Magnetic nanoribbons with embedded cobalt grown inside single-walled carbon nanotubes

Krichevsky, Denis M.; Shi, Lei; Baturin, Vladimir S.; Rybkovskiy, Dmitry V.; Wu, Yangliu; Fedotov, Pavel V.; Obraztsova, E. D.; Kapralov, P. O.; Shilina, P. V.; Fung, Kayleigh L. Y.; Stoppiello, Craig T.; Belotelov, V. I.; Khlobystov, Andrei N.; Chernov, A. I.

doi:10.1039/d1nr06179h

Cited by 5 publications

(8 citation statements)

References 63 publications

(71 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As such, encapsulation within CNTs has also been used to access the formation of atomically precise nanoribbon-like monolayer structures, zigzag strips, and even helical chains derived from 2D vdW crystals by protecting the in-plane dangling bonds from oxidation in ambient conditions. 56,58,60,67 Enabled by the atomic precision of the guest structures inside CNTs, these heterostructures have been used as a reliable platform to investigate the evolution of the photophysics, 57, 58 electron transport, 65 magnetic interactions, 68 and electron-phonon coupling 56 upon encapsulation of a library of guest structures. 19,56,68 From these promising reports, we aim to harness the atomic precision, range of accessible diameters, and long-range order in CNTs to isolate single chains of our model q-1D vdW phase, Sb2Se3, and use the resulting heterostructure to probe the evolution of the structural attributes and photophysical properties of Sb2Se3 upon encapsulation.…”

Section: Introductionmentioning

confidence: 99%

Single Quasi-1D Chains of Sb2Se3 Encapsulated Within Carbon Nanotubes

Milligan

Cordova

Yao

et al. 2023

Preprint

View full text Add to dashboard Cite

The realization of stable monolayers from 2D van der Waals (vdW) solids has fueled the search for exfoliable crystals that possess even lower dimensionalities. To this end, 1D and quasi-1D (q-1D) vdW crystals comprised of weakly-bound chains with sub-nanometer thicknesses have been discovered and demonstrated to exhibit nascent physics in the bulk. Although established micromechanical and liquid phase exfoliation methods have been applied to access single isolated chains from bulk 1D and q-1D vdW crystals, the existence of interchain vdW interactions with non-equivalent strengths has greatly hindered the ability to achieve uniform single isolated chains. Here, we report that encapsulation of the model q-1D vdW crystal, Sb2Se3, within single-walled carbon nanotubes (CNTs) circumvents the relatively stronger vdW interactions between the chains and allows for the isolation of single chains with structural integrity. Comprehensive high-resolution transmission electron microscopy and selected area electron diffraction studies of the Sb2Se3@CNT heterostructure revealed that the structure of the [Sb4Se6]n chain is preserved, enabling us to systematically probe the size-dependent properties of Sb2Se3 from the bulk down to a single chain. We then show that ensembles of the [Sb4Se6]n chains within CNTs display Raman confinement effects and an emergent band-like absorption onset around 600 nm, suggesting a strong blue shift of the near-infrared band gap of Sb2Se3 into the visible range upon encapsulation. First-principles density functional theory calculations further provided a qualitative insight on the structures and interactions that could manifest in the Sb2Se3@CNT heterostructure. From these calculations, spatial visualization of the electron density difference map of the heterostructure indicated the possibility of electron donation from the host CNT to the guest [Sb4Se6]n chain. Altogether, this model system demonstrates that 1D and q-1D vdW crystals with strongly anisotropic vdW interactions can be precisely studied by encapsulation within carbon nanotubes with suitable diameters, thereby opening opportunities in understanding dimension-dependent properties of a plethora of emergent vdW solids at or approaching the sub-nanometer regime.

