Photocatalytic Acetic Acid Production with High Selectivity from Conversion of CH 4 and CO Under Mild Conditions

Abstract Solar‐driven direct carbonylation of CH 4 to value‐added C 2 chemicals, such as acetic acid (CH 3 COOH), offers a promising pathway toward carbon neutrality under mild conditions, but the performance is largely impeded by the ineffective activation of C─H bond and limited control over CH 3 ‒CO coupling. Here, we report that through rational surface decoration of Pd nanoparticles (NPs) and oxygen vacancy (V O ), selective photocatalytic CH 3 COOH production is realized on WO 3 nanosheets from co‐conversion of CH 4 and CO at room temperature and ambient pressure. Under light irradiation, the optimal Pd/V O ‐WO 3 photocatalyst exhibits efficient CH 3 COOH production with a yield rate of 52.7 µmol g −1 h −1 and a selectivity of 63.7% in the presence of H 2 O 2 oxidant. Combined in situ spectroscopies and computational calculations reveal that V O serves as the active site for CH 4 adsorption, while Pd NPs facilitates the activation of H 2 O 2 into ·OH radicals to promote CH 4 dissociation to * CH 3 intermediate, thus leading to subsequent CH 3 ‒CO coupling for CH 3 COOH production over Pd/V O ‐WO 3 . This work paves a new path into photocatalytic CH 4 carbonylation to targeted C 2+ products under mild conditions via synergistic active sites.