Simulated Raman spectra of bulk and low-dimensional phosphorus allotropes

Impellizzeri, Anthony; Vorfolomeeva, Anna A.; Суровцев, Н. В.; Окотруб, А. В.; Ewels, Christopher P.; Rybkovskiy, Dmitry V.

doi:10.1039/d1cp02636d

Cited by 21 publications

(12 citation statements)

References 60 publications

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“…According to DFT calculations, the first peak corresponds to the bending mode, while the higher-frequency peaks are associated with symmetric stretching modes of the P 4 tetrahedron. 36 The Raman spectrum of the red phosphorus sample has a shape characteristic of amorphous forms of red phosphorus. 37,38 A set of low-intensity peaks in the region from 200 to ∼320 cm −1 corresponds to oscillations of the eightmembered P 8 cage, and a wide band between 320 and 490 cm −1 is due to P−P stretching modes in chain structures containing P 8 and P 9 cages.…”

Section: Resultsmentioning

confidence: 99%

Doping of Carbon Nanotubes with Encapsulated Phosphorus Chains

et al. 2022

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Single-walled carbon nanotubes (SWCNTs) are a perfect host for the formation of one-dimensional phosphorus structures and to obtain hybrid materials with a large P–C ratio. This work presents a procedure for high-yield phosphorus filling of commercial Tuball SWCNTs and efficient removal of phosphorus deposits from the external nanotube surface. We probed white and red phosphorus as precursors, varied the synthesis temperature and the ampoule shape, and tested three solvents for sample purification. High-resolution transmission electron microscopy and Raman spectroscopy indicated crystallization of interior phosphorus in a form resembling fibrous red phosphorus. An aqueous sodium hydroxide solution allowed removing the majority of external phosphorus particles. Thermogravimetric analysis of the product determined ∼23 wt % (∼10 atom %) of phosphorus, and the X-ray photoelectron spectroscopy (XPS) data showed that ca. 80% of it is in the form of elemental phosphorus. Externally purified SWCNTs filled with phosphorus were used to study the interaction between the components. Raman spectroscopy and core-level XPS revealed p-type SWCNT doping. Valence-band XPS data and density functional theory calculations confirmed the transfer of the SWCNT electron density to the encapsulated phosphorus.

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Section: Resultsmentioning

confidence: 99%

Doping of Carbon Nanotubes with Encapsulated Phosphorus Chains

et al. 2022

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“…Raman scattering in phosphorous structures gives peaks in the region of 200–600 cm −1 [ 57 ], where the spectrum of o-SWCNTs has no features ( Figure 5 c). The Raman spectrum of phosphorus condensed in an ampoule without SWCNTs (sample P re ) exhibits a set of peaks characteristics of amorphous red phosphorus [ 58 ].…”

Section: Resultsmentioning

confidence: 99%

Single-Walled Carbon Nanotubes with Red Phosphorus in Lithium-Ion Batteries: Effect of Surface and Encapsulated Phosphorus

et al. 2022

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Single-walled carbon nanotubes (SWCNTs) with their high surface area, electrical conductivity, mechanical strength and elasticity are an ideal component for the development of composite electrode materials for batteries. Red phosphorus has a very high theoretical capacity with respect to lithium, but has poor conductivity and expends considerably as a result of the reaction with lithium ions. In this work, we compare the electrochemical performance of commercial SWCNTs with red phosphorus deposited on the outer surface of nanotubes and/or encapsulated in internal channels of nanotubes in lithium-ion batteries. External phosphorus, condensed from vapors, is easily oxidized upon contact with the environment and only the un-oxidized phosphorus cores participate in electrochemical reactions. The support of the SWCNT network ensures a stable long-term cycling for these phosphorus particles. The tubular space inside the SWCNTs stimulate the formation of chain phosphorus structures. The chains reversibly interact with lithium ions and provide a specific capacity of 1545 mAh·g−1 (calculated on the mass of phosphorus in the sample) at a current density of 0.1 A·g−1. As compared to the sample containing external phosphorus, SWCNTs with encapsulated phosphorus demonstrate higher reaction rates and a slight loss of initial capacity (~7%) on the 1000th cycle at 5 A·g−1.

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“…The final theoretical Raman spectra were plotted with Lorentzian broadening. Calculations for bulk phosphorus allotropes show that a better agreement of the vibrational frequencies is obtained within the PBE-D2 approximation . Therefore, although we used PBE-D3 for total energies, we switch to PBE-D2 for the Raman, reoptimizing the atomic geometry.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…Calculations for bulk phosphorus allotropes show that a better agreement of the vibrational frequencies is obtained within the PBE-D2 approximation. 50 Therefore, although we used PBE-D3 for total energies, we switch to PBE-D2 for the Raman, reoptimizing the atomic geometry. Calculated peak positions are nonetheless still shifted slightly when compared to the experimental data, a consequence of the exchange and correlation functional inaccuracy, as shown in a recent study.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…Calculated peak positions are nonetheless still shifted slightly when compared to the experimental data, a consequence of the exchange and correlation functional inaccuracy, as shown in a recent study. 50 We restrict our study to individual chains and crl-[P8]P2[P9]P2[ double chain, as the weak van der Waals coupling in multichain structures is not expected to alter the Raman spectra significantly.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

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“Missing” One-Dimensional Red-Phosphorus Chains Encapsulated within Single-Walled Carbon Nanotubes

et al. 2022

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We identify the “missing” 1D-phosphorus allotrope, red phosphorus chains, formed in the interior of tip-opened single-walled carbon nanotubes (SWCNTs). Via a comprehensive experimental and theoretical study we show that in intermediate diameter cavities (1.6–2.9 nm), phosphorus vapor condenses into linear P8]P2 chains and fibrous red-phosphorus type cross-linked double-chains. Thermogravimetric and X-ray photoelectron spectroscopy analysis estimates ∼7 atom % of elemental phosphorus in the sample, while high-resolution energy dispersive X-ray spectroscopy mapping reveals that phosphorus fills the SWCNTs. High-resolution transmission electron microscopy (HRTEM) shows long chains inside the nanotubes with varying arrangement and packing density. A detailed match is obtained between density functional theory (DFT) simulations, HRTEM, and low-frequency Raman spectroscopy. Notably, a signature spectroscopic signal for phosphorus chain cross-linking is identified. When coupled with reinterpretation of literature data and wide-ranging DFT calculations, these results reveal a comprehensive picture of the diameter dependence of confined 1D-phosphorus allotropes.

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Simulated Raman spectra of bulk and low-dimensional phosphorus allotropes

Abstract: We present a comprehensive theoretical and experimental Raman spectroscopic comparative study of bulk Phosphorus allotropes (white, black, Hittorf’s, Fibrous) and their monolayer equivalents, demonstrating that the application of the Placzek...

Cited by 21 publications

References 60 publications

Doping of Carbon Nanotubes with Encapsulated Phosphorus Chains

Doping of Carbon Nanotubes with Encapsulated Phosphorus Chains

Single-Walled Carbon Nanotubes with Red Phosphorus in Lithium-Ion Batteries: Effect of Surface and Encapsulated Phosphorus

“Missing” One-Dimensional Red-Phosphorus Chains Encapsulated within Single-Walled Carbon Nanotubes

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