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Studies in Surface Science & Catalysis, 159, pp.

413-416, 2006

Effect of ozone pretreatment on low temperature CO oxidation


catalysts
K. Y. Hoa and K. L. Yeungb,*
a

Environmental Engineering Program and Department of Chemical Engineering, the Hong Kong
University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong
b

Department of Chemical Engineering, the Hong Kong University of Science & Technology,
Clear Water Bay, Kowloon, Hong Kong
1. INTRODUCTION
Titanium dioxide supported gold catalysts exhibit excellent activity for CO oxidation even at
temperatures as low as 90 K [1]. The key is the high dispersion of the nanostructured gold
particles over the semiconducting TiO2 support. The potential applications of ambient
temperature CO oxidation catalysts include air purifier, gas sensor and fuel cell [2]. This work
investigates the effects of ozone pretreatment on the performance of Au/TiO2 for CO oxidation.
2. EXPERIMENTAL
Nanostructured TiO2 was prepared by a modified sol-gel method [3]. Five milliliters of titanium
isopropoxide (TIP, 98 %, Acros) was rapidly mixed with an alcohol solution containing 1.5 mL
water in 30 mL isopropanol (IPA, 99.7 %, BDH) at room temperature. The uniform-sized titania
gel-spheres formed by rapid hydrolysis of TIP was collected by vacuum filtration. The dried
powder was recrystallized by thermal treatment [4] to produce nanometer-sized, anatase TiO2 of
controlled crystal and aggregate sizes, crystallinity and surface chemical property [5]. Welldispersed gold catalysts on TiO2 were prepared from an aqueous solution of hydrogen
tetrachloroaurate (III) trihydrate (HAuCl4, ACS, Aldrich) at a neutral pH. Two gold catalysts
were pretreated at 473 K for 5 h in air and in 100 ppm O3/O2 mixture, respectively. Table 1 lists
the gold loading, average TiO2 crystal size, BET surface area of the catalyst, pretreatment
condition and the average gold particle size for three catalyst samples prepared for this study.
The catalysts were tested for CO oxidation in a flow reactor using a 2.5 % CO in dry air mixture
at a fixed flow rate of 200 sccm. Thirty milligrams of the catalyst were used for each
experimental run. The reaction was conducted at 298, 323, 373 and 473 K with 75 minutes
duration at each temperature. The carbon monoxide conversion to carbon dioxide was monitored
by an online gas chromatograph equipped with a CTR-1 column and a thermal conductivity

Author to whom correspondence should be addressed


Tel: 852-2358-7123; Fax: 852-2358-0054; e-mail: kekyeung@ust.hk

Studies in Surface Science & Catalysis, 159, pp. 413-416, 2006

detector. After completing the temperature program, the gas inlet and outlet to the reactor were
shut off to isolate the catalyst. The catalyst was allowed to cool down to room temperature and
left overnight for 16 h. The reaction was resumed next day by flowing in the reaction mixture at
room temperature.
Table 1. Properties of gold catalysts
Sample

Au loading#
(wt.%)

TiO2 crystal
size+ (nm)

BET area
(m2 g-1)

Au/Nano-TiO2

0.59

12 (anatase)

68

Au/Nano-TiO2

0.58

13 (anatase)

70

Au/P25*

0.78

22 (anatase),
37 (rutile)

52

Pre-treatment
O2 at 473 K
for 5 h
100 ppm O3/O2 at
473 K for 5 h
100 ppm O3/O2 at
473 K for 5 h

Au particle size
before (after)
reaction (nm)
2.5 (5.7)
2.7 (2.4)
2.5 (2.8)

Degussa P25 titanium dioxide


Determined by inductively coupled plasma-mass spectrometry of acid digested catalyst samples
+
Calculated from X-ray diffraction peak broadening at (101) for anatase and (110) for rutile TiO2

Mean particle diameter measured from transmission electron microscopy pictures of gold catalysts
#

3. RESULTS AND DISCUSSION


Fig. 1 plots the results of the reaction experiment conducted on the three gold catalysts. The
figure shows that within the range of 298 to 473 K, the reaction conversion is a weak function of
temperature. Catalyst deactivation is observed except for the catalyst pretreated by ozone/oxygen
mixture. Besides the nanostructured TiO2 prepared by the sol-gel process, commercial P25 TiO2
was also used as the support for the gold catalyst. Both the Au/Nano-TiO2 samples treated in
oxygen and ozone/oxygen mixtures are more active than the Au/P25 catalyst.

