Highly Active and Stable Pd/MgAl₂O₄ Catalysts for Methane Catalytic Combustion

Mesoporous MgAl 2 O 4 is synthesized via a novel sol–gel combustion method and the concentration of oxygen defects on the surface is modulated through varying the calcination temperature (850, 900, 1000, and 1100 °C). Notably, the 1Pd/MgAl 2 O 4 ‐1000 catalyst exhibits superior catalytic activity and stability. The turnover frequency (TOF) for 1Pd/MgAl 2 O 4 ‐1000 is 0.079 and 0.058 s −1 under dry conditions (300 °C) and wet conditions (380 °C), respectively. The results of H 2 temperature‐programmed reduction and X‐Ray photoelectron spectroscopy reveal that the principal active species within the Pd/MgAl 2 O 4 ‐y catalyst is PdO. Specifically, the Pd–MgAl 2 O 4 ‐1000 catalyst exhibits the lowest temperature reduction peak (120 °C) and the highest redox capability. Additionally, O 2 temperature‐programmed oxidation further elucidates that PdO x species in the Pd/MgAl 2 O 4 ‐1000 catalyst is prone to decomposition and the resultant palladium metal is readily reoxidized. Consequently, the rapidity of the redox cycle between PdO and Pd 0 emerges as a pivotal factor in CH 4 catalytic combustion. Furthermore, a correlation analysis among catalyst particle size, oxygen defect concentration, and TOF is conducted. The findings illustrate a distinct volcano‐shaped curve in the relationship between oxygen defect concentration and TOF for the 1Pd/MgAl 2 O 4 −y catalysts. A comparable trend is also evident in the correlation between Pd particle size and TOF.