Technology based on fundamental research into functional materials has transformed the world in which live, and it will continue to do so. Energy materials are critical components in fuel cells and batteries (the rapidly growing global market for Li-ion batteries alone is anticipated to be worth £84 bn by 2025). New, cleaner, more efficient catalysts are essential for greening existing processes as well as new ones for non-fossil-fuel based routes to essential chemicals (the catalyst market is worth around £19.5 bn/yr and growing at 4.5% pa). The equipment proposed will increase productivity in strategic UK research areas such as Energy Storage and Catalysis that require understanding of these materials' chemical and structural properties. X-ray absorption spectroscopy is a technique used to measure the oxidation state (chemical information) and local co-ordination environment (structural information) properties of a material. X-ray techniques are especially valuable in probing the working state of materials because they can penetrate deep into working samples/devices. This technique has typically been performed at synchrotron x-ray sources, such as Diamond Light Source in the UK. Recent advances in the hardware available (x-ray sources, optics and detectors) have been exploited to develop laboratory x-ray absorption spectrometers (including one that is commercially available), which now have sufficient x-ray power to enable many experiments to be performed in the laboratory. Such spectrometers are ideal for experiments that do not need high time or spatial resolution (available only at heavily oversubscribed synchrotron sources), especially operando measurements on a working battery or catalyst, where the time is determined by the process and not the x-ray source. Such equipment, while available in Germany or the USA, isn't currently available in the UK and would complement the facilities already available at Diamond. Through this project to procure, commission and operate a laboratory-source x-ray absorption spectrometer (and complementary equipment), we will meet a key need of the UK functional materials research community for wider availability of XAS to support research in strategic areas. The new facility will be housed in the Chemistry Department at Durham University, which has a strong track-record in x-ray science and interactions with industry. The EasyXAFS300 would complement other x-ray facilities in Durham, as well as recent investments in catalysis (£1.1m DU Integrated Chemical Reaction Facility) and materials (£0.75m DU COAST Nanolab). The investigator team span a wide range of disciplines (e.g. solid state chemistry, batteries, catalysis, condensed matter physics, nano-scale engineering) and so will act as advocates and representatives within diverse UK science communities - as demonstrated by the range of letters of support provided. Both Durham and external users in other universities and companies have already indicated interest in using the instrument for a wide range of applications - some examples include: i) Metal nanoparticle catalysts for biomass conversion. ii) Zeolite catalysts for methane activation. iii) Single atom / cluster catalysts for fine chemicals production. iv) C-H bond activation in Mn(I) catalysts. v) Cs co-ordination environment in supported commercial catalysts. vi) Ni based catalysts for dry and steam reforming. vii) Characterisation of carbide, nitride and carbonitride transition metal catalysts. viii) Structure and oxidation state of ceria catalysts for environmental applications ix) Oxide ion conductors in solid oxide fuel cells. x) Electrode materials for Na-ion batteries. xi) Skyrmion chiral magnets for next generation data storage media. xii) 3D-Graphene foams (synthesized with metal salts) for filtration and pollution control. xiii) Fe, Mn and Cu in stain removal and malodour control. xiv) PtCu nanowires in gas sensing arrays.

Plasma discharges are an ideal tool to modify polymeric surfaces used in biomedical research, introducing specific elements or functional groups onto the surface. In particular, plasma processes can transfer cell-adhesive or cell-repulsive groups over small domains, often through the use of masks.One major aim of this study will be to develop new atmospheric pressure plasmas (micro-plasma jets) as platforms to create chemically defined bio-surfaces on the micron scale without the need for masks. Atmospheric pressure plasmas have the advantage over vacuum-based techniques in that the plasmas themselves can be scaled to a size approaching cellular dimensions, offering novel applications in medicine and biology, and are cheap, portable and very efficient in terms of power consumption. The micro-plasma jets will operate in number of different gases and polymerisable monomers and chemical features with specific functionality down to 50 microns dimensions will be defined on a range of polymeric surfaces. The technology will be directly applied to the surface modification of intraocular lens IOL implants to study and control the interaction of human epithelial cells (LEC) on the lens. The adhesion, proliferation and migration of LECs on chemically defined surfaces and gradients will be of prime importance in assessing the technology as a tool for bio-materials engineering. The chemical and physical nature of the polymerized surfaces (analysed using XPS and other surface analytical tools) will be correlated to measurements of the plasma jet composition and also the cell-surface interactions.

