Methodological insights into the dip-and-pull X-ray photoelectron spectroscopy technique: analysing electrochemical interfaces under <i>in situ/operando</i> conditions

Gaining insight into structural and compositional transformations occurring at the electrode/electrolyte interface during the operation of electrochemical systems is fundamental to understanding and, thus, optimizing their performance. Such an analysis must be performed in operando conditions, owing to the potential, electrolyte and time dependence of these transformations. Here, the use of X-ray photoelectron spectroscopy (XPS) is particularly attractive due to its surface sensitivity and ability to provide quantitative information on the oxidation state and chemical environment of an element. In specific instrumental configurations [e.g. in `dip-and-pull' (D&P) or `meniscus' setup], it can be used to analyse not only the electrode but also the electrolyte side of the interface, under in situ/operando conditions. In this article, we discuss how D&P XPS can provide unique information on both sides of the electrode/electrolyte interface, briefly review publications demonstrating its capabilities, highlight the challenges the method faces, and share our views on its future developments. This article aims to provide a practical guide to new D&P synchrotron users and help them to understand the technique, and physical phenomena that may impede the acquisition of reliable data.