Boosting the Electrocatalytic Nitrogen Reduction Reaction Activity on Two-Dimensional Conductive Metal–Organic Frameworks: A Theoretical Study

Electrocatalytic nitrogen reduction reaction (NRR) is a promising alternative to the traditional Haber–Bosch process to generate ammonia (NH 3 ). Exploring NRR electrocatalysts with efficient performance and stability is crucial for NH 3 production. In this work, on the basis of density functional theory (DFT) calculations, we systematically studied various TMO 4 –HTP and TMN 4 –HTP (TM refers to V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ru, Rh, Pd, Ta, W, Re, Os, Ir, and Pt; HTP refers to hexatriphenylene) of conductive two-dimensional (2D) metal–organic frameworks (MOFs) as potential electrocatalysts for the NRR. The strong interaction between TM atoms and the O 4 –HTP/N 4 –HTP substrates could guarantee the thermodynamic and electrochemical stabilities of the designed TMO 4 –HTP and TMN 4 –HTP. The calculated results suggest that ReO 4 –HTP, MoO 4 –HTP, and MoN 4 –HTP could serve as promising electrocatalysts. Moreover, ReO 4 –HTP possesses the highest activity with a calculated limiting potential value of −0.34 V. Notably, ReO 4 –HTP exhibits good NRR selectivity with the effective suppression of the hydrogen evolution reaction (HER). Our results contribute to searching for NRR electrocatalysts and highlight a potentially efficient class of catalysts based on 2D MOF materials for electrochemical reactions.