Search

Mass production of defect-free single-layer graphene flakes (SLGFs) by a cost-effective approach is still very challenging. Here, we report such single-layer graphene flakes (SLGFs) (>90%) prepared by a nondestructive, energy-efficient, and easy up-scalable physical approach. These high-quality graphene flakes are attributed to a novel 10 s microwave-modulated solid-state approach, which not only fast exfoliates graphite in air but also self-heals the surface of graphite to remove the impurities. The fabricated high-quality graphene films (∼200 nm) exhibit a sheet resistance of ∼280 Ω/sq without any chemical or physical post-treatment. Furthermore, graphene-incorporated Ni-Fe electrodes represent a remarkable ∼140 mA/cm2 current for the catalytic water oxidation reaction compared with the pristine Ni-Fe electrode (∼10 mA/cm2) and a 120 mV cathodic shift in onset potential under identical experimental conditions, together with a faradic efficiency of >90% for an ideal ratio of H2 and O2 production from water. All these excellent performances are attributed to extremely high conductivity of the defect-free graphene flakes.

Developing easy and effective surface functionalization approaches has required to facilitate the processability of graphene while seeking novel application areas. Herein, an in situ single-step reductive covalent bromination of graphene has been reported for the first time. Highly brominated graphene flakes (>3% Br) were prepared by only subjecting the bromine-intercalated graphite flakes to a reduction reaction with reactive lithium naphthalide. The bromine-functionalized graphene was characterized by X-ray photoelectron spectroscopy and thermogravimetric analysis. Results revealed that Br2 molecules acted as both an intercalating agent for the graphite and a reactant for the surface functionalization of the graphene. After brominating, the remaining negative charges on the reduced graphene surface were further used for the dual surface functionalization of graphene with a long-chain alkyl group (∼1% dodecyl group addition). The functionalized graphenes were also characterized by Fourier transform infrared and Raman spectroscopy.

Carbon nanotubes (CNTs) are ideal support materials for platinum in fuel cells. However, little is known about the conduction mechanism of Pt-coordinated CNTs. Herein, a coordination complex of pyridine-functionalized single-walled nanotubes (Py-SWNTs) with Pt (Pt/Py-SWNTs) was prepared via the ligand exchange reaction between cis-[Pt(dmso)2Cl2] and Py-SWNTs generated by pyridine diazonium salt addition to SWNTs. The presence of Pt in modified SWNTs was confirmed by X-ray photoelectron spectroscopy (XPS). The N 1s XPS spectra provided evidence of Pt coordination to the pyridine nitrogen atom. Modified SWNTs were further characterized by thermogravimetric analysis coupled with mass spectrometry, ultraviolet-visible-near infrared spectroscopy, Raman spectroscopy, and elemental analysis. The electron conduction mechanism of Pt/Py-SWNT films was best described by a modified quantum tunneling model, identified from a combined analysis of the voltage and temperature dependence of the current.

Pyridinium ylide functionalized single-walled carbon nanotubes (SWCNTs) generated from simple quaternary pyridinium salts covalently bound to the SWCNT surface undergo a 1, 3 dipolar cycloaddition with dimethyl acetylenedicarboxylate in a ‘click’ chemistry type fashion to yield indolizine modified light-emitting SWCNTs. Conversion of quaternary pyridinium salts into indolizines on the SWCNT surface was confirmed by XPS, fluorescence spectroscopy and optical microscopy. The resulting modified SWCNTs were found to emit blue light when excited at 330 nm. Fluorescence quenching experiments performed via nitroaromatic compounds displayed that the fluorescence of the modified SWCNTs was quenched by nitrophenol derivatives in both solution-state and solid-state, probably due to strong H-bonding interaction between host and guest molecules. The functionalized SWCNTs were further characterized using TGA-MS, FTIR and UV-vis-NIR spectroscopy.

