Mechanistic in situ insights into the formation, structural and catalytic aspects of the La2NiO4 intermediate phase in the dry reforming of methane over Ni-based perovskite catalysts

We focus on the stability and bulk/surface structural properties of the Ruddlesden-Popper phase La2NiO4 and their consequences for dry reforming of methane (DRM) activity. Fuelled by the appearance as a crucial intermediate during in situ decomposition of highly DRM-active LaNiO3 perovskite structures, we show that La2NiO4 can be equally in situ decomposed into a Ni/La2O3 phase offering CO2 capture and release necessary for DRM activity, albeit at much higher temperatures compared to LaNiO3. Decomposition in hydrogen also leads to an active Ni/La2O3 phase. In situ X-ray diffraction during DRM operation reveals considerable coking and encapsulation of exsolved Ni, yielding much smaller Ni crystallites compared to on LaNiO3, where coking is virtually absent. Generalizing the importance of intermediate Ruddlesden-Popper phases, the in situ decomposition of Labased perovskite structures yields several obstacles due to the high stability of both the parent perovskite and the Ruddlesden-Popper structures and the occurrence of parasitic structures.

Automated summary

This study focuses on the stability and structural properties of La2NiO4 and its impact on dry reforming of methane (DRM) activity. It shows that La2NiO4 can decompose into a Ni/La2O3 phase providing necessary CO2 capture and release for DRM, though at higher temperatures compared to LaNiO3. The decomposition products cause coking and encapsulation of exsolved Ni during DRM operation, resulting in much smaller Ni crystallites.