A high-pressure x-ray photoelectron spectroscopy instrument for studies of industrially relevant catalytic reactions at pressures of several bars

Abstract

We present a new high-pressure x-ray photoelectron spectroscopy system dedicated to probing catalytic reactions under realistic conditions at pressures of multiple bars. The instrument builds around the novel concept of a “virtual cell” in which a gas flow onto the sample surface creates a localized high-pressure pillow. This allows the instrument to be operated with a low pressure of a few millibar in the main chamber, while simultaneously a local pressure exceeding 1 bar can be supplied at the sample surface. Synchrotron based hard x-ray excitation is used to increase the electron mean free path in the gas region between sample and analyzer while grazing incidence <5° close to total external refection conditions enhances surface sensitivity. The aperture separating the high-pressure region from the differential pumping of the electron spectrometer consists of multiple, evenly spaced, micrometer sized holes matching the footprint of the x-ray beam on the sample. The resulting signal is highly dependent on the sample-to-aperture distance because photoemitted electrons are subject to strong scattering in the gas phase. Therefore, high precision control of the sample-to-aperture distance is crucial. A fully integrated manipulator allows for sample movement with step sizes of 10 nm between 0 and −5 mm with very low vibrational amplitude and also for sample heating up to 500 °C under reaction conditions. We demonstrate the performance of this novel instrument with bulk 2p spectra of a copper single crystal at He pressures of up to 2.5 bars and C1s spectra measured in gas mixtures of CO + H2 at pressures of up to 790 mbar. The capability to detect emitted photoelectrons at several bars opens the prospect for studies of catalytic reactions under industrially relevant operando conditions.We present a new high-pressure x-ray photoelectron spectroscopy system dedicated to probing catalytic reactions under realistic conditions at pressures of multiple bars. The instrument builds around the novel concept of a “virtual cell” in which a gas flow onto the sample surface creates a localized high-pressure pillow. This allows the instrument to be operated with a low pressure of a few millibar in the main chamber, while simultaneously a local pressure exceeding 1 bar can be supplied at the sample surface. Synchrotron based hard x-ray excitation is used to increase the electron mean free path in the gas region between sample and analyzer while grazing incidence <5° close to total external refection conditions enhances surface sensitivity. The aperture separating the high-pressure region from the differential pumping of the electron spectrometer consists of multiple, evenly spaced, micrometer sized holes matching the footprint of the x-ray beam on the sample. The resulting signal is highly dependent o...