Design strategies of two-dimensional metal–organic frameworks toward efficient electrocatalysts for N2 reduction: cooperativity of transition metals and organic linkers

Abstract

Two-dimensional (2D) metal–organic frameworks (MOFs) serve as emerging electrocatalysts due to their high conductivity, chemical tunability, and accessibility of active sites. We herein proposed a series of 2D MOFs with different metal atoms and organic linkers with the formula M₃C₁₂X₁₂ (M = Cr, Mo, and W; X = NH, O, S, and Se) to design efficient nitrogen reduction reaction (NRR) electrocatalysts. Our theoretical calculations showed that metal atoms in M₃C₁₂X₁₂ can efficiently capture and activate N₂ molecules. Among these candidates, W₃C₁₂X₁₂ (X = O, S, and Se) show the best NRR performance due to their high activity and selectivity as well as low limiting potential (−0.59 V, −0.14 V, and −0.01 V, respectively). Moreover, we proposed a d-band center descriptor strategy to screen out the high activity and selectivity of M₃C₁₂X₁₂ for the NRR. Therefore, our work not only demonstrates a class of promising electrocatalysts for the NRR but also provides a strategy for further predicting the catalytic activity of 2D MOFs.