Flash microwave-assisted solvothermal (FMS) synthesis of photoactive anatase sub-microspheres with hierarchical porosity.

The synthesis of nanostructured sub-microspheres of TiO anatase with hierarchical nano- and mesoporosity was successfully achieved by using an innovative approach that applies the principles of acidic digestion to microwave (MW) solvothermal synthesis. This process, termed flash microwave-assisted solvothermal (FMS) synthesis, facilitates the formation of spherical particles without surfactants or templating agents, exploiting the rapid reaction kinetics engendered by MW heating. Unlike many other MW-assisted solvothermal methods, the application of constant MW power leads to a rapid increase of the autogenous pressure, inducing burst-nucleation of small primary crystallites and subsequent rapid agglomeration into secondary particles, with reaction times reduced to minute-timescales.

2D molybdenum disulphide nanosheets incorporated with single heteroatoms for the electrochemical hydrogen evolution reaction.

2D nanosheets give enhanced surface area to volume ratios in particle morphology and they can also provide defined surface sites to disperse foreign atoms. Placing atoms of catalytic interest on 2D nanosheets as Single Atom Catalysts (SAC) represents one of the novel approaches due to their unique but tunable electronic and steric characteristics. Here in this mini-review, we particularly highlight some recent and important developments on heteroatom doped MoS nanosheets (SAC-MoS) as catalysts for the electrochemical hydrogen evolution reaction (HER) from water, which could lead to opening up to a flagship of important renewable technologies in future.

Facile One-Pot Synthesis of Bimetallic Co/Mn-MOFs@Rice Husks, and its Carbonization for Supercapacitor Electrodes.

Novel hybrid nanomaterials comprising metal-organic framework compounds carbonised in the presence of biomass material derived from rice husk have been investigated as a new class of sustainable supercapacitor materials for electrochemical energy storage. Specifically, two synthetic routes were employed to grow Co/Mn metal-organic framework compounds in the channels of rice husks, which had been activated previously by heat treatment in air at 400 °C to produce a highly porous network. Pyrolysis of these hybrid materials under nitrogen at 700 °C for 6 h produced metal-containing phases within the nanocarbon, comprising intimate mixtures of Co, MnO and CoMnO.

Transition metal atom doping of the basal plane of MoS monolayer nanosheets for electrochemical hydrogen evolution.

Surface sites of extensively exposed basal planes of MoS monolayer nanosheets, prepared BuLi exfoliation of MoS, have been doped with transition metal atoms for the first time to produce 2D monolayer catalysts used for the electrochemical hydrogen evolution reaction (HER). Their HER activity is significantly higher than the corresponding thin and bulk MoS layers. HAADF-STEM images show direct proof that single transition metal atoms reside at the surface basal sites, which subtly modify the electro-catalytic activity of the monolayer MoS, dependent on their electronic and stereospecific properties.

The mechanism of electrochemical reduction of hydrogen peroxide on silver nanoparticles.

The reduction of hydrogen peroxide on a silver nanoparticle modified boron doped diamond electrode in a neutral solution is shown to proceed through a CE mechanism. Hydrogen peroxide undergoes a disproportionation reaction to form oxygen (and water) on the silver surface, creating a diffusion layer of oxygen, which, at a sufficiently biased electrode, is then reduced to hydrogen peroxide. Voltammetry and a full mechanistic simulation are undertaken to confirm the mechanism, showing at short times a dependence of the reductive signal on waiting time prior to voltammetric analysis reflecting the extent of the disproportionation step which occurs prior to voltammetric analysis.

Novel Modifications to Carbon-Based Electrodes to Improve the Electrochemical Detection of Dopamine.

In this work, we describe three simple modifications to carbon electrodes that were found to improve the detection of an exemplar neurotransmitter (dopamine) in the presence of physiological interferents (ascorbic acid and/or uric acid). First, the electro-oxidation of ascorbic acid, as a pretreatment, at boron-doped diamond electrode (BDE) interfaces is studied. This treatment did suppress the detection of ascorbic acid oxidation signal, but only in a manner suitable for single-use detection of high concentrations of dopamine (i.

New Routes to Functionalize Carbon Black for Polypropylene Nanocomposites.

Methods for chemical surface functionalization for carbon black (CB) nanoparticles were studied to produce (CB)/polypropylene (PP) nanocomposites with superior electrical and thermal properties. Nanoparticle dispersion is known to directly control the extent to which nanocomposites maximize the unique attributes of their nanoscale fillers. As a result, tailored nanoparticle surface chemistry is a widely utilized method to enhance the interfacial interactions between nanoparticles and polymer matrices, assisting improved filler dispersion.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD.

