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One-dimensional pnictogen allotropes inside single-wall carbon nanotubes

Title: One-dimensional pnictogen allotropes inside single-wall carbon nanotubes
Authors: Hart, M
Chen, J
Michaelides, A
Sella, A
Shaffer, MSP
Salzmann, CG
Item Type: Journal Article
Abstract: The discovery of phosphorene, a single layer of black phosphorus, has accelerated the investigation of pnictogen nanomaterials, leading to the recent identification of arsenene and antimonene. These two-dimensional nanomaterials display physical properties superior to those of graphene for some applications. Recently, single-wall carbon nanotubes (SWCNTs) have been filled with P4 molecules from the melt and As4 molecules from the vapor phase. Confined within SWCNTs, polymerization reactions yielded new one-dimensional pnictogen allotropes. Here, we show using high-resolution electron microscopy that such nanostructures can also be observed upon filling SWCNTs from the vapor phase using red phosphorus as the source material. Using larger-diameter SWCNTs, the vapor phase favors the formation of double-stranded phosphorus zigzag ladders observed here for the first time. Overall, however, SWCNTs were generally found to fill more efficiently with liquid phosphorus; substantial decreases in the filling yields were observed for both phosphorus and arsenic filling of narrow SWCNTs using the vapor route. Attempts to extend the pnitogen series using molten antimony gave very low filling yields. However, the antimony zigzag ladder was observed on two occasions, suggesting that this structural motif dominates across the pnictogens. Computational predictions of the encapsulation energies of the various pnictogen nanostructures are consistent with the observed experimental trends, and band gap calculations predict that the single-stranded zigzag chains of all investigated pnictogens are fully metallic. Using SWCNTs with diameters of >1.5 nm revealed a plethora of complex new phosphorus nanostructures, which highlights an exciting new avenue for future work in this area.
Issue Date: 18-Nov-2019
Date of Acceptance: 1-Nov-2019
URI: http://hdl.handle.net/10044/1/81434
DOI: 10.1021/acs.inorgchem.9b02190
ISSN: 0020-1669
Publisher: AMER CHEMICAL SOC
Start Page: 15216
End Page: 15224
Journal / Book Title: Inorganic Chemistry
Volume: 58
Issue: 22
Copyright Statement: © 2019 American Chemical Society
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
WHITE PHOSPHORUS
BLACK PHOSPHORUS
BAND-GAP
ANTIMONY
RED
SB
SEMICONDUCTOR
NANOSHEETS
ORIGIN
PHASE
Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
WHITE PHOSPHORUS
BLACK PHOSPHORUS
BAND-GAP
ANTIMONY
RED
SB
SEMICONDUCTOR
NANOSHEETS
ORIGIN
PHASE
Inorganic & Nuclear Chemistry
0302 Inorganic Chemistry
0306 Physical Chemistry (incl. Structural)
0399 Other Chemical Sciences
Publication Status: Published
Open Access location: https://discovery.ucl.ac.uk/id/eprint/10086813/
Online Publication Date: 2019-11-06
Appears in Collections:Chemistry