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Abstract
CO oxidation over platinum group metals has been investigated for some eight decades by many researchers and is considered to
be the best understood catalytic reaction. Nevertheless, there has been a renewed interest in CO oxidation recently because of its
technological importance in pollution control and fuel cells. Removal of COx from automobile exhaust is accomplished by catalytic
converters using supported Pt, Pd and Rh catalysts. Catalysts are used in fuel cells to remove traces of COx from the H2 feed gas to
the few ppm level necessary for their efficient operation. Efforts have been made in our laboratory to understand the adsorption of
CO and the kinetics of CO-oxidation on both single crystals and supported metal catalysts over a wide temperature (100 /1000 K)
and pressure (1/10 7 /10 Torr) range. By comparing the results of single crystals, model supported catalysts, and supported
technical catalysts the relationship between particle size and catalytic activity can be better understood. Also discussed is CO
oxidation on model supported Au catalysts, a promising new candidate for low temperature CO oxidation. # 2002 Published by
Elsevier Science Ltd.
this catalytic activity has been shown to be a critical 107 Torr O2 at 1300 K) followed by annealing at 1500
function of the Au cluster size. K. The Ru(0001) crystal was cleaned by oxidation (2 /
In this article, we will compare CO adsorption and 107 Torr O2 at 1450 K for 3 min) followed by
oxidation on single crystals with model supported annealing at 1500 K.
catalysts of Pt, Ir, Rh, Pd and Au. Primary emphasis The IR cell with CaF2 window is connected to the
will be given to the results obtained in our laboratory UHV chamber through a double differentially pumped
over wide temperature (100 /1000 K) and pressure sliding seal. The configuration of the elevated pressure
ranges (1 /107 /10 Torr). The goal of this work is cell is similar to that described by Campbell et al. [65].
an understanding of the effects of temperature, pressure This arrangement allows IR experiments in the pressure
and particle size on CO oxidation that spans the range of 10 8 /103 Torr and also provides convenient
material and pressure ‘gaps’ between ‘real world’ access to the sample without opening the UHV cham-
catalysis and ‘surface science’. ber. The pressure in the IR cell was determined using an
ionization gauge and a capacitance manometer at their
respective working pressure ranges.
2. Experimental TiO2(110) single crystals (Commercial Crystal La-
boratories) were used in these studies mainly due to their
The UHV systems used for this work were equipped suitability for atomically-resolved STM and STS experi-
[64] with Auger electron spectroscopy (AES), a quadru- ments. The n-type semiconductor form, sufficiently
pole mass spectrometer for temperature programmed conductive for STM and electron spectroscopic mea-
desorption (TPD), low energy electron diffraction surements, was prepared by cycles of Ar sputtering
(LEED), scanning tunneling microscopy/spectroscopy and annealing to 700/1000 K. Deposition of the metal
(STM/STS) and an Ar ion sputter gun, contiguous to a was typically accomplished by resistive evaporation of
high-pressure reaction chamber. The single crystal high-purity metal wire wrapped around a W or Ta
samples were mounted on a retractable manipulator,
filament in vacuum. Such dosers provide an excellent
allowing the sample to be moved between the two
means of obtaining a clean and stable metal flux after
chambers in situ. Pt(100), Ir(110) and Pd(110) crystals of
thorough outgassing. By controlling the filament cur-
0.92 cm in diameter and 0.11 cm in thickness were used
rent, doser to substrate distance and the substrate
for the experiments. The Ir(111) sample was elliptical in
temperature, fine control can be exercised over cluster-
shape and 0.75 /0.55 /0.03 cm3 in size. The samples
size and density.
were heated resistively by two high purity (0.051 cm)
Gas chromatography with flame ionization detection
tungsten leads spot-welded to the back of the crystal;
(FID) was used to analyze the reaction products in
sample temperature was measured by a 0.08 cm
which CO and CO2 were catalytically converted to
chromel-alumel thermocouple spot-welded to the sam-
methane before analysis. Rates of reaction are expressed
ple edge.
AES was used to check the cleanliness of the samples. as turnover frequencies (TOF), defined as the number of
In addition, the Pt(100) sample was cleaned of carbon CO2 molecules produced per active metal site per
by O2 adsorption/desorption and of Si and Ca impu- second. For Pd, Rh or Ir, the entire crystal (front,
rities by high temperature oxidation (1123 K, 1 /10 7 back and edge) were included in determining the total
Torr O2) and Ar sputtering. The Pd crystal was cleaned number of sites; for Pt, only the front face was included,
in the reactor with 8 Torr of CO and 8 Torr of O2 and as the back and edge of the crystal were not subjected to
heating to 600 K for 1 /2 min. One to three cycles of this the sputter cleaning procedure. Research grade CO
treatment produced a clean surface. Large carbon (99.99%) and O2 (99.995%) were supplied by Matheson.
impurities were cleaned from the Ir samples by oxida- The CO was further purified by slowly passing it
tion in 1 /105 Torr O2 at 1000 K for 5 /10 min, through a molecular sieve trap at 77 K. No metal
followed by a 3 min anneal to 1600 K. Small traces of carbonyls (e.g. Ni(CO)4 were detected in any experiment
carbon were removed by reaction in 8 Torr O2 and 4 in post-reaction AES analysis.
