Graphdiyne supported single-cluster catalysts catalyzed electrochemical nitrogen reduction reaction: A first-principles investigation

Abstract

The electrochemical reduction reaction of dinitrogen into ammonia (eNRR) has been considered as one of the most promising candidates to replace the traditional Haber-Bosch process. By using the density functional theory calculations, 20 kinds of atomically dispersed tri-atoms supported on graphdiyne monolayer catalysts MxM′yM″3-x-y/GDY (M, M′, M″ = Cr, Mo, W, Fe) were investigated for the eNRR process. It is found that Cr3/GDY, W3/GDY, and Cr2Mo1/GDY exhibit high stability, selectivity, and activity, with limiting potentials of only −0.36, −0.35, and −0.29 V, respectively. Specifically, by further investigating the most active and exemplar Cr2Mo1/GDY system, in the presence of N2 adsorption on the catalyst, it would promote the desorption of the final product NH3. More importantly, by evaluating the growth energy of the supported atomic metal centers, these catalysts have a very broad theoretical energy window, indicating their possibility of synthesizing. These atomically dispersed metal centers cooperating with the GDY monolayer could promote the multi-step protonation process. Our findings shed light on the rational and precise design of novel catalysts for electrochemical energy conversion and storage.