Graphitization by Metal Particles.

Graphitization of carbon offers a promising route to upcycle waste biomass and plastics into functional carbon nanomaterials for a range of applications including energy storage devices. One challenge to the more widespread utilization of this technology is controlling the carbon nanostructures formed. In this work, we undertake a meta-analysis of graphitization catalyzed by transition metals, examining the available electron microscopy data of carbon nanostructures and finding a correlation between different nanostructures and metal particle size. By considering a thermodynamic description of the graphitization process on transition-metal nanoparticles, we show an energy barrier exists that distinguishes between different growth mechanisms. Particles smaller than ∼25 nm in radius remain trapped within closed carbon structures, while nanoparticles larger than this become mobile and produce nanotubes and ribbons. These predictions agree closely with experimentally observed trends and should provide a framework to better understand and tailor graphitization of waste materials into functional carbon nanostructures.

Identification of Graphene Dispersion Agents through Molecular Fingerprints.

The scalable production and dispersion of 2D materials, like graphene, is critical to enable their use in commercial applications. While liquid exfoliation is commonly used, solvents such as N-methyl-pyrrolidone (NMP) are toxic and difficult to scale up. However, the search for alternative solvents is hindered by the intimidating size of the chemical space. Here, we present a computational pipeline informing the identification of effective exfoliation agents. Classical molecular dynamics simulations provide statistical sampling of interactions, enabling the identification of key molecular descriptors for a successful solvent. The statistically representative configurations from these simulations, studied with quantum mechanical calculations, allow us to gain insights onto the chemophysical interactions at the surface-solvent interface. As an exemplar, through this pipeline we identify a potential graphene exfoliation agent 2-pyrrolidone and experimentally demonstrate it to be as effective as NMP. Our workflow can be generalized to any 2D material and solvent system, enabling the screening of a wide range of compounds and solvents to identify safer and cheaper means of producing dispersions.

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.

Formation of 3D graphene foams on soft templated metal monoliths.

Graphene foams are leading contenders as frameworks for polymer thermosets, filtration/pollution control and for use as an electrode material in energy storage devices, taking advantage of graphene's high electrical conductivity and the porous structure of the foam. Here we demonstrate a simple synthesis of a macroporous 3D graphene material templated from a dextran/metal salt gel, where the metal was cobalt, nickel, copper, and iron. The gel was annealed to form a metal oxide foam prior to a methane chemical vapour deposition (CVD). Cobalt metal gels were shown to afford the highest quality material as determined by electron microscopy (SEM and TEM) and Raman spectroscopy.

Graphene film growth on polycrystalline metals.

Graphene, a true wonder material, is the newest member of the nanocarbon family. The continuous network of hexagonally arranged carbon atoms gives rise to exceptional electronic, mechanical, and thermal properties, which could result in the application of graphene in next generation electronic components, energy-storage materials such as capacitors and batteries, polymer nanocomposites, transparent conducting electrodes, and mechanical resonators. With one particularly attractive application, optically transparent conducting electrodes or films, graphene has the potential to rival indium tin oxide (ITO) and become a material for producing next generation displays, solar cells, and sensors. Typically, graphene has been produced from graphite using a variety of methods, but these techniques are not suitable for growing large-area graphene films. Therefore researchers have focused much effort on the development of methodology to grow graphene films across extended surfaces. This Account describes current progress in the formation and control of graphene films on polycrystalline metal surfaces. Researchers can grow graphene films on a variety of polycrystalline metal substrates using a range of experimental conditions. In particular, group 8 metals (iron and ruthenium), group 9 metals (cobalt, rhodium, and iridium), group 10 metals (nickel and platinum), and group 11 metals (copper and gold) can support the growth of these films. Stainless steel and other commercial copper-nickel alloys can also serve as substrates for graphene film growth. The use of copper and nickel currently predominates, and these metals produce large-area films that have been efficiently transferred and tested in many electronic devices. Researchers have grown graphene sheets more than 30 in. wide and transferred them onto display plastic ready for incorporation into next generation displays. The further development of graphene films in commercial applications will require high-quality, reproducible growth at ambient pressure and low temperature from cheap, readily available carbon sources. The growth of graphene on metal surfaces has drawbacks: researchers must transfer the graphene from the metal substrate or remove the metal by etching. Further research is needed to overcome these transfer and removal challenges.

