Band alignment of rutile and anatase TiO2.

The most widely used oxide for photocatalytic applications owing to its low cost and high activity is TiO2. The discovery of the photolysis of water on the surface of TiO2 in 1972 launched four decades of intensive research into the underlying chemical and physical processes involved. Despite much collected evidence, a thoroughly convincing explanation of why mixed-phase samples of anatase and rutile outperform the individual polymorphs has remained elusive. One long-standing controversy is the energetic alignment of the band edges of the rutile and anatase polymorphs of TiO2 (ref. ). We demonstrate, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function. Our results help to explain the robust separation of photoexcited charge carriers between the two phases and highlight a route to improved photocatalysts.

Sensors-on-paper: Fabrication of graphite thermal sensor arrays on cellulose paper for large area temperature mapping.

This paper reports on a fabrication method to obtain multiple thermal sensors by employing an array of graphite thermocouple patterns on commonly available Xerox paper. The graphite thermocouples are patterned using two different grade graphite pencils, which show a stable and reproducible thermal sensitivity. The fabricated paper devices with multiple thermocouple arrays are capable of producing temperature mapping of the desired area. Different thermal conditions were applied to test and confirm the working of these devices. The present work shows that simple graphite trace patterns can convert a piece of paper into a thermal mapping device.

Photocatalytic Degradation of Rhodamine B Dye and Hydrogen Evolution by Hydrothermally Synthesized NaBH4-Spiked ZnS Nanostructures.

Metal sulphides, including zinc sulphide (ZnS), are semiconductor photocatalysts that have been investigated for the photocatalytic degradation of organic pollutants as well as their activity during the hydrogen evolution reaction and water splitting. However, devising ZnS photocatalysts with a high overall quantum efficiency has been a challenge due to the rapid recombination rates of charge carriers. Various strategies, including the control of size and morphology of ZnS nanoparticles, have been proposed to overcome these drawbacks. In this work, ZnS samples with different morphologies were prepared from zinc and sulphur powders via a facile hydrothermal method by varying the amount of sodium borohydride used as a reducing agent. The structural properties of the ZnS nanoparticles were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques. All-electron hybrid density functional theory calculations were employed to elucidate the effect of sulphur and zinc vacancies occurring in the bulk as well as (220) surface on the overall electronic properties and absorption of ZnS. Considerable differences in the defect level positions were observed between the bulk and surface of ZnS while the adsorption of NaBH4 was found to be highly favourable but without any significant effect on the band gap of ZnS. The photocatalytic activity of ZnS was evaluated for the degradation of rhodamine B dye under UV irradiation and hydrogen generation from water. The ZnS nanoparticles photo-catalytically degraded Rhodamine B dye effectively, with the sample containing 0.01 mol NaBH4 being the most efficient. The samples also showed activity for hydrogen evolution, but with less H2 produced compared to when untreated samples of ZnS were used. These findings suggest that ZnS nanoparticles are effective photocatalysts for the degradation of rhodamine B dyes as well as the hydrogen evolution, but rapid recombination of charge carriers remains a factor that needs future optimization.

The relationship between photocatalytic activity and photochromic state of nanoparticulate silver surface loaded titanium dioxide thin-films.

Anatase titania thin-films were prepared by a modified spray-pyrolysis method. Glass substrates were coated at room temperature with an aerosol-spray of a titania sol-gel solution and then annealed at 500 °C to form rough, transparent, crystalline thin-films of anatase TiO(2). Silver nanoparticles were deposited on the surface of these films by a photo-assisted deposition method; films were dip-coated in methanolic solutions of silver nitrate salt and then photo-irradiated for 5 h with UVC light. The AgNO(3) concentration was adjusted to create an array of films with varying silver loadings. The films displayed photochromism; changing colour to orange-brown in UV-light to colourless under white light. The rates of photochromic change, when subjected to four different lighting conditions (UVC, UVA, white light and dark), were analysed by UV-visible spectroscopy. By assessing the photocatalytic activity to these light sources it was found that the initial photochromic state of the material had a profound effect on the films photocatalytic ability. This effect was more pronounced in the more concentrated silver loaded films; where significant enhancements in photoactivity occurred when reactions were initiated from the photo-reduced state. The mode of improved photocatalysis was attributed to the photo-generated electron trapping by silver nanoparticles, which stabilised photo-generated holes and drove photo-oxidation processes. We believe this is the first study in which the relationship between the photochromic state of a thin-film and its subsequent photocatalytic activity is reported.

