Topics in Catalysis Vols. 4243, May 2007 ( 2007) DOI: 10.

1007/s11244-007-0208-9

373

CO Oxidation Studied Using Fast XPS and a Molecular Beam Reactor

Roger A. Bennetta, Isabel Z. Jonesb, and Michael Bowkerc,*
Dept Physics, University of Reading, Reading, RG6 6AD USA b Johnson Matthey, Royston, Cambridgeshire c Wolfson Nanoscience Laboratory, School of Chemistry, Cardi University, Cardi, CF10 3TB UK
a

We have combined the use of a molecular beam reactor with fast XPS in order to correlate changes in the rate of CO oxidation with the coverages of the adsorbates and intermediates on the surface. In the reactor CO oxidation exhibits an isothermal light-off phenomenon in which the rate autocatalytically increases with time. This is due to the desorption of CO which releases extra sites for O2 dissociation which, in turn, removes more CO, and hence the self-acceleration. In eect the reaction can be written as 2COa + O2g + 2S 2CO2g + 4S, the acceleration coming from the release of extra adsorption sites, S, which are involved in the reaction itself. Fast XPS, carried out in-situ during the course of the reaction, shows domination of the surface by COa below 390 K and by Oa above that temperature, with a rapid change in surface coverage over a very narrow temperature window. This is an advance on earlier work, since our measurements are made in a single, continuous experiment, due to the high brightness of the synchrotron source. This also allows the data to be obtained at high energy resolution, in the presence of both gases, and without contamination. On high surface area samples this acceleration is further reinforced due to a rapid temperature increase because of the highly exothermic nature of the overall reaction. KEY WORDS: CO oxidation; light-o; Langmuir-Hinshelwood; Pd(110); XPS of catalysis.

1. Introduction The oxidation of CO on transition element surfaces, especially precious metals, represents an excellent model system for surface studies [1,2], but is also of practical importance [3]. The practical importance stems from its relevance to car exhaust catalysis, where CO is removed by direct oxidation in this way and by the water-gas shift reaction, and from the recent discovery of low temperature CO oxidation on nanoparticulate gold catalysts [4]. The academic importance stems from its utility as a model system for surface reactions and as an illustration of Langmuir-Hinshelwood reaction kinetics. In fact, in many ways, it is NOT a good model for such kinetics, because it is a reaction between a molecular and a dissociated species, for which the kinetics are inherently complex, but also it is counter-intuitive in terms of that system. This is because the reaction becomes poisoned at low temperature by the apparently more weakly-held species (molecular CO), and so it has merited some considerable study due to this level of complexity.

Trieste and the experimental details and methodology have also been reported previously [7].

3. Results and Discussion In previous work we have reported the adsorption of CO and oxygen on Pd(110) [810]. The salient points of this work are that both molecules adsorb eciently on the surface (the initial sticking probability for CO is 0.5 and oxygen is 0.4), CO in molecular form, while oxygen is dissociated into atoms. Both show strong repulsions, which reduce the heat of adsorption at high coverage, and the adsorption of CO is strongly inuenced by the involvement of a weakly-held precursor state, which maintains its adsorption eciency at a higher level than might be expected by its coverage. The desorption peak temperature for CO and the molecular recombination peak of O2 are at 480 K and 760 K respectively. These properties are obviously of import for their reaction together. The oxidation of CO was studied with the molecular beam reactor and the results are shown in gure 1. The reaction proceeds in several stages. First of all, after introduction of the mixed beam onto the clean Pd(110) surface at 315 K, there is uptake of oxygen and CO on the surface, together with fast CO2 production (labelled A in the gure). This shows that clean Pd(110) is a very ecient catalyst for the oxidation of CO even at room temperature. However, after a short while, CO2 production stops (at B in the gure) because CO builds up on the surface to a level which eventually blocks the adsorption of oxygen, thus poisoning the reaction, and
1022-5528/07/0500-0373/0 2007 Springer Science+Business Media, LLC

2. Experimental Due to limited space we will not discuss the details of the experiments here. Suce it to say that the kinetics were measured by use of a molecular beam reactor, which is described in detail elsewhere [5,6]. The fast XPS measurements were carried out at Sincrotrone

* To whom correspondence should be addressed. E-mail: bowkerm@cf.ac.uk

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Figure 1. The oxidation of CO studied with a molecular beam reactor. For details see the text.

