Transition Metal‐dinitrogen Complex Embedded Graphene for Nitrogen Reduction Reaction

Abstract

Conversion of nitrogen to ammonia (NH3) is one of the most important issue in the modern chemical industry. Transition metals (TM) have the special unoccupied and occupied d orbitals to accept the electrons from and backdonate to N2, which is crucial in effective nitrogen reduction reaction (NRR). Herein, we propose TMN4 (TM=Fe, Co, Mo, W, Ru, Rh) embedded graphene as the catalysts for NRR by using the density functional theory calculations. Our results revealed that MoN4 embedded graphene exhibited outstanding catalytic activity for ammonia synthesis at ambient conditions along with small reaction energy barrier of 0.67 eV, as well as against hydrogen evolution reaction. These findings provide a potential paradigm for NRR.

Graphene Derivatives and Graphene Composite Electrocatalysts for N2 Reduction Reaction

“…In addition, the variation of Gibbs free energy is utilized to shed light on the NRR mechanisms, such as the analysis of the potential‐determining step (PDS) and the exploration of optimal NRR pathways. [ 53 ] Generally, excellent NRR electrocatalysts present a low energy barrier at PDS and can stabilize the intermediates along with the coordinates. Xie et al calculated the Gibbs free energy for N 2 reduction on the surface of CeO 2 (111) with distal, alternating, and mixed pathways ( Figure a,b).…”

“…As shown in Table 2, a large number of atom‐level‐doped NRR electrocatalysts have been studied by DFT, and the Mo–Ti dual metal atom doping is an effective way to prepare high‐performance NRR electrocatalysts. [ 52,53,87–93 ] DFT simulations predict numerous catalysts with excellent NRR performances; however, the experimental works are rare that have to be done in future studies.…”

Electrocatalytic Nitrogen Reduction Performance of Si‐doped 2D Nanosheets of Boron Nitride Evaluated via Density Functional Theory

“…Two‐dimensional (2D) nanosheets, such as graphene, graphdiyne, boron carbide (BC), boron nitride (BN), black phosphorus (BP), carbon nitride (e. g. C 3 N 4 & C 2 N), borophene, MXene, and so forth, have been intensively explored for the electro(photo)catalytic nitrogen reduction due to their unique electronic properties and large specific surface area [4,8–26,67–70] . In addition, the strategy of heteroatom doping can be employed to tune the electronic structure of catalytic sites for optimal eNRR activity [11,14,27] .…”

Co-doped graphene edge for enhanced N2-to-NH3 conversion

“…Recently, the single-atom catalysts (SACs), with unique atom coordination environment and novel electronic structure, have been widely applied in the NRR [17][18][19][20][21][22][23] . Li et al [24] proposed the FeN 3 -embedded graphene model as the NRR catalyst.…”