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Bioinspired Activation of N 2 on Asymmetrical Coordinated Fe Grafted 1T MoS 2 at Room Temperature

Inspired by the nitrogen fixation process on MoFe nitrogenase, asymmetrical coordinated Fe grafted onto 1T MoS 2 were successfully synthesized. The unique electron -rich structure with asymmetrical coordination made the 1T Fe 0.1 Mo 0.9 S 2 layered material actively react with water and dinitrogen at room temperature and atmosphere pressure. Subsequently, ammonia can be produced with a yield of 800 pmol (NH 4 + ) g -1 (12.5% yield in mole). The activation, fixation and reduction of dinitrogen were confirmed by isotopically labeled experiments. The location and the specific coordination environment of grafted Fe in Fe-Mo-S were further determined by X-ray absorption spectroscopy analysis. Our work demonstrates that the nitrogen fixation and reduction for ammonia at room temperature without any chemical and electrochemical assistance is distinctly different from traditional bionic -inspired nitrogen fixation process. The mechanism of the activation and reduction of N 2 was further investigated by density functional theory calculation and Raman spectra. Compared with 1T MoS 2 , the enriched electron nature and asymmetrical coordination of Fe in Fe-Mo-S materials play a critical role in the bioinspired activation of N 2 at ambient condition.

1T MoS2↗

Materials Data on FeMo3S4 by Materials Project

Mo3FeS4 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are three inequivalent Mo2+ sites. In the first Mo2+ site, Mo2+ is bonded to five S2- atoms to form a mixture of edge and corner-sharing MoS5 square pyramids. There are a spread of Mo–S bond distances ranging from 2.45–2.52 Å. In the second Mo2+ site, Mo2+ is bonded to five S2- atoms to form a mixture of edge and corner-sharing MoS5 square pyramids. There are a spread of Mo–S bond distances ranging from 2.40–2.57 Å. In the third Mo2+ site, Mo2+ is bonded to five S2- atoms to form a mixture of edge and corner-sharing MoS5 square pyramids. There are a spread of Mo–S bond distances ranging from 2.42–2.62 Å. Fe2+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Fe–S bond distances ranging from 2.37–2.63 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a 5-coordinate geometry to four Mo2+ and one Fe2+ atom. In the second S2- site, S2- is bonded in a 5-coordinate geometry to three Mo2+ and two equivalent Fe2+ atoms. In the third S2- site, S2- is bonded in a 5-coordinate geometry to four Mo2+ and one Fe2+ atom. In the fourth S2- site, S2- is bonded in a 5-coordinate geometry to four Mo2+ and one Fe2+ atom.

36 MATERIALS SCIENCE↗