Single Iron-dimer Catalysts on MoS₂ Nanosheet for Potential Nitrogen Activation

Abstract

Electrocatalytic nitrogen reduction reaction(NRR) is a promising way to produce ammonia(NH₃) at ambient temperature and pressure. Herein, we have constructed single Fe dimer catalysts on a molybdenum disulfide monolayer for potential nitrogen activation. By employing ab initio molecular dynamics simulations, it is suggested that a dual iron-single atom site can be dynamically formed, which exhibits the similar Fe-S-Fe structure as the nitrogenase. We further identify an iron dimer with a sulfur vacancy as the active center for realistic nitrogen activation by the free energy calculations since the bridged sulfur is easy to be released in the form of H₂S during the reduction process. It is shown that N₂ mainly adsorbs on the Fe₂ dimer at the sulfur vacancies in the pattern of side-on configuration, and the nitrogen reduction reaction is proceeded by an enzymatic mechanism. Charge analyses further show that the Fe₂ dimer mainly works as an electron reservoir while MoS₂ substrate with one sulfur vacancy acts as an inert carrier to stabilize the Fe₂ dimer. Overall, our work provides important insights into how N₂ molecules were adsorbed and activated on Fe₂-doped MoS₂, and provides new ideas for the transformation of actual reaction sites during electrochemical reactions.

Keywords

Nitrogen reduction reaction / Ab initio molecular dynamics simulation / Single iron-dimer catalyst

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