Surface Science 600 (2006) 30283035 www.elsevier.

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3D atom probe study of gas adsorption and reaction on alloy catalyst surfaces I: Instrumentation
P.A.J. Bagot
b

a,*

b, A. Cerezo a, G.D.W. Smith , T. Visart de Bocarme

a Department of Materials, University of Oxford, Parks Road, Oxford OX13PH, UK Libre de Bruxelles, Campus Plaine, CP 243, B-1050 Brusssels, Belgium Chemical Physics of Materials, Universite

Received 10 April 2006; accepted for publication 11 May 2006 Available online 9 June 2006

Abstract A versatile gas reaction cell has been developed for a 3D atom probe system to provide a new method for studying the reaction mechanisms of heterogeneous catalysis. We describe the features and advantages of this new system. The reaction cell enables exposure of metal specimens in high temperature (6873 K) and high pressure (61 bar) environments to a wide range of single gases or gas mixtures. Following treatment, specimens are transferred into the UHV analysis chamber of the 3D atom probe, which provides atomic-scale positional and chemical information for adsorbed gas and metal atoms/oxides from selected regions of the specimen apex. Results demonstrating the eects of heating alloy catalysts in vacuo and in air are presented, which validate the instrument design, alongside a sample of data for exposing Pt and Pt-Rh alloys to NO, revealing the power of the 3D atom probe technique in this eld. 2006 Elsevier B.V. All rights reserved.
Keywords: Atom probe; Field ion microscopy; Adsorption; Catalysis; Surface reactions; Surface segregation

1. Introduction Platinum alloys form the basis for automobile exhaust catalysts, one of the most successful and important families of heterogeneous catalysts used in industry today. Despite this, there exists a large gap in detailed knowledge concerning how such devices actually function. Much of this is due to the complexity of the catalysts, both in terms of their physical state (highly dispersed, nano-crystalline particles) and chemical environment (continually varying temperature/composition of atmospheric-pressure gases). In order to design new and improved heterogeneous catalysts, it is becoming increasingly important to understand how such catalyst surfaces work at a fundamental level. Issues requiring investigation include understanding which metal elements are the most ecient for key reactions, which atomic sites are the most reactive, and how stable

Corresponding author. Tel.: +44 0131 451 4113. E-mail address: paul.bagot@gmail.com (P.A.J. Bagot).

such catalyst surfaces are in the face of changing compositions/ow rates of reactive gas molecules. To shed light on these issues, the application of surface science techniques is essential. A wide range of experimental methods are available; these include Scanning Tunneling Microscopy (STM), Electron Microscopy (EM), Temperature Programmed Desorption (TPD), Auger Electron Spectroscopy (AES) and X-ray Photoelectron Spectroscopy (XPS) to name but a few. While these continue to provide valuable information on catalytic reactions, the reaction conditions and/ or catalyst form in such instruments usually diers greatly from the real-life conditions of an industrial catalyst. Furthermore, the pressures of gases used in many surface science experiments are typically in the high-vacuum range, particularly for techniques such as STM and EM. Even when higher pressures are achievable, as in some TPD instruments, the specimen is in the form of an atomically smooth surface. This diers considerably from the nanosized metal particles employed in real catalysts. Thus a pressure gap and a materials gap exist, hindering experimental progress.

