international journal of hydrogen energy 34 (2009) 8912–8920

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Au/TiO2 catalysts prepared by photo-deposition method

for selective CO oxidation in H2 stream

Yi-Fen Yang, Palanivelu Sangeetha, Yu-Wen Chen*

Department of Chemical and Materials Engineering, National Central University, Chung-Li 320, Taiwan

article info abstract

Article history: A series of Au/TiO2 catalysts were prepared by photo-deposition (PD) method. Various
Received 22 June 2009 preparation parameters, such as pH value, power of UV light and irradiation time on the
Received in revised form characteristics of the catalysts were investigated. The catalysts were characterized by
25 August 2009 inductively-coupled plasma-mass spectrometry, X-ray diffraction, X-ray photoelectron
Accepted 28 August 2009 spectroscopy, transmission electron microscopy and high-resolution transmission elec-
Available online 30 September 2009 tron microscopy. The preferential oxidation of CO in H2 stream (PROX) on these catalysts
was carried out in a fixed-bed micro reactor with a feed of CO: O2: H2: He ¼ 1: 1: 49: 49
Keywords: (volume ratios) and a space velocity of 30,000 ml/g h. Limited amount of O2 was used to
Au investigate the selectivity of O2 reacting with CO or H2. Au/TiO2 catalysts prepared by PD
TiO2 method showed narrow particle size distribution of gold particles within few nanometers
Photo-deposition and were found to be w1.5 nm. The particle size of gold nanoparticles deposited on the
Preferential oxidation of CO in support depends on irradiation time, UV light source and pH value of preparation. The
H2 stream electronic structure of Au was a function of particle size. The smaller the Au particle size
Nanometal was, the higher the concentration of Au cation was. Using weak power of UV light,
Gold catalyst appropriate irradiation time and suitable pH value, very fine gold particles on the support
could be obtained even in the powder form. The samples prepared with PD method did not
need heat treatment to reduce Au cation, UV irradiation could reduce it. Therefore it is
easier to have smaller particle size. Au/TiO2 catalysts prepared by PD method were very
active and selective in PROX reaction. In long time test, the catalysts were stable at 80  C for
more than 60 h.
ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction transition metal oxides exhibit a significantly enhanced

activity for CO oxidation, which has been attributed to their
Gold catalysts have gained attention due to their potential for ability to provide reactive oxygen [3]. Fuel cells are potential
many reactions of both industrial and environmental impor- battery replacement, however, platinum electrodes used in
tance. The most remarkable catalytic properties of supported fuel cells are often poisoned by the presence of CO. In order to
gold have been first obtained for CO oxidation at sub-ambient remove CO, highly dispersed gold nanoparticles on metal
temperature by Haruta et al. in 1987 [1]. Supported gold cata- oxides has been extensively investigated for preferential
lyst has gained extremely high activity towards CO oxidation, oxidation (PROX) of carbon monoxide reaction rather than Pt-
especially on a-Fe2O3, TiO2, and Co3O4 supports rather than group metal catalysts, because of its higher activity for CO
fine or gold cluster [2]. Au catalysts supported on reducible oxidation in hydrogen-rich stream. Gold catalysts were

* Corresponding author. Tel.: þ(886) 34227151x34203; fax: þ(886) 34252296.

E-mail address: [email protected] (Y.-W. Chen).
0360-3199/$ – see front matter ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.08.087
 international journal of hydrogen energy 34 (2009) 8912–8920 8913

