Facet-controlled growth and soft-chemical exfoliation of two-dimensional titanium dioxide nanosheets.

TiO2 remains one of the most popular materials used in catalysts, photovoltaics, coatings, and electronics due to its abundance, chemical stability, and excellent catalytic properties. The tailoring of the TiO2 structure into two-dimensional nanosheets prompted the successful isolation of graphene and MXenes. In this review, facet-controlled TiO2 and monolayer titanate are outlined, covering their synthesis route and formation mechanism. The reactive facet of TiO2 is usually controlled by a capping agent. In contrast, the monolayer titanate is achieved by ion-exchange and delamination of layered titanates. Each route leads to 2D structures with unique physical and chemical properties, which expands its utilisation into several niche applications. We elaborate the detailed outlook for the future use and research studies of facet-controlled TiO2 and monolayer titanates. Advantages and disadvantages of both structures are provided, along with suggested applications for each type of 2D TiO2 nanosheets.

The stability of halloysite nanotubes in acidic and alkaline aqueous suspensions.

The long term stability of natural halloysite nanotubes was studied at room temperature (22 ± 2 °C) in pure water, acidic and basic aqueous suspensions. The structural and morphological transformations of nanotubes were studied by TEM, SEM, nitrogen adsorption, XRD Raman and FTIR spectroscopy accompanied by monitoring the concentration of dissolved Si(IV) and Al(III) in solution. It has been revealed that, in 1 mol dm(-3) H(2)SO(4) solution, the dissolution of halloysite is initiated on the inner surface of nanotubes, leading to the formation of amorphous spheroidal nanoparticles of SiO(2) whereas, in 1 mol dm(-3) NaOH solution, dissolution of the inner surface of nanotubes is accompanied by the formation of Al(OH)(3) nanosheets.

Electrodeposited lead dioxide coatings.

Lead dioxide coatings on inert substrates such as titanium and carbon now offer new opportunities for a material known for 150 years. It is now recognised that electrodeposition allows the preparation of stable coatings with different phase structures and a wide range of surface morphologies. In addition, substantial modification to the physical properties and catalytic activities of the coatings are possible through doping and the fabrication of nanostructured deposits or composites. In addition to applications as a cheap anode material in electrochemical technology, lead dioxide coatings provide unique possibilities for probing the dependence of catalytic activity on layer composition and structure (critical review, 256 references).

Carbon Materials as Positive Electrodes in Bromine-Based Flow Batteries.

Bromine based redox flow batteries (RFBs) can provide sustainable energy storage due to the abundance of bromine. Such devices pair Br2 /Br- at the positive electrode with complementary redox couples at the negative electrode. Due to the highly corrosive nature of bromine, electrode materials need to be corrosion resistant and durable. The positive electrode requires good electrochemical activity and reversibility for the Br2 /Br- couple. Carbon materials enjoy the advantages of low cost, excellent electrical conductivity, chemical resistance, wide operational potential ranges, modifiable surface properties, and high surface area. Here carbon based materials for bromine electrodes are reviewed, with a focus on application in zinc-bromine, hydrogen-bromine, and polysulphide-bromine RFB systems, aiming to provide an overview of carbon materials to be used for design and development of bromine electrodes with improved performance. Aspects deserving further R&D are highlighted.

Selection of oxygen reduction catalysts for secondary tri-electrode zinc-air batteries.

Oxygen reduction reaction (ORR) electrocatalysts, which are highly efficient, low-cost, yet durable, are important for secondary Zn-air cell applications. ORR activities of single and mixed metal oxide and carbon electrocatalysts were studied using rotating disc electrode (RDE) measurements, Tafel slope and Koutecky-Levich plots. It was found that MnOx combined with XC-72R demonstrated high ORR activity and good stability-up to 100 mA cm-2. The performance of the selected ORR electrode and a previously optimised oxygen evolution reaction (OER) electrode was thereafter tested in a custom-built secondary Zn-air cell in a tri-electrode configuration, and the effects of current density, electrolyte molarity, temperature, and oxygen purity on the performance of the ORR and OER electrode were investigated. Finally, the durability of the secondary Zn-air system was assessed, demonstrating energy efficiencies of 58-61% at 20 mA cm-2 over 40 h in 4 M NaOH + 0.3 M ZnO at 333 K.

Control over the hierarchical structure of titanate nanotube agglomerates.

An alkaline hydrothermal treatment of several types of ordered macroporous TiO(2) structures, namely, microtubes, sea urchin shapes, and anodic nanotube arrays, has been investigated under stationary conditions. The effect of the size and geometry of these structures on the morphology of the forming hierarchical agglomerates of titanate nanotubes has been systematically studied. It has been revealed that, at sizes larger than the critical value (ca. 1 µm), the whole geometry of the initial ordered TiO(2) structure is maintained under reaction conditions leading to formation of hierarchical structures, in which bulk TiO(2) is replaced with titanate nanotube agglomerates. This principle provides a convenient route for the preparation of multiscale micro- and nanostructures of TiO(2) based materials. The analysis of critical size suggests that, under reaction conditions, due to the limited transport of dissolved Ti(IV) species, the growth of nanotubes occurs locally.

