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Quantitative Tracking of the Oxidation of Black Phosphorus in the Few-Layer Regime.

ABSTRACT: Previous theoretical reports have described the oxidation of few-layer black phosphorus and its effects on the electronic properties. Theoretically, native oxide layers bring opportunities for band gap engineering, but the detection of the different types of oxides is still a challenge at the experimental level. In this work, we uncover a correlation between thermal processes and Raman shift for the A_g ¹, B_2g, and A_g ² vibrational modes. The thermal expansion coefficients (temperature range, 290-485 K) for the A_g ¹, B_2g, and A_g ² were -0.015, -0.027, and -0.028 cm^-1 K^-1, respectively. Differential scanning calorimetry analysis shows an endothermic process centered at 528 K, and it was related with a mass increase according to thermogravimetric analysis. Raman shift temperature dependence was correlated to theoretical lattice thermal expansion, and a significant deviation was detected in the stacking direction at 500 K.

SUBMITTER: Gomez-Perez J

PROVIDER: S-EPMC6644649 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Quantitative Tracking of the Oxidation of Black Phosphorus in the Few-Layer Regime.

Gómez-Pérez Juan J Barna Balázs B Tóth Ildikó Y IY Kónya Zoltán Z Kukovecz Ákos Á

ACS omega 20181003 10

Previous theoretical reports have described the oxidation of few-layer black phosphorus and its effects on the electronic properties. Theoretically, native oxide layers bring opportunities for band gap engineering, but the detection of the different types of oxides is still a challenge at the experimental level. In this work, we uncover a correlation between thermal processes and Raman shift for the Ag 1, B2g, and Ag 2 vibrational modes. The ...[more]

PMID: 31457979

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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.

Dataset Information

Quantitative Tracking of the Oxidation of Black Phosphorus in the Few-Layer Regime.

Publications

Quantitative Tracking of the Oxidation of Black Phosphorus in the Few-Layer Regime.

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