prepared by several methods, such as co-precipitation [4], adjusted at different pH values (pH 6, 9, 10, 11) using 0.1 M
deposition–precipitation (DP) [5], chemical vapor deposition NH4OH before illumination. The light source used was 16 W
[6], laser vaporization [7], modified impregnation [8], and UV lamp (wavelength ¼ 254 nm, Philips TUV 16 W 4P-SE).
photo-deposition (PD) method [9]. DP method has been The irradiation time ranged from 10 min to 60 min with
regarded as the most simple and cost-effective method to a stirring speed of 770 rpm. The nominal Au loading was
prepare gold catalysts. Liu and Vannice [10] have reported that 1 wt.%. During irradiation, the pH was controlled carefully at
the deposition of Au on the surface of TiO2 markedly different pH values (pH 6, 9, 10, 11) using 0.1 M NH4OH and
enhanced the catalytic activity for CO oxidation. Our earlier the temperature of the solution was maintained After irra-
study focused on several catalytic systems such as Au/MnO2– diation, the solution was filtered and washed with deionized
TiO2 catalysts [11] and Au/MgOx–TiO2 catalysts [12] for pref- water until no Cl– was detected with AgNO3 solution. The
erential oxidation of CO. A detailed study on ceria- and samples prepared with PD method did not need heat treat-
manganese oxide-supported gold catalysts for the oxidation ment to reduce the Au cations because UV irradiation could
of carbon monoxide at low temperature was investigated reduce it.
[13,14]. Only a part of gold could be deposited on the support
by DP method [15]. The Au particles prepared by photo-
deposition on TiO2 were smaller compared to those prepared 2.2. Characterization
by deposition–precipitation at similar Au loadings [16–18].
Gold particle size was considered as the most important factor The catalysts were characterized by ICP–MS, powder X-ray
that affects the activity of gold catalysts. Haruta and diffraction (XRD), transmission electron microscopy (TEM),
coworkers [19] have reported that the turnover frequency X-ray photoelectron spectroscopy (XPS) and inductively-
increased with a decrease in the mean diameter of gold coupled plasma-mass spectrometry (ICP-MS).
particles, it is due to the contact structure giving the longest The exact gold content in the catalyst was analyzed
perimeter distance of gold-support interface, which was with ICP–MS (PE-SCIEX ELAN 6100 DRC). A CEM MDS-2000
responsible for active site. The size distribution of metal (CEM, Matthews, NC, USA) microwave apparatus equipped
particles was influenced by the concentration of precursor, pH with Teflon vessels was used to digest the powder samples.
value, irradiation time, and wavelength of the light source. The XRD experiments were performed using a Siemens
According to the literatures [20–24], gold catalysts D500 powder diffractometer. The XRD patterns were collected
supported on metal oxide semiconductor could be prepared using CuKa1 radiation (0.15405 nm) at a voltage and current of
by PD method. Based on the properties of semiconductor 40 kV and 40 mA, respectively. The sample was scanned over
metal oxides, the carrier charge can be excited by the energy the range 2q from 20 to 70 at a rate of 0.05 minÿ1 to identify
of incident light greater than or equal to the band gap of the the crystalline structure. Diffraction peaks of crystalline
metal oxide, and subsequently electrons can move from phases were compared with those of standard compounds
valence band to the conduction band, creating holes in the reported in the JCPDS data file.
valence band. The excited electrons and holes may recom- The gold particle size of the sample was measured by
bine in the materials or react with the adsorbed redox TEM on a JEM-1200 EX II operated at 200 kV and HRTEM on
groups on the surface. Under UV light irradiation with a JEOL JEM-2010 operated at 200 kV. A small amount of
a wavelength less than 387 nm, the illuminated TiO2 sample was put into the sample tube filled with a 95%
(anatase type; band gap energy, Eg ¼ 3.2 eV) could generate ethanol solution. After agitation under supersonic environ-
photo-excited electrons and positive holes in aqueous ment for 40 min, one drop of the dispersed slurry was dip-
medium. AuCl–4 ions adsorbed on the surface of TiO2 parti- ped onto a carbon coated copper mesh (300#) (Ted Pella Inc.,
cles can react with the photogenerated e– to form Au3þ and CA, USA), and dried at room temperature in vacuum over-
Au0 [25]. night. The average Au size diameter estimated by TEM was
Our earlier study focused on Au/TiO2 catalyst prepared by calculated using the following formula: davg ¼ Snidi/ni, where
PD method for CO oxidation [26]. In this study, a series of Au/ ni is the number of Au particles of diameter di. 100 Au
TiO2 catalysts were prepared by PD method under various particles were measured.
conditions. These materials were characterized with ICP–MS, The electronic state of each species on the surface of the
XRD, TEM and XPS. The catalysts were examined for PROX catalyst were measured by X-ray photoelectron spectroscopy
reaction at various temperatures. The main objective of this (XPS) performed with a Thermo VG Scientific Sigma Prob
study was to elucidate the effect of preparation parameters on spectrometer equipped with a hemispherical electron
the catalytic properties of Au/TiO2 catalysts. analyzer and an Al Ka radiation source (1486.7 eV) power at
20 kV and 30 mA, respectively. The powder samples were
pressed into a disk and placed on a sample holder in a vacuum
2. Experimental chamber. The spectrometer was operated at 23.5 eV pass
energy and the base pressure in the analyzing chamber was
2.1. Catalyst preparation maintained on the order of 5  10ÿ9 Torr. The binding energies
(BE) were determined by utilizing C 1s line as a reference with
Gold catalysts were prepared by photo-deposition method a binding energy of 285.0 eV. Peak fitting was done using
using HAuCl4 solution as the gold precursor. Commercially XPSPEAK 4.1 with Shirley background and 30: 70 Lorentzian:
available TiO2 P25 (Degussa, surface area ¼ 50 m2/g) was Gaussian convolution product shapes after the background
used. HAuCl4 containing 8.5  10ÿ4 M of gold and TiO2 were substration.
8914 international journal of hydrogen energy 34 (2009) 8912–8920

