Ultrathin hematite films deposited layer-by-layer on TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe2O3) film deposited on a TiO2 underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO2 underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm−2 at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm−2) illumination. The TiO2 underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe2O3. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.

Size dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

The properties of CdS nanoparticles incorporated onto mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) method were investigated by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). High resolution TEM indicated that the synthesized CdS particles were hexagonal phase and the particle sizes were less than 5 nm when SILAR cycles were fewer than 9. Quantum size effect was found with the CdS sensitized TiO2 films prepared with up to 9 SILAR cycles. The band gap of CdS nanoparticles decreased from 2.65 eV to 2.37 eV with the increase of the SILAR cycles from 1 to 11. The investigation of the stability of the CdS/TiO2 films in air under illumination (440.6 µW/cm2) showed that the photodegradation rate was up to 85% per day for the sample prepared with 3 SILAR cycles. XPS analysis indicated that the photodegradation was due to the oxidation of CdS, leading to the transformation from sulphide to sulphate (CdSO4). Furthermore, the degradation rate was strongly dependent upon the particle size of CdS. Smaller particles showed faster degradation rate. The size-dependent photo-induced oxidization was rationalized with the variation of size-dependent distribution of surface atoms of CdS particles. Molecular Dynamics (MD) simulation has indicated that the surface sulphide anion of a large CdS particle such as CdS made with 11 cycles (CdS11, particle size = 5.6 nm) accounts for 9.6% of the material whereas this value is increased to 19.2% for (CdS3) based smaller particles (particle size: 2.7 nm). Nevertheless, CdS nanoparticles coated with ZnS material showed a significantly enhanced stability under illumination in air. A nearly 100% protection of CdS from photon induced oxidation with a ZnS coating layer prepared using four SILAR cycles, suggesting the formation of a nearly complete coating layer on the CdS nanoparticles.

Potential-dependent surface-enhanced resonance raman spectroscopy at nanostructured TiO2 : A case study on cytochrome b5

Abstract: Nanostructured titanium dioxide (TiO2) electrodes, prepared by anodization of titanium, are employed to probe the electron-transfer process of cytochrome b5 (cyt b5) by surface-enhanced resonance Raman (SERR) spectroscopy. Concomitant with the increased nanoscopic surface roughness of TiO2, achieved by raising the anodization voltage from 10 to 20 V, the enhancement factor increases from 2.4 to 8.6, which is rationalized by calculations of the electric field enhancement. Cyt b 5 is immobilized on TiO2 under preservation of its native structure but it displays a non-ideal redox behavior due to the limited conductivity of the electrode material. The electron-transfer efficiency which depends on the crystalline phase of TiO2 has to be improved by appropriate doping for applications in bioelectrochemistry. Nanostructured TiO2 electrodes are employed to probe the electron-transfer process of cytochrome b5 by surface-enhanced resonance Raman spectroscopy. Concomitant with the increased nanoscopic surface roughness of TiO2, the enhancement factor increases, which can be attributed to the electric field enhancement. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable electric field enhancement and redox chemistry on TiO2 island films via covalent attachment to Ag or Au nanostructures

Abstract Ag-TiO2 and Au-TiO2 hybrid electrodes were designed by covalent attachment of TiO2 nanoparticles to Ag or Au electrodes via an organic linker. The optical and electronic properties of these systems were investigated using the cytochrome b5 (Cyt b5) domain of sulfite oxidase, exclusively attached to the TiO2 surface, as a Raman marker and model redox enzyme. Very strong SERR signals of Cyt b 5 were obtained for Ag-supported systems due to plasmonic field enhancement of Ag. Time-resolved surface-enhanced resonance Raman spectroscopic measurements yielded a remarkably fast electron transfer kinetic (k = 60 s -1) of Cyt b5 to Ag. A much lower Raman intensity was observed for Au-supported systems with undefined and slow redox behavior. We explain this phenomenon on the basis of the different potential of zero charge of the two metals that largely influence the electronic properties of the TiO2 island film. © 2013 American Chemical Society.

Numerical investigation of deformation and failure mechanisms of osteopontin-hydroxyapatite interfaces and mineralized collagen fibril arrays

This thesis is a comprehensive study of deformation and failure mechanisms in bone at nano- and micro-scale levels. It explores the mechanical behaviour of osteopontin-hydroxyapatite interfaces and mineralized collagen fibril arrays, through atomistic molecular dynamics and finite element simulations. This thesis shows some main factors contributing to the excellent material properties of bone and provides some guidelines for development of new artificial biological materials and medical implants.

