Proton transport through one-atom-thick crystals.

Graphene is increasingly explored as a possible platform for developing novel separation technologies. This interest has arisen because it is a maximally thin membrane that, once perforated with atomic accuracy, may allow ultrafast and highly selective sieving of gases, liquids, dissolved ions and other species of interest. However, a perfect graphene monolayer is impermeable to all atoms and molecules under ambient conditions: even hydrogen, the smallest of atoms, is expected to take billions of years to penetrate graphene's dense electronic cloud. Only accelerated atoms possess the kinetic energy required to do this. The same behaviour might reasonably be expected in the case of other atomically thin crystals. Here we report transport and mass spectroscopy measurements which establish that monolayers of graphene and hexagonal boron nitride (hBN) are highly permeable to thermal protons under ambient conditions, whereas no proton transport is detected for thicker crystals such as monolayer molybdenum disulphide, bilayer graphene or multilayer hBN. Protons present an intermediate case between electrons (which can tunnel easily through atomically thin barriers) and atoms, yet our measured transport rates are unexpectedly high and raise fundamental questions about the details of the transport process. We see the highest room-temperature proton conductivity with monolayer hBN, for which we measure a resistivity to proton flow of about 10 Ω cm(2) and a low activation energy of about 0.3 electronvolts. At higher temperatures, hBN is outperformed by graphene, the resistivity of which is estimated to fall below 10(-3) Ω cm(2) above 250 degrees Celsius. Proton transport can be further enhanced by decorating the graphene and hBN membranes with catalytic metal nanoparticles. The high, selective proton conductivity and stability make one-atom-thick crystals promising candidates for use in many hydrogen-based technologies.

A facile electrochemical route to the preparation of uniform and monoatomic copper shells for gold nanoparticles.

Copper on gold forms a monolayer deposit via underpotential deposition. For gold particles adsorbed at a liquid-liquid interface this results in a uniform one monolayer thick shell. This approach offers a new route for the uniform functionalisation of nanoparticles and presents a way to probe fundamental processes that underlie nanoparticle synthesis.

The offset droplet: a new methodology for studying the solid/water interface using x-ray photoelectron spectroscopy.

The routine study of the solid-water interface by XPS is potentially revolutionary as this development opens up whole new areas of study for photoelectron spectroscopy. To date this has been realised by only a few groups worldwide and current techniques have significant restrictions on the type of samples which can be studied. Here we present a novel and uniquely flexible approach to the problem. By introducing a thin capillary into the NAP-XPS, a small droplet can be injected onto the sample surface, offset from the analysis area by several mm. By careful control of the droplet size a water layer of controllable thickness can be established in the analysis area-continuous with the bulk droplet. We present results from the solid-water interface on a vacuum prepared TiO2(110) single crystal and demonstrate that the solid/liquid interface is addressable.

The significance of bromide in the Brust-Schiffrin synthesis of thiol protected gold nanoparticles.

The mechanism of the two-phase Brust-Schiffrin synthesis of alkane thiol protected metal nanoparticles is known to be highly sensitive to the precursor species and reactant conditions. In this work X-ray absorption spectroscopy is used in conjunction with liquid/liquid electrochemistry to highlight the significance of Br- in the reaction mechanism. The species [AuBr4]- is shown to be a preferable precursor in the Brust-Schiffrin method as it is more resistant to the formation of Au(i) thiolate species than [AuCl4]-. Previous literature has demonstrated that avoidance of the Au(i) thiolate is critical to achieving a good yield of nanoparticles, as [Au(i)X2]- species are more readily reduced by NaBH4. We propose that the observed behavior of [AuBr4]- species described herein explains the discrepancies in reported behavior present in the literature to date. This new mechanistic understanding should enable nanoparticle synthesis with a higher yield and reduce particle size polydispersity.

Sieving hydrogen isotopes through two-dimensional crystals.

One-atom-thick crystals are impermeable to atoms and molecules, but hydrogen ions (thermal protons) penetrate through them. We show that monolayers of graphene and boron nitride can be used to separate hydrogen ion isotopes. Using electrical measurements and mass spectrometry, we found that deuterons permeate through these crystals much slower than protons, resulting in a separation factor of ≈10 at room temperature. The isotope effect is attributed to a difference of ≈60 milli-electron volts between zero-point energies of incident protons and deuterons, which translates into the equivalent difference in the activation barriers posed by two-dimensional crystals. In addition to providing insight into the proton transport mechanism, the demonstrated approach offers a competitive and scalable way for hydrogen isotope enrichment.

How to get between the sheets: a review of recent works on the electrochemical exfoliation of graphene materials from bulk graphite.

Since the beginning of the 'graphene era' post-2004, there has been significant interest in developing a high purity, high yield, and scalable fabrication route toward graphene materials for both primary research purposes and industrial production. One suitable approach to graphene production lies in the realm of electrochemical exfoliation, in which a potential difference is applied between a graphite anode/cathode in the presence of an electrolyte-containing medium. Herein we review various works on the electrochemical fabrication of graphene materials specifically through the use of electrochemical intercalation and exfoliation of a graphite source electrode, focusing on the quality and purity of products formed. We categorise the most significant works in terms of anodic and cathodic control, highlighting the merits of the respective approaches, as well as indicating the challenges associated with both procedures.

Treatment of dyehouse effluents with a carbon-based adsorbent using anodic oxidation regeneration.

Adsorption is an attractive route for the removal of coloured, toxic and non-biodegradable organics from wastewater as very low discharge standards can be achieved. This paper reports on the use of a novel carbon-based material, Nyex100, as an adsorbent material for the treatment of dyehouse effluent. The adsorbent has low porosity and high electrical conductivity and these factors have allowed the adsorbent to be electrochemically regenerated. This work has demonstrated that the adsorbent can be cycled through the process of adsorption and regeneration a number of times with little drop in adsorptive capacity. However regeneration appears to modify the preference for organic species adsorption. Electrochemical regeneration can be rapidly achieved (15-20 minutes) using low current densities (< 20 mA cm(-2)). However, the low adsorptive capacity of the adsorbent, because of its small surface area, means that large quantities of adsorbent would need to be cycled within the process to treat the effluent volume generated in even small dyehouses. Thus, it is believed that operating the process in this mode limits the practical application of this technology.

High-yield electro-oxidative preparation of graphene oxide.

Herein, we report a green electrochemical oxidative approach to convert large quantities of graphite into graphene oxide (GO). The resulted GO flakes have been characterized using various analytical techniques. It was possible to control the degree of oxidation of the produced GO via controlling the electrochemical parameters of the process.