Graphene synthesis: relationship to applications.

Graphene is a true wonder material that promises much in a variety of applications that include electronic devices, supercapacitors, batteries, composites, flexible transparent displays and sensors. This review highlights the different methods available for the synthesis of graphene and discusses the viability and practicalities of using the materials produced via these methods for different graphene-based applications.

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.

Formylation of single-walled carbon nanotubes.

We report an improved, elegant method for the covalent formylation of single-wall carbon nanotubes (SWNTs) via formyl transfer from N-formylpiperidine, which could potentially open the gateway for more versatile chemical modification of carbon nanotube (CNT) walls than is possible via other reported functionalisation methods. The formylation reaction does not inflict damage upon the pristine CNT structure, unlike the currently commonly used carboxylation route, and involves much fewer steps, and takes considerably less time, than most other reported routes. The modified SWNTs have been characterised by Raman spectroscopy, ultraviolet-visible-near infrared (UV-vis-NIR) spectroscopy and "covalent tagging" with derivatising groups followed by thermogravimetric analysis-mass spectroscopy (TGA-MS). UV-vis-NIR spectroscopy shows that there is only limited disruption of the intrinsic electronic structure of the SWNTs. This is confirmed from estimates of the extent of functionalisation from TGA-MS, which suggest that it may be as low as 2 atomic per cent.

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.

Heterogenised N-heterocyclic carbene complexes: synthesis, characterisation and application for hydroformylation and C-C bond formation reactions.

The imidazolium salts: 1-mesityl-3-(3-trimethoxysilylpropyl)imidazolium iodide and 1-tert-butyl-3-(3-trimethoxysilylpropyl)imidazolium iodide, abbreviated as (tmpMes)HI (3a) and (tmp(t)Bu)HI (3b), respectively, have been synthesised. The palladium(ii) complexes (η(3)-C(3)H(5)) (tmpMes)PdCl (5a) and (η(3)-C(3)H(5))(tmp(t)Bu)PdCl (5b), rhodium(i) and iridium(i) complexes (η(4)-1,5-COD) (tmpMes)MCl, M = Rh (6a), Ir (7a) and (η(4)-1,5-COD)(tmp(t)Bu)MCl, where M = Rh (6b), Ir (7b), were synthesised by silver transmetallation reactions using the silver(i) complexes (tmpMes)AgI (4a) and (tmp(t)Bu)AgI (4b). The iridium complex 7b has been structurally characterised. The Pd(ii) and Rh(i) complexes have been immobilised by attachment to chemically modified MCM-41. The immobilised palladium(ii) materials have been tested as recyclable catalysts for Suzuki type C-C bond formation reactions in water and the immobilised rhodium(i) materials have been examined for their catalytic ability for the hydroformylation of 1-octene.

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.

The electronic fine structure of 4-nitrophenyl functionalized single-walled carbon nanotubes.

Controlling the electronic structure of carbon nanotubes (CNTs) is of great importance to various CNT based applications. Herein the electronic fine structure of single-walled carbon nanotube films modified with 4-nitrophenyl groups, produced following reaction with 4-nitrobenzenediazonium tetrafluoroborate, was investigated for the first time. Various techniques such as x-ray and ultra-violet photoelectron spectroscopy, and near edge x-ray absorption fine structure studies were used to explore the electronic structure, and the results were compared with the measured electrical resistances. A reduction in number of the pi electronic states in the valence band consistent with the increased resistance of the functionalized nanotube films was observed.

Stable crystalline annulated diaminocarbenes: coordination with rhodium(I), iridium(I) and catalytic hydroformylation studies.

Stable annulated diaminocarbene ligands 7,9-bis(2,4,6-trimethylphenyl)-6b,9a-dihydroace naphtha[1,2-d]imidazolin-2-ylidene and 7,9-bis(2,6-diisopropylphenyl)-6b,9a-dihydroacenaphtho[1,2-d]imidazolin-2-ylidene; designated as (BIAN-SIMes, 5a,) and (BIAN-SIPr, 5b), respectively, have been prepared. The base dependent decomposition of imidazolinium salts via ring opening at the backbone was also observed. The corresponding rhodium(I) and iridum(I) complexes (4-1,5-COD)M(BIAN-SIMes)Cl and (4-1,5-COD)M(BIAN-SIPr)Cl; M= Rh (6a, 6b) and Ir (7a, 7b) have been synthesised by the reaction of free carbene with [M(4-1,5-COD)(-Cl)]2; where M= Rh, Ir. The cationic Ir(I) complexes [(4-1,5-COD)Ir(BIAN-SIMes)Py]BF4 8a and [(4-1,5-COD)Ir(BIAN -SIPr)Py]PF6 8b have also been synthesised. Compounds 4b, 5a, 6a, 6b, 7b and 8b have been structurally characterised. The catalytic activities for the rhodium(I) complexes 6a and 6b were evaluated for the hydroformylation of 1-octene.