Herein, a versatile method to introduce ester functional groups to the surface of single-walled carbon nanotubes (SWCNTs) was defined. Ester-modified SWCNTs were prepared via the direct reaction of haloformates with reduced SWCNTs [(nBu–SWCNT n− ) Li + ] generated by n-butyl lithium. Ultraviolet–Visible–near infrared and Raman spectroscopy verified the evidence of covalent surface functionalization. Solubility of functionalized SWCNTs (f-SWCNTs) enhanced compared to purified SWCNTs. Gold tagging to positively charged SWCNTs displayed the presence and distribution of functional groups, confirming the conversion of esters into amides. f-SWCNTs were further characterized by thermo-gravimetric analysis coupled with mass spectrometry and fourier-transform infrared spectroscopy.

Covalently interconnected single walled carbon nanotube (SWNT) networks have attracted a particular interest due to their enhanced accessible surface area. Herein, an elegant way of preparing covalently interconnected SWNTs is demonstrated for the first time via coupling reactions. Sonogashira and Ullmann coupling reactions offer a versatile route for the preparation of molecularly-bridged SWNTs (MBSWNTs). Couplings create C C bonds between SWNTs yielding MBSWNTs with conductive 1,2-diphenyl-diacetylene and biaryl bridges. Elemental composition analysis done by XPS shows the evidence of successful couplings while mass traces of the interconnected SWNTs corroborating with fragmentations corresponding to conjugated linkers.

Pyridine-functionalized single-walled carbon nanotubes (SWNTs) are prepared from the addition of a pyridine diazonium salt to nanotubes. The location and distribution of the functional groups is determined by atomic force microscopy using electrostatic interactions with gold nanoparticles. The pyridine-functionalized SWNTs are able to act as cross-linkers and hydrogen bond to poly(acrylic acid) to form SWNT hydrogels. The pyridine-functionalized SWNTs are further characterized using Raman, FTIR, UV/vis-NIR, and X-ray photoelectron spectroscopy and thermogravimetric analysis-mass spectrometry.

Formyl or aldehyde groups are transferred to the surface of single-walled carbon nanotubes (SWCNTs) by reaction of reduced carbon nanotubes with N-formylpiperidine. This could open the way for more versatile chemical modification reactions of carbon nanotubes than is currently possible using functionalization methods reported to date. The formylated SWCNTs were characterized by thermogravimetric analysis-mass spectrometry and Raman, UV-vis-NIR and FTIR spectroscopy. The location and distribution of the functional groups was determined by AFM using electrostatic interactions with gold nanoparticles. The formylated SWCNTs were further derivatized with a fluorescent dye and studied using fluorescence spectroscopy. (C) 2010 Elsevier Ltd. All rights reserved.

Gold nanoparticles (AuNPs) can be evenly deposited on single-walled carbon nanotubes (SWCNTs) via the reduction of the highly stable complex, chloro(triphenylphosphine) gold(I), with SWCNT anions ('nanotubides'). This methodology highlights the unusual chemistry of nanotubides and provides a blueprint for the generation of many other hybrid nanomaterials.

Sonicating pure N-methyl pyrrolidone (NMP) rapidly produces contaminating organic nanoparticles, at increasing concentration with time, as investigated by AFM, as well as UV-vis, IR and NMR spectroscopies. The contamination issue affects carbon nanotube, and likely other nanomaterial, dispersions processed by sonication in organic solvents.

Previously, reduced single-walled carbon nanotube anions have been used for effective processing and functionalization. Here we report individually separate and distinct (that is, discrete) single-walled carbon nanotube cations, directly generated from a pure anode using a non-aqueous electrochemical technique. Cyclic voltammetry provides evidence for the reversibility of this nanoion electrochemisty, and can be related to the complex electronic density of states of the single-walled carbon nanotubes. Fixed potentiostatic oxidation allows spontaneous dissolution of nanotube cations ('nanotubium'); Raman spectroscopy and transmission electron microscopy show that sequential fractions are purified, separating amorphous carbon and short, defective single-walled carbon nanotubes, initially. The preparation of nanotubium, in principle, enables a new family of nucleophilic grafting reactions for single-walled carbon nanotubes, exploited here, to assemble nanotubes on amine-modified Si surfaces. Other nanoparticle polyelectrolyte cations may be anticipated.

