Highly Efficient and Stable Methane Dry Reforming Enabled by a Single-Site Cationic Ni Catalyst

Zeolite-supported nickel (Ni) catalysts have been extensively studied for the dry reforming of methane (DRM). It is generally believed that prior to or during the reaction, Ni is reduced to a metallic state to act as the catalytic site. Here, we employed a ligand-protected synthesis method to achieve a high degree of Ni incorporation into the framework of the MFI zeolite. The incorporated Ni species retained their cationic nature during the DRM reaction carried out at 600 °C, exhibiting higher apparent catalytic activity and significantly greater catalytic stability in comparison to supported metallic Ni particles at the same loading. From theoretical and experimental evidence, we conclude that the incorporation of Ni into the zeolite framework leads to the formation of metal-oxygen (Ni^δ+-O^(2-ξ)-) pairs, which serve as catalytic active sites, promoting the dissociation of C-H bonds in CH₄ through a mechanism distinct from that of metallic Ni. The conversion of CH₄ on cationic Ni single sites follows the CH oxidation pathway, which is characterized by the rapid transformation of partial cracking intermediates CH^*, effectively inhibiting coke formation. The presence of the CH oxidation pathway was experimentally validated by identifying the reaction intermediates. These new mechanistic insights elucidate the exceptional performance of the developed Ni-MFI catalyst and offer guidance for designing more efficient and stable Ni-based DRM catalysts.