Torr CO for 2 min at 600/625 K, followed by a brief The experimental procedure has been described in
flash to 1600 K. The Pt sample was cleaned by detail elsewhere [64]. Briefly, after cleaning, the sample
sputtering at 1100 K in 5/105 Torr of Ar for 30 was moved to the reactor and charged with reactants.
min (1 kV beam energy) mainly to remove Si and Ca Most experiments were performed with 16 Torr of CO
impurities. This treatment was followed by heating in and 8 Torr O2. The sample is heated to the desired
0.1 Torr of O2 at 1100 K for 30 min to remove traces of temperature for a specified time, the products are then
carbon and then annealing at 1300 K. Repeated cycles allowed to mix for 15 min and then an aliquot of the
of this procedure produced a clean Pt surface, which product mixture was analyzed by GC. The reactor was
could not be oxidized under UHV conditions at high then evacuated, and the sample returned to the UHV
temperature. Rh crystals were cleaned by oxidation (2 / chamber for post-reaction analysis.
A.K. Santra, D.W. Goodman / Electrochimica Acta 47 (2002) 3595 /3609 3597
Fig. 4. IR spectra of CO on Pd(100) as a function of sample temperature at CO pressures of (a) 1.0 Torr and (b) 1/10 6 Torr [85a,85b].
crystal Pd(100) and Pd(111) surfaces as discussed in the cm 1 at 500 K can be attributed to a combination of 3-
previous section. The broad peak corresponding to 1894 fold hollow and bridge-bound CO species, shifting
Fig. 5. Temperature dependent IR spectra of CO adsorbed on uPd /5.0 and 1.0 ML Pd/Al2O3/Ta(110) catalysts at 1/10 5 Torr [86].
3600 A.K. Santra, D.W. Goodman / Electrochimica Acta 47 (2002) 3595 /3609
Fig. 6. Arrhenius plot of the CO/O2 specific rates of reaction (TOF) for (a) single crystal (Pd, Ir and Pt) and their supported catalysts and (b) for Rh
single crystals [10,11].
Fig. 8. O2 partial pressure dependence at constant CO pressure and temperature: (a) on Pd(110), (b) on Ir(111) and (c) on Rh(111) and Rh(100)
[10,11].
ing that under these experimental conditions no strongly on Rh single crystal surfaces wherein the CO2 deso-
bound, deactivating oxygen species is present. In order rption temperature differs by /50K on Rh(100) and
to form a similar species on Pt, much higher O2 pressure Rh(111) surfaces. The Rh(100) surface shows signifi-
and/or temperatures would be necessary, conditions not cantly higher reaction rates compared with that on the
accessible in our experiments. Rh(111) surface. The other difference between the two
systems is that on Rh(100) all CO is oxidized to CO2,
4.1.2. Structure sensitivity and particle size effects whereas on Rh(111) a fraction of the CO desorbs. The
Although it appears from the data in Fig. 1 that the reason for such high activity and selectivity on Rh(100)
CO-oxidation reaction is structure insensitive, it should towards CO2 formation is assumed to be due to the
be noted that the single crystal rates are compared with surface reaction step, COads/Oads 0/CO2(g), being in-
the least dispersed supported catalyst. Very recently, trinsically faster on Rh(100) than on Rh(111). In
under UHV conditions structure sensitivity has also contrast to the high-pressure data (Fig. 7c and Fig.
been observed by Niemantsverdriet and co-workers [90] 8c), the reaction exhibits first order kinetics with respect
A.K. Santra, D.W. Goodman / Electrochimica Acta 47 (2002) 3595 /3609 3603
Fig. 9. CO partial pressure dependence as a function of temperature at constant oxygen pressure on Pt(100). (a) The Arrhenius plot for CO oxidation
on Pt(100) is shown to illustrate the temperature regimes in which (b) the CO pressure dependence data were obtained [10].
to both the partial pressure of CO and O2 under UHV Fig. 11. Effect of particle size on the CO2 formation rate on Ir/SiO2
conditions, however, the structure sensitivity is consis- and Ir single crystal catalysts [38].
tent with the high-pressure data (Fig. 7c and Fig. 8).
