Single-Atom Anchored g-C₃N₄ Monolayer as Efficient Catalysts for Nitrogen Reduction Reaction

Electrochemical N₂ reduction reaction (NRR) is a promising approach for NH₃ production under mild conditions. Herein, the catalytic performance of 3d transition metal (TM) atoms anchored on s-triazine-based g-C₃N₄ (TM@g-C₃N₄) in NRR is systematically investigated by density functional theory (DFT) calculations. Among these TM@g-C₃N₄ systems, the V@g-C₃N₄, Cr@g-C₃N₄, Mn@g-C₃N₄, Fe@g-C₃N₄, and Co@g-C₃N₄ monolayers have lower ΔG(*NNH) values, especially the V@g-C₃N₄ monolayer has the lowest limiting potential of -0.60 V and the corresponding limiting-potential steps are *N2+H++e-=*NNH for both alternating and distal mechanisms. For V@g-C₃N₄, the transferred charge and spin moment contributed by the anchored V atom activate N₂ molecule. The metal conductivity of V@g-C₃N₄ provides an effective guarantee for charge transfer between adsorbates and V atom during N₂ reduction reaction. After N₂ adsorption, the p-d orbital hybridization of *N₂ and V atoms can provide or receive electrons for the intermediate products, which makes the reduction process follow acceptance-donation mechanism. The results provide an important reference to design high efficiency single atom catalysts (SACs) for N₂ reduction.