Ambient pressure photoelectron spectroscopy: a new tool for surface science and nanotechnology

Progress in science often follows or parallels the development of new techniques. The optical microscope helped convert medicine and biology from a speculative activity in old times to today's sophisticated scientific disciplines. The telescope changed the study and interpretation of heavens from mythology to science. X-ray diffraction enabled the flourishing of solid state physics and materials science. The technique object of this review, Ambient Pressure Photoelectron Spectroscopy or APPES for short, has also the potential of producing dramatic changes in the study of liquid and solid surfaces, particularly in areas such as atmospheric, environment and catalysis sciences. APPES adds an important missing element to the host of techniques that give fundamental information, i.e., spectroscopy and microscopy, about surfaces in the presence of gases and vapors, as encountered in industrial catalysis and atmospheric environments. APPES brings electron spectroscopy into the realm of techniques that can be used in practical environments. Decades of surface science in ultra high vacuum (UHV) has shown the power of electron spectroscopy in its various manifestations. Their unique property is the extremely short elastic mean free path of electrons as they travel through condensed matter, of the order of a few atomic distances in the energy range from a few eV to a few thousand eV. As a consequence of this the information obtained by analyzing electrons emitted or scattered from a surface refers to the top first few atomic layers, which is what surface science is all about. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), Ultraviolet photoelectron spectroscopy (UPS), and other such techniques have been used for decades and provided some of the most fundamental knowledge about surface crystallography, composition and electronic structure available today. Unfortunately the high interaction cross section of electrons with matter also prevents them from traveling long distances unscattered in gas environments. Above the millibar pressure range this distance is reduced to less that a millimeter, effectively preventing its use in the most relevant environments, usually between millibars and atmospheric pressures. There is therefore a large gap of several orders of magnitude where information about surfaces is scarce because these powerful electron spectroscopies cannot operate. One characteristic of surfaces in ambient pressure environments is that they are covered by dense layers of molecules, even when their binding energy is weak. Water for example is known to form layers several molecules thick at room temperature in humid environments. Metals readily form oxide films several layers thick in oxygen atmospheres. Dense layers of adsorbed molecules can also be produced in ultra high vacuum, often by the simple and expedient method of cooling the sample to cryogenic temperatures. A large amount of data has been obtained in the past in UHV by surface scientists using this method. While this has provided valuable information it begs the question of whether the structures formed in this manner represent equilibrium structures or metastable ones, kinetically trapped due to high activation energies that cannot be overcome at low temperature. From a thermodynamic point of view is interesting to consider the entropic contribution to the Gibbs free energy, which we can call 'the pressure factor', equal to kT.logP. This factor amounts to a sizeable 0.3 eV difference at room temperature between UHV (<10{sup -8} Pascal) and atmospheric pressures. Such change if free energy can definitely result in changes in surface structure and stability. Entire areas of the phase diagram are out of reach due to the pressure gap. Even when cooling is not necessary, many surface treatments and most chemical reactions necessitate the presence of gases at pressures ranging from millibar to bars. What is the structure and chemical nature of the species formed on the surface in equilibrium with such gases? As we shall illustrate in this review, APPES provides a much needed electron spectroscopy to analyze surface electronic structure and composition in equilibrium with gases

In situ x-ray photoelectron spectroscopy studies of gas/solid interfaces at near-ambient conditions

X-ray photoelectron spectroscopy (XPS) is a quantitative, chemically specific technique with a probing depth of a few angstroms to a few nanometers. It is therefore ideally suited to investigate the chemical nature of the surfaces of catalysts. Because of the scattering of electrons by gas molecules, XPS is generally performed under vacuum conditions. However, for thermodynamic and/or kinetic reasons, the catalyst’s chemical state observed under vacuum reaction conditions is not necessarily the same as that of a catalyst under realistic operating pressures. Therefore, investigations of catalysts should ideally be performed under reaction conditions, that is, in the presence of a gas or gas mixtures. Using differentially pumped chambers separated by small apertures, XPS can operate at pressures of up to 1 Torr, and with a recently developed differentially pumped lens system, the pressure limit has been raised to about 10 Torr. Here, we describe the technical aspects of high-pressure XPS and discuss recent applications of this technique to oxidation and heterogeneous catalytic reactions on metal surfaces

