Schottky Junctions with Bi Cocatalyst for Taming Aqueous Phase N(2) Reduction toward Enhanced Solar Ammonia Production

Solar‐powered N(2) reduction in aqueous solution is becoming a research hotspot for ammonia production. Schottky junctions at the metal/semiconductor interface have been effective to build up a one‐way channel for the delivery of photogenerated electrons toward photoredox reactions. However, their applications for enhancing the aqueous phase reduction of N(2) to ammonia have been bottlenecked by the difficulty of N(2) activation and the competing H(2) evolution reaction (HER) at the metal surface. Herein, the application of Bi with low HER activity as a robust cocatalyst for constructing Schottky‐junction photocatalysts toward N(2) reduction to ammonia is reported. The introduction of Bi not only boosts the interfacial electron transfer from excited photocatalysts due to the built‐in Schottky‐junction effect at the Bi/semiconductor interface but also synchronously facilitates the on‐site N(2) adsorption and activation toward solar ammonia production. The unidirectional charge transfer to the active site of Bi significantly promotes the photocatalytic N(2)‐to‐ammonia conversion efficiency by 65 times for BiOBr. In addition, utilizing Bi to enhance the photocatalytic ammonia production can be extended to other semiconductor systems. This work is expected to unlock the promise of engineering Schottky junctions toward high‐efficiency solar N(2)‐to‐ammonia conversion in aqueous phase.