Highly Efficient Electrocatalytic N₂ Reduction to Ammonia over Metallic 1T Phase of MoS₂ Enabled by Active Sites...

The 1T phase of MoS₂ has been widely reported to be highly active toward the hydrogen evolution reaction (HER), which is expected to restrict the competitive nitrogen reduction reaction (NRR). However, in this work, a prototype of active sites separation over 1T-MoS₂ is proposed by DFT calculations that the Mo-edge and S atoms on the basal plane exhibit different catalytic NRR and HER selectivity, and a new role-playing synergistic mechanism is also well enabled for the multistep NRR, which is further experimentally confirmed. More importantly, a self-sacrificial strategy using g-C₃ N₄ as templates is proposed to synthesize 1T-MoS₂ with an ultrahigh 1T content (75.44%, named as CNMS, representing the composition elements of C, N, Mo, and S), which yields excellent NRR performances with an ammonia formation rate of 71.07 µg h^-1 mg^-1 _cat. at -0.5 V versus RHE and a Faradic efficiency of 21.01%. This work provides a promising new orientation of synchronizing the selectivity and activity for the multistep catalytic reactions.