Photo-electro-chemical (PEC) water splitting represents a promising technology towards an artificial photosynthetic device but many fundamental electronic processes, which govern long-term stability and energetics are not well understood. X-ray absorption spectroscopy (XAS), particularly its high energy resolution fluorescence-detected (HERFD) mode, emerges as a powerful tool to study photo-excited charge carrier behavior under operating conditions. The established thin film device architecture of PEC cells provides a well-defined measurement geometry, but it puts many constraints on conducting operando XAS experiments. So far, operando cells have not been developed that enable to concurrently measure highly intense X-ray fluorescence and photo-electro-chemical current without experimental artifacts caused by O<sub>2</sub> and H<sub>2</sub> bubbles formation. Moreover, we are missing a standardized thin film exchange procedure. Here, we address and overcome the instrumental limitations for operando HERFD-XAS to investigate photo- and electrochemical thin film devices. Our cell establishes a measurement routine that will provide experimental access to a broader scientific community, particularly due to the ease of sample exchange. Our operando photo-electro-chemical cell is optimized for the HERFD-XAS geometry and we demonstrate its operation by collecting high-resolution Fe K-edge spectra of hematite (α-Fe<sub>2</sub>O<sub>3</sub>) and ferrite thin film (MFe<sub>2</sub>O<sub>4</sub>, M= Zn, Ni) photoelectrodes during water oxidation.<br>
Construction of Artificial Photosynthetic Cell
