Demonstration of Diameter-Selective Reactivity in the Sidewall Ozonation of SWNTs by Resonance Raman Spectroscopy

Banerjee, Sarbajit; Wong, Stanislaus S.

doi:10.1021/nl049261n

Cited by 99 publications

(95 citation statements)

References 44 publications

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“…5). 98 According to the Kataura-Plot, different photon energies determine whether the small diameter tubes that are resonantly enhanced are metallic or semiconducting. At exc D 633 nm (Fig.…”

Section: Change Of G-band Line Shapementioning

confidence: 99%

Raman spectroscopy of covalently functionalized single‐wall carbon nanotubes

Graupner

2007

J Raman Spectroscopy

305

229

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Raman spectroscopy is one of the most extensively employed methods for the characterization of carbon nanotubes. In this review article, an overview about Raman spectroscopy as a tool for the characterization of functionalized single-walled carbon nanotubes (SWCNTs) is given. First, the relevant Raman modes in SWCNTs are introduced. Then, in a phenomenological approach, the effects that are observed for the individual modes in the Raman spectra are compiled and discussed. It is shown that special care has to be taken in order to separate the effects of functionalization, which are specific to a subset of the SWCNTs (metallic/semiconducting or diameter dependent), from changes in sample morphology or doping effects.

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Section: Change Of G-band Line Shapementioning

confidence: 99%

Raman spectroscopy of covalently functionalized single‐wall carbon nanotubes

Graupner

2007

J Raman Spectroscopy

305

229

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“…[24] Incidentally, treatment of nanotubes with ozone has been proposed as a means of their purification, controlled oxygenation, and rational sidewall functionalization. [25][26][27][28][29][30] In the current Progress report, as in a prior Review, [31] we focus primarily on covalent methodologies for nanotube functionalization because of the intrinsic flexibility of introducing a variety of chemical moieties onto the ''bare'' surface of nanotubes with the explicit goal of tailoring physicochemical properties of nanotube surfaces. Moreover, covalent functionalization of carbon nanotubes can readily deal with fundamental issues of purification, solubilization, and processing, as we have previously discussed.…”

Section: Challenges In Nanotube Processingmentioning

confidence: 99%

Functional Covalent Chemistry of Carbon Nanotube Surfaces

2009

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In this Progress Report, we update covalent chemical strategies commonly used for the focused functionalization of single‐walled carbon nanotube (SWNT) surfaces. In recent years, SWNTs have been treated as legitimate nanoscale chemical reagents. Hence, herein we seek to understand, from a structural and mechanistic perspective, the breadth and types of controlled covalent reactions SWNTs can undergo in solution phase, not only at ends and defect sites but also along sidewalls. We explore advances in the formation of nanotube derivatives that essentially maintain and even enhance their performance metrics after precise chemical modification. We especially highlight molecular insights (and corresponding correlation with properties) into the binding of functional moieties onto carbon nanotube surfaces. Controllable chemical functionalization suggests that the unique optical, electronic, and mechanical properties of SWNTs can be much more readily tuned than ever before, with key implications for the generation of truly functional nanoscale working devices.

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“…By using the modified Kataura plot [11b] it is possible to assign the peaks to the (12,6), (9,6), (10,4), and (9,3) chirality indices. In the regime of the metallic tubes, the intensity changes in the RBM region at 532 nm excitation caused by the alkylation are correlated inversely with the changes in the D-band intensities (Figure 2).…”

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confidence: 99%

Preferred Functionalization of Metallic and Small‐Diameter Single‐Walled Carbon Nanotubes by Nucleophilic Addition of Organolithium and ‐Magnesium Compounds Followed by Reoxidation

Wunderlich

Hauke

Hirsch

2008

Chemistry A European J

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Covalent sidewall addition to single-walled nanotubes (SWNTs) of a series of organolithium and organomagnesium compounds (nBuLi, tBuLi, EtLi, nHexLi, nBuMgCl, tBuMgCl) followed by reoxidation is reported. The functionalized R(n)-SWNTs were characterized by Raman and NIR emission spectroscopy. The reaction of SWNTs with organolithium and magnesium compounds exhibits pronounced selectivity: in general, metallic tubes are more reactive than semiconducting ones. The reactivity of SWNTs toward the addition of organometallic compounds is inversely proportional to the diameter of the tubes. This was determined simultaneously and independently for both metallic and semiconducting SWNTs. The reactivity also depends on the steric demands of the addend. Binding of the bulky t-butyl addend is less favorable than addition of primary alkyl groups. Significantly, although tBuLi is less reactive than, for example, nBuLi, it is less selective toward the preferred reaction with metallic tubes. This unexpected behavior is explained by fast electron transfer to the metallic SWNTs having low-lying electronic states close to the Fermi level, a competitive initial process. The NIR emission of weakly functionalized semiconducting SWNTs, also reported for the first time, implies interesting applications of functionalized tubes as novel fluorescent reporter molecules.

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Demonstration of Diameter-Selective Reactivity in the Sidewall Ozonation of SWNTs by Resonance Raman Spectroscopy

Cited by 99 publications

References 44 publications

Raman spectroscopy of covalently functionalized single‐wall carbon nanotubes

Raman spectroscopy of covalently functionalized single‐wall carbon nanotubes

Functional Covalent Chemistry of Carbon Nanotube Surfaces

Preferred Functionalization of Metallic and Small‐Diameter Single‐Walled Carbon Nanotubes by Nucleophilic Addition of Organolithium and ‐Magnesium Compounds Followed by Reoxidation

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