Recent study demonstrated that the performance of α-SnWO4/NiOx photoabsorbers prepared by pulsed laser deposition (PLD) is limited by the interfacial properties; [1] understanding this interface is therefore crucial for further improvement. A thorough α-SnWO4/NiOx interface investigation by means of hard X-ray photoelectron spectroscopy (HAXPES) is presented and correlated with photoelectrochemistry measurements. PLD NiOx introduces strong upwards band bending (~500 meV) at the interface. However, photoemission spectra simulation indicates that at the same time a thin SnO2 layer is formed at the interface. The implications of this SnO2 layer to the interface junction properties and the limited photovoltage will be discussed. [1] Kölbach et al. Chem Mater. 30 (2018) 8322-8331
Local build-up of pH gradients is a major concern in near-neutral photoelectrochemical water splitting since it leads to efficiency losses due to concentration overpotentials. Here, we monitor in-situ pH changes during water splitting in a (photo)electrochemical cell by a fluorescence-based technique and compared with multi-physics simulations. We found that the pH distribution within the cell is affected by natural convection generated by the electrochemical reactions. Based on this observation, we developed a model that considers natural convection driven by buoyancy forces due to local changes in the density of the electrolyte. Only when the buoyancy effect is considered does the model accurately reproduces the measured pH profile. This study reveals the importance of natural convection driven by electrochemical reactions and highlights the implications for designing efficient photoelectrochemical devices.
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