Nitrogen Photofixation over III‐Nitride Nanowires Assisted by Ruthenium Clusters of Low Atomicity

In many heterogeneous catalysts, the interaction of supported metal species with a matrix can alter the electronic and morphological properties of the metal and manipulate its catalytic properties. III‐nitride semiconductors have a unique ability to stabilize ultra‐small ruthenium (Ru) clusters (ca. 0.8 nm) at a high loading density up to 5 wt %. n‐Type III‐nitride nanowires decorated with Ru sub‐nanoclusters offer controlled surface charge properties and exhibit superior UV‐ and visible‐light photocatalytic activity for ammonia synthesis at ambient temperature. A metal/semiconductor interfacial Schottky junction with a 0.94 eV barrier height can greatly facilitate photogenerated electron transfer from III‐nitrides to Ru, rendering Ru an electron sink that promotes N≡N bond cleavage, and thereby achieving low‐temperature ammonia synthesis.