Nickel oxide-based catalysts currently represent the state of the art in electrochemical water oxidation in alkaline pH. However, much of their functionality remains poorly understood, particularly regarding catalytically active sites...

The interaction between (001) n-Si and NiO x was investigated with regard to the oxygen evolution reaction (OER), applicable either for water splitting or CO 2 reduction. Thin layers of nickel oxide were deposited step by step by reactive sputter deposition and analyzed in-situ after each step using X-ray photoelectron spectroscopy (XPS). This was performed for silicon with different surface preparations: H-termination, thermally grown oxide (2 Å) and a monolayer of native oxide (4 Å). Upon contact formation the initial flatband like situation in the Si substrates changed to a 0.35 to 0.4 eV upward band bending for all three heterojunctions, with an alignment of the valence bands favorable to hole extraction. With near identical heterojunction performance and identical NiO x catalyst layers (η(10 mA/cm 2 ) = 0.44 ± 0.01 V vs. RHE on Ni) an equally identical performance for the OER would be expected. While the native oxide covered sample shows the expected performance in cyclic voltammetry measurements the others fall short of expectations. Using chopped light measurements, this under-performance could be attributed to a higher density of defect states at the silicon surface. Apparently a 4Å SiO 2 layer is sufficient protection to prevent the formation of defect states during NiO x deposition, thinner protective layers or none at all result in increased defect states, while thicker layers perform poorly due to their high resistance. Direct photoelectrochemical devices are an exciting approach to the storage of renewable energies. Depending on the preferred energy cycle they can be used either for water splitting or CO 2 reduction, in the end it is only a question of the employed catalysts and necessary overpotentials. A direct photoelectrochemical device has two main functional parts, which do not necessarily have to be physically separate. First, there is the photoabsorber, basically a solar cell, who has to supply the necessary photovolage U ph and photocurrent J ph to power the desired redox reaction. Second, the catalytic surface, which is in direct contact with the electrolyte and should be catalytically active, thus allowing high current densities at low overpotentials η. In an ideal case the total device performance should be a result of those two contributions only.Initial research on water splitting was focused on a single semiconducting material performing well in both functions. This was first demonstrated on a TiO 2 electrode by Fujishima and Honda in 1972. 1 In such a device the photoabsorber functionality is defined by the interface junction between semiconductor and electrolyte. Investigated materials were mostly wide bandgap materials, as they could, in theory, provide the necessary U ph .However, the double function of the semiconductor electrolyte interface makes an evaluation of such devices difficult, as it is hard to determine whether a lack of performance is a result from poor current voltage (IE) behavior of the junction or the poor catalytic performance of the material. Furthermore, t...

Water photolysis is a key technology to convert solar energy into clean, sustainable fuel. Hematite Fe2O3 thin films are considered as a potential photoanode for this purpose. The performance of hematite‐based devices is limited by charge carrier transport and recombination, which are intimately linked to the electronic structure. Investigations of the electronic structure of hematite by photoemission exhibit pronounced differences in the reported spectra. A combination of structural and spectroscopic characterization methods is used to unravel the relation between the crystalline and the electronic structure of hematite thin films, which provides unique fingerprint spectra for different crystalline states. The combination with valence band DOS calculations from literature allows for an assignment of the contribution of iron and oxygen (hybrid‐) states to the valence band DOS.

Landfill leachate pretreated in an aerobic biological stage was studied with respect to the adsorption behaviour of its organic components with and without preoxidation by different amounts of ozone. Isotherm data evaluated by adsorption analysis showed that the fractions of non-adsorbable and weakly adsorbable species had been increased after preoxidation. As a result, the carbon capacity in a fixed-bed adsorption process was expected to be significantly lower for preoxidized leachate. This conclusion was confirmed by data from column experiments. The breakthrough curves under operating conditions typical for leachate treatment could be predicted quite well by the homogeneous surface diffusion model when no preoxidation was applied. After preozonation about 40% of the remaining organic substances were biodegradable. Data evaluation revealed that biodegradation took place inside the activated carbon beds. Therefore the total removal of ozonated leachate in activated carbon columns will be higher than the removal due to adsorption processes. An economic analysis must show in any practical case whether a combination of preoxidation and adsorption will be more cost-efficient than either of the single processes. The modelling technique applied in this study can be a useful tool for that purpose.

Figure 6 on page H3126 should appear as