Chemically Bonded Schottky Junction for Efficient N₂ Photofixation

Construction of the Schottky junction is a promising strategy for realizing efficient photocatalytic N₂ fixation; however, the reported Schottky junction photocatalysts are mainly constructed via physical stacking or Van der Waals interaction with much room to improve performance. Herein, a chemically bonded Schottky junction photocatalyst is constructed for the fixation of N₂ to NH₃ production. The photocatalyst exhibits a unique 1D necklace-like morphology with hollow ZnCo bimetal sulfide (ZnCoS_x) nanocages strung by carbon nanotubes (CNTs). Experimental and theoretical results reveal that the formation of C-O-Co chemical bonds at the interface not only provides an atomic transportation highway for charge transfer but also modulates the electronic structure of Co active sites toward enhanced N₂ chemisorption and activation. The elaborately designed CNT/ZnCoS_x junction with a chemically bonded interface exhibits superior nitrogen fixation activity with an NH₃ yield of 1644 μmol g^-1 h^-1 in pure water. This study paves the way for the development of efficient Schottky junction photocatalysts for their applications.