Theoretical Screening of Single Transition Metal Atoms Embedded in MXene Defects as Superior Electrocatalyst of Nitrogen Reduction Reaction

Abstract

The MXene‐supported single transition metal systems have been reported as promising electrocatalysts for hydrogen evolution reaction (HER) and carbon dioxide reduction reaction. Herein, the potential performance of MXene‐based catalysts was explored on nitrogen reduction reaction (NRR). Density functional theory computations are carried out to screen a series of transition metal atoms confined in a vacancy of MXene nanosheet (Mo2TiC2O2). The results reveal that the Zr, Mo, Hf, Ta, W, Re, and Os supported on defective Mo2TiC2O2 layer can significantly promote the NRR process. Among them, Zr‐doped single atom catalyst (Mo2TiC2O2‐ZrSA) possesses the lowest barrier (0.15 eV) of the potential‐determining step, as well as high selectivity over HER competition. To the best of knowledge, 0.15 eV is the lowest barrier of potential‐determining step that has been reported for NRR so far. Besides, the formation energy of Mo2TiC2O2‐ZrSA is much more negative than that of the synthesized Mo2TiC2O2‐PtSA catalyst, suggesting that the experimental preparation of Mo2TiC2O2‐ZrSA is feasible. This work thus predicts an efficient electrocatalyst for the reduction of N2 to NH3 at ambient conditions.

Mo2B, an MBene member with high electrical and thermal conductivities, and satisfactory performances in lithium ion batteries

“…17) were also developed through selective etching of (Mo 2/3 Sc 1/3 ) 2 AlC and (W 2/3 M 1/3 ) 2 AlC (M ¼ Sc, Y), respectively. Until now, approximately thirty MXene members have been synthesized, 18 which have been demonstrated to show widespread applications, such as energy storage, [19][20][21] electromagnetic shielding, 22 sewage treatment, 23 nuclide adsorption, 24 photothermal therapy, 25 multicolor cellular imaging, 26 electrocatalysts, 27,28 etc.…”

The FeN3 Doped Fluorographene for N2 Fixation: A Density Functional Theory Study

“…Besides the activity, since the most severe challenge for aqueous NRR is the poor efficiency ascribed to the competitive HER, the selectivity between HER vs NRR is further considered . Figure (c) presents the adsorption affinity of *N 2 and *H on FeN 3 moiety.…”

“…Single atom catalyst is one of the hottest topics in heterogeneous catalysis due to its high atomic utilization and the adjustable reactivity . For the given heteroatoms, the presented substrate leads to the distinct activity . Considering the unique physical/chemical property, the two‐dimension graphene and its derivatives are commonly adopted to hold the transition metal atom .…”

Recent Progress in MXene‐Based Materials: Potential High‐Performance Electrocatalysts

“…Single transition metal (TM) atom, such as Mo, Ru, and Au, can effectively improve the electrocatalytic NRR performance of MXene. According to DFT calculations, Li et al [77] systematically studied a series of single TM atoms confined in a vacancy of MXene nanosheet (Mo 2 TiC 2 O 2 ). The results revealed that the Zr, Mo, Hf, Ta, W, Re, and Os supported on the defective Mo 2 TiC 2 O 2 layer could significantly promote the NRR process.…”