Grafting Nanolayers of Ni and Co Catalysts Around the Edges of Hierarchical Zeolite 13X by Leveraging the Crystal's Defects for CO₂ Methanation

Abstract

Catalytic CO₂ methanation offers a sustainable approach to convert waste CO₂ into high-value methane (CH₄). However, designing highly efficient and stable catalysts that operate under harsh conditions remains a significant challenge. The interaction between the active metal and the support material (MSI) plays a critical role in determining the activity and stability of the catalyst. Here, we report the tailoring of MSI by regioselective anchoring of Ni and Co around the edges of hierarchical porous zeolite 13X (h13X), leveraging crystal defects modulated by amine and silanol groups. Scanning transmission electron microscopy and electron energy loss spectroscopy analysis confirmed the growth of approximately 3-nm thick nanolayers of Ni and Co around the edges of h13X crystals. The XPS and H₂-TPR analysis of the catalysts revealed shifts in binding energies and reduced H₂ consumption, corroborating stronger MSI and electronic interaction between Ni and Co. The optimized catalyst (AF-7.5NiCo/h13X) exhibited a maximum CO₂ conversion of 74.4% with a CH₄ selectivity of 98% at 20 bar and 400°C under a GHSV of 60,000 mL g_cat^-1 h^-1 and an activation energy of 55 kJ mol^-1. More importantly, the catalyst demonstrated stability, with consistent CO₂ conversion performance over a month, showing no discernible decrease. The enhanced and stable performance of the catalyst is attributed to the stronger MSI and the sub-5-nm thin layers of Ni and Co over h13X.

Keywords

CO₂ conversion / crystal defects / hierarchical zeolite / metal–support interaction / nickel nanolayers

References

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