Rate (mmol s -1gAu-1)

298 K

323 K

373 K

473 K

15
12
9
6
3
0
0

100
200
Time (min)

300

Fig. 1. Rate of CO oxidation of ( ) O2-treated Au/Nano-TiO2, () O3/O2-treated Au/Nano-TiO2 and


() O3/O2-treated Au/P25 from 298 to 473 K.

-1
-1

2.5

Rate (mmol s gAu )

-1

-1

ln Rate (mmol s gAu )

Studies in Surface Science & Catalysis, 159, pp. 413-416, 2006

2
1.5
2

2.5
3
-1
1000/T (K )

3.5

Fig. 2. Arrhenius plots for the rate of CO


oxidation over ( ) O2-treated Au/NanoTiO2, () O3/O2-treated Au/Nano-TiO2 and
() O3/O2-treated Au/P25.

15
12
9
6
3
0
0

100
200
Time (min)

300

Fig. 3. Rate of CO oxidation of ( ) O2treated Au/Nano-TiO2, () O3/O2-treated


Au/Nano-TiO2 at 298 K.

The Arrhenius plots of the CO conversion rate in Fig. 2 indicate that the activation energy for the
Au/Nano-TiO2 catalysts is nearly zero. Haruta et al. [6] also reported similar observations. They
suggest that this occurs when the CO adsorbed on gold particles reacts with adsorbed O2 on the
support at the interfacial junction between the two surfaces.
Fig. 3 plots the reaction rates of the catalysts versus time at room temperature. The reaction was
conducted 16 h from the first set of experimental run. The O2-treated Au/Nano-TiO2 lost half of
its activity after 45 minutes of reaction, while O3/O2-treated Au/Nano-TiO2 displays a constant
activity. It is clear from these results that Au/Nano-TiO2 catalyst pretreated with ozone exhibits
better and more stable catalyst performance. The transmission electron microscope pictures of the
O2-treated Au/Nano-TiO2 shown in Fig. 4 display an increase in the gold particle size to as large
as 17 nm after the reaction, while the O3/O2-treated catalyst did not show any changes in the gold
particle size. Coarsening of gold particles [7,8] is one of the reasons for catalyst deactivation and
the ozone pretreatment is seen to inhibit this process. XPS analysis of the fresh catalysts shows
that the O3/O2-treated gold catalyst has broader Au 4f peaks indicating the presence of
nonmetallic gold that may be responsible for the enhanced stability of this catalyst (Fig. 5).

Au

Au

Fig. 4. High resolution TEM of O2-treated Au/Nano-TiO2 (a) before and (b) after CO oxidation.

Studies in Surface Science & Catalysis, 159, pp. 413-416, 2006

80

84
88
92
Binding Energy (eV)
Fig. 5. Binding Energy of the
Au 4f region for (a) O2-treated
Au/Nano-TiO2, (b) O3/O2treated Au/Nano-TiO2.

K-M unit

Rel. I

473K
373K
323K
298K

K-M unit

1650

1450

1250
-1

Wavenumber (cm )

1650

1450
1250
-1
Wavenumber (cm )

Fig. 6. FTIR spectra of carbonate region of (a)


O2-treated Au/Nano-TiO2 and (b) O3/O2-treated
Au/Nano-TiO2.

The accumulation of carbonates is another reason for gold catalyst deactivation [9]. The in-situ
FTIR experiments in Fig. 6 show that the carbonate build-up is slower in the O3/O2-treated gold
catalyst (Fig. 6a) compared to the air-treated sample (Fig. 6b). Also, the air-treated catalyst
displays a strong band at 1435 cm-1 corresponding to the non-coordinated carbonate. Although
our understanding of the process is incomplete, it is clear from the results that O3 pretreatment
inhibits the deactivation of gold catalyst.
ACKNOWLEDGEMENT
The authors would like to acknowledge the financial support from the Hong Kong Innovation and
Technology Fund (ITS/176/01C).
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