Potential‐Induced Spin Changes in Fe/N/C Electrocatalysts Assessed by In Situ X‐ray Emission Spectroscopy
Viktoriia A. Saveleva, Kathrin Ebner, Lingmei Ni, Grigory Smolentsev, Daniel Klose, Andrea Zitolo, Elena Marelli, Jingkun Li, M. Medarde, Оlga V. Safonova, Maarten Nachtegaal, Frédéric Jaouen, Ulrike I. Kramm, Thomas J. Schmidt, Juan Herranz
Abstract
Abstract The commercial success of the electrochemical energy conversion technologies required for the decarbonization of the energy sector requires the replacement of the noble metal‐based electrocatalysts currently used in (co‐)electrolyzers and fuel cells with inexpensive, platinum‐group metal‐free analogs. Among these, Fe/N/C‐type catalysts display promising performances for the reduction of O 2 or CO 2 , but their insufficient activity and stability jeopardize their implementation in such devices. To circumvent these issues, a better understanding of the local geometric and electronic structure of their catalytic active sites under reaction conditions is needed. Herein we shed light on the electronic structure of the molecular sites in two Fe/N/C catalysts by probing their average spin state with X‐ray emission spectroscopy (XES). Chiefly, our in situ XES measurements reveal for the first time the existence of reversible, potential‐induced spin state changes in these materials.