The role of surfaces in catheter-associated infections.

In this critical review the biocidal efficacies of a variety of antimicrobial coatings currently in use for catheter surfaces are discussed to formulate the best strategy for decreasing the risk of catheter-associated infections. The development of new coatings containing antimicrobial chemicals and light-activated antimicrobial agents, and their applicability for use in catheters are summarised (132 references).

Woven Stainless-Steel Mesh as a Gas Separation Membrane for Alkaline Water-Splitting Electrolysis.

A 316-grade woven stainless-steel mesh membrane was investigated as a gas-separation membrane for alkaline water-splitting electrolysis. Its resistance was measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV), with the conclusion that it presented approximately half the resistance of a comparable commercial alternative (ZirfonTM). Its gas-separation performance was analysed using gas chromatography (GC) at 140 mA cm-2, where it achieved 99.25% purity at the hydrogen outlet of the electrolyser. This fell to 97.5% under pumped circulation, which highlights that it is sensitive to pressure differentials. Nevertheless, this mixture is still more than a factor two inside the upper flammability limit of hydrogen in oxygen. It is hoped that such a low-cost material may bring entry-level electrolysis to many hitherto discounted applications.

Low dimensional nanostructures of fast ion conducting lithium nitride.

As the only stable binary compound formed between an alkali metal and nitrogen, lithium nitride possesses remarkable properties and is a model material for energy applications involving the transport of lithium ions. Following a materials design principle drawn from broad structural analogies to hexagonal graphene and boron nitride, we demonstrate that such low dimensional structures can also be formed from an s-block element and nitrogen. Both one- and two-dimensional nanostructures of lithium nitride, Li3N, can be grown despite the absence of an equivalent van der Waals gap. Lithium-ion diffusion is enhanced compared to the bulk compound, yielding materials with exceptional ionic mobility. Li3N demonstrates the conceptual assembly of ionic inorganic nanostructures from monolayers without the requirement of a van der Waals gap. Computational studies reveal an electronic structure mediated by the number of Li-N layers, with a transition from a bulk narrow-bandgap semiconductor to a metal at the nanoscale.

The interaction between gold nanoparticles and cationic and anionic dyes: enhanced UV-visible absorption.

The interactions of charge stabilised gold nanoparticles with cationic and anionic dyes are reported. The nanoparticles were synthesised by the Turkevich citrate reduction method. It was found that when a solution of thiazine dye is titrated against gold citrate hydrosol, at a critical concentration of dye there is an enhanced maximum absorption in the dye. The extinction coefficient is increased up to ten-fold. This enhancement was observed for a number of cationic thiazine dyes, of which methylene blue and toluidine blue are established light-activated antimicrobial agents. The same enhancement was not observed for anionic, acidic dyes such as rose bengal which showed no communication with the gold nanoparticles and showed UV-visible titration experiments with well formed isosbestic points. By studying the interaction of the dye and gold nanoparticles under conditions of different ionic strength and by using a zetasizer and TEM to measure the gold nanoparticle size it was demonstrated that the cause of enhancement was not due to nanoparticle aggregation. It is proposed that thiazine cationic dyes coordinate around a gold nanoparticle and give significantly enhanced UV-visible absorptions.

Powering the Hydrogen Economy from Waste Heat: A Review of Heat-to-Hydrogen Concepts.

