Surface Science 601 (2007) L124L126 www.elsevier.

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Surface Science Letters

CO oxidation on ruthenium: The nature of the active catalytic surface

D.W. Goodman *, C.H.F. Peden 1, M.S. Chen
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, TX 77842-3012, United States Received 20 March 2007; accepted for publication 3 August 2007 Available online 11 August 2007

Keywords: CO oxidation; Ruthenium; Ruthenium oxide; Ru(0 0 0 1); RuO2(1 1 0)

The oxidation of CO, i.e. CO + 1=2 O2 ! CO2, over metal surfaces is one of the most studied catalytic reactions. The details of the reaction mechanism under ultrahigh vacuum (UHV) conditions have been well understood for some time [1]. Under reducing or mildly oxidizing conditions for Pt, Pd, and Rh, metals used in automotive catalytic converters, the reaction proceeds via the LangmuirHinshelwood (LH) mechanism between CO molecules and O atoms, both strongly chemisorbed to the metal surface. Under such conditions, the surface is predominantly covered by adsorbed CO and the reaction rate is controlled by the rate at which desorption of CO opens adsorption/ dissociation sites for O2. The measured reaction kinetics at reducing or mildly oxidizing conditions for Pt, Pd, and Rh support this mechanistic picture showing a rst order dependence on O2 pressure and a negative rst-order dependence on CO pressure, with an apparent activation energy for CO2 formation on each metal approximately equal to the corresponding CO desorption energy [2]. On the other hand, CO oxidation on Ru, in particular the nature of the active catalytic surface, is controversial and the subject of this letter. Here we discuss whether the active surface at near atmospheric pressures and at typical reaction temperatures is a one monolayer oxygen-covered Ru surface or multilayer RuO2. The catalytic oxidation of CO over Ru has been the subject of considerable attention particularly because of its anomalous behavior in several respects. Notably, while
Corresponding author. Tel.: +1 979 845 0214; fax: +1 974 845 6822. E-mail address: goodman@mail.chem.tamu.edu (D.W. Goodman). 1 Adjunct Professor and Laboratory Fellow, Institute for Interfacial Catalysis, Pacic Northwest National Laboratory, Richland, WA 99352, United States. 0039-6028/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.susc.2007.08.003
*

supported and unsupported Ru catalysts are more active for CO oxidation compared with Pt, Pd, Ir, and Rh at elevated pressures [3,4], low pressure experiments, i.e. UHV studies, show Ru to be the least active [5]. Since these early studies in the late 1980s, some 200 papers have been published related to CO oxidation on Ru catalysts. Much of the recent attention has focused on RuO2 after the high activity for Ru(0 0 0 1) was attributed to a RuO2(1 1 0) epitaxial lm proposed to form under reaction conditions [610]. Note that this proposal was based on measurements at reactant pressures <104 Torr. Density functional theoretical (DFT) studies have suggested that a tri-layer RuO2 layer should serve as a transition between chemisorbed oxygen and the oxide phase [11]. Accordingly considerable experimental and theoretical eorts have been expended in studying the details of CO adsorption and reaction on RuO2 [1215]. Recently, it has been proposed that the socalled pressure gap related to the dierences in the catalytic behavior of Ru toward CO oxidation at low (<$104 mbar) and high pressures (101102 mbar) can be bridged by invoking the formation of RuO2 on Ru catalysts at elevated reactant pressures [12]. However if RuO2 is the active surface for CO oxidation at elevated pressure (101102 mbar) then: (i) why did the early reaction studies on Ru(0 0 0 1) by Peden and Goodman [4] show only 1 monolayer (ML) of surface oxygen following reaction? (ii) why did the IRAS study of Peden et al. [16] show that the binding energy for CO to an active surface under reaction conditions is <40 kJ/mol given that RuO2 has been shown to bind CO with a binding energy of $120 kJ/mol [15,17]? (iii) why are supported Ru catalysts deactivated under O2-rich reaction conditions [3,1820] and, similarly, why are RuO2 powders less active and less stable than prereduced powders [21]? (iv) why do recent elevated-pressure

