Fe Foam-Supported FeS₂-MoS₂ Electrocatalyst for N₂ Reduction under Ambient Conditions

Highly efficient catalysts with enough selectivity and stability are essential for electrochemical nitrogen reduction reaction (e-NRR) that has been considered as a green and sustainable route for synthesis of NH₃. In this work, a series of three-dimensional (3D) porous iron foam (abbreviated as IF) self-supported FeS₂-MoS₂ bimetallic hybrid materials, denoted as FeS₂-MoS₂@IF, x = 100, 200, 300, and 400, were designed and synthesized and then directly used as the electrode for the NRR. Interestingly, the IF serving as a slow-releasing iron source together with polyoxomolybdates (NH₄)₆Mo₇O₂₄·4H₂O as a Mo source were sulfurized in the presence of thiourea to form self-supported FeS₂-MoS₂ on IF (abbreviated as FeS₂-MoS₂@IF₂₀₀) as an efficient electrocatalyst. Further material characterizations of FeS₂-MoS₂@IF₂₀₀ show that flower cluster-like FeS₂-MoS₂ grows on the 3D skeleton of IF, consisting of interconnected and staggered nanosheets with mesoporous structures. The unique 3D porous structure of FeS₂-MoS₂@IF together with synergy and interface interactions of bimetallic sulfides would make FeS₂-MoS₂@IF possess favorable electron transfer tunnels and expose abundant intrinsic active sites in the e-NRR. It is confirmed that synthesized FeS₂-MoS₂@IF₂₀₀ shows a remarkable NH₃ production rate of 7.1 ×10^-10 mol s^-1 cm^-2 at -0.5 V versus the reversible hydrogen electrode (vs RHE) and an optimal faradaic efficiency of 4.6% at -0.3 V (vs RHE) with outstanding electrochemical and structural stability.