0039-6028/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.susc.2006.05.026

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To provide a new insight into heterogeneous catalysis and to attempt to avoid some of the problems of existing techniques, we have designed a unique instrument which is described in detail here. This is based on the 3D atom probe technique, which provides both chemical identication and atomic-scale positional mapping of atoms on the end of sharp needle-shaped metal specimens. This new instrument is constructed specically to investigate the properties of heterogeneous catalysts, and is called a Catalytic Atom Probe (CAP). This system is well suited for studying a wide variety of gas-surface interactions; in this work the CAP was employed exclusively to study the processes occurring on automobile exhaust catalysts. This is a critically important application of heterogeneous catalysis, which protects the ambient air from a range of toxic gases including NOx, CO and the indirect production of ground-level ozone (O3). In this paper we discuss the details of the instrument alongside some sample results, while subsequent papers will present a range of results for gaseous reactions on Pt-alloy specimens, and will provide a theoretical treatment of the surface segregation behaviour observed from the experiments. 2. 3D atom probe The 3D atom probe (3DAP) has to date been used to provide atomic-scale compositional analyses for a wide range of materials, including aerospace aluminium alloys [1], magnetic thin-lm materials [2], and the eects of hardening [3] and radiation damage [4] in steels. A general introduction to the atom probe technique and its many applications can be found elsewhere [5,6]. Previous workers have used 1D atom probe systems to study catalysis-related phenomena. For example Tsong et al. observed surface segregation in PtRh alloys heated in vacuo to high temperatures (>1000 K) [7]. Kellogg carried out a number of experiments on platinum group metal oxidation, identifying Rh2O3 on oxygen-treated Rh [8,9]. Kruse et al. have also contributed extensively to the knowledge of reactions on atom probe specimens, using Pulsed Field Desorption Mass Spectrometry (PFDMS similar to 1D atom probe) to study the desorption of NO from Pt [10], the formation of carbonyls on Rh [11] and the reaction of both NO and CO together on Rh [12]. Fuller accounts of previous eld-ion microscopy (FIM)/atom probe studies on gaseous adsorption and metal segregation are available [5,13]. The instrument developed during the present work is shown in Fig. 1. It is a 3-chamber design (main chamber, preparation and loadlock), with an energy-compensated 3DAP with reectron [14] and delay line detector. This detector has three sets of lines rather than the usual two, which gives improved multi-hit detection capability [15,16]. A reaction cell and gas-dosing rig were designed and integrated into the machine to allow specimens to be exposed to various gas mixtures at pressures of up to one atmosphere and at temperatures of up to 873 K.
Fig. 1. (a) Schematic diagram of the chamber layout in the CAP, as seen from the top (b) general view of the instrument, including the gas-dosing rig (right hand side).

3. Reaction cell The reaction cell (Fig. 2) was required to expose specimens in pressures of up to 1 bar without leakage into the adjacent UHV preparation chamber. The cell was manufactured by Polaron-CVT (now Oxford nanoScience Ltd). It was mounted in the CAP preparation chamber and consisted of a xed cylindrical section (LHS of Fig. 2(a)) and a movable face plate (RHS of Fig. 2(a)). When moved into the open position, this plate allowed specimen insertion into the heating stage cell, which could be closed against the xed section forming a seal with a Viton O-ring. The heating stage contained two narrow ($4 mm diameter) gas supply lines, connected to the outside, two built-in thermocouples, and a screw-hole for the specimen stub. Screwing a specimen into the stage using the magnetic transfer arm provided a seal sucient to hold 1 bar in the inner cell, with the outer, dierentially-pumped, section holding roughly 103 mbar. All components that might be exposed to gases within the cell were constructed from stainless steel. This minimised the possibility of side reactions occurring within the cell. The only exception to this rule was the crimp tubes that hold the specimen wires in the stub, which were pure nickel. Steel tubes were tested, but these proved dicult to work with. Furthermore tests showed no dierence in chemical species identied in the CAP from specimens crimped into either nickel or steel tubes. Fig. 2(b) shows the reaction cell installed onto the preparation chamber of the CAP. A calibration was carried out to obtain an accurate determination of the true specimen temperature. For this

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minimise contamination. It was developed to supply up to 6 gases simultaneously (7 including bursts of SO2), over a pressure range of 51000 mbar. Once a gas ow was established using the mass-ow controllers, valves connecting to the reaction cell could be opened to admit the gas mixture to the cell. Using a combination of a diaphragm pump (Vacuubrand) and turbo pump (Pfeier), residual gases in the rig were exhausted to a fume cupboard after experiment completion. As the toxic gases carbon monoxide, nitric oxide and sulphur dioxide were employed in experiments, the safe venting and secure sealing of the rig was crucial. Leak detection in the rig was made easy by the fact that when not supplying a gas mixture, the system was continually pumped out via the turbo pump to pressures of around 107 mbar. Any leak that developed would be quickly spotted as a higher base pressure, well before any toxic gases were supplied to the lines. Finally, there was also the facility to sample the gas ow either to or from the reaction cell using the in-built mass spectrometer (Pfeier). This was used occasionally to conrm no side reactions inside the reaction cell were occurring, and also that the supply of gas to the reaction cell was as expected. Using this, little contamination (typically 61% trace water, nitrogen) was seen in the gas supply to and from the reaction cell. 5. Reaction cell treatment procedure
Fig. 2. (a) Close-up of reaction cell internals prior to cell installation (b) View from side of CAP showing cell mounted onto UHV preparation chamber.

