Heterogeneous ice nucleation is an important process in many fields, particularly atmospheric science, but is still poorly understood. All known inorganic ice nucleating particles are relatively large in size and tend to be hydrophilic. Hence it is not obvious that carbon nanomaterials should nucleate ice. However, in this paper we show that four different readily water-dispersible carbon nanomaterials are capable of nucleating ice. The tested materials were carboxylated graphene nanoflakes, graphene oxide, oxidized single walled carbon nanotubes and oxidized multiwalled carbon nanotubes. The carboxylated graphene nanoflakes have a diameter of ∼30 nm and are among the smallest entities observed so far to nucleate ice. Overall, carbon nanotubes were found to nucleate ice more efficiently than flat graphene species, and less oxidized materials nucleated ice more efficiently than more oxidized species. These well-defined carbon nanomaterials may pave the way to bridging the gap between experimental and computational studies of ice nucleation.

The DO ice VI to ice XV hydrogen ordering phase transition at ambient pressure is investigated in detail with neutron diffraction. The lattice constants are found to be sensitive indicators for hydrogen ordering. The a and b lattice constants contract whereas a pronounced expansion in c is found upon hydrogen ordering. Overall, the hydrogen ordering transition goes along with a small increase in volume, which explains why the phase transition is more difficult to observe upon cooling under pressure. Slow-cooling ice VI at 1.4 GPa gives essentially fully hydrogen-disordered ice VI. Consistent with earlier studies, the ice XV obtained after slow-cooling at ambient pressure is best described with P-1 space group symmetry. Using a new modelling approach, we achieve the atomistic reconstruction of a supercell structure that is consistent with the average partially ordered structure derived from Rietveld refinements. This shows that C-type networks are most prevalent in ice XV, but other structural motifs outside of the classifications of the fully hydrogen-ordered networks are identified as well. The recently proposed Pmmn structural model for ice XV is found to be incompatible with our diffraction data, and we argue that only structural models that are capable of describing full hydrogen order should be used.

Gold(I) salts are found to mediate the decarboxylation of a variety of aromatic and heteroaromatic carboxylic acids at significatively lower temperatures (as low as 60 8C) than the currently used copper(I) (180-190 8C) and silver(I) (80-140 8C) systems. In contrast to silver(I)-and copper(I)-mediated decarboxylations, the resulting aryl-gold(I) complexes are stable towards protodemetallation and can be readily isolated.

Graphene nanoflakes (GNF) of diameter ca. 30 nm and edge-terminated with carboxylic acid (COOH) or amide functionalities were characterised electrochemically after drop-coating onto a boron-doped diamond (BDD) electrode. In the presence of the outer-sphere redox probe ferrocenemethanol there was no discernible difference in electrochemical response between the clean BDD and GNF-modified electrodes. When ferricyanide or hydroquinone were used as redox probes there was a marked difference in response at the electrode modified with COOH-terminated GNF in comparison to the unmodified BDD and amide-terminated GNF electrode. The response of the COOH-terminated GNF electrode was highly pH dependent, with the most dramatic differences in response noted at pH < 8. This pH range coincides with partial protonation of the carboxylic acid groups as determined by titration. The acid edge groups occupy a range of bonding environments and are observed to undergo deprotonation over a pH range ca. 3.7 to 8.3. The protonation state of the GNF influences the oxidation mechanism of hydroquinone and in particular the number of solution protons involved in the reaction mechanism. The voltammetric response of ferricyanide is very inhibited by the presence of COOH-terminated GNF at pH < 8, especially in low ionic strength solution. While the protonation state of the GNF is clearly a major factor in the observed response, the exact role of the acid group in the redox process has not been firmly established. It may be that the ferricyanide species is unstable in the solution environment surrounding the GNF, where dynamic protonation equilibria are at play, perhaps through disruption to ion pairing.

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Carboxylic anhydrides exist in dynamic equilibrium with carboxylic acid groups at the graphene edge. These can be used for chemical functionalization with amine nucleophiles in a simple, straight-forward manner.

Nano graphene-oxide (nGO) is used in a wide range of applications including cellular imaging, drug delivery, desalination and energy storage. Current preparation protocols are similar as for standard graphene oxide (GO) and typically rely on mixtures of sulfuric acid and potassium permanganate. We present a new route to nGO (~30 nm diameter) using a quite defective arc-discharge carbon source and only 9 M nitric acid as the oxidising agent. The preparation can be scaled up proportionately with current GO protocols with 50 mL of half-concentrated nitric acid able to process one gram of arc-discharge material. The workup is straight forward and involves neutralisation with sodium hydroxide which precipitates the sodium salt of nGO from solution. The only by-product of the new procedure is aqueous sodium nitrate which makes this protocol the cleanest route yet to nGO. The presence and quantities of functional groups in our nGO are determined and compared with standard GO. We anticipate that this new route to nGO will foster a range of new applications. The presence of highly reactive carboxylic anhydride groups on our nGO material in particular offers an excellent opportunity for purpose-specific chemical functionalization.

Graphitic carbon nitrides (GCNs) represent a family of 2D materials composed of carbon and nitrogen with variable amounts of hydrogen, used in a wide variety of applications. We report a method of room temperature thin film deposition which allows ordered GCN layers to be deposited on a very wide variety of substrates, including conductive glass, flexible plastics, nanoparticles and nano-structured surfaces, where they form a highly conformal coating on the nanoscale. Film thicknesses of below 20 nm are achievable. In this way we construct functional nanoscale heterojunctions between TiO nanoparticles and GCN, capable of producing H photocatalytically under visible light irradiation. The films are hydrogen rich, have a band gap around 1.7 eV, display transmission electron microscopy lattice fringes as well as X-ray diffraction peaks despite being deposited at room temperature, and show characteristic Raman and IR bands. We use cluster etching to reveal the chemical environments of C and N in GCN using X-ray photoelectron spectroscopy. We elucidate the mechanism of this deposition, which operates via sequential surface adsorption and reaction analogous to atomic layer deposition. The mechanism may have implications for current models of carbon nitride formation.