Cellulose-Derived Supercapacitors from the Carbonisation of Filter Paper.

Advanced carbon materials are important for the next-generation of energy storage apparatus, such as electrochemical capacitors. Here, the physical and electrochemical properties of carbonised filter paper (FP) were investigated. FP is comprised of pure cellulose and is a standardised material.

Surface Characterization and in situ Protein Adsorption Studies on Carbene-Modified Polymers.

Polystyrene thin films were functionalized using a facile two-step chemical protocol involving carbene insertion followed by azo-coupling, permitting the introduction of a range of chemical functional groups, including aniline, hexyl, amine, carboxyl, phenyl, phosphonate diester, and ethylene glycol. X-ray photoelectron spectroscopy (XPS) confirmed the success of the two-step chemical modification with a grafting density of at least 1/10th of the typical loading density (10(14)-10(15)) of a self-assembled monolayer (SAM). In situ, real-time quartz crystal microbalance with dissipation (QCM-D) studies show that the dynamics of binding of bovine serum albumin (BSA) are different at each modified surface.

Interfacial electron-shuttling processes across KolliphorEL monolayer grafted electrodes.

Covalently grafted KolliphorEL (a poly(ethylene glycol)-based transporter molecule for hydrophobic water-insoluble drugs; MW, ca. 2486; diameter, ca. 3 nm) at the surface of a glassy-carbon electrode strongly affects the rate of electron transfer for aqueous redox systems such as Fe(CN)6(3-/4-).

Amplified electron transfer at poly-ethylene-glycol (PEG) grafted electrodes.

"Amplified" electron transfer is observed purely based on electron transfer kinetic effects at modified carbon surfaces. An anodic attachment methodology is employed to modify the surface of glassy carbon or boron doped diamond electrodes with poly-ethylene glycols (PEGs) for polymerisation degrees of n = 4.5 to 9.

Glutamate biosensors based on diamond and graphene platforms.

l-Glutamate is one of the most important neurotransmitters in the mammalian central nervous system, playing a vital role in many physiological processes and implicated in several neurological disorders, for which monitoring of dynamic levels of extracellular glutamate in the living brain tissues may contribute to medical understanding and treatments. Electrochemical sensing of glutamate has been developed recently mainly using platinum, carbon fibre and carbon nanotube electrodes. In the present work, we explore the fabrication and properties of electrochemical glutamate sensors fabricated on doped chemical vapour deposition diamond electrodes and graphene nanoplatelet structures.

Hydrothermal conversion of one-photon-fluorescent poly(4-vinylpyridine) into two-photon-fluorescent carbon nanodots.

A novel two-photon-fluorescent N,O-heteroatom-rich carbon nanomaterial has been synthesized and characterized. The new carbon nanoparticles were produced by hydrothermal conversion from a one-photon-fluorescent poly(4-vinylpyridine) precursor (P4VP). The carbonized particles (cP4VP dots) with nonuniform particle diameter (ranging from sub-6 to 20 nm with some aggregates up to 200 nm) exhibit strong fluorescence properties in different solvents and have also been investigated for applications in cell culture media.

Shape selective plate-form Ga(2)O(3) with strong metal-support interaction to overlying Pd for hydrogenation of CO(2) to CH(3)OH.

A stronger metal-support interaction between Pd and plate-form Ga(2)O(3) nanocrystals covered with the predominant 002 surface than other Ga(2)O(3) surfaces is found, which gives higher methanol yield in catalytic CO(2) hydrogenation.

Plasma electrochemistry: development of a reference electrode material for high temperature plasma.

This report describes the development of a high temperature reference electrode material for gas phase electrochemistry investigations. The electrode is constructed by careful assessment of different metal/metal oxide materials and operational stability in flame electrolyte medium. This will enable reliable dynamic electrochemistry investigations into redox reactions at the solid/gas interface, free of any solvent defined potential window restrictions.

Shape-dependent acidity and photocatalytic activity of Nb2O5 nanocrystals with an active TT (001) surface.

Nb(2)O(5) nanorods and nanospheres were synthesized, and their photocatalytic activity for methylene blue decomposition in water compared. Nb(2)O(5) nanorods clearly displayed higher activity, despite their comparable surface area. With a shape-dependent surface acidity, hydrothermal stability, and high photoactivity, these Nb(2)O(5) nanorods are a unique and exciting nanomaterial for non-classical photocatalytic mineralization of organic compounds in water.