Nickel based electrocatalysts for oxygen evolution in high current density, alkaline water electrolysers.

A number of nickel based materials are investigated as potential oxygen evolution catalysts under conditions close to those met in modern, high current density alkaline water electrolysers. Microelectrodes are used to avoid distortion of voltammetric data by IR drop even at the high current densities employed in such water electrolysers. High surface area nickel metal oxides prepared by cathodic deposition and mixed oxides prepared by thermal methods are considered. A mixed Ni/Fe oxide is the preferred electrocatalyst. The influence of hydroxide ion concentration and temperature on the voltammetry is defined. Preliminary stability tests in a zero gap cell with an OH(-) conducting membrane show no significant increase in overpotential during 10 days operation in 4 M NaOH electrolyte at a current density of 1 A cm(-2) at 333 K.

Experimental and computation assessment of thermomechanical effects during auxetic foam fabrication.

Auxetic foams continue to interest researchers owing to their unique and enhanced properties. Existing studies attest to the importance of fabrication mechanisms and parameters. However, disparity in thermo-mechanical parameters has left much debate as to which factors dominate fabrication output quality. This paper provides experimental, computational, and statistical insights into the mechanisms that enable auxetic foams to be produced, using key parameters reported within the literature: porosity; heating time; and volumetric compression ratio. To advance the considerations on manufacturing parameter dominance, both study design and scale have been optimised to enable statistical inferences to be drawn. Whilst being unusual for a manufacturing domain, such additional analysis provides more conclusive evidence of auxetic properties and highlights the supremacy of volumetric compression ratio in predicting Poisson's ratio outcomes in the manufacture process. Furthermore statistical results are exploited to formulate key recommendations for those wishing to maximise/optimise auxetic foam production.

3D Hierarchically Structured CoS Nanosheets: Li+ Storage Mechanism and Application of the High-Performance Lithium-Ion Capacitors.

Lithium-ion capacitors possess excellent power and energy densities, and they can combine both of those advantages from supercapacitors and lithium-ion batteries, leading to novel generation hybrid devices for storing energy. This study synthesized one three-dimensional (3D) hierarchical structure, self-assembled from CoS nanosheets, according to a simple and efficient manner, and can be used as an anode for lithium ion capacitors. This CoS anode, based on a conversion-type Li+ storage mechanism dominated by diffusion control, showed a large reversible capacity, together with excellent stability for cycling. The CoS shows a discharge capacity ≈434 mA h/g at 0.1 A/g. The hybrid lithium-ion capacitor, which had the CoS anode as well as the biochar cathode, exhibits excellent electrochemical performance with ultrahigh energy and power densities of 125.2 Wh/kg and 6400 W/kg, respectively, and an extended cycling life of 81.75% retention after 40 000 cycles. The CoS with self-assembled 3D hierarchical structure in combination with a carbon cathode offers a versatile device for future applications in energy storage.

Polymer nanocomposites having a high filler content: synthesis, structures, properties, and applications.

The recent development of nanoscale fillers, such as carbon nanotubes, graphene, and nanocellulose, allows the functionality of polymer nanocomposites to be controlled and enhanced. However, conventional synthesis methods of polymer nanocomposites cannot maximise the reinforcement of these nanofillers at high filler content. Approaches for the synthesis of high content filler polymer nanocomposites are suggested to facilitate future applications. The fabrication methods address the design of the polymer nanocomposite architecture, which encompasses one, two, and three dimensional morphologies. Factors that hamper the reinforcement of nanostructures, such as alignment, dispersion of the filler and interfacial bonding between the filler and polymer, are outlined. Using suitable approaches, maximum potential reinforcement of nanoscale fillers can be anticipated without limitations in orientation, dispersion, and the integrity of the filler particle-matrix interface. High filler content polymer composites containing emerging materials such as 2D transition metal carbides, nitrides, and carbonitrides (MXenes) are expected in the future.

Extraction of hydrophobic analytes from organic solution into a titanate 2D-nanosheet host: Electroanalytical perspectives.

