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

D V Rybkovskiy; V O Koroteev; A Impellizzeri; A A Vorfolomeeva; E Yu Gerasimov; A V Okotrub; A Chuvilin; L G Bulusheva; C P Ewels

doi:10.1021/acsnano.1c11349

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

ACS Nano. 2022 Apr 26;16(4):6002-6012. doi: 10.1021/acsnano.1c11349. Epub 2022 Apr 4.

Authors

D V Rybkovskiy^{1

2}, V O Koroteev³, A Impellizzeri⁴, A A Vorfolomeeva⁵, E Yu Gerasimov⁶, A V Okotrub⁵, A Chuvilin^{3

7}, L G Bulusheva⁵, C P Ewels⁴

Affiliations

¹ Skolkovo Institute of Science and Technology, Bolshoy Boulevard 30, Building 1, 121205 Moscow, Russia.
² Prokhorov General Physics Institute of the Russian Academy of Sciences, Vavilov Street 38, 119991 Moscow, Russia.
³ CIC NanoGUNE BRTA, Tolosa Hiribidea 76, E-20018 Donostia, San Sebastian, Spain.
⁴ Université de Nantes, CNRS, Institut des Matériaux Jean Rouxel, IMN, F-44000 Nantes, France.
⁵ Nikolaev Institute of Inorganic Chemistry, SB RAS, 3 Acad. Lavrentiv Avenue, 630090 Novosibirsk, Russia.
⁶ Boreskov Institute of Catalysis, SB RAS, 5 Acad. Lavrentiv Avenue, 630090 Novosibirsk, Russia.
⁷ Basque Foundation of Science, IKERBASQUE, 48013 Bilbao, Spain.

PMID: 35377145
DOI: 10.1021/acsnano.1c11349

Abstract

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.

Keywords: Raman scattering; allotrope; carbon nanotube filling; density functional theory; encapsulation; phosphorus; transmission electron microscopy.