Defective 2D silicon phosphide monolayers for the nitrogen reduction reaction: a DFT study

Electroreduction of N-2 is a highly promising route for NH3 production. The lack of efficient catalysts that can activate and then reduce N-2 into NH3 limits this as a pragmatic application. In this work, a 2D layered group IV-V material, silicon phosphide (SiP), is evaluated as a suitable substrate for the electrochemical nitrogen reduction reaction (ENRR). To capture N-2, one phosphorus (P) defect was introduced on the plane of SiP. DFT calculations found that the defective SiP monolayer (D1-SiP, which is defined by the P-defect on SiP) exhibits enormous prospects towards the ENRR because of enhanced electron conductivity, good activation on N-2, lower limiting potential (U-L = -0.87 V) through the enzymatic pathway, smooth charge transfer between the catalyst and the reaction species, and robust thermal stability. Importantly, D1-SiP demonstrates the suppressed activities on producing of H-2 and N2H4 side-products. This research demonstrates the potential of 2D metal-free Si-based catalysts for nitrogen fixation and further enriches the study of group IV-V materials for the ENRR.