Role of Iron on the Structure and Stability of Ni3.2Fe/Al2O3 during Dynamic CO2 Methanation for P2X Applications

An energy scenario, mainly based on renewables, requires efficient and flexible Power‐to‐X (P2X) storage technologies, including the methanation of CO2. As active Ni0 surface sites of monometallic nickel‐based catalysts are prone to surface oxidation under hydrogen‐deficient conditions, we investigated iron as “protective” dopant. A combined operando X‐ray absorption spectroscopy and X‐ray diffraction setup with quantitative on‐line product analysis was used to unravel the structure of Ni and Fe in an alloyed Ni−Fe/Al2O3 catalyst during dynamically driven methanation of CO2. We observed that Fe protects Ni from oxidation and is itself more dynamic in the oxidation and reduction process. Hence, such “sacrificial” or “protective” dopants added in order to preserve the catalytic activity under dynamic reaction conditions may not only be of high relevance with respect to fine‐tuning of catalysts for future industrial P2X applications but certainly also of general interest. Iron as protective hero: In an energy scenario based on renewables, new and efficient storage technologies, such as Power‐to‐Gas (PtG) are needed. However, monometallic Ni catalysts are highly sensitive to dynamic reaction conditions, as present in Power‐to‐X applications. In this operando study we investigated the deactivation of a Ni‐based catalyst and unraveled the protective role of “sacrificial” iron in a Ni3.2Fe catalyst during dynamic methanation of CO2.