resulting in a near-zero steady-state rate of CO2 production. In fact, detailed experiments with pre-dosing CO and then measuring the sticking probability of O2 indicates that the critical CO coverage is 0.60(0.06) monolayers, though the reaction is extremely slow even at coverages a little below this value [9]. In other words, approximately half a monolayer of CO is required to block oxygen dissociation. After this the sample is heated and the rst thing that happens is that CO begins to desorb from the surface above 360 K, as it does on the clean surface [8,9]. Once sucient has desorbed (as described above), then oxygen adsorption begins and so CO2 production also re-commences, since the surface reaction between CO and adsorbed oxygen atoms is very ecient. Note that then, between 360 K and 400 K, the rate accelerates from a low rate to high rate within a very short time and temperature interval (point C in gure 1). We can call this the light-o phenomenon, though in this case (due to the very large thermal mass of the Pd single crystal compared to the surface) it is an isothermal light-o process, which is, admittedly, something of a contradiction in terms. It is better described as an autocatalytic increase in rate, and the bi-stability of such phenomena between high and low rate branches has been considered in detail elsewhere [10]. Note that in this heating period, although the temperature continually increases, the rate goes through a sharp maximum at point C, then drops to a lower level, presumably due to dramatic changes in coverage on the surface, which is conrmed by the experiments described below. Upon further heating there is a slight maximum in CO2 production, but above 420 K the rate then diminishes again to a very low level, and we can assume that this is due to a diminishing surface coverage of CO, since this is above its normal peak desorption temperature. The molecular beam reactor is very useful for such kinetic analysis and can give us some idea of what species may be present of the surface. However it is much

better to combine this information with spectroscopic identication of the surface species which are present, and XPS has a lot of merit in this respect since it is a surface sensitive, and atomically specic technique. However, most XPS work has insucient time resolution to follow a reaction such as that shown in gure 1. Since synchrotrons have much higher radiation ux than the usual lab-based systems, then we can take data in a much faster timescale, and so it is possible to carry out fast XPS measurements. We have used the Superesca beam line at Elettra (Sincrotrone Trieste) for just this purpose. Here each scan can be carried out in $1 sec, though in the experiments shown in gure 2 the timescale of each elemental range scan was $10 s., and the whole experiment took around 80 minutes. It must be noted that, for this length of scan, the resolution of the spectra was still very good (the O(1s) peak being $1.2 eV FWHM). The gure is shown as a series of vertically stacked lines, which represent the XPS scan in terms of varying colour, which relates to the signal intensity. This experiment is carried out on a slightly longer timescale than that in gure 1, but essentially follows the same sequence. At the beginning, as the gases are admitted, the presence of both COa and Oa on the surface is identied (point A in the gure) as

Figure 2. XPS montage of spectra in the O(1s) region, showing lighto as a sharp transition from adsorbed CO (at $ 532.5 eV binding energy) to adsorbed oxygen atoms ($ 530 eV) at 390 K.

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XPS peaks at 286.0 eV and $533 eV (the C(1s) and O(1s) signals for COa) and at 530.4 eV (for Oa) are seen. However, the Oa remains for only a short period, and is cleaned o by CO shortly after the beginning of the experiment. We might ask the question, why does atomic oxygen actually appear at all, since the CO cleano reaction takes place so readily? In fact, this relates to the important eect of decreased heat of adsorption and therefore strength of binding with increased adsorbate coverage mentioned above. The activation energy for the surface reaction is high at low coverage of both adsorbates. Certainly, the adsorption heat/desorption energy of CO on Pd surfaces is high at low coverage ($150 kJ mol)1), but much lower at high coverage ($100 kJ mol)1), being much reduced as the coverage goes up [810,11]. Thus the oxygen is removed again as the oxidation rate increases. CO dominates the coverage because of the less stringent site requirement for molecular adsorption (point B in gure 1), and the ease of removal of atomic oxygen, due to a low activation energy for reaction. Thus, after this initial period in gure 2, CO is the only signicant species present on the surface, with an XPS O(1s) binding energy of $533 eV. There may be very small amounts of residual Oa, as seen by the very low intensity at 530.4 eV binding energy. The CO intensity appears to diminish continually after heating commences (just after point B) due to desorption, and there is a gradual increase in Oa after 350 K when the CO coverage has dropped below $0.55 monolayers. This remains the case until a temperature of $390 K, when there is a dramatic decrease in the coverage of COa and Oa sharply increases, the light-o, point C in gure 2. Thereafter COa coverage diminishes further, Oa stays high, and even increases a little. In fact, although light-o appears sudden in the stacked plot of XPS images, if we examine individual spectra in this range where the temperature varies very little, we can see the autocatalytic nature of the reaction since COa decreases and Oa increases in an almost isothermal regime. In this way we can clearly see that light-o occurs due to a drop of COa below a critical coverage at which oxygen can adsorb, which in turn results in an accelerated loss of COa and an increase in free sites for O2 dissociation. The coverages of the adsorbates can be determined from the XPS and are plotted in gure 3, together with the product of the two, which is part of equation 2 below, describing the surface reaction in LangmuirHinshelwood terms. Here it is seen that the product of coverages follows a COa Oa ! CO2g 1

