Exceptionally stable sol-immobilization derived Pd/SBA-15 catalysts for methane combustion

Abstract

Pd-Based catalysts are efficient for methane combustion but impractical at high temperatures due to the sintering effect. Herein, we report a thermally stable Pd/SBA-15 catalyst that was prepared by using the sol-immobilization (SI) method, instead of the conventional incipient wetness impregnation (IWI) method. Pd nanoparticles retain the small size of ∼5 nm in the channels of SBA-15 in Pd/SBA-15-SI even after aging at 800 °C in air for 3 days, while those in the Pd/SBA-15-IWI samples aggregate into particles larger than 10 nm over the surface. The thermally stable Pd/SBA-15-SI indeed displays excellent catalytic activity for methane combustion at low temperatures with T₅₀ at ∼300 °C and T₉₀ at ∼350 °C and high stability during cyclic operations, which are much superior to those of the Pd/SBA-15-IWI catalysts. Interestingly, hydrothermal treatment of the Pd/SBA-15-SI catalysts leads to partial re-dispersion of Pd to form smaller particles of ∼1.6 nm, while the catalytic activity decreases a bit. Steam in the reactant mixture has a negative effect on the catalytic activity of Pd/SBA-15-SI catalysts, presumably due to the competitive adsorption of H₂O to O₂/CH₄. Significantly, the size of Pd nanoparticles is essential to the catalytic performance and those having sizes of ∼5 nm are the most active. Finally, the catalytic activity of the catalysts in the presence of CO₂ was studied. This work might be helpful in designing stable metal catalysts using porous materials for reactions under harsh conditions.