Photocatalytic Formamide Synthesis via Coupling of Electrophilic and Nucleophilic Radicals over Atomically Dispersed Bi Sites

Formamide (HCONH 2 ) plays a pivotal role in the manufacture of a diverse array of chemicals, fertilizers, and pharmaceuticals. Photocatalysis holds great promise for green fabrication of carbon‐nitrogen (C−N) compounds owing to its environmental friendliness and mild redox capability. However, the selective formation of the C−N bond presents a significant challenge in the photocatalytic synthesis of C−N compounds. This work developed a photocatalytic radical coupling method for the formamide synthesis from co‐oxidation of ammonia (NH 3 ) and methanol (CH 3 OH). An exceptional formamide yield rate of 5.47±0.03 mmol ⋅ g cat −1 ⋅ h −1 (911.87±5 mmol ⋅ g Bi −1 ⋅ h −1 ) was achieved over atomically dispersed Bi sites (Bi SAs ) on TiO 2 . An accumulation of 45.68 mmol ⋅ g cat −1 (2.0 g ⋅ g cat −1 ) of formamide was achieved after long‐term illumination, representing the highest level of photocatalytic C−N compounds synthesis. The critical C−N coupling for formamide formation originated from the “σ–σ” interaction between electrophilic ⋅CH 2 OH with nucleophilic ⋅NH 2 radical. The Bi SAs sites facilitated the electron transfer between reactants and photocatalysts and enhanced the nucleophilic attack of ⋅NH 2 radical on the ⋅CH 2 OH radical, thereby advancing the selective C−N bond formation. This work deepens the understanding of the C−N coupling mechanism and offers an intriguing photocatalytic approach for the efficient and sustainable production of C−N compounds.