Forensic investigations frequently involve the analysis of body fluids spilled during the commissioning of a crime, leading to deposits on a wide range of surfaces such as carpets, walls, clothing, bedlinen and skin. Testing of, for example, bloodstains for the presence of drugs and drug-related metabolites or other biomarkers can be a highly complex procedure, and the success rate of such analyses can be severely limited due to loss of material during extraction, as well as a lack of absolute sensitivity. Moreover, the inherently destructive nature of these tests - specimens need to be removed from the bulk item before any extraction can be carried out - is a major issue, as is the fact that analysis is invariably carried out at a laboratory remote from the scene. The necessity for remote analysis does also add potentially crucial time to the investigative process, as well as carrying an inherent risk of sample degradation and contamination in transit and subsequent storage. Perhaps most importantly: if it is not feasible to remove a suitable sample from an item, potentially useful information will not be available to investigating officers. Therefore, forensic practitioners have considerable interest in technologies which could potentially overcome at least some of these important limitations.In this proposal we intend to undertake a feasibility study to assess a novel application of the established technique of mass spectrometry in such forensic investigations. Mass spectrometry is a very powerful and well-established technique able to detect minute amounts of materials with very high sensitivity and specificity. Unfortunately, it has some serious drawbacks which severely restrict its applicability. These drawbacks chiefly concern the sampling of the materials under investigation, which have to be capable of being in the gas phase. This tends to be especially difficult from solid substrates, necessitating physical removal and dissolution of the material of interest, bombardment of the sample with highly energetic ions in an ultrahigh vacuum chamber, or illumination of the sample with an intense laser beam after application of a matrix material. All these methods are highly problematic in the field of forensic analysis, where integrity of the subject is of utmost importance. A methodology to volatilise materials of interest for mass spectrometric analysis which is compatible with forensic requirements would thus have great potential.The newly-introduced technique of DESI, short for desorption electrospray ionisation, has such potential, as yet to be realised, to become a fully-fledged routine surface analytical tool, marrying the analytical capabilities of mass spectrometry with a sampling facility convenient for forensic analyses. As opposed to most other such techniques, it is applicable under a wide range of environmental conditions and suitable for a wide array of samples including surfaces of biological, pharmaceutical, polymer, metal and mineral materials. Moreover, current technical capabilities are such that a great deal of miniaturisation is possible, leading to a desktop-sized or potentially even a portable device.The proposed work focuses on the application of the technique to forensically relevant subjects and materials, more specifically the detection of drugs and drug metabolites in body fluid stains found at scenes of crime. Direct comparisons will be made with mass spectra generated using two established mass spectrometry techniques capable of surface analysis available in the School of Pharmacy, secondary ion mass spectrometry (SIMS) and matrix assisted laser desorption-ionisation (MALDI), which both employ different methods of volatilisation. It should be stressed that whereas this proposal concentrates on a very specific sample type, the technique has the clear potential for application to a much wider range of samples in the forensic science field.

Electron attachment plays an important role in radiation chemistry, for example in DNA damage and ozone depletion. Detailed understanding and quantification of electron attachment processes in isolated molecules and condensed environments is therefore essential to model radiation effects on the nanoscale. My EPSRC CAF probes electron attachment dynamics and reactive pathways in selected biomolecular clusters, building on recent advances such as the observation of electron driven proton transfer in Watson Crick pairs [Bowen et al. ChemPhysChem 11 (2010) 880]. However, relatively little is known about how clustering modifies the absolute probabilities for electron attachment induced processes. While theoretical calculations by my collaborators Fabrikant and Gorfinkiel [J. Chem. Phys. 136 (2012) 184301] have provided evidence for strong enhancements in specific cluster configurations, absolute experimental data for electron attachment to clusters are extremely rare. This project is centered on developing an original technique to produce neutral mass-selected beams with known target density for electron attachment experiments. The method involves neutralization of mass-selected cluster anions by electron photo-detachment from specific weakly-bound anionic states, with minimal change in stability and hence dissociation. The project will provide a breakthrough in quantifying the effects of the local chemical environment on electron attachment induced processes.

Future energy demand can be addressed by using renewable and inexhaustible solar energy, providing clean, unlimited, economical and green energy. The world global photovoltaic (PV) capacity currently stands at >140 GW and is expected to reach levels of 1 TW within the next decade. Electricity generation from the sun employing PV technology is currently dominated by Si-based PV and requires expensive equipment and process and schemes for cost reduction on a large scale are limited. Thin film technologies such as CdTe and Cu(In,Ga)Se2 (CIGS), provide a lower cost alternative primarily due to the use of in-line and low-temperature processes. While considerable efforts have been made to increase efficiency and reduce costs, thin film PV currently relies on scarce and therefore expensive resources and/or toxic elements. Alternative thin film materials would therefore provide routes to reduce PV cost-per-watt while still exhibiting lower input energy requirements. Solar cells based on Cu2ZnSn(S,Se)4 (CZTSSe) absorber layers offer such an alternative. Despite its young history CZTSSe record efficiency stands at 12.6% and the major limitations are (i) a lower than expected open circuit voltage accompanied by a low efficiency at converting and collecting carriers from low energy photons; (ii) the difficulty in controlling the kesterite crystal structure throughout the fabrication process; and (iii) the use of hydrazine, a highly toxic chemical, in the fabrication process to achieve the record efficiencies. This project will use nanocrystal dispersions (inks) of CZTS fabricating from hot injection as the starting material. This technique can reliably control crystal structure, composition and doping and does not present any environmental risks. Inks are easily spin coated or sprayed on substrates and a heat treatment under selenium rich atmosphere promotes grain growth without loss of the crystal structure. In order to fabricate record efficiencies using this technique the microstructure of the absorber and back contact layers need to be engineered to provide large grains extending the full thickness of the absorber combined with a small interfacial layer to ensure a good ohmic contact. This will be achieved by the removal of long hydrocarbon chained ligand in the nanocrystal fabrication alongside modifications of the selenization procedures. In addition the role of substrates and process impurities affecting devices performances will be quantified. I will produce nanoparticle inks, solar absorber and PV devices and demonstrate world leading results.