X-ray spectroscopy methods can be used for genuine operando analyses of catalysts and other functional materials. The redox dynamics of sulfur with Ni/GDC anode during solid oxide fuel cell (SOFC) operation at mid- and low-range temperatures in an operando S K-edge XANES have been studied. Ni is a typical catalyst material for the anode in high temperature SOFCs.
The operando spectro-electrochemical cell for this high temperature gas-solid reaction study under electrochemical conditions was based on a typical high temperature heterogeneous catalysis cell, which was further equipped with electric terminals.
Very early method development for operando studies on PEM-FC fuel cells was done by Haubold et al. at Forschungszentrum Jülich and HASYLAB. Specifically they developed plexiglas spectro-electrochemical cells for XANES, EXAFS and SAXS and ASAXS studies with control of the electrochemical potential of the fuel cell. Under operation of the fuel cell they determined the change of the particle size of and oxidation state and shell formation of the platinum electrocatalyst. In contrast to the SOFC operation conditions, this was a PEM-FC study in liquid environment under ambient temperature.
The same operando method is applied to battery research and yields information on the changes of the oxidation state of electrochemically active elements in a cathode such as Mn via XANES, information on coronation shell and bond length via EXAFS, and information on microstructure changes during battery operation via ASAXS. Since lithium ion batteries are intercalation batteries, information on the chemistry and electronic structure going on in the bulk during operation are of interest. For this, soft x-ray information can be obtained using hard X-ray Raman scattering.
Fixed energy methods (FEXRAV) have been developed and applied to the study of the catalytic cycle for the oxygen evolution reaction on iridium oxide. FEXRAV consists of recording the absorption coefficient at a fixed energy while varying at will the electrode potential in an electrochemical cell during the course of an electrochemical reaction. It allows to obtain a rapid screening of several systems under different experimental conditions (e.g., nature of the electrolyte, potential window), preliminary to deeper XAS experiments.
The soft X-Ray regime (i.e. with photon energy < 1000 eV) can be profitably used for investigating heterogeneous solid-gas reaction. In this case, it is proved that XAS can be sensitive both to the gas phase and to the solid surface states.