In situ Low-Energy Electron Microscopy of Chemical Waves on a Composite V-oxide/Rh(110) Surface.

Chemical wave patterns and V-oxide redistribution in catalytic methanol oxidation on a VOx/Rh(110) surface have been investigated in the 10-4 mbar range with low-energy electron microscopy (LEEM) and micro spot low-energy electron diffraction (micro-LEED) as in situ methods. V coverages of θV=0.2 and 0.4 MLE (monolayer equivalents) were studied. Pulses display a c(2×2) pattern in the reduced part and (1×2) and c(2×8) structures in the oxidized part of the surface. At θV=0.4 MLE (1×2)/(1×4) patterns with streaks along the [001]-direction at the 1/8 positions are present on the oxidized part of the surface. This phase can be assigned to V-oxide. On a tentative basis, an excitation mechanism for pulses is presented, Annealing the surface to 990 K under reaction conditions results in a macroscopic hole pattern in which holes of low VOx coverage are surrounded by a V-oxide layer. Chemical waves propagate inside the holes as well as on the VOx covered parts of the surface. The results demonstrate for the first time that also in supported oxidic overlayers selforganization processes can take place leading to chemical waves and a large scale redistribution of the oxide.

Stationary stripe patterns and chemical waves on the bimetallic Rh(110)/Ni surface during the H2 + O2 reaction.

Chemical wave patterns that develop in the O2 + H2 reaction on a bimetallic Rh(110)/Ni surface have been studied with photoelectron emission microscopy (PEEM) in the 10-6 to 10-4 mbar range. The bifurcation diagram for Ni coverages up to 3 monolayers (ML) was mapped out for T = 770 K. Stationary concentration patterns of macroscopic stripes as well as target patterns and irregular chemical waves were observed.

Identification of the surface species in electrochemical promotion: ethylene oxidation over a Pt/YSZ catalyst.

The electrochemical promotion of the C2H4 + O2 total oxidation reaction over a Pt catalyst, interfaced to yttrium stabilized zirconia (YSZ), has been studied at 0.25 mbar and T = 650 K using near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) as an in situ method. The electrochemical promoter effect is linked to the presence of a several layers thick graphitic overlayer that forms on the Pt surface in the presence of C2H4. Our NAP-XPS investigation reveals that electrochemical pumping of the Pt/YSZ catalyst, using a positive potential, leads to the spillover of oxygen surface species from the YSZ support onto the surface of the Pt electrode. Based on the XP spectra, the spillover species on Pt is identical to oxygen chemisorbed from the gas-phase.

On the Promotion of Catalytic Reactions by Surface Acoustic Waves.

Surface acoustic waves (SAW) allow to manipulate surfaces with potential applications in catalysis, sensor and nanotechnology. SAWs were shown to cause a strong increase in catalytic activity and selectivity in many oxidation and decomposition reactions on metallic and oxidic catalysts. However, the promotion mechanism has not been unambiguously identified. Using stroboscopic X-ray photoelectron spectro-microscopy, we were able to evidence a sub-nanosecond work function change during propagation of 500 MHz SAWs on a 9 nm thick platinum film. We quantify the work function change to 455 µeV. Such a small variation rules out that electronic effects due to elastic deformation (strain) play a major role in the SAW-induced promotion of catalysis. In a second set of experiments, SAW-induced intermixing of a five monolayers thick Rh film on top of polycrystalline platinum was demonstrated to be due to enhanced thermal diffusion caused by an increase of the surface temperature by about 75 K when SAWs were excited. Reversible surface structural changes are suggested to be a major cause for catalytic promotion.

Chemical waves in the O2 + H2 reaction on a Rh(111) surface alloyed with nickel. I. Photoelectron emission microscopy.

Chemical waves that arise in the H2 + O2 reaction on a bimetallic Rh(111)/Ni surface have been studied in the 10-6 and 10-5 mbar range at T = 773 K with photoelectron emission microscopy (PEEM), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES). Nickel coverages of 0.3, 0.6, and 1.0 monolayers were investigated. Coadsorbed with some oxygen, Ni starts to penetrate the Rh bulk region substantially only beyond 900 K. In the 10-5 mbar range, chemical waves are characterized by three distinct gray levels in PEEM. This number reduces to only two levels in the 10-6 mbar range. In situ LEED showed the periodic appearance of a (n × 1) (n = 8, 10) pattern during chemical waves which was assigned to a 2D-Ni oxide. With in situ AES, one observes that the bright phase in PEEM correlates with a high Ni coverage and the dark phase with a low Ni coverage.

