Ag‐ZnO Nanoflowers Enable Highly Selective Photocatalytic Conversion of CH4 to CH3OH at Atmospheric Pressure: Unraveling Reactive Interfaces and Intermediate Control

Abstract At atmospheric pressure, the main challenge in the photocatalytic oxidation of CH 4 to CH 3 OH is to absorb and activate the inert C─H bond while preventing excessive oxidation of CH 3 OH. In this study, metal‐supported ZnO nanoflowers (Ag‐ZnO) are designed to produce abundant active interfacial oxygen sites for CH 4 oxidation at atmospheric pressure, with a CH 3 OH yield reaching 1300 µmol g cat −1 h −1 and the selectivity is 94%. DFT calculation and in situ analysis show that the addition of Ag regulates the electron state density and band center of O, which is beneficial to the adsorption of CH 4 , and decreases the dissociation energy barrier of C─H bond at O L (Lattice oxygen) site. The further selective conversion of ·CH 3 to CH 3 OH involves two different pathways: one pathway consists of the oxidation of ·CH 3 by O L , and the other pathway is the combination of ·CH 3 and ·OH generated from dissolved O 2 (0.28 m m ) in water. Notably, in the photochemical flow device, the yield of CH 3 OH is increased to 5200 µmol g cat −1 h −1 and the selectivity is close to 100%. This work offers valuable insights into reactive interfaces, morphological engineering, and the control of intermediate evolution toward selective conversion of CH 4 to oxygenates at atmospheric pressure.