Exsolution of Metallic Cobalt in Co/CoCr ₂ O ₄ for Enhanced Anti‐Coking via CH _x O‐Mediated Pathway in CH ₄ Dry Reforming

ABSTRACT The dry reforming of methane (DRM) offers a compelling method to transform greenhouse gases into valuable syngas. However, the deactivation of DRM catalysts remains a significant challenge. Herein, we report a Co/CoCr 2 O 4 spinel composite in which metallic Co are ex‐solved in situ, generating highly active and durable metal–oxide interfaces, which delivers high CH 4 (∼65.2%) and CO 2 (∼75.1%) conversion at 300 000 mL·g cat −1 ·h −1 (GHSV) and CH 4 reaction rate of ∼762 µmol·g cat −1 ·s −1 for DRM reaction. The obtained catalyst was stable at 650°C with only 1.30 wt% coke produced. Impressively, the superior H 2 /CO ratio of 0.84 proved the high selectivity of Co/CoCr 2 O 4 , revealed that the undesired side reactions, such as RWGS reaction was weakened. The exsolved cobalt particles were embedded into CoCr 2 O 4 and created unique Co─O─Cr interface, which was the inherent active center for CH 4 activation. The metal‐oxide interface facilitated CH x * to CH x O* pathway, suppressing methane deep dissociation as well as coke formation.