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

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

    Cite this: ACS Nano 2022, 16, 4, 6002–6012
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    https://doi.org/10.1021/acsnano.1c11349
    Published April 4, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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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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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.1c11349.

    • SEM and EDS data spectrum of purified P@SWCNTs, XPS survey and P 2p spectra of P@SWCNT sample before and after purification, TG and DTG curves measured for purified P@SWCNTs sample, Raman spectra of P@SWCNT sample before and after purification and recrystallized phosphorus, Raman spectra of purified P@SWCNT sample measured at different excitations, HAADF-STEM images and EDS mappings for P@SWCNT samples, HRTEM images showing phosphorus-filled SWCNTs of different diameter, calculated Raman spectra for the single-chain structures, calculated phonon eigenvectors of the most intense peaks for the phosphorus chain structures, calculated energies of phosphorus structures confined within effective cylindrical potential, cycling performance of P@SWCNTs in lithium-ion cells, table with observed carbon nanotubes data with different number of visible phosphorus chains inside (PDF)

    • Video S1: Image series of P@SWNT with 0.1 second exposure (AVI)

    • Video S2: Image series of P@SWCNT with 0.1 second exposure with SWCNT removed by FFT filtering (AVI)

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    ACS Nano

    Cite this: ACS Nano 2022, 16, 4, 6002–6012
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.1c11349
    Published April 4, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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