Electrochemical Fixation of Nitrogen by Promoting N₂ Adsorption and N–N Triple Bond Cleavage on the CoS₂/MoS₂ Nanocomposite

Abstract

An electrochemical N₂ reduction reaction (NRR), as an environmentally benign method to produce NH₃, is a suitable alternative to substitute the energy-intensive Haber-Bosch technology. Unfortunately, to date, it is obstructed by the lack of efficient electrocatalysts. Here, a CoS₂/MoS₂ nanocomposite with CoS₂ nanoparticles decorated on MoS₂ nanosheets is fabricated and adapted as a catalyst for the NRR. As unveiled by experimental and theoretical results, the strong interaction between CoS₂ and MoS₂ modulates interfacial charge distribution with electrons transferring from CoS₂ to MoS₂. Consequently, a local electrophilic region is formed near the CoS₂ side, which enables effective N₂ absorption. On the other hand, the nucleophilic area formed near the MoS₂ side is in favor of breaking stable N≡N, the potential-determining step (*N₂ → *N₂H) which brings about a much decreased energy barrier than that on pure MoS₂. As a result, this catalyst exhibits an excellent NRR performance, NH₃ yield and Faradaic efficiency of 54.7 μg·h^-1·mg^-1 and 20.8%, respectively, far better than most MoS₂-based catalysts.