Metal/n-pyrite (metal=Pt, Au, Nb) Schottky barrier type diodes were fabricated on electrochemically reduced either synthetic or natural (100) and (111) surfaces of single crystalline n-FeS2. The temperature dependence of I-V curves in darkness were analyzed in the range of 200–350 K on the basis of thermionic emission and recombination models. The calculated effective barrier height was ∼0.60 eV and the activation energy for recombination ∼0.50 eV for all investigated n-FeS2/Pt samples. The doping density and the extrapolated potential (pseudo flatband situation) from the Mott–Schottky plot, obtained from capacities deduced from potentiostatic complex impedance measurements, were 2.0×1016 cm−3 and 0.25 eV vs Pt for the synthetic n-pyrite crystal, respectively. From the donor density and barrier height a band bending of 0.5 eV was deduced. Photovoltaic parameters like open-circuit photovoltage and short-circuit photocurrent were studied down to temperatures of 200 K. The main phenomenon preventing the generation of a photopotential approaching the band bending (0.50 eV) appears to be the pinning of the Fermi-level by recombination centers located in the middle of the band gap (Eg=0.95 eV) of pyrite.

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A new inlet system for the application of the differential electrochemical mass spectroscopy to massive electrodes is presented. The main advantage of our electrochemical cell is the free access of the massive electrode surface, which allows a homogeneous illumination of the electrode/electrolyte interface as well as measurements in the presence of strong gas evolution (high current densities). Because the cell is directly connected to the high-vacuum chamber of the mass spectrometer unit, a good sensitivity is achieved with a relatively simple experimental setup. As an example for a photoelectrochemical system, p-InP(111) single crystals were investigated in the dark and under illumination during cathodic scans in 0.5 M H2S04. Simultaneous to the hydrogen evolution, a photocorrosion can be observed via the mass signal of phosphine (PH3). Energy dispersed analysis of X-ray fluorescence and scanning electron microscopy measurements reveal the formation of metallic indium sites at the electrode surface due to the corrosion process. It is shown that the electrodeposition of platinum onto the surface of a bare p-InP(1 11) electrode leads to a catalytically enhanced hydrogen evolution whereas the corrosion process is drastically suppressed.

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The evolution of oxygen in acid aqueous solution on thin porous titanium dioxide (anatase) electrodes under illumination was monitored with DEMS. By adding Cl− in the electrolyte, a Cl2 mass signal is additionally observed. This latter increases as a function of Cl− concentration while O2 mass signal decreases, although the photocurrent‐potential characteristics remain unchanged. This example illustrates a competitive oxidation which cannot be discriminated by only recording photocurrent‐potential curves.

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The Chevrel type chalcogenide with the stoichiometry Mo6.,M,Xs (M=transition metal, e.g., M,=Ru2; X=Chalcogene atom, e.g., S, Se) containing octahedral mixed-metal clusters of transition-metal atoms was investigated with respect to the oxygen reduction process in an in situ electrochemical enviroment via the EXAFS technique. The spectra analysis on Ru and MO edges as a function of applied electrode potential revealed that ruthenium centers were preferentially modified by the presence of oxygen in the electrolyte. The variation in distance between Ru-(Ru, MO) was more sensitive in oxygen saturated solution as compared to MO-(Ru, MO) and RuSe .