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X-ray photoelectron spectroscopic (XPS) data [22] show no direct correlation between the CO oxidation activity and the amount of RuO2 present on the surface? and (v) why do recent STM studies [23] of RuO2 show the surface to be passivated toward CO oxidation by carbonate formation after exposure to CO subsequent to atmospheric O2 exposure? Early studies by Peden and Goodman [4] demonstrated that the activity of a Ru(0 0 0 1) surface in a stoichiometric CO and O2 mixture near one atmosphere is essentially identical to that of a supported Ru catalyst. Furthermore the measured pressure dependencies observed for Ru(0 0 0 1) were quite dierent from those for Pt, Pd, Rh, and Ir. Whereas a stoichiometric mixture of CO and O2 reacts over predominantly CO-covered surfaces of Pt, Pd, Rh, and Ir, the same reaction mixture leads to the formation of an oxygen-covered surface on Ru. For Ru(0 0 0 1) the oxygencovered surface following reaction was characterized as 1 monolayer (ML). The oxygen coverage was quantied by comparison of the AES signal relative to that found for a saturation exposure of oxygen to Ru(0 0 0 1) in UHV that forms a (2 1)O structure corresponding to 0.5 ML. Temperature programmed desorption studies also corroborated the AES data with respect to the amount of surface oxygen following reaction. Recently, we have used XPS, AES, and LEED to ex-situ study the active phase of Ru(0 0 0 1) for CO oxidation under stoichiometric condition (CO/O2 ratio of 2). This study indicated an oxygen coverage of one monolayer with a (1 1) LEED pattern, conrming the early results of Peden and Goodman [4]. Furthermore, similar to Ru, we have found that the catalytic activity behavior of Pt-group metals for CO oxidation near atmospheric reaction conditions on oxygen-covered ($1 ML) Rh, Pd and Pt surfaces at O2/CO ratios well in excess of stoichiometry are 23 orders of magnitude higher than the corresponding rates on oxygen-decient surfaces [24]. To conrm the reactivity of the oxygen-covered surface following reaction on Ru(0 0 0 1), the surface oxygen formed during reaction with a CO/O2 mixture was titrated after reaction with CO alone [4]. In these experiments the Ru(0 0 0 1) surface was precovered with 1 ML of oxygen by running a CO oxidation reaction at elevated pressures (CO/O2 = 1, PT = 21 mbar, T = 500 K) [4]. The oxygencovered surface so formed was then exposed to elevated pressures of CO (10.5 mbar) at various temperatures and the attenuation of the surface oxygen assessed by AES. CO2 formation rates were then estimated assuming that each removed surface oxygen atom gives rise to one CO2 molecule. The CO2 formation rates as a function of temperature, extrapolated to a surface oxygen coverage of 1 ML, showed kinetic parameters identical to those observed at steady-state for a Ru(0 0 01) catalyst operating near stoichiometric CO/O2 reaction conditions at elevated pressures. The close correspondence of these two sets of data proves that the surface oxygen observed following reaction is indeed the active oxygen reactant in the CO oxidation reaction under steady-state conditions.

A recent study by He et al. [25] directly answers the question as to whether the oxygen-covered Ru surface observed in the Peden and Goodman [4] experiments could indeed be RuO2. Using surface X-ray diraction (SXRD) combined with an elevated-pressure reaction chamber, these authors investigated the oxidation of a Ru(0 0 0 1) model catalyst in situ under various CO oxidation reaction conditions. With a CO:O2 mixture of P O2 18 mbar and PCO = 10 mbar, and a reaction temperature of 630 K, no RuO2 appeared within 700 s as monitored by SXRD [25]. These experiments showed that formation of RuO2 on Ru(0 0 0 1) requires a critical minimum ratio of O2 to CO (P O2 18 mbar, PCO = 10 mbar), a critical temperature (T > 630 K), and a critical reaction time (>700 s). These reaction conditions far exceed any encountered in the kinetic studies of Peden and Goodman (P O2 11 mbar, PCO = 21 mbar, T = 380600 K, reaction time = 200 s) [4]. Note that in the Peden and Goodman kinetic experiments the O2 partial pressure was lower and the CO partial pressure higher than the conditions used by He et al. to establish the critical conditions for formation of RuO2, i.e. the oxygen chemical potential in the Peden and Goodman experiments was well below the critical level for RuO2 formation. Therefore this SXRD study [25] shows unequivocally that RuO2 was not formed in the Peden and Goodman experiments [4]. Studies [7,17] of CO on RuO2(1 1 0) indicate that a strongly bound CO ($120 kJ/mol) combines with either bridging O-atoms [26,27] or O-atoms residing at undercoordinated Ru atoms (cus-sites) [15] on the oxide surface to form CO2. If the active surface were indeed RuO2(1 1 0) for CO oxidation on Ru(0 0 0 1) at elevated reaction pressures, vibrational spectroscopy should readily see this strongly bound CO at typical elevated pressure reaction conditions. Early IRAS studies by Peden et al. [16] investigated the CO oxidation reaction over Ru(0 0 0 1) in situ at pressures up to $10 Torr. Under steady-state reaction conditions of CO/O2 6 2, no adsorbed CO was evident at 500 K suggesting that the adsorptive properties of the active surface are entirely dierent from metallic Ru. Given that the oxygen coverage is 1 ML as measured by AES and XPS and that a (1 1) LEED pattern was observed for a Ru(0 0 0 1) surface quenched from reaction condition, this one monolayer oxygen-covered surface can be described as Ru(0 0 0 1)(1 1)O. In fact no CO could be adsorbed on this surface in UHV at 85 K. From these results an upper limit of the CO adsorption energy on a Ru(0 0 0 1)(1 1)O surface was estimated to be <40 kJ/mol. A recent study by Bottcher et al. [6], based on CO adsorption at <55 K, estimates the CO binding to Ru(0 0 0 1)(1 1)O to be $20 kJ/mol. The evidence then is that the active surface for CO oxidation on Ru at elevated pressures is a one monolayer oxygencovered surface, and that the reaction takes place on a surface with very low steady-state concentrations of CO due to a very low binding energy of CO to Ru(0 0 0 1) (1 1)O [4,16].