Ever-increasing energy demands and environmental concerns require new and clean energy supplies, many of which are intermittent and do not correlate with demand. To balance supply with demand, a universal energy vector should be employed such that intermittent renewable energy can be stored and transported and then used when needed. Hydrogen is the perfect universal energy vector and a possible solution that ensures environmental cleanliness, maximum utilization of renewable energy sources, and high efficiency, whereby the combustion of the fuel yields only water. One abundant and freely available energy source-both anthropogenic and natural-is heat. Heat can be obtained from industrial processes and is indeed often viewed as a waste product with a premium to remove but is notoriously difficult to capture, store, and transport. Capturing and storing low-grade heat therefore provides a significant opportunity and can be achieved by coupling thermoelectric generators and water electrolyzers. A thermoelectric generator is placed within a thermal energy gradient and produces a flow of current that is fed to the electrolysis unit with which it produces hydrogen and oxygen as the final products. The hydrogen can be stored for long periods and transported for "on-demand" use in fuel cells for electricity from hydrogen burners for a return to thermal energy. This Review summarizes the current state-of-the-art research into implementing thermoelectric generators and utilizing heat as a primary energy source to produce hydrogen, which could replace the need for extra electric power to run hydrogen production units. Furthermore, suitable requirements, modifications, and other related aspects associated with such a new and novel method of hydrogen generation are discussed. Hydrogen produced from otherwise-wasted energy sources can be considered to be green.

Photocapacitive CdS/WOx nanostructures for solar energy storage.

Through a facile solvothermal procedure, a CdS/WOx nanocomposite has been synthesised which exhibits photocapacitive behaviour under white light illumination at a radiant flux density of 99.3 mW cm-2. Photoelectrochemical experiments were undertaken to examine the self-charging properties of the material and to develop an understanding of the underlying electronic band structure responsible for the phenomenon. By employing XPS, UPS and UV-Vis diffuse reflectance spectroscopy for further characterisation, the ability of the composite to generate current following the removal of incident light was related to the trapping of photoexcited electrons by the WOx component. The presence of WOx yielded an order of magnitude increase in the transient photocurrent response relative to CdS alone, an effect attributed to the suppression of electron-hole recombination in CdS due to hole transfer across the CdS/WOx interface. Moreover, current discharge from the material persisted for more than twenty minutes after final illumination, an order of magnitude improvement over many existing binary composites. As a seminal investigation into the photocapacitive characteristics of CdS/WOx composites, the work offers insight into how the constituent materials might be utilised as part of a future self-charging solar device.

Active removal of waste dye pollutants using Ta3N5/W18O49 nanocomposite fibres.

A scalable solvothermal technique is reported for the synthesis of a photocatalytic composite material consisting of orthorhombic Ta3N5 nanoparticles and WOx≤3 nanowires. Through X-ray diffraction and X-ray photoelectron spectroscopy, the as-grown tungsten(VI) sub-oxide was identified as monoclinic W18O49. The composite material catalysed the degradation of Rhodamine B at over double the rate of the Ta3N5 nanoparticles alone under illumination by white light, and continued to exhibit superior catalytic properties following recycling of the catalysts. Moreover, strong molecular adsorption of the dye to the W18O49 component of the composite resulted in near-complete decolourisation of the solution prior to light exposure. The radical species involved within the photocatalytic mechanisms were also explored through use of scavenger reagents. Our research demonstrates the exciting potential of this novel photocatalyst for the degradation of organic contaminants, and to the authors' knowledge the material has not been investigated previously. In addition, the simplicity of the synthesis process indicates that the material is a viable candidate for the scale-up and removal of dye pollutants on a wider scale.

Assembly of porous hierarchical copolymers/resin proppants: New approaches to smart proppant immobilization via molecular anchors.

