Two-dimensional MoS2/Fe-phthalocyanine hybrid nanostructures as excellent electrocatalysts for hydrogen evolution and oxygen reduction reactions

Abstract

Two-dimensional (2D) MoS₂ nanostructures have been extensively investigated in recent years because of their fascinating electrocatalytic properties. Herein, we report 2D hybrid nanostructures consisting of 1T′ phase MoS₂ and Fe-phthalocyanine (FePc) molecules that exhibit excellent catalytic activity toward both the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). X-ray absorption spectra revealed an increased Fe–N distance (2.04 Å) in the hybrid complex relative to the isolated FePc. Spin-polarized density functional theory calculations predicted that the Fe center moves toward the MoS₂ layer and induces a non-planar structure with an increased Fe–N distance of 2.05 Å, which supports the experimental results. The experiments and calculations consistently show a significant charge transfer from FePc to stabilize the hybrid complex. The excellent HER catalytic performance of FePc-MoS₂ is characterized by a low Tafel slope of 32 mV dec⁻¹ at a current density of 10 mA cm⁻² and an overpotential of 0.123 V. The ORR catalytic activity is superior to that of the commercial Pt/C catalyst in pH 13 electrolyte, with a more positive half-wave potential (0.89 vs. 0.84 V), a smaller Tafel slope (35 vs. 87 mV·dec⁻¹), and a much better durability (9.3% vs. 40% degradation after 20 h). Such remarkable catalytic activity is ascribed to the HER-active 1T′ phase MoS₂ and the ORR-active nonplanar Fe–N₄ site of FePc.