Chemical waves in the O2 + H2 reaction on a Rh(111) surface alloyed with nickel. II. Photoelectron spectroscopy and microscopy.

Chemical waves in the H2 + O2 reaction on a Rh(111) surface alloyed with Ni [ΘNi < 1.5 monolayers (ML)] have been investigated in the 10-7 and 10-6 mbar range at T = 773 K using scanning photoelectron microscopy and x-ray photoelectron spectroscopy as in situ methods. The local intensity variations of the O 1s and the Ni 2p signal display an anticorrelated behavior. The coincidence of a high oxygen signal with a low Ni 2p intensity, which seemingly contradicts the chemical attraction between O and Ni, has been explained with a phase separation of the oxygen covered Rh(111)/Ni surface into a 3D-Ni oxide and into a Ni poor metallic phase. Macroscopic NiO islands (≈1 µm size) formed under reaction conditions have been identified as 2D-Ni oxide. Titration experiments of the oxygen covered Rh(111)/Ni surface with H2 demonstrated that the reactivity of oxygen is decreased by an order of magnitude through the addition of 0.6 ML Ni. An excitation mechanism is proposed in which the periodic formation and reduction of NiO modulate the catalytic activity.

Hole patterns in ultrathin vanadium oxide layers on a Rh(111) surface during catalytic oxidation reactions with NO.

Various oxidation reactions with NO as oxidant have been investigated on a partially VOx covered Rh(111) surface (θV = 0.3 MLE) in the 10-4 mbar range, using photoelectron emission microscopy (PEEM) as spatially resolving method. The PEEM studies are complemented by rate measurements and by low-energy electron diffraction. In catalytic methanol oxidation with NO and in the NH3 + NO reaction, we observe that starting from a homogeneous surface with increasing temperature first a stripe pattern develops, followed by a pattern in which macroscopic holes of nearly bare metal surface are surrounded by a VOx film. These hole patterns represent just the inverse of the VOx distribution patterns seen if O2 instead of NO is used as oxidant.

Island Ripening via a Polymerization-Depolymerization Mechanism.

In catalytic methanol oxidation on ultrathin vanadium oxide layers on Rh(111) (Θ_{V}≈0.2 monolayer equivalent) we observe a 2D ripening of the VO_{x} islands that is controlled by the catalytic reaction. Neighboring VO_{x} islands move under reaction conditions towards each other and coalesce. The motion and the coalescence of the islands are explained by a polymerization-depolymerization equilibrium that is sensitive to gradients in the adsorbate coverages.

Traveling interface modulations and anisotropic front propagation in ammonia oxidation over Rh(110).

The bistable NH3 + O2 reaction over a Rh(110) surface was explored in the pressure range 10(-6)-10(-3) mbar and in the temperature range 300-900 K using photoemission electron microscopy and low energy electron microscopy as spatially resolving methods. We observed a history dependent anisotropy in front propagation, traveling interface modulations, transitions with secondary reaction fronts, and stationary island structures.

Excitability in the H2+O2 reaction on a Rh(110) surface induced by high coverages of coadsorbed potassium.

By means of photoemission electron microscopy as spatially resolving method, the effect of high coverages of coadsorbed potassium (0.16 ≤ θ(K) ≤ 0.21) on the dynamical behavior of the H2 + O2 reaction over a Rh(110) surface was investigated. We observe that the originally bistable system is transformed into an excitable system as evidenced by the formation of target patterns and spiral waves. At K coverages close to saturation (θ(K) ≈ 0.21) mass transport of potassium with pulses is seen.

The electrochemical promotion of ethylene oxidation at a Pt/YSZ catalyst.

The electrochemical promotion of the C(2)H(4)+O(2) reaction to form CO(2) and H(2)O is studied in the 10(-5) and 10(-4) mbar range with a Pt catalyst interfaced as working electrode to yttrium-stabilized zirconia (YSZ). Photoemission electron microscopy (PEEM) was used as spatially resolving method. Under open-circuit conditions, that is, without an external voltage applied, the CO(2) production exhibits a pronounced hysteresis upon cyclic variation of p(C(2)H(4)). The hysteresis is attributed to the build-up of a carbonaceous CH(x) layer inhibiting O(2) adsorption and hence poisoning the reaction. It is shown that the application of a positive potential of 1 V triggers a transition from the unreactive branch of the reaction to an active branch. The large non-Faradayicity reported in the literature for this reaction system is explained as an ignition effect caused by the partial removal of the inhibiting carbonaceaous layer.

