Highly efficient nitrogen fixation over S-scheme heterojunction photocatalysts with enhanced active hydrogen supply.

Abstract

Photocatalytic N2 fixation is a promising strategy for ammonia (NH3) synthesis; however, it suffers from relatively low ammonia yield due to the difficulty in the design of photocatalysts with both high charge transfer efficiency and desirable N2 adsorption/activation capability. Herein, an S-scheme CoSx/ZnS heterojunction with dual active sites is designed as an efficient N2 fixation photocatalyst. The CoSx/ZnS heterojunction exhibits a unique pocket-like nanostructure with small ZnS nanocrystals adhered on a single-hole CoSx hollow dodecahedron. Within the heterojunction, the electronic interaction between ZnS and CoSx creates electron-deficient Zn sites with enhanced N2 chemisorption and electron-sufficient Co sites with active hydrogen supply for N2 hydrogenation, cooperatively reducing the energy barrier for N2 activation. In combination with the promoted photogenerated electron-hole separation of the S-scheme heterojunction and facilitated mass transfer by the pocket-like nanostructure, an excellent N2 fixation performance with a high NH3 yield of 1175.37 μmol g-1 h-1 is achieved. This study provides new insights into the design of heterojunction photocatalysts for N2 fixation.