Enhanced TiO2 surface electrochemistry with carbonised layer-by-layer cellulose-PDDA composite films.

In this report we demonstrate a versatile (and potentially low-cost) cellulose nano-whisker-based surface carbonisation method that allows well-defined films of TiO(2) nanoparticles surface-modified with carbon to be obtained. In a layer-by-layer electrostatic deposition process based on TiO(2) nanoparticles, cellulose nano-whiskers, and poly(diallyl-dimethylammonium) or PDDA are employed to control the ratio of surface carbon to TiO(2). Characterisation based on optical, AFM, XRD, and XPS methods is reported.

Permselective properties of polystyrene opal films at diamond electrode surfaces.

The permselective properties of stable opal films formed by polystyrene nanospheres on boron-doped diamond (BDD) electrodes were studied for the first time by means of electrochemical voltammetric and impedance techniques. Films formed from spheres with a diameter above 200 nm are highly porous and have little influence on electrochemical properties. In contrast, porous films formed from 50 nm spheres have a selective influence on the electrochemistry observed, providing an enhancement in the redox peak current for neutral (ferrocenemethanol, dopamine) and positively-charged redox probe mediators (Ru(NH(3))(6)(3+)) and suppressing the current due to a negatively-charged redox species Fe(CN)(6)(4-).

Carbon nanoparticle surface functionalisation: converting negatively charged sulfonate to positively charged sulfonamide.

The surface functionalities of commercial sulfonate-modified carbon nanoparticles (ca. 9-18 nm diameter, Emperor 2000) have been converted from negatively charged to positively charged via sulfonylchloride formation followed by reaction with amines to give suphonamides. With ethylenediamine, the resulting positively charged carbon nanoparticles exhibit water solubility (in the absence of added electrolyte), a positive zeta-potential, and the ability to assemble into insoluble porous carbon films via layer-by-layer deposition employing alternating positive and negative carbon nanoparticles.

Focused ion beam fabrication of boron-doped diamond ultramicroelectrodes.

The fabrication of ultramicroelectrodes (UMEs) for analytical electrochemical applications has been explored, using boron-doped diamond as the active electrode material in an insulating coating formed by deposition of electrophoretic paint. Because of the rough nature of the diamond film, the property of such coatings that is normally exploited in the fabrication of UMEs, namely the tendency to retract automatically from sharp protrusions, cannot be used in the present instance. Instead focused ion beam (FIB) sputtering was employed to controllably produce UMEs with well-defined geometry, critical dimension of a few micrometers, and very thin insulating coatings.

Redox properties of undoped 5 nm diamond nanoparticles.

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(4-/3-) was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction.

Chemical functionalization of diamond surfaces by reaction with diaryl carbenes.

A rapid route to the chemical functionalization of hydrogen-terminated diamond surfaces deposited by chemical vapor deposition involving their reaction with substituted diaryl carbenes has been investigated. To avoid difficulties in the handling of highly reactive compounds, the carbene is generated in situ from the thermal decomposition at 400 K of a thin film of the corresponding diaryl diazomethane precursor deposited at the diamond interface. X-ray photoelectron spectroscopy (XPS) has been used to verify that surface functionalization using two starting compounds, bis(4-iodophenyl) diazomethane and bis(4-nitrophenyl) diazomethane, can be achieved using this approach in agreement with recent theoretical studies.

Hot filament chemical vapour deposition of diamond ultramicroelectrodes.

The hot filament chemical vapour deposition of boron-doped diamond was optimised for the fabrication of diamond ultramicroelectrodes. Applications of ultramicroelectrodes require thin, conformal and non-porous diamond coatings, which display electrochemical properties similar to those associated with good quality doped diamond electrodes. The growth conditions to attain these goals are elucidated.

Fabrication of boron-doped diamond ultramicroelectrodes for use in scanning electrochemical microscopy experiments.

Boron-doped diamond (BDD) ultramicroelectrode (UME) tips were fabricated by the growth of BDD films by chemical vapor deposition onto sharpened tungsten wires. Both nanocrystalline and microcrystalline forms of diamond coatings were examined. The diamond-coated wires were selectively insulated with nail varnish, electrophoretic paint, or fast-setting epoxy to form UME tips of critical dimensions of 1-25 microm.