Synergetic Atom‐Island and Metal Alloy Triggering Tandem Reaction for CH ₄ Photooxidation to CH ₃ OH

Abstract CH ₃ OH is the most desired product of photocatalytic CH ₄ conversion. The prominent metal‐decorated photocatalyst is challenging in both high yield and selectivity for CH ₃ OH products due to over‐oxidation by •OH mechanism. Here, interstitial Zn is fabricated into Zn _i O to induce the formation of Zn atom island for rapid single electron reduction of O ₂ into •OOH instead of •OH for the selective combination with methyl into CH ₃ OOH. AuPd alloy is simultaneously decorated on Zn _i O surface for tuning CH ₃ OOH adsorption and reduction into CH ₃ OH. The synergy of Zn atom island and AuPd alloy achieve a tandem reaction pathway (CH ₄ →CH ₃ OOH→CH ₃ OH) for an unprecedented CH ₃ OH yield of 2444 mmol g _AuPd ⁻¹ h ⁻¹ (or 8800 µmol g _cat ⁻¹ h ⁻¹ ) with 98.3% selectivity, which bypasses the •OH mechanism for tuning the high selectivity of CH ₃ OH. An apparent quantum efficiency of 18.53% at 370 nm for CH ₄ conversion are super to the reported photocatalytic systems. Thus, this work provides the new strategy of the synergetic atom island and metal alloy photocatalysts through a tandem reaction pathway to mediate the photocatalytic selective oxidation of CH ₄ into the desired CH ₃ OH.