Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

The photo-/electrocatalytic nitrogen reduction reaction (NRR) is an up and coming method for sustainable NH₃ production; however, its practical application is impeded by poor Faradaic efficiency originating from the competing hydrogen evolution reaction (HER) and the inert N≡N triple bond activation. In this work, we put forth a method to boost NRR through construction of donor-acceptor couples of dual-metal sites. The synergistic effect of dual active sites can potentially break the metal-based activity benchmark toward efficient NRR. By systematically evaluating the stability, activity, and selectivity of 28 heteronuclear dual-atom catalysts (DACs) of M1M2/g-C₃N₄ candidates, FeMo/g-C₃N₄ is screened out as an effective electrocatalyst for NRR with a particularly low limiting potential of -0.23 V for NRR and a rather high potential of -0.79 V for HER. Meanwhile, TiMo/g-C₃N₄, NiMo/g-C₃N₄, and MoW/g-C₃N₄ with suitable band edge positions and visible light absorption can be applied to NRR as photocatalysts. The excellent catalytic activity is attributed to the tunable composition of metal dimers, which play an important role in modulating the binding strength of the target intermediates. This work may pave a new way for the rational design of heteronuclear DACs with high activity and stability for NRR, which may also apply to other reactions.