Engineering the Quaternary Hydrotalcite-Derived Ce-Promoted Ni-Based Catalysts for Enhanced Low-Temperature CO₂ Hydrogenation into Methane

Ce-promoted NiMgAl mixed-oxide (NiCex-C, x = 0, 1, 5, 10) catalysts were prepared from the quaternary hydrotalcite precursors for CO₂ hydrogenation to methane. By engineering the Ce contents, NiCe5-C showed its prior catalytic performance in low-temperature CO₂ hydrogenation, being about three times higher than that of the Ce-free NiCe0-C catalyst (turnover frequency of NiCe5-C and NiCe0-C: 11.9 h^-1 vs. 3.9 h^-1 @ 225 °C). With extensive characterization, it was found that Ce dopants promoted the reduction of NiO by adjusting the interaction between Ni and Mg(Ce)AlOx support. The highest ratio of surface Ni⁰/(Ni²⁺ + Ni⁰) was obtained over NiCe5-C. Meanwhile, the surface basicity was tailored with Ce dopants. The strongest medium-strength basicity and highest capacity of CO₂ adsorption was achieved on NiCe5-C with 5 wt.% Ce content. The TOF tests indicated a good correlation with medium-strength basicity over the NiCex-C samples. The results showed that the high medium-strength and Ce-promoted surface Ni⁰ species endows the enhanced low-temperature catalytic performance in CO₂ hydrogenation to methane.