Selective covalent surface modification of single-walled carbon nanotubes (SWNTs) is of great importance to various carbon nanotube-based applications as it might offer an alternative method for enriching metallic and semiconducting nanotubes. Herein, we report on the surface modification of SWNTs through 1,3-dipolar cycloaddition of 3-phenyl-phthalazinium-1-olate, which is a stable and reactive azomethine imine. For this reaction, microwave heating was found to be more efficient than conventional and solvent-free heating. The sensitivity of cycloaddition to the molecular structure of SWNTs was probed using resonance Raman spectroscopy with three different laser excitations. Based on the obtained results, azomethine imine addition to the surface of nanotubes is selective for metallic and large-diameter semiconducting SWNTs. Thermogravimetric analysis coupled with mass spectrometry showed that fragments released at high temperatures corresponded to the phenylphthalazine group, thus confirming the covalent surface functionalization. Modified SWNTs were further characterized by X-ray photoelectron and UV/Vis-NIR spectroscopies.

Single-walled carbon nanotubes (SWNTs) are a fundamental family of distinct molecules, each bearing the possibility of different reactivities due to their intrinsically distinct chemical properties. SWNT syntheses generate a heterogeneous mixture of species with varying electronic character, lengths, diameters and helicities, (n,m), as well as other amorphous, graphitic and metal catalyst impurities. In recent years, selective syntheses and post-synthetic separation strategies have advanced, driven by the requirement for pure SWNTs displaying particular features. Covalent surface modifications are widely-used to adapt SWNTs for specific applications with modified solubility, compatibility and specific functionalities. In many cases, such reactions have been found to be selective, illuminating the fundamentally distinct chemistry of each (n,m) species. This differential reactivity has found immediate utility in facilitating the sorting of nanotubes according to specific diameter, electronic properties and, most importantly, helicity. In this tutorial review, we discuss a wide range of selective reactions, the mechanisms that are thought to govern selectivity, and the challenges of separating, characterising and regenerating the modified SWNTs.

Pyridinium ylides generated from simple Krohnke salts undergo a 1,3-dipolar cycloaddition to single-walled carbon nanotubes (SWNTs) offering a simple and convenient method for the covalent modification of carbon nanotubes. The indolizine functionalized SWNTs generated, emit blue light when excited at 335 nm. The location and distribution of the functional groups was determined by AFM using electrostatic interactions with gold nanoparticles. While resonance Raman spectroscopy showed that the 1,3-dipolar cylcloaddition of the pyridinium ylides to the nanotube surface was selective for metallic and large diameter semiconducting SWNTs. The indolizine functionalized SWNTs were further characterized using FTIR, UV-vis-NIR, TGA-MS, and XPS.

Single-walled carbon nanotubes (SWNTs) are a fundamental family of distinct molecules, each bearing the possibility of different reactivities due to their intrinsically distinct chemical properties. SWNT syntheses generate a heterogeneous mixture of species with varying electronic character, lengths, diameters and helicities, (n,m), as well as other amorphous, graphitic and metal catalyst impurities. In recent years, selective syntheses and post-synthetic separation strategies have advanced, driven by the requirement for pure SWNTs displaying particular features. Covalent surface modifications are widely-used to adapt SWNTs for specific applications with modified solubility, compatibility and specific functionalities. In many cases, such reactions have been found to be selective, illuminating the fundamentally distinct chemistry of each (n,m) species. This differential reactivity has found immediate utility in facilitating the sorting of nanotubes according to specific diameter, electronic properties and, most importantly, helicity. In this tutorial review, we discuss a wide range of selective reactions, the mechanisms that are thought to govern selectivity, and the challenges of separating, characterising and regenerating the modified SWNTs.