HYPOTHESIS: The assembly of temperature/pH sensitive complex microparticle structures through chemisorption and physisorption provides a responsive system that offers application as routes to immobilization of proppants in-situ. EXPERIMENTS: Thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) along with energy dispersive X-ray analysis (EDX) have been used to characterize a series of bi-functionalized monolayers and/or multilayers grown on alumina microparticles and investigate the reactive nature of both temperature sensitive cross-linker (epoxy resin) with the layers and pH-responsive bridging layer (polyetheramine). FINDINGS: The bifunctional acids, behaving as molecular anchors, allow for a controlled reaction with a cross-linker (resin or polymer) with the formation of networks, which is either irreversible or reversible based on the nature of the cross-linker. The networks results in formation of porous hierarchical particles that offer a potential route to the creation of immobile proppant pack.

Nanoparticle-sulphur "inverse vulcanisation" polymer composites.

Composites of sulphur polymers with nanoparticles such as PbS, with tunable optical properties are reported. A hydrothermal route incorporating pre-formed nanoparticles was used, and their physical and chemical properties evaluated by transmission and scanning electron microscopy, thermogravimetric and elemental analyses. These polymers are easily synthesised from an industrial waste material, elemental sulphur, can be cast into virtually any form and as such represent a new class of materials designed for a responsible energy future.

Anatase/rutile bi-phasic titanium dioxide nanoparticles for photocatalytic applications enhanced by nitrogen doping and platinum nano-islands.

Titanium dioxide (TiO2) bi-phasic powders with individual particles containing an anatase and rutile hetero-junction have been prepared using a sequential layer sol-gel deposition technique to soluble substrates. Sequential thin films of rutile and subsequently anatase TiO2 were deposited onto sodium chloride substrates yielding extremely fragile composite layered discs that fractured into "Janus-like" like powders on substrate dissolution. Nitrogen doped and platinum sputtered analogues were also prepared, and analysed for photocatalytic potential using the photodegradation of Rhodamine B, a model organic pollutant under UV and visible light irradiation. The materials were characterised using X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy and scanning electron microscopy. This paper sheds light on the relationship between anatase and rutile materials when in direct contact and demonstrates a robust method for the synthesis of bi-phasic nanoparticles, ostensibly of any two materials, for photocatalytic reactions or otherwise.

Bi-phasic titanium dioxide nanoparticles doped with nitrogen and neodymium for enhanced photocatalysis.

Bi-phasic or multi-phasic composite nanoparticles for use in photocatalysis have been produced by a new synthetic approach. Sol-gel methods are used to deposit multiple layers of active material onto soluble substrates. In this work, a layer of rutile (TiO2) was deposited onto sodium chloride pellets followed by an annealing step and a layer of anatase. After dissolving the substrate, bi-phasic nanoparticles containing half anatase and half rutile TiO2; with "Janus-like" characteristics are obtained. Nitrogen and neodymium doping of the materials were observed to enhance the photocatalytic properties both under UV and white light irradiation. The unique advantage of this synthetic method is the ability to systematically dope separate sides of the nanoparticles. Nitrogen doping was found to be most effective on the anatase side of the nanoparticle while neodymium was found to be most effective on the rutile side. Rhodamine B dye was effectively photodegraded by co-doped particles under white light.

Silver enhanced TiO2 thin films: photocatalytic characterization using aqueous solutions of tris(hydroxymethyl)aminomethane.

The photocatalytic activity in aqueous solutions of TiO2 and Ag enhanced TiO2 sol-gel produced films was characterized using tris(hydroxymethyl)aminomethane (Tris) under black light (365 nm) and the observed differences in efficiency were further investigated by O2 adsorption studies using the same probe. Hydrogen abstracting species, such as hydroxyl radicals formed upon photocatalysis, are able to abstract hydrogen from Tris. This reaction leads to the formation of formaldehyde which was detected and quantified through a modified version of the Hantzsch reaction. It was found that the Ag enhanced TiO2 film increased the apparent quantum yield from 7% to 12%, partly as a result of a Schottky barrier formation at the metal-semiconductor interface and partly as the sensitizing effect of Ag nanoparticles extends the visible light absorption, which through electron transfer processes enable an efficient charge separation in the TiO2 by attracting acceptor species more efficiently than pure TiO2. The O2 adsorption studies in this paper showed that the Ag enhanced TiO2 film has a stronger adsorption affinity than pure TiO2 towards O2, which make the reduction of O2 more efficient with a subsequent enhanced electron-hole lifetime. It was also found that the Ag enhanced TiO2 film had a poorer adsorption affinity for Tris than the pure TiO2 film, which is a consequence of fewer available surface adsorption sites due to the Ag coverage at 64% which agrees well with the obtained adsorption equilibrium constants (K(LH(TiO2)) = 615 M(-1) and K(LH(Ag-TiO2)) = 320 M(-1)).