Dramatic structure sensitivity has been observed on the dispersion values obtained by Cant and co-workers
Ir/SiO2 catalyst [38] (Fig. 11). It is clear from Fig. 11 [38]. It is noteworthy that the single crystal data in Fig.
that larger particles are more active for CO oxidation 11 corresponds to the supported data extrapolated to a
and the data more comparable to the single crystal data. particle size of 40 nm. This is close to the ‘effective’
The data for the larger particles were calculated from particle size of the single crystals used in this study,
3604 A.K. Santra, D.W. Goodman / Electrochimica Acta 47 (2002) 3595 /3609
Fig. 15. A set of 50 /50 nm2 STM images (2.0 V, 1.0 nA) of TiO2(110) /(1/1) with different Au coverage (uAu): (A) 0.10 ML, (B) 0.25 ML, (C) 0.50
ML, (D) 1.0 ML, (E) 2.0 ML and (F) 4.0 MLE. With increasing coverage, Au clusters grow and gradually cover the surface [103].
in cluster density is minimal. However, even at uAu /4.0 1). Three-dimensional Au clusters, imaged as bright
ML, some portions of the TiO2 substrate are still visible. protrusions, have average diameters of /2.6 nm and
In Fig. 16A, the constant current STM micrograph of heights of /0.7 nm (corresponding to 2/3 atoms thick)
Au (uAu /0.25 ML) deposited onto single crystal and are preferentially nucleated at the step edges. Quasi-
TiO2(110) /(1 /1) [55,103] is shown. The metal deposi- two-dimensional clusters are characterized by heights of
tion was performed at 300 K, followed by annealing to 1 /2 atomic layers. Previous studies have shown that the
850 K for 2 min to stabilize the clusters. In Fig. 16A only Au clusters upon annealing form large microcrystals
the Ti cations are visible; whereas the O2 anion are not with well-defined hexagonal shapes.
seen. The inter-atomic distance between the 001 rows Fig. 16B shows STS taken over various clusters on the
is /0.65 nm, which can be observed along the terraces surface, where the tunneling current (I) as a function of
corresponding to the length of the unit cell along the bias voltage (V) across the STM tip is measured. The I/
[110] direction of the unreconstructed TiO2(110) /(1 / V curves correlate with the Au cluster size on the TiO2
A.K. Santra, D.W. Goodman / Electrochimica Acta 47 (2002) 3595 /3609 3607
Fig. 16. (a) A CCT /STM image of a Au (uAu /0.25 ML) deposited
onto TiO2(110) /(1/1) prepared just prior to a CO:O2 reaction. The
sample had been annealed to 850 K for 2 min; (b) STS data acquired
for Au clusters of varying sizes on the TiO2(110) /(1/1). An STS of
TiO2 substrate, having a wider band-gap than the Au cluster, is also
shown as a point of reference [55]. Fig. 18. The specific activity for CO conversion as a function of
reaction time at 300 K on a model Au/TiO2/Mo(100) catalyst. The Au
coverage (uAu) was 0.25 ML, corresponding to an average cluster size
surface. The length of the observed plateau at the zero
of /2.4 nm [103].
tunneling current is a measure of band-gap (along the
bias voltage axis) of electrons tunneling between the
GaAs(110) [104]. Very small clusters then are non-
valence and conduction band of the cluster and tip. The
metallic and exhibit electronic and chemical properties
electronic character of these clusters vary between that
unlike those of the corresponding bulk metal.
of a metal and a non-metal depending on their size.
With an increase in size the clusters gradually exhibit
4.2.2. Particle size effects
metallic character with an enhanced density of states at Interestingly, a marked correlation between the clus-
the Fermi level. Note that clusters of 2.5 /0.7 nm2 size ter size and catalytic activity has been observed for CO
have a larger band gap than that for a cluster 5.0 /2.5 oxidation over Au/TiO2 system [54,55,60 /63]. Studies
nm2 in size. Smaller clusters have a non-metallic have been carried out on Au/TiO2/Mo(100) as well as on
character resulting in significant band-gap and a re- Au/TiO2(110) /(1 /1) for comparison. Fig. 17a and b
duced density of states near the Fermi level. A similar show plots of CO oxidation activity (TOF) at 350 K as a
metal to non-metal transition with respect to cluster size function of Au cluster size supported on TiO2(110) /
has also been observed for Fe clusters deposited on (1 /1) and TiO2 /Mo(100) substrates, respectively.
3608 A.K. Santra, D.W. Goodman / Electrochimica Acta 47 (2002) 3595 /3609
These results show similarities in the structure sensitivity optimum reaction temperature, deactivation, etc. Fi-
of CO oxidation with a maximum activity evident at /3 nally it has been shown that ultra-small gold particles,
nm Au cluster size on both TiO2 supports. For each unlike bulk gold metal, are promising catalysts for low
catalyst, the activity and the selectivity of the supported temperature CO oxidation.
Au clusters are markedly size-dependent. Although the
TiO2 supported Au catalysts exhibit a high activity for
the low-temperature CO oxidation, rapid deactivation Acknowledgements
was observed as a function of reaction time. Fig. 18
shows a plot of TOF versus time for CO oxidation at The support of this work by the Department of
300 K on a Au(uAu /0.25 ML)/TiO2/Mo(100) model Energy, Office of Basic Energy Sciences, Division of
catalyst. The model catalyst, which exhibited a high Chemical Sciences, and the Robert A. Welch Founda-
initial activity, deactivated after a CO/O2 (1:5) reaction tion is gratefully acknowledged.
of /120 min at 40 Torr. This deactivation is due to
agglomeration of the Au clusters with reaction time, as
detailed by post-reaction STM measurements. The STM References
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