The procedure for treating a specimen in the reaction cell was as follows: Insert specimen into main chamber Clean specimen by eld-ion imaging and eld evaporation Transfer specimen to preparation chamber Prime gas-dosing rig with gases of interest Transfer specimen to pre-heated reaction cell Isolate cell Admit gases to cell and hold for required dosing time Close gas supply valves after treatment Wait briey for cell pressure to drop below $104 mbar Open cell to preparation chamber Transfer specimen back to main chamber All specimens were prepared by electropolishing highpurity Pt metal and Pt alloy wires (Alfa-Aesar) in a molten salt mixture of 4:1 NaNO3:NaCl. Following specimen preparation, the rst stage of any experiment was to produce a clean specimen surface using eld evaporation during eld-ion imaging, then to align the specimen on the region under investigation. Once aligned, the specimen position (tilt/rotation angles of the cryostat) was noted (within 60.5). This method was found to be a reproducible way of aligning specimens post-treatment without the need for additional FIM imaging. Checks were also made on two occasions that the areas selected for atom probe analysis

a separate K-type thermocouple was inserted into a stub and placed in the reaction cell. This provided a sensor at a location as close as possible to that where specimens were located. Even in vacuo, the temperature at the specimen was within 5 K of the set point. Only above around 773 K was a signicant dierence noted. This dierence would likely diminish when 10 mbar of gas was present in the cell, as heating by gas conduction would occur in addition to that by radiation and conduction through the metal stub. Temperatures presented were therefore taken directly from the built-in thermocouple readings and are not adjusted. It was not possible to test the temperature response of the cell while gas was present. 4. Gas-dosing rig To treat the specimens with mixtures of various gases, a gas-dosing rig was designed and constructed at Oxford University (Fig. 1(b)), supplying a range of gases to the reaction cell, controlled by pressure and/or ow rates via mass-ow controllers (MKS Instruments). This rig was constructed using stainless steel tubing, chambers and allmetal leak valves (MDC Vacuum Products) in order to

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using the FIM were the same areas of the specimen actually analysed. Once the cell had been set and stabilised at the temperature of interest, the gas-rig was primed with the gas or gases to be studied. The mass-ow controllers were eectively used as electronic valves to ll the central steel tubing to the required pressure, monitored by the baratron. The specimen was removed from the main chamber using the transfer arm and inserted into the reaction cell, which was then isolated. At this point the gas-valves were opened to admit the gas/gases to the cell. Exposures were timed over a duration of typically 15 min. By monitoring the total gas pressure at the baratron, a variation of no more than 10% from the intended gas pressure was easily achieved. At the end of the allotted exposure time, the gas supply valves were closed, and after approximately 1 min the base pressure in the dierentially-pumped volume of the reaction cell was suciently low ($104 mbar) to allow transfer back to the main chamber. During the exposures this volume typically held a pressure of 103 mbar with an inner cell pressure of 10 mbar. Gas leaked slowly into the outer region via the screw thread on the stub, Fig. 2 (a), which by its nature was impossible to seal completely. This throughput however served as a means to remove the gas post-treatment, which enabled a swifter turnaround from treatment to 3DAP analysis. Once removed from the cell, the specimen was realigned for FIM or 3DAP analysis as desired. 6. Collection of data Traditionally the 3DAP has been employed to study bulk materials, collecting hundreds of thousands if not millions of ions in a single experiment. When analysing a specic feature in the atomic volume, such as metal clusters, there are usually numerous examples within the atom probe data. In contrast, surface science experiments carried out with the CAP collected typically 2000 ions following each treatment, of which half or less represented surface metal atoms directly interacting with the gases. Thus it was crucial to perform numerous experiments using the same treatment parameters in order to improve counting statistics for composition measurements and hence increase reliability of the results. When analysing multiple results it is important to critically assess the data from each run. On some occasions, contaminants were apparent on the specimen apex, usually from residual gas left over from the previous mix used. Purging the reaction cell with a nitrogen ow at P773 K usually prevented such contamination occurring, but when present the run in question was rejected from the overall results. It was found that using hydrocarbons in the reaction cell generated signicant contamination in the form of carbon and hydrogen peaks, which required repeated purging in order to ensure its removal. Furthermore, it was also important following such runs to clean the stubs thoroughly in an ultrasonic bath.