Titanate nanosheets (single layer, typically 200 nm lateral size) deposited from aqueous colloidal solution onto electrode surfaces form lamellar hosts that bind redox active molecular redox probes. Here, hydrophobic redox systems such as anthraquinone, 1-amino-anthraquinone, deca-methylferrocene, 5,10,15,20-tetraphenyl-21H,23H-porphine manganese (III) chloride (TPPMnCl), and α-tocopherol are shown to bind directly from cyclopentanone solution (and from other types of organic solvents) into the titanate nanosheet film. For anthraquinone derivatives, stable voltammetric responses are observed in aqueous media consistent with 2-electron 2-proton reduction, however, independent of the pH of the outside solution phase environments. For decamethylferrocene a gradual decay of the voltammetric response is observed, but for TPPMnCl a more stable voltammetric signal is seen when immersed in chloride containing (NaCl) electrolyte. α-Tocopherol exhibits chemically irreversible oxidation and is detected with 1 mM-20 mM linear range and approximately 10-3 M concentration limit of detection. All redox processes exhibit an increase in current with increasing titanate film thickness and with increasing external electrolyte concentration. This and other observations suggest that important factors are analyte concentration and mobility within the titanate host, as well as ion exchange between titanate nanosheets and the outside electrolyte phase to maintain electroneutrality during voltammetric experiments. The lamellar titanate (with embedded tetrabutyl-ammonium cations) behaves like a hydrophobic host (for hydrophobic redox systems) similar to hydrophobic organic microphase systems. Potential for analytical applications is discussed.

Voltammetric characterisation of diferrocenylborinic acid in organic solution and in aqueous media when immobilised into a titanate nanosheet film.

Diferrocenylborinic acid (Fc2BOH, 1) has been synthesized in good yield via an improved synthetic path. Characterisation by nuclear magnetic resonance (NMR), mass spectrometry (HRMS), infrared spectroscopy (FTIR), X-ray crystallography, and by electrochemical methods reveal two one-electron oxidation processes for the two electronically coupled ferrocenyl moieties. The oxidation of 1 dissolved in organic media is contrasted to the oxidation of 1 in aqueous environments (by incorporation of 1 into a lamellar film of 2D titanate nanosheets on a glassy carbon electrode). Data from cyclic voltammetry and from square wave voltammetry suggest that the bridging boron can bind to nucleophiles (hydroxide, fluoride) upon oxidation of the ferrocenyl groups. A multi-pathway ECE reaction scheme is proposed. Potential applications in sensing are discussed.

Apparent two-dimensional behavior of TiO2 nanotubes revealed by light absorption and luminescence.

Optical absorption and photoluminescence (PL) properties of colloidal TiO(2) nanotubes, produced by the alkali hydrothermal method, were studied at room temperature in the range 300-700 nm. Nanotubes having an internal diameter in the range 2.5-5 nm have very similar optical properties, in contrast to the expected behavior for quasi-1-D systems. This is explained by the complete thermal smearing of all 1-D effects, due to the large effective mass of charge carriers in TiO(2), resulting in an apparent 2-D behavior of TiO(2) nanotubes.

Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes.

The sorption of hydrogen between the layers of the multilayered wall of nanotubular TiO2 was studied in the temperature range of -195 to 200 degrees C and at pressures of 0 to 6 bar. Hydrogen can intercalate between layers in the walls of TiO2 nanotubes forming host-guest compounds TiO2 x xH2, where x < or = 1.5 and decreases at higher temperatures. The rate of hydrogen incorporation increases with temperature and the characteristic time for hydrogen sorption in TiO2 nanotubes is several hours at 100 degrees C. The rate of intercalate formation is limited by the diffusion of molecular hydrogen inside the multilayered walls of the TiO2 nanotube. 1H NMR-MAS and XRD data confirm the incorporation of hydrogen between the layers in the walls of TiO2 nanotubes. The nature and possible applications of the observed intercalates are considered.

Hierarchical tube-in-tube structures prepared by electrophoretic deposition of nanostructured titanates into a TiO2 nanotube array.

Multiwalled nanotubular titanates have been incorporated inside the pores of a wide TiO2 nanotube array using electrophoretic deposition under vigorous stirring. The resulting hierarchical electrodes combine both benefits of open channels for rapid transport of ions and high specific surface area.

An aqueous, alkaline route to titanate nanotubes under atmospheric pressure conditions.

A significant reduction in the temperature for alkaline synthesis of titanate nanotubes is reported. Nanotubular titanates have been synthesized from TiO(2) at 100 °C in a mixture of concentrated, aqueous solutions of KOH and NaOH. After 48 h of refluxing, essentially complete conversion was achieved. For a given temperature, the composition of KOH and NaOH in the binary mixture was chosen to achieve a particular concentration of Ti(IV), which favoured the formation of nanotubes. The morphology, surface area and crystal structure of the titanate nanotubes produced were similar to those produced in a solution of pure NaOH at a higher temperature (≈140 °C).

Electrochemical removal of metal ions from aqueous solution: a student workshop.

An environmental electrochemistry workshop program on metal ion removal is described. The program was designed for undergraduate students in chemistry, chemical engineering or environmental science and teaches environmental electrochemistry through a combination of hands-on experiments, understanding of research concepts, completion of project reports and in class discussion. The students are encouraged to quantitatively describe the performance of the electrochemical cells (containing 2-D and 3-D carbon cathodes) and to consider the advantages and shortcomings of electrochemical routes to environmental treatment.