Methods to improve the energy output of dye sensitized solar cell arrays

The work examined the operation and optimisation of dye-sensitised solar cell arrays, informing ways to improve performance through materials choices and geometrical design. Methods to improve the output of solar arrays under shading by external objects like trees or building were developed.

Compensation for higher order mode coupling between inclined coupling slots and radiating slots in planar slotted waveguide arrays

Summary form only given. Geometric simplicity, efficiency and polarization purity make slot antenna arrays ideal solutions for many radar, communications and navigation applications, especially when high power, light weight and limited scan volume are priorities. Resonant arrays of longitudinal slots have a slot spacing of one-half guide wavelength at the design frequency, so that the slots are located at the standing wave peaks. Planar arrays are implemented using a number of rectangular waveguides (branch line guides), arranged side-by-side, while waveguides main lines located behind and at right angles to the branch lines excite the radiating waveguides via centered-inclined coupling slots. Planar slotted waveguide arrays radiate broadside beams and all radiators are designed to be in phase.

Design and fabrication of linear pixel arrays for organic photovoltaic modules to achieve scalable power output

We describe a design and fabrication method to enable simpler manufacturing of more efficient organic solar cell modules using a modified flat panel deposition technique. Many mini-cell pixels are individually connected to each other in parallel forming a macro-scale solar cell array. The pixel size of each array is optimized through experimentation to maximize the efficiency of the whole array. We demonstrate that integrated organic solar cell modules with a scalable current output can be fabricated in this fashion and can also be connected in series to generate a scalable voltage output.

Scalable and flexible large display arrays: A novel approach to the architectural enhancement of a prototype large display array

Large Display Arrays (LDAs) use Light Emitting Diodes (LEDs) in order to inform a viewing audience. A matrix of individually driven LEDs allows the area represented to display text, images and video. LDAs have undergone rapid development over the past 10 years in both the modular and semi-flexible formats. This thesis critically analyses the communication architecture and processor functionality of current LDAs and presents an alternative method, that is, Scalable Flexible Large Display Arrays (SFLDAs). SFLDAs are more adaptable to a variety of applications because of enhancements in scalability and flexibility. Scalability is the ability to configure SFLDAs from 0.8m2 to 200m2. Flexibility is increased functionality within the processors to handle changes in configuration and the use of a communication architecture that standardises two-way communication throughout the SFLDA. While common video platforms such as Digital Video Interface (DVI), Serial Digital Interface (SDI), and High Definition Multimedia Interface (HDMI) are considered as solutions for the communication architecture of SFLDAs, so too is modulation, fibre optic, capacitive coupling and Ethernet. From an analysis of these architectures, Ethernet was identified as the best solution. The use of Ethernet as the communication architecture in SFLDAs means that both hardware and software modules are capable of interfacing to the SFLDAs. The Video to Ethernet Processor Unit (VEPU), Scoreboard, Image and Control Software (SICS) and Ethernet to LED Processor Unit (ELPU) have been developed to form the key components in designing and implementing the first SFLDA. Data throughput rate and spectrophotometer tests were used to measure the effectiveness of Ethernet within the SFLDA constructs. The result of testing and analysis of these architectures showed that Ethernet satisfactorily met the requirements of SFLDAs.

Supramolecular control of the magnetic anisotropy in two-dimensional high-spin Fe arrays at a metal interface

Magnetic atoms at surfaces are a rich model system for solid-state magnetic bits exhibiting either classical(1,2) or quantum(3,4) behaviour. Individual atoms, however, are difficult to arrange in regular patterns(1-5). Moreover, their magnetic properties are dominated by interaction with the substrate, which, as in the case of Kondo systems, often leads to a decrease or quench of their local magnetic moment(6,7). Here, we show that the supramolecular assembly of Fe and 1,4-benzenedicarboxylic acid molecules on a Cu surface results in ordered arrays of high-spin mononuclear Fe centres on a 1.5nm square grid. Lateral coordination with the molecular ligands yields unsaturated yet stable coordination bonds, which enable chemical modification of the electronic and magnetic properties of the Fe atoms independently from the substrate. The easy magnetization direction of the Fe centres can be switched by oxygen adsorption, thus opening a way to control the magnetic anisotropy in supramolecular layers akin to that used in metallic thin films.