Precision Covalent Chemistry for Fine-Size Tuning of Sandwiched Nanoparticles between Graphene Nanoplatelets.

The covalent functionalization of graphene for enhancing their stability, improving their electrical or optical properties, or creating hybrid structures has continued to attract extensive attention; however, a fine control of nanoparticle (NP) size between graphene layers via covalent-bridging chemistry has not yet been explored. Herein, precision covalent chemistry-assisted sandwiching of ultrasmall gold nanoparticles (US-AuNP) between graphene layers is described for the first time. Covalently interconnected graphene (CIG) nanoscaffolds with a preadjusted finely tuned graphene layer-layer distance facilitated the formation of sandwiched US-AuNPs (∼1.94 ± 0.20 nm, 422 AuNPs). The elemental composition analysis by X-ray photoelectron spectroscopy displayed an aniline group addition per ∼55 graphene carbon atoms. It provided information on covalent interconnection via amidic linkages, while Raman spectroscopy offered evidence of covalent surface functionalization and the number of graphene layers (≤2-3 layers). High-resolution transmission electron microscopy images indicated a layer-layer distance of 2.04 nm, and low-angle X-ray diffraction peaks (2θ at 24.8 and 12.5°) supported a layer-layer distance increase compared to the characteristic (002) reflection (2θ at 26.5°). Combining covalent bridging with NP synthesis may provide precise control over the metal/metal oxide NP size and arrangement between 2D layered materials, unlocking new possibilities for advanced applications in energy storage, electrochemical shielding, and membranes.

Defect-Free Single-Layer Graphene by 10 s Microwave Solid Exfoliation and Its Application for Catalytic Water Splitting.

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.

Key factors affecting photoelectrochemical performance of g-C3N4 polymer films.

We investigated the relationship between crystallinity, deep trap states and PEC performance of g-C3N4 photoelectrodes. Long-lived charge carriers were present in the more poorly crystalline samples, due to deeper trap states, which inversely correlated with photoelectrochemical performance. The charge diffusion length in a compact g-C3N4 film was determined to be ca. 1000 nm.

Charged Carbon Nanomaterials: Redox Chemistries of Fullerenes, Carbon Nanotubes, and Graphenes.

Since the discovery of buckminsterfullerene over 30 years ago, sp2-hybridised carbon nanomaterials (including fullerenes, carbon nanotubes, and graphene) have stimulated new science and technology across a huge range of fields. Despite the impressive intrinsic properties, challenges in processing and chemical modification continue to hinder applications. Charged carbon nanomaterials (CCNs), formed via the reduction or oxidation of these carbon nanomaterials, facilitate dissolution, purification, separation, chemical modification, and assembly. This approach provides a compelling alternative to traditional damaging and restrictive liquid phase exfoliation routes. The broad chemistry of CCNs not only provides a versatile and potent means to modify the properties of the parent nanomaterial but also raises interesting scientific issues. This review focuses on the fundamental structural forms: buckminsterfullerene, single-walled carbon nanotubes, and single-layer graphene, describing the generation of their respective charged nanocarbon species, their interactions with solvents, chemical reactivity, specific (opto)electronic properties, and emerging applications.

Gram-scale production of nitrogen doped graphene using a 1,3-dipolar organic precursor and its utilisation as a stable, metal free oxygen evolution reaction catalyst.

For the first time, a one-step scalable synthesis of a few-layer ∼10% nitrogen doped (N-doped) graphene nanosheets (GNSs) from a stable but highly reactive 1,3-dipolar organic precursor is reported. The utilization of these N-doped GNSs as metal-free electrocatalysts for the oxygen evolution reaction (OER) is also demonstrated. This process may open the path for the scalable production of other heteroatom doped GNSs by using the broad library of well-known, stable 1,3-dipolar organic compounds.

Carbon nanotube anions for the preparation of gold nanoparticle-nanocarbon hybrids.

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.

Sonochemical degradation of N-methylpyrrolidone and its influence on single walled carbon nanotube dispersion.

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.

Giant cationic polyelectrolytes generated via electrochemical oxidation of single-walled carbon nanotubes.

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.

Probing the selectivity of azomethine imine cycloaddition to single-walled carbon nanotubes by resonance Raman spectroscopy.

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.

Unweaving the rainbow: a review of the relationship between single-walled carbon nanotube molecular structures and their chemical reactivity.

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.

Pyridine-functionalized single-walled carbon nanotubes as gelators for poly(acrylic acid) hydrogels.

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.

Fluorescent single-walled carbon nanotubes following the 1,3-dipolar cycloaddition of pyridinium ylides.

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.