Atomic modulation and phase engineering of MoS₂ for boosting N₂ reduction

Abstract

Electrochemical nitrogen reduction reaction (ENRR) has emerged as a potential alternative to the conventional Haber-Bosch process for ammonia production. However, ENRR technology is still restricted by the limited Faradaic efficiency due to the hard-to-break N-N triple bond. Herein, inspired by the biomimetic catalyst, we developed a Fe-modulated MoS₂ catalyst (named Fe@MoS₂) as an efficient ENRR catalyst. Raman spectra, coupled with the X-ray absorption spectroscopy, demonstrate the introduction of Fe into the MoS₂ lattice and achieve partial 2H to 1T phase conversion. The presence of S-vacancies on MoS₂ substrates was observed on scanning transmission electron microscopy images. Operando infrared absorption spectroscopy confirms that the constructed catalytic site significantly reduces barriers to nitrogen activation. The synthesized Fe@MoS₂, with its superior geometric and electronic structures, exhibits a remarkable Faradaic efficiency of 19.7 ± 5.5% at -0.2 V vs. Reversible Hydrogen Electrode and a high yield rate of 20.2 ± 5.3 μg h^-1 mg^-1 at -0.8 V vs. Reversible Hydrogen Electrode. Therefore, this work provides a fresh direction for designing novel catalysts, eventually boosting the nitrogen reduction reaction kinetics and accelerating the ENRR application.

Keywords

Nitrogen reduction / heteroatom doping / molybdenum disulfide / phase engineering

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