The promising 2D monolayers supported single f-electrons atom (Ce, Th, and U) catalysts in the ammonia synthesis via electrochemical nitrogen reduction reaction.

This article focuses on the theoretical investigation of single-atom catalysts (SACs) containing f-electron metals (Ce, Th, U) supported on two-dimensional monolayers—N atom doped graphene sheet (GN4), graphdiyne (GDY), and Ti2CO2—for electrocatalytic nitrogen reduction reaction (NRR) and hydrogen evolution reaction (HER) under ambient conditions. Density functional theory calculations reveal that uranium anchored on GN4 (U@GN4) exhibits superior catalytic activity for NRR via the distal pathway, with a low potential-determining step energy barrier (ΔG = 0.64 eV), attributed to synergistic electron donation and backdonation involving U d and f orbitals. Additionally, thorium anchored on GN4 and Ti2CO2 (Th@GN4 and Th@Ti2CO2) show promising HER performance, while U@GN4 favors NRR over HER, indicating its potential as an efficient and selective electrocatalyst for environmentally friendly ammonia synthesis.