Ultrathin <scp>PdAu</scp> Nanowires with High Alloying Degree for the Direct Oxidation of Methane to <scp>C1</scp> Oxygenates

Comprehensive Summary The direct oxidation of methane (CH 4 ) into high‐valued C1 oxygenates production has garnered increased attention in effectively using vast CH 4 and alleviating the global energy crisis. However, due to the high cleavage energy of C—H bond and low polarity of CH 4 molecule, it is difficult to activate the first C—H bond. Furthermore, C1 oxygenates are readily inclined to be oxidized to CO 2 , because their weaker C—H bond comparing with CH 4 molecule, resulting in poor selectivity. Herein, we designed ultrathin Pd x Au y alloy NWs supported on ZSM‐5 (Z‐5) to investigate the direct oxidation of CH 4 to high value‐added oxygenate under mild conditions. By precisely adjusting the molar ratio of Pd/Au and alloying degree, Pd 9 Au 1 NWs/Z‐5 showed an excellent yield of 11.57 mmol·g –l ·h –1 and the outstanding selectivity of 95.1% for C1 oxygenates (CH 3 OH, CH 3 OOH and HCOOH). The in‐situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd 9 Au 1 NWs/Z‐5 was ascribed to the stable one‐dimensional nanostructure and the strong synergy effect with high alloying PdAu, which could increase the adsorption capacity of CH 4 molecules on Pd atoms to promote the CH 4 conversion. This work offers valuable insights into the design concept of high‐efficient catalysts and the structure‐activity relationship for the direct oxidation of CH 4 .