7. Calibration runs Before studying treated specimens, it was vital to establish that the atom probe data from the sample bulk corresponded closely to the quoted compositions of the alloys. A series of runs (400020,000 ions) were carried out over a range of specimen temperatures (20150 K) and pulse fractions (1030%). A nal operating temperature of 60 K was selected, which when combined with a pulse fraction of 20% yielded alloy compositions that agreed within 1% of the stated values. This pulse fraction was identical to that used by other atom probe groups to study PtRh [1719]. The compositions obtained at 60 K were independent of the plane studied. This is expected, since Pt and Rh have very similar evaporation elds on all planes, as predicted by simple image hump models [5]. 8. Initial results Examples of FIM data from the CAP are shown in Fig. 3. Image (a) shows an untreated PtRh specimen, while (b) shows the same specimen after exposure to NO gas at 573 K, 10 mbar. Note the large dark regions in this image, which indicate that a degree of faceting has occurred on these areas. After eld evaporation the faceting was removed to recover the typical smooth hemispherical end-form of FIM specimens similar to that shown in (a). This demonstrates the ability of the FIM to observe marked eects of morphological changes to catalyst surfaces following exposure to reactive gases. These results are also in agreement with the previous works of Voss and Kruse, considering oxygen-induced reconstruction of Rh [20], and NO-induced reconstruction of Pt [21] and Rh [22]. The structural changes to the PtRh specimens under oxidising gases observed under FIM are complemented by a chemical change to the surface seen in the 3DAP data. Brightly-imaging oxide species were identied in the FIM images of specimens treated in oxidising atmospheres, which produced patterns similar to those seen in an earlier study on PtRh oxidisation [23]. Fig. 4 shows two mass spectra from the {1 1 1} crystallographic region of a Pt Rh specimen heated at (a) 295 K and (b) 673 K in 10 mbar of NO. Note at the lower temperature intact NO molecules are detected on the surface, while at 673 K these have all dissociated, generating greater numbers of oxygen atoms and rhodium/platinum oxides. The data represented by the spectra can be used to better eect in atom maps, which give a complete picture of the chemistry of the surface in 3D. In this way the CAP, combining FIM and 3DAP, provides a complete instrument for investigation of both structural and chemical changes to the catalyst surfaces. Fig. 5(a) shows such an atom map from the {0 1 2}-type plane of pure Pt after a 10 mbar NO gas treatment at 292 K. On this pure Pt surface, much less NO was dissociated than on PtRh at the same temperature, conrming the higher relative activity of Rh for NO

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Fig. 3. FIM images of {0 0 1}-orientated PtRh (a) before, and (b) after 15 min treatment of NO at 10 mbar, 573 K (a) 6.6 kV (b) 6.8 kV. Fig. 4. Mass spectra from PtRh{1 1 1} surface after exposure to 10 mbar NO for 15 min at (a) 295 K (b) 693 K.

dissociation [24]. At higher temperatures (331 K), the extent of dissociation is much greater on this and all other surfaces tested, although some NO molecules are still de-

tected. Such results lie in close agreement with XPS studies of NO interaction on Pt single-crystal surfaces [25].

Fig. 5. (a) Pt{0 1 2} atom map after exposure to 10 mbar NO for 15 min at 292 K (b) FIM image of untreated Pt{0 1 2} region at same scale.

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Fig. 6. Atom map of Pt{0 0 1} surface after exposure to 10 mbar NO for 15 min at 292 K.

