Theoretical study on the NO reduction electrocatalytic performance of graphdiyne supported Fe1–5 cluster

Precise number of Fe atom clusters supported by Graphdiyne (GDY) were investigated by using of spin polarized density function theory (DFT). Our goal was to expound the relationship between catalyst structure and the electrochemical reduction of NO gas performance. The results indicated that Fe1–5@GDY all demonstrated good structure stability. Compared with Fe1–2@GDY, Fe3–5@GDY exhibit improved NORR performance due to their better activation effect of NO. In particular, Fe4@GDY, with high thermal stability, could efficiently synthesized ammonia from NO with a limiting potential of – 0.11 V. By analyzing the microkinetic model of the optimal reaction route for Fe4@GDY, we found that the turnover frequency (TOF) of ammonia synthesis through NORR was 6.04 × 104 s−1 ∙ site−1 at 400 K. Such fast reaction rate demonstrate that Fe4@GDY is a good catalyst candidate for electrochemistry synthesis of ammonia from NO. The excellent catalytic performance of Fe4@GDY can be attributed to the high d-band center of Fe4 atoms and the electron reservoir effect of GDY.