Bimetallic <scp>MIL</scp> ‐68 for methane selective oxidation: Trade‐off photon utilization and radical generation

Abstract Methane selective oxidation was regarded as the “Holy Grail” reaction in C 1 chemistry but remained limited by low yield and selectivity. Here, we reported an indium‐iron bimetallic catalyst (In x Fe y ) with tunable In/Fe ratios for efficient oxidation of methane to methanol. Quenching experiments revealed that photogenerated holes derived CH 4 activation, ·OOH coupled with ·CH 3 to form CH 3 OH whereas ·OH caused overoxidation. Photoelectric testing indicated that Fe 3+ incorporation increased surface electron density and Fe 3+ centers, enhancing light absorption, charge separation, and ·CH 3 /·OOH generation. Excessive Fe 3+ shifted the HOMO positively and favored ·OH formation. In 0.6 Fe 0.4 achieved an optimal balance between ·CH 3 /·OOH generation and ·OH suppression, reaching the highest yield and selectivity (52.2 μmol·g −1 ·h −1 , 94.3%). This work highlighted reactive species regulation and band‐structure design, and provided a guideline for designing photothermal catalysts for methane selective oxidation to future demands.