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.

中文翻译：

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二维π共轭金属双（二硫代戊二烯）络合物纳米片上的氮电还原：密度泛函理论研究

基于密度泛函理论计算，研究了含十三种不同中心金属的π共轭金属双（二硫代戊二烯）配合物纳米片上的氮还原反应（NRR）。发现NRR催化活性与MC4S4的中心金属原子密切相关。在速率确定步骤的反应自由能与-NH2中间体的吸附之间发现了火山类型的关系。速率确定步骤的反应自由能按以下顺序增加：OsC4S4 <RuC4S4 <MnC4S4 <CrC4S4 <FeC4S4 <IrC4S4 <RhC4S4 <CoC4S4 <MoC4S4 <WC4S4。