Density functional theory study of nitrogen-doped black phosphorene doped with monatomic transition metals as high performance electrocatalysts for N2reduction reaction

Abstract

Ammonia (NH₃) is an essential resource in human production and living activities, and its demand has been rising in recent years. The catalytic synthesis of NH₃from N₂under mild conditions, inspired by biological nitrogen fixation, has piqued the interest of researchers. In this paper, density functional theory (DFT) calculations were used to investigate the catalytic activity, mechanism, and selectivity of the TM embedded nitrogen-doped phosphorene as high-performance nitrogen reduction reaction (NRR) electrocatalysts in depth. The results show that Nb- and Mo-doped catalysts present excellent catalytic performance, with low limiting potentials of -0.41 and -0.18 V, respectively. The Mo-N₃-BP catalyst, for example, not only has an extremely low overpotential (-0.02 V), but also presents superior selectivity to effectively inhibit the HER competition reaction. A deeper look into the catalytic mechanism reveals a volcano relationship between the d-band center and the catalytic activity (Mo and Nb are located near the peak of the volcano-type curve). The d-band center and charge of the metal center can be regarded as effective descriptors for NRR activity on TM embedded nitrogen-doped phosphorene electrocatalysts, which hope to serve as a guiding principle for the design of high performance NRR single-atom catalyst in the future.

Keywords: Black phosphorene; DFT; N2 reduction; electrocatalysis; single-atom catalyst.