
Cu-Ce-Zr Cu-Ce-Zr
(a Ce-Zr
) Cu-Ce Cu-Ce CeO2

CeO2 Ce-Zr

TPO curves of (a) fresh and (b) aged catalysts .

Reaction atmosphere: 10% O2+1000ppm NO + N2.
Aging treatment: in static air at 800oC for 20h
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 Optimization of the Cu/Ce ratio
(a) Without (b)
catalyst Fresh
Aged

Cu ： 5-10%

Fresh
Without Aged
catalyst

Samples Samples

(a) Activity and (b) selectivity of Cu-Ce catalysts.

Aging condition: 7%steam/air, 800oC for 20h

Ti ： at which the conversion of soot reaches 5%

CO2
Selectivity to CO2: SCO 2 (%)   100 9
CO  CO2
 Structure of Cu-Ce mixed oxides

Fresh (a) Segregation and growth of

CuOx at high temperatures

Aged (b)

CuOx clusters are finely dispersed

on ceria particles instead of
forming Cu-Ce solid solutions.

XRD patterns of (a) fresh and (b) aged catalysts 10

Synergistic effect between Cu and Ce
Surface composition and valence state of the samples
Samples Cu/Ce Cu/Ce Ce 4+ Cu 0  Cu 
(Nominal) (measured Cu 0  Cu   Cu 2
Ce3+  Ce 4+
)
CeO2-F - - 0.83 -
Cu5-F 0.053 0.194 0.85 1
Cu20-F 0.25 0.492 0.87 0.44
CeO2-A - - 0.84 -
Cu5-A 0.053 0.42 0.85 0.89
Cu20-A 0.25 0.552 0.87 0.3

Cu+ Ce4+ Cu+ CuO1-x

O2- O2-
Ce 4   O  Cu 2 
Ce4+ Ce4+ Ce4+ Ce3+
CeO2 Ce 4   VO..  Cu 
O2- O2- O2-
Ce 3+
Ce4+
Ce4+ Ce 3  VO..  Cu 
active sites 11
Scheme of the Cu-Ce interface
Strong interaction between Cu and Ce
A B C
CO 2production

Mixture

Cu-Ce synergetic effect

CuOx nanoparticles

CuOx clusters
Temperature
CO-TPR profiles

 A: Cu-Ce interaction CuO particles

 B: Bulk CuO
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 C: CeO2
Oxidative adsorption of NO in soot-TPO

Cux+: oxidizing NO to NO2

Without
catalyst
Cex+: coordinated to adjacent
sites to store NO2-
derived species

Evolution of NO concentration
Reaction atmosphere:1000ppmNO+10%O2+N2

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Reaction mechanism in NO+O2
+ C-O*

NO O2
O O (3) (4)
(1) O O
N
(2) NO2*
spillover Soot COx (g)
N N
O O O O O + O2
M M M M

Catalyst

Scheme of Cu-Ce+soot reaction in NO+O2

（1 NO  O2  Cat .  Cat.  NO3

）

（2 Cat.  NO3  O2  Cat.  O  NO2

）
? Cat.  NO 
3  C f  Cat.  C (O)  NO
（3 NO2  Cf  C (O)  NO
）
（4 C (O)  O 2  CO 2  Cf
） 14
 Enhanced thermal stability of Cu-Ce-Al
CuCeAl2
CuCe
Fig. TPO curves of the aged catalysts
under loose contact conditions.
Reaction conditions: 1000ppm NO+10%O2+N2
Ageing conditions: in dry air at 800°C for 10h
CuCeAl2
√ ×
Fig. TPO curves of the fresh, hydrothermal aged
and sulfated Cu-Ce-Al under loose contact.
Reaction conditions: 1000ppm NO + 10% O2 + N2.
√ Hydrothermal ageing: in 10H2O/air at 800°C for 10h
× SO2 poisoning: in 1000ppmSO2/10%H2O/air at 800°C, 10h
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Active surface nitrates
Symmetric nitrates Inert Asymmetric nitrates Active

Time evolution of FT-IR spectra of the hydrothermal aged (a) Cu–Ce

and (b) Cu–Ce–Al exposed to 1000 ppm NO + 10% O2 at 50℃.
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Improved resistance to SO2 by adding K
 Preparation: impregnation, 500oC for 3h
 SO2 treatment: in 400ppmSO2/air at 400oC for 2 h

Tm and CO2 selectivity of the fresh and poisoned catalysts

Sample (wt.%) Tm (ºC) S (%)

Fresh 378 81
Cu5K2/CeO2
Poisoned 410 85
Fresh 359 58
Cu2K5/CeO2
Poisoned 380 86

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Preferential sulfurization of potassium

Nitrates

Carbonates

Sulfates

SO2

IR spectra of the fresh and SO2-poisoned catalysts.

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Combination of POC and LNT
K salts
• Solubility;
• Volatility;
• Corrosiveness.

Replaced by Ba

Tm of CuCe and Ba1CuCe in the presence of different NO concentrations

Catalysts preparation:
Ce(NO3)3, Citric acid sol-gel Loading Ba(Ac)2
CuCe BaCuCe
Cu(NO3)2 500 ℃, 3h 550 ℃, 1h
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Conclusions
Cu-Ce is a good candidate as NO2-assisted soot oxidation catalyst
with the Ce4+–O2-–Cu2+ pairs at the interface as active sites, which
presents high activity comparable to commercial PM catalysts.

By modification of alumina, potassium or barium, the resistances to

hydrothermal ageing and sulfur dioxide of Cu-Ce catalysts can be
enhanced.

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Challenges in mixed oxide catalysts
Performance:
 The performance of catalysts are still not satisfying
 low-temperature activity and lifetime (like thermal stability
and resistance to SO2)
 How to improve the activity of catalysts
 in trace NO or without NO?
Mechanism:
 Active NOx species
 surface nitrates, the decomposed NO2, the oxidized NO2 or
just NO itself?
 Possible and important intermediates during soot oxidation
 surface oxygen complexes (SOCs) and surface nitrogen
complexes (SNCs) if possible
 Corresponding in situ characterizations
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Acknowledgements
Financed by the Ministry of Science and Technology of China.

Thanks to: Team leader: Prof. Duan Weng

Ph.D candidate: Jia Li
Master: Qing Liang and Haibo Xu
Master candidate: Fan Lin

Thank you for your attention!

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