Comparative Study of Ce-MOF-Derived Mesoporous CeO ₂ Architectures for Enhanced CO ₂ Methanation over Ni/CeO ₂ Catalysts

Metal–organic frameworks (MOFs) are promising precursors for constructing high-performance catalysts due to their ordered porous architectures, high surface areas, and tunable compositions. In this work, mesoporous CeO 2 supports derived from Ce-BTC, Ce-UiO-66, and Ce-BDC were prepared and used to construct 10 wt % Ni/CeO 2 catalysts for CO 2 methanation. The catalysts were characterized by XRD, SEM, TEM, XPS, H 2 -TPR, CO 2 -TPD, and in situ DRIFTS to investigate their structural properties, redox behavior, and reaction mechanism. Compared with the commercial CeO 2 -supported catalyst (10Ni/CeO 2 –C), the Ce-MOF-derived mesoporous CeO 2 -supported catalysts exhibited significantly enhanced performance. At 330 °C, the CO 2 conversions over 10Ni/CeO 2 –BTC, 10Ni/CeO 2 –BDC, and 10Ni/CeO 2 –UiO-66 reached 86.0%, 85.3%, and 82.8%, respectively, substantially higher than that of 10Ni/CeO 2 –C (57.0%). The corresponding CH 4 selectivity reached 99.8%, 99.8%, and 99.7%, respectively, also superior to that of 10Ni/CeO 2 –C (98.7%). The superior activity was attributed to the inherited mesoporous framework, enlarged specific surface area, and strengthened metal–support interaction, which collectively promoted Ni dispersion, CO 2 adsorption/activation, and H 2 dissociation. The in situ DRIFTS results indicated that CO 2 methanation over these catalysts predominantly proceeded via a formate-mediated pathway. These findings provided new insights into the rational design of high-performance Ni-based catalysts for CO 2 methanation.