Selective Polycarboxylation of Semiconducting Single-Walled Carbon Nanotubes by Reductive Sidewall Functionalization

Gebhardt, Benjamin; Hof, Ferdinand; Backes, Claudia; Müller, M.; Plocke, Thomas; Maultzsch, Janina; Thomsen, C.; Hauke, Frank; Hirsch, Andreas

doi:10.1021/ja206818n

Cited by 62 publications

(73 citation statements)

References 84 publications

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“…Metallic tubes were also reported preferentially etched away by water and methane plasma because of their higher reactivity (13,14). On the other hand, H 2 O 2 (15), azomethineylides (16), and gaseous SO 3 (17) preferentially attacked s-SWCNTs, and recently s-SWCNTs were also shown to be preferentially polycarboxylated via reductive sidewall functionalization (18). However, it has not been studied yet if confinement of metal cluster catalysts within metallic and semiconducting SWCNTs affects chemical reactions differently.…”

mentioning

confidence: 99%

Tuning the redox activity of encapsulated metal clusters via the metallic and semiconducting character of carbon nanotubes

Zhang

Pan

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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We demonstrate that reactions confined within single-walled carbon nanotube (SWCNT) channels are modulated by the metallic and semiconducting character of the hosts. In situ Raman and X-ray absorption near-edge structure spectroscopies provide complementary information about the electronic state of carbon nanotubes and the encapsulated rhenium species, which reveal electronic interactions between encapsulated species and nanotubes. More electrons are transferred from metallic tubes (m-SWCNTs) to oxidic rhenium clusters, leading to a lower valence state rhenium oxide than that in semiconducting tubes (s-SWCNTs). Reduction in 3.5% (vol/vol) H 2 /Ar leads to weakened host-guest electronic interaction. The high valence state Re within s-SWCNTs is more readily reduced when raising the temperature, whereas only a sluggish change is observed for Re within m-SWCNTs. Only at 400°C does Re reach a similar electronic state (mixture of Re 0 and Re 4+ ) in both types of tubes. Subsequent oxidation in 1% O 2 /Ar does not show changes for Re in s-SWCNTs up to 200°C. In comparison, m-SWCNTs facilitate the oxidation of reduced rhenium (160°C). This can be exploited for rational design of active catalysts with stable species as a desired valence state can be obtained by selecting specific-type SWCNTs and a controlled thermal treatment. These results also provide a chemical approach to modulate reversibly the electronic structure of SWCNTs without damaging the sidewalls of SWCNTs.confined catalysis | confinement effect A n increasing number of studies reveal that confinement of metal or metal oxide nanoparticles inside carbon nanotubes (CNTs) often leads to significantly enhanced catalytic activity with respect to the same bare metal nanoparticles or those deposited on the outer walls of CNTs (1-3). Such a different behavior originates from both the physical (spatial restriction of the channels) and chemical factors (electronic interaction of confined species with the curved graphene walls) inside CNTs (1-5). In this sense, single-walled carbon nanotubes (SWCNTs) are very interesting because they have a higher degree of uniformity and smaller channel compared with multiwalled CNTs (6). More interestingly, they exhibit intrinsically either metallic or semiconducting properties with different electronic structure around the Fermi level. Metallic and semiconducting SWCNTs (m-SWCNTs and s-SWCNTs, respectively) have been demonstrated to vary significantly in reactivity toward covalent and noncovalent functionalization of their sidewalls (7-9). For example, diazonium salts (10), nitronium ions (NO 2 + ) (11), and OsO 4 (12) reacted selectively with metallic tubes, which was attributed to their higher electron density near the Fermi level. Metallic tubes were also reported preferentially etched away by water and methane plasma because of their higher reactivity (13,14). On the other hand, H 2 O 2 (15), azomethineylides (16), and gaseous SO 3 (17) preferentially attacked s-SWCNTs, and recently s-SWCNTs were also shown to be preferentially...

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mentioning

confidence: 99%

Tuning the redox activity of encapsulated metal clusters via the metallic and semiconducting character of carbon nanotubes

Zhang

Pan

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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“…While comparing the position of the bands in the G-region shows that for the spectra recorded at 532 and 632 nm shows a shift of ≤5 cm Studies by Mevellec et al and Gebhardt et al showed in the Raman studies (noting these studies were Raman not SERS studies) that SWCNTs with covalently functionalized chemical groups attached showed changes in RBM frequencies and transition energies dependent upon the both the size of the side group and also the chemical nature of the side group e.g. when oxygen atoms lie close to the tubes a larger shift in transition energy occurs as compared to that of other carbonaceous chains [34,42]. Mevellec et al [34] reported a blueshift of RBM frequencies for carbon based moieties (example SWCNT-(CH 2 ) 11 -R) compared to oxygenated moieties (example SWCNT-CO 2 (-R)) of c.a.…”

