Photoemission from Liquid Aqueous Solutions

Heterogeneous chemical reactions at vapor/solid interfaces play an important role in many processes in the environment and technology. Ambient pressure X-ray photoelectron spectroscopy (APXPS) is a valuable tool to investigate the elemental composition and chemical specificity of surfaces and adsorbates on the molecular scale at pressures of up to 130 mbar. In this review we summarize the historical development of APXPS since its introduction over forty years ago, discuss different approaches to minimize scattering of electrons by gas molecules, and give a comprehensive overview about the experimental systems (vapor/solid interfaces) that have been studied so far. We also present several examples for the application of APXPS to environmental science, heterogeneous catalysis, and electrochemistry.

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Investigation of solid/vapor interfaces using ambient pressure X-ray photoelectron spectroscopy

Molecular beam experiments on model catalysts

During the past decade, the application of ambient pressure photoemission spectroscopy (APPES) has been recognized as an important in situ tool to study environmental and materials science, energy related science, and many other fields. Several APPES endstations are currently under planning or development at the USA and international light sources, which will lead to a rapid expansion of this technique. The present work describes the design and performance of a new APPES instrument at the Advanced Light Source beamline 9.3.2 at Lawrence Berkeley National Laboratory. This new instrument, Scienta R4000 HiPP, is a result of collaboration between Advanced Light Source and its industrial partner VG-Scienta. The R4000 HiPP provides superior electron transmission as well as spectromicroscopy modes with 16 μm spatial resolution in one dimension and angle-resolved modes with simulated 0.5° angular resolution at 24° acceptance. Under maximum transmission mode, the electron detection efficiency is more than an order...

New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2

Photoelectron Spectroscopy of Ionic Liquid-Based Interfaces

The kinetics of the adsorption system CO/Pt(111) has been studied by time-resolved high-resolution x-ray photoelectron spectroscopy using third generation synchrotron radiation at BESSY II. CO is dosed by a supersonic molecular beam device which allows for a high sample pressure (here up to 10−6 mbar) and a fast switching of the pressure. The site-specific occupation of CO adsorbed on on-top and bridge sites is determined quantitatively from C 1s spectra, which can be taken with a minimum collection time of 1.5 s per spectrum. Based on the observation of thermal equilibrium between the two sites, we perform a phenomenological analysis of the data, assuming a constant binding energy difference ΔE. From the on-top/bridge occupation ratio as a function of coverage obtained by uptake measurements we extract a value of ΔE=41 meV. With the same ansatz, ΔE is calculated from temperature-dependent measurements at a constant coverage. Finally, determination of the coverage during isothermal desorption is used to o...

Kinetic parameters of CO adsorbed on Pt(111) studied by in situ high resolution x-ray photoelectron spectroscopy

In an effort to extend the pressure range for electron-based spectroscopies from ultrahigh vacuum into the so-called pressure gap region, we have built a new apparatus for in situ x-ray photoelectron spectroscopy up to 1mbar. The principle of the experimental setup is based on a modified hemispherical electron energy analyzer, a modified twin anode x-ray source, and several differential-pumping stages between sample region and electron detection. The reaction gas is provided in situ either by background dosing or, as a new feature, by beam dosing, using a directed gas beam from a small tube. The latter allows for higher local pressures. The performance of the new setup is discussed, deriving normalization procedures from the analysis of the attenuation of the substrate photoemission intensity by the increasing gas phase pressure. In addition, the change of the work function due to changes in surface composition can be evaluated in situ by analyzing the binding energy shift of the gas phase core-level peak...

J. Pantförder

Papers

Kinetic parameters of CO adsorbed on Pt(111) studied by in situ high resolution x-ray photoelectron spectroscopy

New setup for in situ x-ray photoelectron spectroscopy from ultrahigh vacuum to 1 mbar

Growth and electronic properties of thin Zn layers on Cu(111)

Formation of a new type of chromium oxide by deposition of chromium onto water precovered Cu(111)