20.500.12556/RUL-178396 Impact of mass transport on meniscus electrochemistry determined by time-resolved operando X-ray photoelectron spectroscopy Ambient pressure X-ray photoelectron spectroscopy (APXPS) combined with the dip-and-pull method can be used for operando studies of electrochemical systems. A complete coupling between the spectroscopic and the electrochemical measurements is generally challenging due to an inherent difference between the meniscus and the bulk electrolyte – the mass transport. This work investigates meniscus mass transport and its effect on the meniscus electrochemical processes by simultaneously conducting time-resolved APXPS and chronoamperometry for two types of electrochemical processes: capacitive and faradaic. Additionally, experiments are complemented with simulations based on a purposefully constructed transmission line model. In the investigated system, based on a gold electrode and carbonate electrolyte, the meniscus resistance is shown to be over 1000 times larger than the bulk electrolyte resistance. Consequently, during faradaic processes, considerable iR drop in the meniscus results in two to three orders of magnitude slower rate of charge transfer in the meniscus than in the bulk electrolyte. Using the acquired understanding of the meniscus mass transport, we suggest an experimental practice to quantify the iR drop and propose possible remedies for experiments where any impact of the iR drop must be avoided. electrochemistry spectroscopy electrolytes measurements elektrokemija spektroskopija elektroliti meritve true false true Angleški jezik Slovenski jezik Članek v reviji 2026-01-26 13:57:32 2026-01-26 13:57:33 2026-01-27 04:23:10 0000-00-00 00:00:00 2025 0 0 Str. 7456-7466 iss. 14 Vol. 27 2025 0000-00-00 Zaloznikova Objavljeno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 544.5/.6 1463-9084 10.1039/D5CP00168D 232466947 d5cp00168d.pdf d5cp00168d.pdf 1 2F06F755CEB3AFC0646B0EFC947ECE44 05d040c390e24adbab832d1d3fff53a82b3739b5d73e86ccf8f13eb5fe7ec389 e8d9939e-fab6-11f0-a1ba-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=226203 https://pubs.rsc.org/en/content/articlelanding/2025/cp/d5cp00168d 0 df8b4a42-fab6-11f0-a1ba-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=226202 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0