Single-metal atom sandwiched by graphdiyne and BN-doped graphdiyne sheets as an electrocatalyst for nitrogen reduction: a first-principles study.

The exploration of efficient single-atom catalysts provides a prospective pattern for the sustainable development of electrocatalytic nitrogen fixation. We systematically researched the nitrogen reduction properties of catalysts with a single transition metal (TM) atom sandwiched between BN-doped graphdiyne and graphdiyne (labeled BN-TM-G) by first-principles calculations. The TM atom in the novel sandwich structure provides electrons to the adjacent B atom, which acts as the active site, thus driving the fixation and reduction of N. In the BN-TM-G system, the NRR catalytic activity is bound up with the positive charge polarization level of the TM atom. Among them, BN-Sc-G, BN-Ti-G, BN-V-G, and BN-Cr-G systems showed higher catalytic ability, and the competitive HER was inhibited. In particular, the lowest limiting potential of BN-Cr-G is -0.63 V is promising for the NRR catalyst.