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Several recent studies contradict RuO2 being the active working surface in catalytic CO oxidation by Ru at stoichiometric CO/O2 conditions and pressures at or near one atmosphere: (1) CO oxidation reaction on polycrystalline powdered Ru catalysts in the temperature range 363453 K [19,20] suggest that under catalytic conditions, the active state is an ultrathin Ru oxide lm of undetermined stoichiometry, whereas fully oxidized RuO2 particles, formed at higher temperatures, exhibit lower activity. Recent work by Wakita et al. [28] likewise showed that under oxidizing conditions supported Ru catalysts were deactivated for CO oxidation while the addition of a reductant (NH3) restored the lost activity. Indeed a study by Bottcher, et al. showed that the oxidation of CO was entirely quenched on a Ru(0 0 0 1) surface by the formation of a lm of RuO2 [29]. These studies are in complete agreement with the early works of Cant et al. [3] and Kiss and Gonzalez [18] that showed supported Ru catalysts deactivate for CO oxidation under O2-rich reaction conditions. (2) Recent studies by Blume et al. [22] using elevatedpressure XPS within the pressure range 104 101 mbar show no distinct dierence in catalytic activity between stoichiometic RuO2(1 1 0) and a poorly ordered surface oxide, i.e. no direct correlation between the CO oxidation activity and the amount of RuO2 present on a Ru(0 0 0 1) catalyst. (3) A very recent study by Rossler, et al. [23] investigated a RuO2(1 1 0) lm grown epitaxially on a Ru(0 0 0 1) surface by STM. The surface was rst exposed to an oxygen atmosphere at 200 mbar and 300 K followed by pure CO up to 21 mbar. A species was identied as strongly bound carbonate that desorbed in subsequent TPD with peak maxima at 520 and 570 K. These authors concluded that RuO2 cannot be a catalyst for CO oxidation at moderate temperatures simply because the surface is covered with carbonate. A desorption peak maximum of 570 K is consistent with deactivation of Ru catalysts at higher temperatures and pressures where one anticipates a saturation of the surface by this carbonate species. The obvious conclusion from the body of literature currently available is that the distinctive characteristic of a Ru catalyst, in contrast to Pt, Pd, Rh, and Ir, for CO oxidation near stoichiometric reaction conditions of CO and O2 and at elevated pressures is that the Ru surface forms an oxygen-covered surface that is more active by several orders of magnitude than clean Ru. RuO2 likely exhibits residual activity for CO oxidation under reaction conditions sucient to reduce the surface, however, its steady-state activity at elevated temperatures/pressures and near stoichiometric reaction conditions is decidedly below that of the oxygen-covered surface given the ample evidence that oxi-

dation of supported Ru catalysts leads to deactivation. Studies directed toward the active, working catalyst should focus on the oxygen-covered surface of Ru consisting of $1 monolayer. Acknowledgements We gratefully acknowledge the support for this work by the Department of Energy, Oce of Basic Energy Sciences, Division of Chemical Sciences/Geosciences/Biosciences, Catalysis and Chemical Transformations Program, and the Robert A. Welch Foundation. References
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