2.3. Catalytic activity

Catalytic reaction tests were performed as reported previously

[26]. The preferential oxidation of CO in hydrogen stream was
carried out in a downward, fixed-bed continuous-flow, pyrex
glass-tubular reactor loaded with 0.1 g of catalyst. The reac-
tant gas containing 1.33% CO, 1.33% O2 and 65.33% H2, and He
for balance was fed into the reactor with a total flow rate of
50 cm3/min. The reactor was heated with a temperature
regulated furnace with a heating rate of 1 C/min and the
temperature was measured by a thermocouple placed inside
the catalyst bed. The effluent gases were analyzed on-line by
a gas chromatograph (China Chromatography 8700 T) equip-
ped with MS-5A column and thermal conductivity detector.
Calibration of the gases was done with a standard gas con-
taining known concentration of the components. Blank
experiments using a reactor filled with a quartz powder alone
showed that no reaction occurs. The CO conversion and Fig. 1 – XRD patterns of Au/TiO2 catalysts prepared by
selectivity of O2 reacting with CO (S%) were calculated as different pH values and irradiated for 10 min: (a) pH 6 (b) pH
follows: 9 (c) pH 10 (d) pH 11.

½COŠin ÿ½COŠout
CO conversionðXCO %Þ ¼  100% (1)
½COŠin

ÿ
½O2 Šin ÿ½O2 Šout 3.2. XRD

O2 conversion XO2 % ¼  100% (2)
½O2 Šin
Fig. 1 shows the XRD patterns of Au/TiO2 catalysts prepared at
0:5  XCO different pH values (pH ¼ 6, 9, 10, 11). All catalysts containing
Selectivity of O2 reacting with CO ðS%Þ ¼  100%
XO2 TiO2 support showed intense XRD peaks for anatase phase
¼ mol of O2 reacting with CO=mol of O2 consumed (3) 2q ¼ 25.23 (101), 37.72 (004), 47.89 (200), 53.77 (105) and
62.51 (204) and rutile phase 2q ¼ 27.45 (110), 36.10 (101) and
54.36 (211) as expected. After UV irradiation, the crystalline
phase of TiO2 did not change. No distinct gold peaks at
2q ¼ 38.2 , 44.5 and 64.5 was observed, because the particle
3. Results and discussion size of gold was too small to detect. This confirms that Au
particle size was less than 4 nm.
3.1. ICP-MS
3.3. TEM
In Table 1, ICP–MS results showed the actual amount of gold
loading on the support. The original amount of gold in the
The particle size of Au strongly affects the catalytic activity of
starting material in each sample was 1 wt.%. When pH value
supported gold catalysts. Kozlov et al. [27] illustrated that the
increased during preparation, the amount of gold deposited
gold catalysts had high activity when the particle size of Au
on the support decreased. The results are in accordance with
was less than 3 nm. If the particle size was greater than 5 nm,
the literature for the samples prepared by deposition–precip-
gold catalysts lost their unique property. Chang et al. [26]
itation. The reason is that the charge on the surface of support
showed that increasing the irradiation time (from 3 to 10 min
was negative if the pH of the solution was higher than the
by 400 W lamp) lead to the aggregation of gold particles
isoelectric point (IEP) of the support. The AuClx(OH)4ÿx
(>5 nm). Similar observation was found by Herrmann et al.
adsorbed easily on positive surface of support. After UV irra-
[28] which showed that silver initially formed particles
diation, these species were reduced to metallic state.
between 3 and 8 nm in diameter. For larger amounts of silver
deposited and longer illumination times, large crystallites (up
to 400 nm) were observed. Fig. 2 shows the TEM micrographs
and the corresponding gold particle size distribution of Au/
Table 1 – Actual gold loading of the catalysts prepared at
TiO2 catalysts prepared by 16 W UV lamp with different irra-
different pH values.
diation times. The semi-spherical gold nanoparticles were
Catalyst Nominal Au loading Actual Au loading
observed as dark spots that were homogeneously dispersed
(wt.%) (wt.%)
on the support. After 10 min irradiation, the size distribution
Au/TiO2 (pH 6) 1 0.902 confirmed the uniform distribution of gold nanoparticles on
Au/TiO2 (pH 9) 1 0.837
TiO2 with a mean gold particle size of 1.3 nm and the gold
Au/TiO2 (pH 10) 1 0.795
particle size was in the range between 1 and 2.4 nm. It should
Au/TiO2 (pH 11) 1 0.784
be noted that the deposition–precipitation method cannot
 international journal of hydrogen energy 34 (2009) 8912–8920 8915

