Cooperativity Between Free Radicals Promotes Selective Methane Oxidation

Catalytic strategies that can accelerate methane oxidation and control its selectivity have far-reaching environmental and economic implications. Free radicals are known to remove methane from the earth's atmosphere and are active species in the selective upgrading of methane to methanol. Conventional wisdom on determining active species focuses on their reactivity. Consequently, prevailing theories and models on room temperature methane oxidation focus exclusively on the role of hydroxyl radicals. Here, we report the discovery of a positive cooperative effect between two radicals with distinct reactivities that accelerates the rate of methane oxidation. We also demonstrate a decoupled-and-stepwise reaction strategy that boosts desired selectivity over traditional approaches. This research illustrates intriguing opportunities for leveraging active-species cooperativity to promote catalytic transformations.