The Department of Physics, Stockholm University
Wednesday 22 May
13:00 - 15:00
X-ray Photoelectron Spectroscopy (XPS) provides an element-specific surface sensitive probe of the chemical composition in a system, and is consequently one of the workhorses of surface science and catalysis research. The obtained information on the chemical and physical state of the catalyst and adsorbates is essential in the endeavor to achieve a fundamental understanding how chemical reactions are facilitated by the catalyst. Due to the short mean free path of electrons in gaseous media most of the XPS experiments so far are done in the range between ultra-high vacuum (<10-7 mbar) and near-ambient pressure (1-10 mbar) regimes. For certain reactions, such as the hydrogenation of CO and CO2, higher pressures (comparable to one bar or higher) are needed in order to give a more realistic representation of the system.
This thesis concerns the theoretical background, design, build-up and the first results of an instrument with the goal to bridge the pressure gap between operando conditions at the solid gas interface and surface science model systems. Thanks to a new design of the electron analyzer front cone we have built an instrument where the relevant length scales are reduced to match the electron inelastic mean free path in pressurized atmospheres above one bar. A number of key factors make this possible, but most prominently it is the unique sample environment using a “virtual pressure cell” in combination with a grazing incidence geometry below the critical angle of total reflection. Furthermore, the instrument utilizes hard x-rays to generate high-kinetic energy electrons and thereby increase the mean free path in the pressurized atmosphere. Lastly, the instrument uses a laser-based heating solution which removes the effect of electric and magnetic fields.
With this we have been able to (1) record spectra of Rh above 2 bar of inert atmosphere, as well as with reaction mixtures of CO2 + O2 up to 1 bar and (2) probe surface species and observe temperature dependent chemistry during CO2 hydrogenation during ongoing reactions at 150 mbar.