Fig. 2 – TEM images and size distribution of Au/TiO2 prepared by 16 W UV light for different irradiation times: (a) 10 min, (a1)
HRTEM image, 10 min, (b) 30 min, (c) 60 min.

prepare the Au particles down to 1.5 nm for the powder reduce the Au cations. UV irradiation can reduce it. The
samples, and only the photo-deposition method can prepare results are in accordance with XRD studies. No intense gold
so tiny Au particles. In addition, the samples prepared by XRD peaks were found for Au/TiO2 catalysts as the particle
photo-deposition method do not need heat treatment to size of gold was too small to detect. When the irradiation time
8916 international journal of hydrogen energy 34 (2009) 8912–8920

Table 2 – XPS analysis of Au catalysts prepared by UV

light with 16 W lamp and illuminated for 10 min.
Catalysts Surface composition
(atomic %)

Au0 Au3þ

Au/TiO2 (pH 6) 76 24
Au/TiO2 (pH 9) 85 15
Au/TiO2 (pH 10) 68 32
Au/TiO2 (pH 11) 86 14

and 32% Au3þ species and the Au0/Au3þ ratio was lower than
those of other catalysts The concentration of metallic gold in
the used catalysts was higher than that of the fresh one. The
cationic Au was reduced to metallic state by CO and H2 during
reaction.

3.5. Catalytic activity on PROX reaction

A series of Au/TiO2 catalysts have been prepared by different

UV light power and irradiated for different time intervals and
under different pH values. Table 4 reveals that different irra-
diation times and pH values of preparation conditions
affected the catalytic activity significantly. Using suitable
power of UV light at appropriate irradiation time, one was able
to deposit very tiny gold particles on the support in the powder
form, which was also very active for PROX reaction. The
catalyst prepared by 16 W UV lamp with 10 min irradiation
Fig. 3 – XPS Au 4f spectra obtain from Au/TiO2: (a) pH 6, (b)
time and at pH 10 showed the maximum CO conversion (95%)
pH 9, (c) pH 10, (d) pH 11.

increased, the particle size of gold also increased due to the

aggregation of gold particles.

3.4. XPS

XPS analysis was carried out in order to obtain the electronic

state of gold supported on TiO2. The deconvolution of XPS
spectra for all the catalysts suggests that Au species existed in
different states as metallic gold (Au0) and Au3þ. The Au 4f was
characterized by the doublet of two spin orbit components,
viz., Au 4f7/2 and Au 4f5/2 [26]. The peaks for metallic gold were
centered at 84.0 eV (Au 4f7/2) and 87.7 eV (Au 4f5/2). The peaks
for Au3þ located at 86.3 eV (Au 4f7/2) and 89.6 eV (Au 4f5/2).
Fig. 3 shows the XPS spectra of Au catalysts. The binding
energy of Au 4f shifted to higher one on Au/TiO2 (pH 10) than
those of other catalysts, indicating that Au supported on TiO2
has strong metal-support interaction. Table 2 shows the
surface composition of Au/TiO2 catalysts prepared at different
pH values. Before and after the PROX reaction, there was
a change in the electronic state of gold. Fig. 4 shows that Au
species exists in two states, one is metallic gold Au0 and the
other is oxide gold Au3þ. Table 3 shows the electronic states of
gold before and after reaction. The Au/TiO2 catalyst prepared Fig. 4 – XPS spectra of Au 4f, (a) before reaction; (b) after
at pH 10 had the surface composition of about 68% Au0 species reaction.
 international journal of hydrogen energy 34 (2009) 8912–8920 8917

Table 3 – XPS analysis of Au catalyst prepared at pH 10 by

UV light with 16 W lamp and illuminated for 10 min.
Catalysts Surface composition
(atomic %)

Au0 Au3þ

Before reaction 68 32
After reaction 83 17

and CO selectivity (47%) for PROX reaction among all the

samples.

