Photosynthesis of Urea by Cooperative Radicals Addition Using a Peptide as a Photocatalyst

Abstract Innovative strategies for efficient photocatalytic urea production are desirable due to the wide applications of urea and derivatives in agriculture and pharmaceuticals, which remain highly challenging. Here, we introduce a simple but efficient radical addition approach to address this challenge by fully utilizing the in situ, synchronously generated aminyl radical (·NH 2 ) and hydroperoxyl radical (HO 2 ·) via the coupling of photocatalytic NH 3 oxidation and O 2 reduction. The two radicals reassembled and cooperatively reacted with NH 2 COOH to form urea with markedly lower kinetic barrier than the industrial process. This approach not only achieved record‐high urea production and conversion rates (42.6 mmol g cat −1 h −1 and 70%, respectively) but also enabled the direct, single‐step synthesis of unsymmetrical urea derivatives with good yields.