ABSTRACT. It has been more than 40 years since Fujishima and Honda demonstrated water splitting using TiO2, yet there is still no clear mechanism by which surface holes on TiO2 oxidize water. In this article, we use a range of complementary techniques to study this reaction that provide a unique insight into the reaction mechanism. Using transient photocurrent (TPC) and 2 transient absorption spectroscopy (TAS), we measure both the kinetics of electron extraction (t50% ~200 µs, 1.5 VRHE) and the kinetics of hole oxidation of water (t50% ~100 ms, 1.5 VRHE) as a function of applied potential, demonstrating the water oxidation by TiO2 holes is the kinetic bottleneck in this water splitting system. Photo-induced absorption spectroscopy (PIAS) measurements under 5 s LED irradiation are used to monitor the accumulation of surface TiO2 holes under conditions of photo-electrochemical water oxidation. Under these conditions we find that the surface density of these holes increases non-linearly with photocurrent density. In alkali (pH 13.6), this corresponded to a rate law for water oxidation that is 3 rd order with respect to surface hole density, with a rate constant = 22 ± 2 nm 4 .s -1 . Under neutral (pH = 6.7) and acidic (pH = 0.6) conditions the rate law was 2 nd order with respect to surface hole density, indicative of a change in reaction mechanism. Although a change in reaction order was observed, the rate of reaction did not change significantly over the wide pH range examined (with TOFs per surface hole in the region of 20 -25 s -1 at ~1 sun irradiance). This showed that the rate limiting step does not involve OH -nucleophilic attack and demonstrated the versatility of TiO2 as an active water oxidation photocatalyst over a wide range of pH.TOC graphic

The prevalence of healthcare-associated infection caused by multidrugresistant bacteria is of critical concern worldwide. It is reported on the development of a bactericidal surface prepared by use of a simple, upscalable, two-step dipping strategy to incorporate crystal violet and di(octyl)-phosphinic-acid-capped zinc oxide nanoparticles into medical grade silicone, as a strategy to reduce the risk of infection. The material is characterized by UV-vis absorbance spectroscopy, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-optical emission spectroscopy (ICP-OES) and transmission electron microscopy (TEM) and confi rmed the incorporation of the ZnO nanoparticles in the polymer. The novel system proves to be a highly versatile bactericidal material when tested against both Staphylococcus aureus and Escherichia coli , key causative micro-organisms for hospitalacquired infection (HAI). Potent antimicrobial activity is noted under dark conditions, with a signifi cant enhancement exhibits when the surfaces are illuminated with a standard hospital light source. This polymer has the potential to decrease the risk of HAI, by killing bacteria in contact with the surface.

We report a systematic study into the importance of carrier solvent on the Aerosol-Assisted Chemical Vapour Deposition (AACVD) of fluorine-doped tin oxide (FTO) films. In particular, the resultant effects on both the optical transparency and electrical conductivity properties are reported with optimised films showing figures-of merit significantly beyond commercial products. Depositions were carried out at substrate temperatures of 500, 550 and 600 C using either N 2 or air as the carrier gas. The carrier solvent was found to have a marked effect on film quality and performance characteristics. Hall Effect results indicate that use of propan-2-ol as carrier solvent and air as carrier gas gave the best performing n-type FTO thin films overall that exhibited high optical transparency (>80% at 550 nm) and resistivity values of 4 Â 10 À4 U cm, with charge carrier density and carrier mobility values of 4 Â 10 20 cm À3 and 39 cm 2 V À1 s À1 respectively, in addition to haze values of 10-15%. Such parameters are ideal for thin film solar cell applications and have significantly higher figures of merit compared to current commercial materials. Success of this method of deposition is attributed, in part, to a halide transfer reaction in which part fluorine substitution of the tin precursor occurs in the solvent resulting in a direct tin-fluorine bond. The work shows the key role carrier solvents play in AACVD in directing the system chemistry.

We present a novel approach towards achieving high visible transmittance for vanadium dioxide (VO(2)) coated surfaces whilst maintaining the solar energy transmittance modulation required for smart-window applications. Our method deviates from conventional approaches and utilizes subwavelength surface structures, based upon those present on the eyeballs of moths, that are engineered to exhibit broadband, polarization insensitive and wide-angle antireflection properties. The moth-eye functionalised surface is expected to benefit from simultaneous super-hydrophobic properties that enable the window to self-clean. We develop a set of design rules for the moth-eye surface nanostructures and, following this, numerically optimize their dimensions using parameter search algorithms implemented through a series of Finite Difference Time Domain (FDTD) simulations. We select six high-performing cases for presentation, all of which have a periodicity of 130 nm and aspect ratios between 1.9 and 8.8. Based upon our calculations the selected cases modulate the solar energy transmittance by as much as 23.1% whilst maintaining high visible transmittance of up to 70.3%. The performance metrics of the windows presented in this paper are the highest calculated for VO(2) based smart-windows.

Two-dimensional (2D) Janus materials with opposing components and properties on two sides have recently attracted fevered attention from various research fields for use as, for example, oil/water separating membranes, interfacial layers for mass transfer, 2D sensors and actuators. The Janus structure allows for a unidirectional transportation system and programmed response to certain stimuli to be achieved. Graphene, the 2D honeycomb network formed from one atomic layer of carbon atoms, has also received substantial research interest because of its intriguing structure and fascinating properties. The high mechanical strength, flexibility and optical transparency make graphene a unique candidate as a building block of 2D Janus materials through asymmetric modification with different functional groups on the graphene surfaces. This article reviews graphene-based 2D Janus materials, starting with a theoretical understanding of the behavior of Janus graphene. Then, different strategies for fabricating Janus graphene and its derivatives are reviewed in detail according to the chemical strategies of the modification methods. The applications of graphene-based Janus materials are discussed with a specific focus on the Janus structures that lead to bandgap engineering, as well as the construction of a responsive system on graphene.