Density Functional Theory Investigation on the Nitrogen Reduction Mechanism in Two-Dimensional Transition-Metal Boride with Ordered Metal Vacancies

The creation of ordered collective vacancies in experiment proves challenging within a two-dimensional lattice, resulting in a limited understanding of their impact on catalyst performance. Motivated by the successful experimental synthesis of monolayer molybdenum borides with precisely ordered metal vacancies [Zhou et al. Science 2021, 373, 801-805] through dealloying, the nitrogen reduction reaction (NRR) in monolayer borides was systematically investigated to elucidate the influence of such ordered metal vacancies on catalytic reactions and the underlying mechanisms. The results reveal that the N-containing intermediates tend to dissociate, facilitating the NRR process with reduced U-L. The emergence of ordered metal vacancies modulates the electronic properties of the catalyst and partially facilitates the decomposition of N-containing intermediates. However, the U-L for NRR in Mo4/3B2 and W4/3B2 exhibits a significant increase. The compromised electrochemical performance is explained through the development of a simple electronic descriptor of the d-p band center (Delta d(M)-p(B)). Among these materials, Mo4/3Sc2/3B2 exhibits the most superior catalytic activity with a U-L of -0.5 V and favorable NRR selectivity over the HER. Our results provide mechanistic insights into the role of ordered metal vacancies in transition-metal boride for the NRR and highlight a novel avenue toward the rational design of superior NRR catalysts.