Cytotoxicity and inflammatory potential of soot particles of low-emission diesel engines

We evaluated, in vitro, the inflammatory and cytotoxic potential of soot particles from current low-emission (Euro IV) diesel engines toward human peripheral blood monocyte-derived macrophage cells. The result is surprising. At the same mass concentration, soot particles produced under low-emission conditions exhibit a much highertoxic and inflammatory potential than particles from an old diesel engine operating under black smoke conditions. This effect is assigned to the defective surface structure of Euro IV diesel soot, rendering it highly active. Our findings indicate that the reduction of soot emission in terms of mass does not automatically lead to a reduction of the toxic effects toward humans when the structure and functionality of the soot is changed, and thereby the biological accessibility and inflammatory potential of soot is increased

In situ XPS study of Pd(111) oxidation. Part 1: 2D oxide formation in 10 3 mbar O2

The oxidation of the Pd(111) surface was studied by in situ XPS during heating and cooling in 3 · 10 3 mbar O2. A number of adsorbed/dissolved oxygen species were identified by in situ XPS, such as the two dimensional surface oxide (Pd5O4), the supersaturated Oads layer, dissolved oxygen and the ð ffiffiffiffiffi p67 ffiffiffiffiffi p67ÞR12.2 surface structure. Exposure of the Pd(111) single crystal to 3 · 10 3 mbar O2 at 425 K led to formation of the 2D oxide phase, which was in equilibrium with a supersaturated Oads layer. The supersaturated Oads layer was characterized by the O 1s core level peak at 530.37 eV. The 2D oxide, Pd5O4, was characterized by two O 1s components at 528.92 eV and 529.52 eV and by two oxygen-induced Pd 3d5/2 components at 335.5 eV and 336.24 eV. During heating in 3 · 10 3 mbar O2 the supersaturated Oads layer disappeared whereas the fraction of the surface covered with the 2D oxide grew. The surface was completely covered with the 2D oxide between 600 K and 655 K. Depth profiling by photon energy variation confirmed the surface nature of the 2D oxide. The 2D oxide decomposed completely above 717 K. Diffusion of oxygen in the palladium bulk occurred at these temperatures. A substantial oxygen signal assigned to the dissolved species was detected even at 923 K. The dissolved oxygen was characterised by the O 1s core level peak at 528.98 eV. The ‘‘bulk’’ nature of the dissolved oxygen species was verified by depth profiling. During cooling in 3 · 10 3 mbar O2, the oxidised Pd2+ species appeared at 788 K whereas the 2D oxide decomposed at 717 K during heating. The surface oxidised states exhibited an inverse hysteresis. The oxidised palladium state observed during cooling was assigned to a new oxide phase, probably the ð ffiffiffiffiffi p67 ffiffiffiffiffi p67ÞR12.2 structure

In situ XPS study of methanol reforming on PdGa near-surface intermetallic phases

In situ X-ray photoelectron spectroscopy and low-energy ion scattering were used to study the preparation, (thermo)chemical and catalytic properties of 1:1 PdGa intermetallic near-surface phases. Deposition of several multilayers of Ga metal and subsequent annealing to 503-523 K led to the formation of a multi-layered 1:1 PdGa near-surface state without desorption of excess Ga to the gas phase. In general, the composition of the PdGa model system is much more variable than that of its PdZn counterpart, which results in gradual changes of the near-surface composition with increasing annealing or reaction temperature. In contrast to near-surface PdZn, in methanol steam reforming, no temperature region with pronounced CO2 selectivity was observed, which is due to the inability of purely intermetallic PdGa to efficiently activate water. This allows to pinpoint the water-activating role of the intermetallic/support interface and/or of the oxide support in the related supported PdxGa/Ga2O3 systems, which exhibit high CO2 selectivity in a broad temperature range. In contrast, corresponding experiments starting on the purely bimetallic model surface in oxidative methanol reforming yielded high CO2 selectivity already at low temperatures (similar to 460 K), which is due to efficient O-2 activation on PdGa. In situ detected partial and reversible oxidative Ga segregation on intermetallic PdGa is associated with total oxidation of intermediate C-1 oxygenates to CO2. (c) 2012 Elsevier Inc. All rights reserved