3.5.1. Effect of pH
Moreau et al. [5] studied in great detail the effect of the pH
value on the preparation of Au/TiO2 catalysts. At low pH
Fig. 5 – CO conversion of Au/TiO2 catalysts with various pH
values, the surface of the TiO2 is positively charged and the
values.
species in solution anionic, hence an electrostatic mechanism
can explain the deposition of Au. However, the uptake is rapid,
large particles form and the catalysts have low catalytic
activity. As the pH value increased, the amount of gold
deposited on the support decreased but the activity increased. O2. The CO conversion of Au/TiO2 (pH 10) had a higher CO
Moreau et al. [29] noted that above pH 8 the adsorbed gold conversion than other catalysts from room temperature to
complex is substantially chlorine-free which leads to a cata- 120  C. Au/TiO2 prepared at (pH 10) had the highest CO
lyst containing little chlorine (which is an effective poison for conversion of 95% at 80  C. It indicates that H2 competed with
CO oxidation) and consisting of small particles, hence the CO to react with oxygen. Thermodynamically the exothermic
catalysts display high activity. enthalpy of H2 reacting with oxygen is lower than that of CO.
Figs. 5 and 6 show the effect of pH value in preparation for At high temperature, it is estimated that H2 will keep CO from
PROX over gold catalysts. When the reaction temperature adsorbing on Au active site.
increased, both CO and H2 reacted simultaneously with O2. All
the catalysts showed an increase in CO conversion with an 3.5.2. O2 consumption
increase in reaction temperature until the temperature Fig. 7 shows the oxygen consumption by H2 and CO reaction at
reached up to 80  C, then, the CO conversion started to 80  C in PROX reaction for the samples prepared at different
decrease with increasing reaction temperature. At high reac- pH values. Since the O2/CO feed ratio was 1, CO was
tion temperature (>80  C), H2 competed with CO to react with completely consumed when the dark gray bar was 50%. The
catalyst prepared by 16 W UV lamp at pH 6 exhibited the lower
activity for CO and H2 oxidation than other catalysts since the

Table 4 – CO conversion and selectivity of Au/TiO2

catalysts (using 8.5 3 10L4 M Au precursor solution at
a reaction temperature of 80 8C).
Light pH value in Irradiation CO CO
power preparation time (min) conversion selectivity
(%) (%)

16 W 6 10 20 28
9 10 71 43
10 10 95 47
10 30 56 51
10 60 31 56
11 10 56 32

10W 6 30 49 39
6 60 62 37
6 120 76 47
6 180 55 51
9 120 90 45
10 120 88 44

400W 6 3 7 25
6 6 18 42
Fig. 6 – CO selectivity of Au/TiO2 catalysts with various pH
6 10 14 34
values.
8918 international journal of hydrogen energy 34 (2009) 8912–8920

Fig. 9 – CO selectivity of Au/TiO2 (pH 10) catalysts prepared

Fig. 7 – O2 consumption at 80 8C. with various irradiation times.

consumption of oxygen by CO was less. For the catalyst and CO selectivity (47%) for PROX reaction. When the irradi-
prepared at pH 10, the O2 was completely consumed by CO ation time increased from 10 to 60 min, the small gold parti-
and H2 and thereby exhibiting higher activity for CO oxidation cles aggregated to form larger gold particles. The catalytic
in H2 stream. activity of Au/TiO2 decreased with an increase in gold particle
Oxygen was consumed quickly by H2 oxidation when the size.
temperature increased from 25 to 80  C. Thus the catalyst The life time test results for Au/TiO2 (prepared at pH 10 and
prepared by the 16 W UV lamp and at pH 10 exhibited a higher 10 min irradiation time) at 80  C for 60 h are shown in Fig. 10.
activity for CO than the catalysts prepared at pH 6, 9 and 11. The CO conversion was greater than 90% and CO selectivity
When the oxygen consumption was nearly 100%, the CO also maintained above 42%. The results clearly demonstrated
conversion started to decrease. A limited amount of oxygen that the catalyst was stable for a long time.
was used to oxidize either CO or H2. With raising temperature,
the relative strengths of adsorption may also move in favor of 3.5.4. Active sites of Au/TiO2
hydrogen. The mechanism of CO oxidation in hydrogen-rich stream is
similar to Langmuir–Hinshelwood (L–H) model [30]. The
3.5.3. Effect of irradiation time theoretical calculation for CO oxidation suggest that CO and
Figs. 8 and 9 clearly depict the relationship between the irra- oxygen molecule are vicinally co-adsorbed on gold, and the
diation time of UV light in preparation and catalytic activity of CO oxidation takes place over gold clusters through L–H
the catalyst. For the catalyst prepared with irradiation time of mechanism rather than Eley–Redeal (E–R) mechanism [31].
10 min, the catalyst showed the highest CO conversion (95%) According to the density functional theory calculations, the

Fig. 10 – CO conversion and selectivity of Au/TiO2 catalysts

Fig. 8 – CO conversion of Au/TiO2 (pH 10) catalysts prepared (prepared at pH 10 and 10 min irradiation time) at 80 8C for
with various irradiation times. 60 h.
 international journal of hydrogen energy 34 (2009) 8912–8920 8919

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