Lanthanum-Modified MCF-Derived Nickel Phyllosilicate Catalyst for Enhanced CO₂ Methanation: A Comprehensive Study

For the traditional preparation method, it is challenging to fabricate a supported nickel catalyst with fine size at high loading. In this work, a group of La-modified mesostructured cellular foam (MCF)-derived nickel phyllosilicates was designed and synthetized by a hydrothermal method followed by an impregnation-modification of La₂O₃, whose Ni contents varied from 25.3 to 32.2 wt %. Both the special property of phyllosilicate and the addition of a La₂O₃ modifier played significant roles in achieving high Ni dispersion and excellent catalytic performance. The formed nickel phyllosilicate was beneficial to obtain small Ni nanoparticles (<5 nm) due to its strong metal-support interaction and high specific surface area; the addition of the La₂O₃ modifier could further reduce the Ni particle size and decrease the reduction difficulty of the fabricated samples. On the contrary, a large Ni particle size of 13.0 nm was observed on the impregnated Ni/MCF (N/M-Im) catalyst with a Ni content of 31.7 wt %. As a result, the nickel phyllosilicate catalyst showed higher catalytic activity than the impregnated one, and the La modifier could further improve the catalytic activity especially at low temperature (<400 °C). Among all catalysts, the modified phyllosilicate catalyst N/M-P-32-5L with 180 °C-32 h-hydrothermal treatment and La₂O₃ content of 5 wt % was the best owing to its small-sized Ni particles, high H₂ and CO₂ chemisorption capacity, large turnover frequency (TOF) value, and low activation energy of 69.83 kJ mol^-1. In addition, the intermediates of formate and CO were detected through in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis. In a 100 h-lifetime test under harsh conditions and 600 °C-steam treatment, N/M-P-32-5L showed both high sintering resistance of Ni particles and high thermal stability without the collapse of pores as well as decrease of catalytic activity, which was attributed to the special physical and chemical properties of MCF-derived nickel phyllosilicate, strong metal-support interaction over the catalyst, and the promotion of the La₂O₃ modifier.