Poly(ethylene) glycol/single-walled carbon nanotube composites.

Single-walled carbon nanotubes have been shown to exhibit extraordinary electronic and mechanical properties. However, their relative inertness limits their use in many applications. Chemical functionalization can significantly modify their properties which, in addition to improving their processibility, when mixed in polymers can enhance the overall mechanical and electrical properties of the composites. In this work, we present the results of our investigation on the chemical modification of single-walled carbon nanotubes with aryl groups containing nitro substituents, and the incorporation of the modified nanotube material into a host matrix of poly(ethylene) glycol. The carbon nanotubes and composites were characterized by a combination of cyclic voltammetry, thermogravimetric analysis (TGA), Raman spectroscopy, Dynamic Mechanical Analysis (DMA) and electrical resistance (I-V) measurements.

A new route to the production and nanoscale patterning of highly smooth, ultrathin zirconium oxide films.

Metal-stabilized bilayers, prepared by the self-assembly of octadecyltrichorosilane on an oxidized silicon surface followed by the Langmuir-Blodgett deposition of a monolayer of octadecylphosphonic acid, have been used to generate 1.6 nanometer thick, highly uniform, zirconium oxide films following annealing. Patterning of the thin films on the nanometre scale was achieved using nanodisplacement methodology, by careful control of an atomic force microscope (AFM) probe, which allowed the selective removal of the upper leaflet of the bilayer.

Spatially controlled Suzuki and Heck catalytic molecular coupling.

The initiation and control of chemical coupling has the potential to offer much within the context of "bottom up" nanofabrication. We report herein the use of a palladium-modified, catalytically active, AFM probe to initiate and spatially control surface-confined Suzuki and Heck carbon-carbon coupling reactions. These "chemically written reactions", detectable by lateral force and chemically specific optical and topographic labeling, were patterned with line widths down to 15 nm or approximately 20 molecules. Catalyzed organometallic coupling was, in this way, carried out at subzeptomolar levels. By varying the catalyst-substrate interaction times, turnover numbers of (0.6-1.2) x 10(4) and (3.0-5.0) x 10(4) molecules s(-1) were resolved for Suzuki and Heck reactions, respectively.

Spatially resolved Suzuki coupling reaction initiated and controlled using a catalytic AFM probe.

Appropriately modified proximal probes can be utilized in the spatially resolved chemical coupling of surface-bound and solution-phase reagents. Herein we report a chemically specific Suzuki coupling reaction between a surface-confined aryl bromide and boronic acid reagents in solution achieved using a catalytic AFM probe.

Chemical and biochemical sensing with modified single walled carbon nanotubes.

The nano dimensions, graphitic surface chemistry and electronic properties of single walled carbon nanotubes make such a material an ideal candidate for chemical or biochemical sensing. Carbon nanotubes can be nondestructively oxidized along their sidewalls or ends and subsequently covalently functionalized with colloidal particles or polyamine dendrimers via carboxylate chemistry. Proteins adsorb individually, strongly and noncovalently along nanotube lengths. These nanotube-protein conjugates are readily characterized at the molecular level by atomic force microscopy. Several metalloproteins and enzymes have been bound on both the sidewalls and termini of single walled carbon nanotubes. Though coupling can be controlled, to a degree, through variation of tube oxidative pre-activation chemistry, careful control experiments and observations made by atomic force microscopy suggest that immobilization is strong, physical and does not require covalent bonding. Importantly, in terms of possible device applications, protein attachment appears to occur with retention of native biological structure. Nanotube electrodes exhibit useful voltammetric properties with direct electrical communication possible between a redox-active biomolecule and the delocalized pi system of its carbon nanotube support.