Synergetic Atom‐Island and Metal Alloy Triggering Tandem Reaction for CH4 Photooxidation to CH3OH

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.