Fig. 5(b) shows a Pt FIM image of a clean {0 1 2} pole, which in shape correlates with the NO positions of (a). It is also possible to observe the extent of gas penetration into the surface using the atom maps. Fig. 6 shows a side-on atom map from an identically treated Pt{0 0 1} pole, where adsorption is seen conned to the rst few layers, and has clearly occurred at the edges of the distinct atomic planes. Another approach to analysing data from the CAP is by a cumulative plot, which is used for alloy specimens to plot the total number of metal species detected (in this case Rh, Pt and any metal oxides) against the number of a single metal species, usually rhodium. An example cumulative plot is presented in Fig. 7, taken from PtRh{0 1 2} region after exposure to 1 bar of air at 573 K for 30 min. The horizontal axis eectively represents depth into the specimen, approximately 1 nm in total, although the exact scaling depends on the apex radius. The key information from cumulative plots comes from the slope of the graph, which allows the determination of the local composition. If no segregation were present, a constant slope of 17.4% would indicate bulk composition throughout the depth of the specimen. In the case of Fig. 7 however note the Rh enrichment of the specimen followed by a region of Rh depletion. This suggests possible diusion of Rh species up to the surface,

which coincides with the oxygen and oxide species identied in the mass spectrum. It is imperative to have a suitable control experiment when interpreting such cumulative plots. These were provided by experiments heating specimens in either vacuo or with inert gases. Fig. 8 shows two cumulative plots from (a) PtRh{0 0 1} surface following heating in vacuum at 823 K for 20 min, and (b) PtRh{1 1 1} following heating in 10 mbar CO at 573 K for 15 min. Note in both cases that

Fig. 7. Cumulative plot from PtRh{0 1 2} surface after exposure to 1 bar of air for 30 min at 573 K.

Fig. 8. Cumulative plots from (a) PtRh{0 0 1} surface after heating in vacuum for 20 min at 823 K, (b) PtRh{111} after exposure to 10 mbar CO for 15 min at 573 K.

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Fig. 9. Atom maps from PtRh{1 1 1} surface after exposure to 10 mbar NO for 15 min at (a) 295 K, (b) 673 K.

the slope remains uniform, demonstrating no alloy segregation occurring. The corresponding mass spectra were also relatively clean, showing no oxides, only small amounts of CO, C and O in the latter case. Similarly clean spectra were obtained on exposing all regions of PtRh under consideration to 100 mbar nitrogen at room temperature, the surface again remained clean, with no segregation behaviour noted. Other gases such as ethene (423 K treatment) also revealed very little in the way of segregation behaviour. In general little contamination was seen in all experiments. Such control runs demonstrate that the adsorption and segregation trends are reliable and specic to individual gases/surfaces. If employed correctly, paying attention to regular baking/purging under nitrogen, the reaction cell therefore oers a clean base environment for allowing indepth studies of gas adsorption and metal segregation. Thermal treatments alone at the temperatures employed here are not sucient to cause chemical changes to the surfaces. This is in agreement with earlier atom probe studies of heating Pt-Rh in vacuo, which demonstrate that temperatures of at least 873 K are required to induce signicant segregation [7,18]. FIM observations also conrmed little interaction between any surface and the gases N2, C2H2 and CO, at least within the temperatures of interest in this work. Fig. 9 shows two atom maps taken from the {1 1 1}-orientated region of a PtRh specimen treated with 10 mbar NO at 295 K/673 K for 15 min. Note at the lower temperature (image (a)) most of the NO molecules are still intact, whereas on raising the temperature to 673 K the NO has dissociated into oxygen, which also forms oxide species, and nitrogen, which appears to have desorbed, in agreement with the literature [26]. A full range of results from the CAP are presented in later papers, while a general review of automobile exhaust catalysis exploring the contribution of FIM/AP alongside other techniques has already been published [13].

Acknowledgements T. Visart (postdoctoral researcher) gratefully acknowledges nancial support by the Fonds National de la Recherche Scientique (F.N.R.S.). P. Bagot thanks EPSRC for D.Phil funding, while grants from J.R.E.I and J.I.F. enabled the construction of the CAP. R. Davies of Oxford NanoScience Ltd. is thanked for detailed designs of the reaction cell. References
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