Section: Resultsmentioning

confidence: 99%

Surface-enhanced Raman scattering spectra of radial breathing and G band modes in functionalised nanotubes

Al-Alttar¹,

Kopf²,

Flavin³

et al. 2013

Chemical Physics Letters

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Publication informationChemical Physics Letters, 568-569 : 95-100Publisher Elsevier Item record/more information http://hdl.handle.net/10197/4451 Publisher's statementThis is the author's version of a work that was accepted for publication in . Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. AbstractIn this paper we perform surface enhanced Raman scattering studies of two functionalised nanotubes, an oxidised SWCNT and a SWCNT with a fluorescein side group covalently attached to the nanotube was compared with pristine SWCNTs. Our studies showed that in the G-band a significant shift was seen, while relatively little change occurred in the G+ and RBM spectral regions. These results indicate that SERS is broadly in line with Raman studies of chemically altered SWCNTs.

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“…3 mg of HiPco SWCNTs (batch n. HP27-078) were dispersed in 5 ml milliQ H 2 O with the assistance of sonication (30 min). The two solutions were mixed and the resulting suspension was sonicated for further 30 centrifuged at 1000 rpm for 1 h. A fraction (70%) of the supernatant solution was collected and directly used for the absorption and emission measurements. A fraction of the solution was deposited by spin coating on SiO 2 surface for Raman spectroscopy characterization.…”

Section: Ndi1mentioning

confidence: 99%

Selective Interaction of a Water Soluble Naphthalenediimide with Single-Walled Carbon Nanotubes

Syrgiannis

Rigodanza

Prato

2017

ECS J. Solid State Sci. Technol.

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Carbon Nanotubes (CNTs) are amongst the more used nanomaterials of the last decades. They have been applied to different fields, including electronics, solar cells, catalysis and nanomedicine.1,2 One of the main drawbacks for their use in most applications is the strong tendency to aggregate and the poor solubility in any solvent, organic or aqueous. Chemical functionalization is the best solution to make this material not only easier to manipulate and to handle, 3 but also more biocompatible. 4 However, covalent functionalization may modify the sp 2 character of the carbon framework and consequently can influence their properties. 5,6 Non-covalent approaches take advantage of supramolecular interactions, where the adsorption of organic and inorganic molecules on the surface of CNTs lead to stable suspensions. 7The possibility to recognize and sort selected types of CNTs is of prominent interest, since the electronic and optical properties strongly depend on their structural parameters (diameter and helicity). 8 As a consequence, a structural control of SWCNTs is required for their use, especially in electronic and optical applications. Although several methods for the selective synthesis of specific types of SWCNTs have been devised, there are still problems of size heterogeneity. Therefore, post growth separation approaches, such as density gradient ultracentrifugation, 9 electrophoresis, 10 chromatography 11 and molecule assisted selective extractions [12][13][14] are currently employed to minimize size dispersion. While the use of n-type semiconductors for selective adsorption on SWCNTs have been successfully reported, 15,16 here we discuss the non-covalent interaction of a water soluble naphthalenediimide derivative (NDI1) with SWCNTs. The naphthalenediimides are the smallest n-type semiconductor analogs in the family of rylenes.17 Their shape and rich π system makes them as good candidates for the formation of interesting hybrid materials with SWCNTs. Only a few articles employing NDIs as surfactants for CNTS have been reported. 18,19 In this work, we have used a bis-cationic NDI (Scheme 1), which can interact strongly with the scaffold of SWCNTs. This interaction appears to be selective to some types of SWCNTs, by adsorbing on the smaller diameter nanotubes. Methods NDI1with Iodide as counter anion was synthesized as reported previously. 20 The bis-chloride derivative was synthesized by following the procedure that is reported in the Supplementary Material. The hybrid with SWCNTs was prepared by using the following procedure: 3 mg of NDI1 were solubilized in 5 ml of milliQ H 2 O. 3 mg of HiPco SWCNTs (batch n. HP27-078) were dispersed in 5 ml milliQ H 2 O with the assistance of sonication (30 min). The two solutions were mixed and the resulting suspension was sonicated for further 30 min, followed by magnetic stirring (2 h). The final mixture was filtered and washed several times with H 2 O. The solid was redispersed in D 2 O and z E-mail: zsyrgiannis@units.it; prato@units.it Scheme 1. Structure of NDI1.c...

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Selective Polycarboxylation of Semiconducting Single-Walled Carbon Nanotubes by Reductive Sidewall Functionalization

Cited by 62 publications

References 84 publications

Tuning the redox activity of encapsulated metal clusters via the metallic and semiconducting character of carbon nanotubes

Tuning the redox activity of encapsulated metal clusters via the metallic and semiconducting character of carbon nanotubes

Surface-enhanced Raman scattering spectra of radial breathing and G band modes in functionalised nanotubes

Selective Interaction of a Water Soluble Naphthalenediimide with Single-Walled Carbon Nanotubes

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