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A new scanning tunneling microscope reactor used for high-pressure and high-temperature catalysis studies Review of Scientific Instruments 79, 084101 (2008) To enable atomic-scale observations of model catalysts under conditions approaching those used by the chemical industry, we have developed a second generation, high-pressure, high-temperature scanning tunneling microscope (STM): the ReactorSTM. It consists of a compact STM scanner, of which the tip extends into a 0.5 ml reactor flow-cell, that is housed in a ultra-high vacuum (UHV) system. The STM can be operated from UHV to 6 bars and from room temperature up to 600 K. A gas mixing and analysis system optimized for fast response times allows us to directly correlate the surface structure observed by STM with reactivity measurements from a mass spectrometer. The in situ STM experiments can be combined with ex situ UHV sample preparation and analysis techniques, including ion bombardment, thin film deposition, low-energy electron diffraction and x-ray photoelectron spectroscopy.

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The adsorption, decomposition, and oxidation of methanol (CH3OH) has been studied on Ir(111) using temperature-programmed desorption and high-energy resolution fast XPS. Molecular methanol desorption from a methanol-saturated surface at low temperature shows three desorption peaks, around 150 K (α), around 170 K (β1), and around 220 K (β2), respectively. The α peak is assigned to methanol adsorbed on top of the first, chemisorbed layer, whereas β1 and β2 are both assigned to methanol directly coordinated to the metal surface atoms (chemisorbed). The CH3OHad responsible for the β2 desorption peak appears as a separate component in the C 1s core level spectra. A part of the initially adsorbed methanol decomposes into COad and Had around (or even below) 175 K. Intermediate CH x O species of CH3OH decomposition were not observed. The formation of a small amount of CH x ad indicates that (H x )C−O(H) bond scission occurs as well. Temperature-programmed desorption experiments confirm that CH x ad species form, as evidenced by a high-temperature (500 K) H2 formation peak due to decomposition of CHad. The presence of Oad causes a downward shift in the C 1s and O 1s BEs of molecularly adsorbed methanol, but the desorption barrier for molecular methanol desorption is not significantly influenced by the presence of Oad. A stable reaction intermediate, most probably methoxy (CH3Oad), was observed in the presence of Oad, between 160 and 220 K. It is an intermediate in the formation of both formate (HCO2ad) and COad, which occurs around 220 K. Formate decomposes around 350 K into CO2 (g) and Had (which reacts with the remaining oxygen to H2O), whereas the COad reacts with Oad around 400 K.