0.8 0.7 0.6 0.5 0.4 0.3

Coverage/ monolayers

CO +O
a

CO xO x15
a a

0.2 0.1 0 320 360 400 440 480 520 560 600

CO

Temperature/K

Figure 3. The temperature dependence of the coverages of oxygen atoms, CO molecules, their sum and their product. The coverages are determined from integration of the O(1s) peak intensities.

similar shape to that of the reaction curve in g 1, and so the whole reaction is dominated by these terms, rather than by the rate constant and its variation with temperature. A more detailed consideration of the eect of temperature for a bimolecular surface reaction is given elsewhere [12]. The reason, then, for the light-o phenomenon can be described as follows. The overall reaction equation in the low-temperature, COa-dominated regime is 2COa O2g 2S ! 2CO2g 4S and so the reaction becomes auto-catalytic in nature. This is because the surface sites are involved in the forward reaction equation (because oxygen needs two sites on which to dissociate), but more of them are produced by the reaction itself. Thus the concentration of the free surface sites, S, increases during the course of the reaction and accelerates it. O2 adsorption is accelerated by CO desorption, which, in turn, is also accelerated by oxygen adsorption and reactive removal. This is a non steady-state phenomenon, because the COa coverage changes during the course of this phase of the reaction. This autocatalytic step is an essential part of the rate oscillation phenomenon which has been observed by very many workers for many precious metals, including for the Pd(110) surface [13], for CO oxidation. In conclusion, we have shown that XPS can be used to study catalytic reactions in-situ and in real time. In this case it has been applied to the oxidation of CO on Pd(110), and conrms that the reaction follows basic Langmuir-Hinshelwood kinetics, that is, the shape of the temperature dependence of the rate is largely dictated by the shape of the product of adsorbed reac-

Rate k[COa ].[Oa ]

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R. A. Bennett et al./CO Oxidation Studied Using Fast XPS and a Molecular Beam Reactor

tant coverages, [COa].[Oa]. Light-o occurs at $ 370 K due to the opening up of surface sites by the desorption of CO, which dominates the low temperature, low rate branch of the reaction. This is an example of isothermal light-o (that is, rate acceleration does not require heat input) and is due to an autocatalytic reaction; as CO desorbs, so sites are created for O2 dissociation, which removes more CO by reaction, giving a positive feedback to the process.

References
[1] T. Engel and G. Ertl (1982) in The Chemical Physics of Sol. Surf. and Het Cat., eds D.A.King and D.P. Woodru Elsevier, Amsterdam, 4, 73. [2] B.C. Gates (1992) Catalytic Chemistry John Wiley and Sons. [3] See, for instance, M. Shelef and G. Graham, (1994) Cat. Rev.-Sci. Eng., 36:433. [4] M. Haruta, T. Kobayashi, H. Sano and N. Yamada, (1987) Chemistry Letters, 405. [5] M. Bowker, P. Pudney and C.J. Barnes, J. Vac. Sci. Tech. A8 (1990) 816. [6] M. Bowker, Applied Catal 160 (1997) 89. [7] A. Baraldi, M. Barnaba, B. Brena, D. Cocco, G. Comelli, S. Lizzit, G. Paolucci and R. Rosei, J. Electron Spectr. Rel. Phen 76 (1995) 145. [8] I. Jones, R. Bennett and M. Bowker, Surface Sci. 4024 (1998) 595. [9] I. Jones, R. Bennett and M. Bowker, Surface Sci. 439 (1999) 235 48. [10] I. Jones, PhD thesis, University of Reading. [11] T. Engel, J. Chem. Phys. 69 (1978) 373. [12] See, for instance V. Zhdanov and B. Kasemo, (1997) Phys. Rev. B55:4105 and references therein. [13] M. Ehsasi, M. Berdau, T. Rebitzki, K. Charle, K. Christmann and J.H. Block, J. Chem. Phys. 98 (1993) 9177.

Acknowledgments We are grateful to the EPSRC for funding for a studentship for IJ and to Johnson Matthey for partial support of her studentship, to EPSRC for a postdoctoral fellowship for RAB under grant GR/L22584, and to the University of Reading for the provision of appropriate facilities for the work. We are grateful to the EU and to Sincrotrone Trieste for support for the visit to Trieste, and to F.Esch, A. Baraldi, S. Lizzit and G. Comelli for their invaluable assistance and expertise during the course of the synchrotron runs.