The surface and near-surface region of an active catalyst and the adjacent gas-phase reactants were investigated simultaneously under reaction conditions using in situ X-ray photoelectron spectroscopy (XPS). This investigation of methanol oxidation on a copper catalyst showed that there was a linear correlation between the catalytic activity of the sample and the presence of a sub-surface oxygen species that can only be observed in situ. The concentration profile of the sub-surface oxygen species within the first few nanometers below the surface was determined using photon energy-dependent depth-profiling. The chemical composition of the surface and the near-surface region varied strongly with the oxygen-tomethanol ratio in the reactant stream. The experiments show that the pure metal is not an active catalyst for the methanol oxidation reaction, but that a certain amount of oxygen has to be present in the sub-surface region to activate the catalytic reaction. Oxide formation was found to be detrimental to formaldehyde production. Our results demonstrate also that for an understanding of heterogeneous catalysts a characterization of the surface alone may not be sufficient, and that sub-surface characterization is essential.

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The reduction behavior of Co/TiO 2 and Co/Mn/TiO 2 catalysts for Fischer-Tropsch synthesis has been investigated by soft X-ray absorption spectroscopy (XAS). In situ XAS measurements of the L 2,3 edges of Co and Mn have been carried out during reduction treatments of the samples in H 2 at a pressure of 2 mbar and at temperatures up to 425°C. The changes of Co and Mn 3d valences and the symmetries throughout the reduction have been determined by comparison with theoretical calculations based on the charge transfer multiplet code. Furthermore, bulk Co 3 O 4 has been reduced under the same conditions to evaluate the effect of TiO 2 as a support on the reducibility of Co oxides. The average Co valence at the various temperatures has been determined from a linear combination of the reference spectra. It was found that the unsupported Co 3 O 4 was easily reduced to Co 0 at 425°C, whereas the Co 3 O 4 supported on TiO 2 catalysts was only reduced to a mixture of CoO and Co 0 , even after 12 h reduction at 425°C. The presence of Mn further retards the reduction of the supported Co 3 O 4 particles. The Mn III ions were easily reduced to MnO at temperatures lower than 300°C, and they remained in this oxidation state even after further temperature increase. In addition, catalytic tests in the Fischer-Tropsch synthesis reaction at a pressure of 1 bar indicate that the selectivity of these catalysts might be related to the extent of Co reduced after the activation treatment (i.e., the reduction with H 2 ).

The oxidation of the Pd(111) surface was studied by in situ XPS during heating and cooling in 0.4 mbar O 2 . The in situ XPS data were complemented by ex situ TPD results. A number of oxygen species and oxidation states of palladium were observed in situ and ex situ. At 430 K, the Pd(111) surface was covered by a 2D oxide and by a supersaturated O ads layer. The supersaturated O ads layer transforms into the Pd 5 O 4 phase upon heating and disappears completely at approximately 470 K. Simultaneously, small clusters of PdO, PdO seeds, are formed. Above 655 K, the bulk PdO phase appears and this phase decomposes completely at 815 K. Decomposition of the bulk oxide is followed by oxygen dissolution in the near-surface region and in the bulk. The oxygen species dissolved in the bulk is more favoured at high temperatures because oxygen cannot accumulate in the near-surface region and diffusion shifts the equilibrium towards the bulk species. The saturation of the bulk "reservoir" with oxygen leads to increasing the uptake of the near-surface region species. Surprisingly, the bulk PdO phase does not form during cooling in 0.4 mbar O 2 , but the Pd 5 O 4 phase appears below 745 K. This is proposed to be due to a kinetic limitation of PdO formation because at high temperature the rate of PdO seed formation is compatible with the rate of decomposition.

Ethylene epoxidation over silver was investigated by combined in-situ X-ray photoelectron spectroscopy (XPS) and proton-transfer reaction mass-spectrometry (PTRMS) at temperatures from 300 to 520 K and in the pressure range from 0.07 to 1 mbar. Ethylene oxide was present among the reaction products at T ≥ 420 K and P ≥ 0.3 mbar. The catalytically active surface contains two oxygen species -nucleophilic and electrophilic oxygen. The observed correlation between the abundance of electrophilic oxygen and the yield of ethylene oxide expressed as C 2 H 4 O partial pressure indicates that namely this oxygen species oxidizes ethylene to ethylene oxide. Opposite trend is observed for nucleophilic oxygen: the higher is the abundance of this species, the lower is the yield of ethylene oxide. This result is in line with the known fact that nucleophilic oxygen due to its oxidic nature is active in total oxidation of ethylene to CO 2 and H 2 O. The low activity of silver at T < 420 K is caused by the presence of carbonates and carbonaceous residues at the silver surface that reduce the available silver surface area for the catalytic reaction. Reduction of the surface area available for the formation of active species due to accumulation of the embedded oxygen species explains also the decrease of the rate of ethylene oxide formation with time observed for T ≥ 470 K.

The oxidation of the Pd(111) surface was studied by in situ XPS during heating and cooling in 3×10 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 O 2 , the oxidised Pd 2+ 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 ( 67 67 × )R12.2° structure.

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The reaction between CH4 and O2 (1:5) was studied by in situ XPS during heating and cooling in a 0.33 mbar reaction mixture. During heating, the reaction rate exhibited an activity maximum at 650 K, whereas no activity maximum was found during the subsequent cooling ramp. This kinetic hysteresis was assigned to the spectroscopically observed difference in the surface oxidation state. During heating, the reaction rate approached the 650 K maximum in the stability range of bulk PdO seeds among the otherwise Pd5O4 2D oxide covered surface. On the other hand, no PdO seeds were formed during cooling, most likely due to kinetic limitations of PdO nucleation on a passivating surface oxide layer containing less oxygen than Pd5O4.