Constructing Bimetallic Photoredox Sites to Synergistically Modulate Carbon‐Oxygen Intermediate Species Toward Efficient Methanol Synthesis from Methane

ABSTRACT Selective photocatalytic methane (CH 4 ) conversion into high‐value liquid methanol (CH 3 OH) using O 2 in aqueous media under mild conditions offers a promising sustainable route for chemical manufacturing. However, in previous catalytic systems, inadequately engineered catalytic sites impede the precise regulation of reactive carbon‐oxygen intermediate formation, which triggers undesired overoxidation by‐products and severely restricts both the activity and selectivity of CH 4 transformation. Herein, a facile bimetallic photoredox site design strategy is reported to construct TiO 2 photocatalysts co‐modified with palladium nanoparticles (Pd NPs) and iron oxide sub‐nanoclusters (FeO x SCs) for the highly active (5.25 times that of pristine TiO 2 ) and selective (78.60%) transformation of CH 4 to CH 3 OH. Mechanistic studies demonstrate that uniformly dispersed FeO x facilitates CH 4 adsorption and oxidation to efficiently generate CH 3 * intermediates, while the adjacent Pd precisely steers O 2 into a side‐on adsorption configuration, promoting its reduction toward methanol‐productive hydroxyl radicals (•OH). Benefiting from the interfacial synergy between bimetallic redox sites, key carbon‐oxygen intermediates are directionally and precisely generated and then efficiently coupled, achieving selective CH 4 ‐to‐CH 3 OH transformation. This work highlights the substantial potential of rationally designing bimetallic photoredox sites to selectively modulate intermediates in photoredox half‐reactions for sustainable photochemical synthesis.