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Few-layer black phosphorus enables nitrogen fixation under ambient conditions.

ABSTRACT: Nitrogen (N₂) fixation is a key reaction in biological and industrial chemistry, which does not occur spontaneously under ambient conditions but often depends on very specific catalysts and harsh reaction processes. Here we show that exposing exfoliated black phosphorus to the open air triggers, concomitantly, the oxidation of the two-dimensional (2D) material and the fixation of up to 100 parts per million (0.01%) of N₂ on the surface. The fixation also occurs in pristine non-exfoliated material. Besides, other allotropic forms of phosphorus, like red P, also fixes N₂ during ambient oxidation, suggesting that the N₂ fixation process is intrinsic with phosphorus oxidation and does not depend on the chemical structure or the dimensionality of the solid. Despite the low amounts of N₂ fixed, this serendipitous discovery could have fundamental implications on the chemistry and environmental stability of phosphorous and the design of related catalysts for N₂ fixation.

SUBMITTER: Garnes-Portoles F

PROVIDER: S-EPMC10839751 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature

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Few-layer black phosphorus enables nitrogen fixation under ambient conditions.

Garnes-Portolés Francisco F Lloret Vicent V Vidal-Moya José Alejandro JA Löffler Mario M Mayrhofer Karl J J KJJ Cerón-Carrasco Jose Pedro JP Abellán Gonzalo G Leyva-Pérez Antonio A

RSC advances 20240101 7

Nitrogen (N<sub>2</sub>) fixation is a key reaction in biological and industrial chemistry, which does not occur spontaneously under ambient conditions but often depends on very specific catalysts and harsh reaction processes. Here we show that exposing exfoliated black phosphorus to the open air triggers, concomitantly, the oxidation of the two-dimensional (2D) material and the fixation of up to 100 parts per million (0.01%) of N<sub>2</sub> on the surface. The fixation also occurs in pristine ...[more]

PMID: 38318612

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Project description:The usage of flame retardants in flammable polymers has been an effective way to protect both lives and material goods from accidental fires. Phosphorus flame retardants have the potential to be follow-on flame retardants after halogenated variants, because of their low toxicity, high efficiency and compatibility. Recently, the emerging allotrope of phosphorus, two-dimensional black phosphorus, as a flame retardant has been developed. To further understand its performance in flame-retardant efficiency among phosphorus flame retardants, in this work, we built model materials to compare the flame-retardant performances of few-layer black phosphorus, red phosphorus nanoparticles, and triphenyl phosphate as flame-retardant additives in cellulose and polyacrylonitrile. Aside from the superior flame retardancy in polyacrylonitrile, few-layer black phosphorus in cellulose showed the superior flame-retardant efficiency in self-extinguishing, ~1.8 and ~4.4 times that of red phosphorus nanoparticles and triphenyl phosphate with similar lateral size and mass load (2.5~4.8 wt%), respectively. The char layer in cellulose coated with the few-layer black phosphorus after combustion was more continuous and smoother than that with red phosphorus nanoparticles, triphenyl phosphate and blank, and the amount of residues of cellulose coated with the few-layer black phosphorus in thermogravimetric analysis were 10 wt%, 14 wt% and 14 wt% more than that with red phosphorus nanoparticles, triphenyl phosphate and blank, respectively. In addition, although exothermic reactions, the combustion enthalpy changes in the few-layer black phosphorus (-127.1 kJ mol-1) are one third of that of red phosphorus nanoparticles (-381.3 kJ mol-1). Based on a joint thermodynamic, spectroscopic, and microscopic analysis, the superior flame retardancy of the few-layer black phosphorus was attributed to superior combustion reaction suppression from the two-dimensional structure and thermal nature of the few-layer black phosphorus.

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Few-layer black phosphorus enables nitrogen fixation under ambient conditions.

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Few-layer black phosphorus enables nitrogen fixation under ambient conditions.

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