Origin of non-Faradayicity in electrochemical promotion of catalytic ethylene oxidation.

The electrochemical promotion of catalytic C(2)H(4) oxidation has been investigated under low pressure conditions (p approximately 10(-6)-10(-4) mbar) with a Pt film on yttrium stabilized zirconia (YSZ) as catalyst. All measurements were conducted with a UHV system with a differentially pumped quadruple mass spectrometer (QMS) for rate measurements and a photoelectron emission microscope (PEEM) for spatially resolved measurements. A pronounced rate hysteresis upon cyclic variation of p(C(2)H(4)) was observed under open circuit conditions which is attributed to carbonaceous CH(x) adlayer inhibiting O(2) adsorption and hence poisoning the reaction. Application of a positive potential causes a partial removal of the inhibiting CH(x) adlayer by spillover oxygen thus triggering a transition from thus poisoned state of the surface to an active state with reduced carbon coverage. The ignition effect and therefore also the electrochemical promotion effect are linked to the presence of a carbon adlayer on the surface. The non-Faradayicity which is observed in this reaction system is explained as an ignition effect.

Dynamics of Ultrathin Vanadium Oxide Layers on Rh(111) and Rh(110) Surfaces During Catalytic Reactions.

Over the past 35 years rate oscillations and chemical wave patterns have been extensively studied on metal surfaces, while little is known about the dynamics of catalytic oxide surfaces under reaction conditions. Here we report on the behavior of ultrathin V oxide layers epitaxially grown on Rh(111) and Rh(110) single crystal surfaces during catalytic methanol oxidation. We use photoemission electron microscopy and low-energy electron microscopy to study the surface dynamics in the 10-6 to 10-2 mbar range. On VO x /Rh(111) we find a ripening mechanism in which VO x islands of macroscopic size move toward each other and coalesce under reaction conditions. A polymerization/depolymerization mechanism of VO x that is sensitive to gradients in the oxygen coverage explains this behavior. The existence of a substructure in VO x islands gives rise to an instability, in which a VO x island shrinks and expands around a critical radius in an oscillatory manner. At 10-2 mbar the VO x islands are no longer stable but they disintegrate, leading to turbulent redistribution dynamics of VO x . On the more open and thermodynamically less stable Rh(110) surface the behavior of VO x is much more complex than on Rh(111), as V can also populate subsurface sites. At low V coverage, one finds traveling interface pulses in the bistable range. A state-dependent anisotropy of the surface is presumably responsible for intriguing chemical wave patterns: wave fragments traveling along certain crystallographic directions, and coexisting different front geometries in the range of dynamic bistability. Annealing to 1000 K causes the formation of macroscopic VO x islands. Under more reducing conditions dendritic growth of a VO x overlayer is observed.

Simulation of traveling interface pulses in bistable surface reactions.

A couple of bistable oxidation reactions on Rh(110), the CH_{3}OH+O_{2} and the NH_{3}+O_{2} reactions, exhibit localized excitations at the interface between oxygen-poor and oxygen-rich phase that propagate in a pulselike manner along the interface. A three-variable reaction-diffusion model is set up based on a mechanism that explains the localized excitations as being caused by temporary structural defects generated in the vicinity of the interface. The structural defects are a consequence of different densities of surface atoms in the oxygen-induced reconstruction phases and in the nonreconstructed (1×1) phase. One- and two-dimensional simulations show that traveling interface pulses (TIPs) exist in a region of so-called double metastability adjacent to the equistability point of the bistable system. As in the experiment, we observe triangular-shaped TIPs that move fast along the interface. Diffusional anisotropy is not required for the occurrence of TIPs. All essential features of the experiment are reproduced by the simulations.

Catalytic CO oxidation on Pt under near ambient pressure: A NAP-LEEM study.

A near ambient pressure low-energy electron microscope (NAP-LEEM) has recently been constructed, that allows in situ imaging of surfaces up to a pressure of 10-1 mbar. Here we report on pattern formation in catalytic CO oxidation on a Pt(110) single crystal surface and on a polycrystalline Pt foil in the 10-2 mbar range, operating the microscope in the mirror electron microscopy (MEM) and in the LEEM mode. Excitations localized at structural defects and spiral wave fragments have been observed.

Nucleation of spiral wave patterns at surface defects.

The nucleation of spiral waves at a surface defect during catalytic CO oxidation on Pt(110) has been studied with a low energy electron microscope system. It is found that reaction fronts originate from a boundary layer between the defect and the surrounding Pt(110) area. The findings are corroborated by numerical simulations within a realistic reaction-diffusion model of the surface reaction.