Newly designed photocatalyst of Fe₄ single clusters on g-C₆N₆ for nitrogen reduction reaction

The current industrial synthesis of ammonia proceeds through Haber–Bosch process, in which the adsorbed N₂ are directly dissociated, and the reaction is limited by Brønsted–Evans–Polanyi (BEP) relation. In this work, the catalytic properties of Fe₄ clusters fixed on g-C₆N₆ for nitrogen reduction reaction (NRR) are explored by first-principle calculations. The studies on the structural stability, adsorption capacity for N₂ and the change of Gibbs free energy proves that Fe₄ cluster catalyst exhibits excellent catalytic activity and high selectivity for NRR. The “acceptance-donation” interaction between Fe₄@g-C₆N₆ and N atoms presented by PDOS and Bader charge analysis will facilitate the breaking of N[tbnd]N bonds. The 100 % Faraday efficiency further proves the high NRR selectivity. The results provide an effective strategy for designing high-performance electrochemical NRR catalysts.