show abstract

Section: Introductionmentioning

confidence: 99%

Single Quasi-1D Chains of Sb2Se3 Encapsulated Within Carbon Nanotubes

Milligan

Cordova

Yao

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…This result is unexpected because the highly charged, hydrophilic nature of [P 2 W 18 O 62 ] 6– anions and the charge-neutral hydrophobic BNNT cavity are seemingly incompatible. Therefore, it is important to identify the driving forces and mechanism for this process using our observations combined with prior knowledge of POM interactions with carbon nanotubes. , We address this challenge first by assessing the state of the guest-molecule within the BNNT cavity versus free POMs. In this context, the optical transparency of BNNTs (unlike CNTs) offers new opportunities for probing the vibrational, electronic, and optical states of the encapsulated molecules, which we utilize here to ascertain the nature of interactions between the guest-molecules and host-nanotubes.…”

Section: Discussionmentioning

confidence: 99%

“…Elemental analysis by EDX spectroscopy revealed a lower relative content of potassium in POM@BNNT prepared under ambient conditions (Figure b) than in the dark (Figure c). While the difference is subtle, it seems to indicate that at least some POM molecules can be encapsulated as anions ([P 2 W 18 O 62 ] 6– ) without some or all charge-balancing cations (K + ), like the encapsulation process in carbon nanotubes. ,, However, when performing our encapsulation experiments in the dark, most POM guest-molecules entered the BNNTs as ion pairs (K 6 [P 2 W 18 O 62 ]) (Figure ) indicated by the 0.9:3 K:W atomic ratio.…”

Section: Discussionmentioning

confidence: 99%

“…The structure, dynamic behavior, and chemical reactions studied at the single-molecule level within these nano-test tubes can reveal fundamental chemical information that bulk measurements cannot access . On a practical level, nanotubes enable the functional properties of entrapped molecules to be effectively harnessed for catalysis and electrochemical and magnetic applications . A critical step in applications of these nanotube materials is the process of encapsulation of molecules within nanotubes, which requires a substantial thermodynamic driving force for the molecules to enter the nanoscale channel.…”

Section: Introductionmentioning

confidence: 99%

“…CNTs are excellent nano-test tubes, but they suffer from an important drawbackthe lack of optical transparency associated with strong absorption of as-grown CNTs across the entire electromagnetic spectrum (the blackest material in the world). While CNTs are an ideal nanocontainer for electrochemical and electron microscopy investigations of guest-molecules, , the opaque nature of CNTs creates significant hurdles for any spectroscopy methods to directly probe the guest-molecules. Recently, boron nitride nanotubes (BNNTs) entered the area of nanocontainers as a new type of host structure .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Host–Guest Chemistry in Boron Nitride Nanotubes: Interactions with Polyoxometalates and Mechanism of Encapsulation

et al. 2022

Self Cite

View full text Add to dashboard Cite

Boron nitride nanotubes (BNNTs) are an emerging class of molecular container offering new functionalities and possibilities for studying molecules at the nanoscale. Herein, BNNTs are demonstrated as highly effective nanocontainers for polyoxometalate (POM) molecules. The encapsulation of POMs within BNNTs occurs spontaneously at room temperature from an aqueous solution, leading to the self-assembly of a POM@BNNT host–guest system. Analysis of the interactions between the host-nanotube and guest-molecule indicate that Lewis acid–base interactions between WO groups of the POM (base) and B-atoms of the BNNT lattice (acid) likely play a major role in driving POM encapsulation, with photoactivated electron transfer from BNNTs to POMs in solution also contributing to the process. The transparent nature of the BNNT nanocontainer allows extensive investigation of the guest-molecules by photoluminescence, Raman, UV–vis absorption, and EPR spectroscopies. These studies revealed considerable energy and electron transfer processes between BNNTs and POMs, likely mediated via defect energy states of the BNNTs and resulting in the quenching of BNNT photoluminescence at room temperature, the emergence of new photoluminescence emissions at cryogenic temperatures (<100 K), a photochromic response, and paramagnetic signals from guest-POMs. These phenomena offer a fresh perspective on host–guest interactions at the nanoscale and open pathways for harvesting the functional properties of these hybrid systems.

show abstract

Single Quasi-1D Chains of Sb₂Se₃ Encapsulated within Carbon Nanotubes

Milligan,

Yao,

Cordova

et al. 2024

Chem. Mater.

