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

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 N-2 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.

Automated summary

In this study, a series of 2D metal-organic frameworks were designed as efficient electrocatalysts for nitrogen reduction reaction (NRR), with W3C12X12 exhibiting the best performance. A d-band center descriptor strategy was proposed to screen high activity and selectivity of MOFs for NRR, demonstrating potential for further predicting catalytic activity in 2D MOFs.