Direct conversion of methane to high-value-added chemicals is a major challenge in catalysis, which usually requires high-energy input to overcome the reaction barrier. We report that graphene-confined single Fe atoms can be used as an efficient non-precious catalyst to directly convert methane to C1 oxygenated products at room temperature. A series of graphene-confined 3d transition metals (Mn, Fe, Co, Ni, and Cu) were screened, yet only single Fe atoms could catalyze the methane conversion. Combining in operando time-of-flight mass spectrometry, ¹³C nuclear magnetic resonance, and density functional theory calculations, we found that methane conversion proceeds on the O–FeN₄–O active site along a radical pathway to produce CH₃OH and CH₃OOH first, and then the generated CH₃OH can be further catalyzed to form HOCH₂OOH and HCOOH at room temperature.

甲烷直接转化为高附加值化学品是催化的主要挑战，通常需要高能量输入才能克服反应障碍。我们报道石墨烯限制的单个Fe原子可以用作有效的非贵金属催化剂，在室温下将甲烷直接转化为C1氧化产物。筛选了一系列石墨烯限制的3d过渡金属（Mn，Fe，Co，Ni和Cu），但只有单个Fe原子可以催化甲烷转化。结合飞行时间质谱，¹³ C核磁共振和密度泛函理论计算，我们发现甲烷的转化沿自由基途径在O–FeN ₄ –O活性位点发生，从而生成CH ₃首先是OH和CH ₃ OOH，然后可以在室温下进一步催化生成的CH ₃ OH形成HOCH ₂ OOH和HCOOH。