View full text Add to dashboard Cite

The realization of stable monolayers from 2D van der Waals (vdW) solids has fueled the search for exfoliable crystals with even lower dimensionalities. To this end, 1D and quasi-1D (q-1D) vdW crystals comprising weakly bound subnanometer-thick chains have been discovered and demonstrated to exhibit nascent physics in the bulk. Although established micromechanical and liquid-phase exfoliation methods have been applied to access single isolated chains from bulk crystals, interchain vdW interactions with nonequivalent strengths have greatly hindered the ability to achieve uniform single isolated chains. Here, we report that encapsulation of the model q-1D vdW crystal, Sb 2 Se 3 , within single-walled carbon nanotubes (CNTs) circumvents the relatively stronger c-axis vdW interactions between the chains and allows for the isolation of single chains with structural integrity. High-resolution transmission electron microscopy and selected area electron diffraction studies of the Sb 2 Se 3 @CNT heterostructure revealed that the structure of the [Sb 4 Se 6 ] n chain is preserved, enabling us to systematically probe the size-dependent properties of Sb 2 Se 3 from the bulk down to a single chain. We show that ensembles of the [Sb 4 Se 6 ] n chains within CNTs display Raman confinement effects and an emergent band-like absorption onset around 600 nm, suggesting a strong blue shift of the near-infrared band gap of Sb 2 Se 3 into the visible range upon encapsulation. First-principles density functional theory calculations further provided qualitative insight into the structures and interactions that could manifest in the Sb 2 Se 3 @CNT heterostructure. Spatial visualization of the calculated electron density difference map of the heterostructure indicated a minimal degree of electron donation from the host CNT to the guest [Sb 4 Se 6 ] n chain. Altogether, this model system demonstrates that 1D and q-1D vdW crystals with strongly anisotropic vdW interactions can be precisely studied by encapsulation within CNTs with suitable diameters, thereby opening opportunities in understanding dimension-dependent properties of a plethora of emergent vdW solids at or approaching the subnanometer regime.

show abstract

Magnetic nanoribbons with embedded cobalt grown inside single-walled carbon nanotubes

Abstract: Molecular magnetism and specifically magnetic molecules are recently gaining plenty of attention as key elements for quantum technologies, information processing, and spintronics. Transition to the nanoscale and implementation of ordered...

Cited by 5 publications

References 63 publications

Single Quasi-1D Chains of Sb2Se3 Encapsulated Within Carbon Nanotubes

Single Quasi-1D Chains of Sb2Se3 Encapsulated Within Carbon Nanotubes

Host–Guest Chemistry in Boron Nitride Nanotubes: Interactions with Polyoxometalates and Mechanism of Encapsulation

Single Quasi-1D Chains of Sb₂Se₃ Encapsulated within Carbon Nanotubes

Contact Info

Product

Resources

About

Magnetic nanoribbons with embedded cobalt grown inside single-walled carbon nanotubes

Abstract: Molecular magnetism and specifically magnetic molecules are recently gaining plenty of attention as key elements for quantum technologies, information processing, and spintronics. Transition to the nanoscale and implementation of ordered...

Cited by 5 publications

References 63 publications

Single Quasi-1D Chains of Sb2Se3 Encapsulated Within Carbon Nanotubes

Single Quasi-1D Chains of Sb2Se3 Encapsulated Within Carbon Nanotubes

Host–Guest Chemistry in Boron Nitride Nanotubes: Interactions with Polyoxometalates and Mechanism of Encapsulation

Single Quasi-1D Chains of Sb2Se3 Encapsulated within Carbon Nanotubes

Contact Info

Product

Resources

About

Single Quasi-1D Chains of Sb₂Se₃ Encapsulated within Carbon Nanotubes