Nitrogen electroreduction on two-dimensional π-conjugated metal bis(dithiolene) complex nanosheets: A density functional theory study

Nitrogen reduction reaction (NRR) on π-conjugated metal bis(dithiolene) complex nanosheets with thirteen different central metals has been studied based on density functional theory computations. It was found that the NRR catalytic activity is closely related to the central metal atom of MC4S4. A volcano-type relationship was found between the reaction free energy of the rate-determining step and the adsorption of -NH2 intermediate. The reaction free energy of the rate-determining step increases in the following order: OsC4S4 < RuC4S4 < MnC4S4 < CrC4S4 < FeC4S4 < IrC4S4 < RhC4S4 < CoC4S4 < MoC4S4 < WC4S4.