Photo-assisted high performance single atom electrocatalysis of the N2 reduction reaction by a Mo-embedded covalent organic framework

The development of highly efficient, low cost and environment-friendly solutions for the conversion of nitrogen gas to ammonia under ambient conditions has great industrial and academic significance. Single-atom catalysis (SAC) is recognized to have high potential in this area due to its rich chemical and physical properties. In this work, we proposed a Mo atom anchored covalent organic framework (MoPc-TFPN) for photo-assisted electrocatalysis of the N-2 reduction reaction using first-principles calculations. Our theoretical results demonstrated that this MoPc-TFPN catalyst has a considerably low onset potential of -0.24 V, which is comparable to or better than those of widely used noble catalysts. Because Mo denotes electrons to the Pc-TFPN substrate, the positive charged Mo has low binding affinity to H, thus greatly suppressing the competing hydrogen evolution reaction (HER). More importantly, the MoPc-TFPN has appropriate band edges with high light-absorption efficiency, which could be beneficial to improve the electrocatalytic efficiency of the NRR. This work uncovers a promising strategy for nitrogen fixation by photo-enhanced electrocatalysis under ambient conditions which could combine the ultimate functions of 2D semiconducting nanostructures for high performance catalysis.

Automated summary

This study introduces a Mo atom anchored covalent organic framework (MoPc-TFPN) for the photo-assisted electrocatalysis of N-2 reduction reaction, exhibiting low onset potential and effective suppression of competing reactions. Moreover, the catalyst possesses appropriate band edges and high light absorption efficiency, potentially enhancing the electrocatalytic efficiency of NRR.