Shining light on materials--a self-sterilising revolution.

This review focuses on the development of light activated antimicrobial surfaces. These surfaces kill microbes by the action of light and have potential applications in domestic and healthcare settings. The inspiration for the new self-cleaning surfaces originates from photodynamic therapy where light is used to locate and destroy tumours. The first generation photosensitiser molecules, based on a porphyrin ring structure, could be considered as bioinspired and chemically related to chlorophyll. The review looks at developments of both soft polymeric surfaces with either surface bound or impregnated photosensitiser molecules; and hard inorganic surfaces such as modified titanium dioxide. The bacterial kill mechanisms are looked into with both surface types showing primary microbial kill through a radical induced pathway. The hard inorganic surfaces also show low bacterial adherence by means of a light activated photo-wetting of the surfaces meaning that they are "Easy Clean" and wash off microbes uniformly.

The effect of glove material upon the transfer of methicillin-resistant Staphylococcus aureus to and from a gloved hand.

BACKGROUND: Although disposable gloves can protect the hands of a health care worker from acquiring bacteria, during patient care the glove surface itself can become heavily contaminated making cross transmission via contaminated gloved hands likely. The aim of this study was to determine whether the type of glove worn by health care workers could influence the spread of methicillin-resistant Staphylococcus aureus (MRSA). METHODS: Laboratory studies were conducted to assess the ease with which MRSA was transferred between different types of glove and surfaces likely to be found within the ward environment. RESULTS: In the absence of simulated body fluid, mean bacterial transfer to and from the different gloves ranged from 0.1% to 16% and from 0.01% to 19.5%, respectively. Glove material and glove hydrophobicity were identified as the 2 most important factors influencing bacterial transfer. Nitrile gloves were associated with the lowest transfer rates. The highest numbers of bacteria were transferred to and from the most hydrophilic and most hydrophobic glove, respectively. The adsorption of simulated body fluids altered the physiochemical properties of the gloves. Bacterial transfer significantly increased and was similar to and from all glove types. CONCLUSION: Disposable glove type can affect cross-contamination rates among patient, health care worker, and environment. Nonetheless, choice of glove should be considered less important than the correct use of gloves and proper hand hygiene.

Nitrogen-doped TiO2 thin films: photocatalytic applications for healthcare environments.

N-doped TiO(2) has for many years received interest as visible light photocatalytic materials. Here we give our perspective on the subject with special consideration towards the use of visible light photocatalysts in the field of antimicrobial materials with applications in healthcare environments. The subject is reviewed and critiqued from synthetic techniques to characterisation and assessment of functional properties. N-doped TiO(2) has huge potential to form commercially viable antimicrobial surfaces that are easily implemented within the healthcare environment. We aim to shed light on the illusive nature of the mechanism of the different types of N-doping and comment on how these affect the properties of the catalysts themselves. Small concentrations of nitrogen doped under mild conditions lead to interstitial doping, which also promotes the creation of oxygen vacancies. Many believe that it is these oxygen vacancies that actually promote the formation of visible light photocatalysis and hence there is an indirect correlation between the interstitial doping and the photocatalysis. As the concentration of interstitial nitrogen increases the oxygen vacancies increase, however the presence of oxygen vacancies in turn encourages substitutional doping which then fills the oxygen vacancies. This cyclic relationship leads to photocatalysts that are very sensitive to changing nitrogen concentration.