The simple, light, hydrocarbons methane (CH4), ethane (H3CCH3) and propane (H3CCH2CH3) are abundant natural resources. For example it has been estimated that there are approximately 200 Trillion m3 of methane reserves world-wide. As manufacturing feedstocks for the essential chemicals and materials that modern humankind needs simple hydrocarbons offer immense potential. However, while it has been estimated that over 95% (by weight) of organic chemicals in use come from adding value to (i.e., valorisation of) a small pool of simple hydrocarbon precursors, only 3% of current production is actually used for chemical manufacturing. The remaining 97% is simply burnt for its calorific value (e.g. transportation) or flared off - both being an incredible waste of a natural resource and also a significant contributor to climate change (CO2 emissions) or erosion of air quality. The increasing availability of bio-methane, and the shift to "non-conventional" shale gas, places even more importance on efficient light alkane valorisation for "net zero" carbon sustainability. This mismatch between the abundance and the potential of light alkanes is a significant fundamental scientific challenge and a huge technological opportunity. At its heart, the challenge of converting these feedstocks is one of catalysis, in which the perfect catalyst activates a specific C-H bond at low temperatures with 100% conversion to a desired product. Herein lies the challenge, as alkanes are some of the very poorest, and least reactive, ligands known. This means forming the key encounter complex, that precedes C-H activation, between the catalyst (nearly always metal-based) and the alkane is very challenging. Simply put, if this complex does not form, then C-H activation does not take place and the valuable chemical transformation that we want to perform on the alkane does not happen. This is a so-called "pre-equilibrium" problem. Such complexes between an alkane and a metal centre are called sigma-complexes and their synthesis using methane, ethane and propane lie at the heart of this proposal. While these problems can be overcome in an industrial setting by high temperatures and pressures using heterogeneous catalysts, this is energy inefficient and can lead to poor selectivity - leading to a downstream energy cost for product separation (it has been estimated that 10-15% of the world's total energy consumption is involved in chemical separations). We propose that this "pre-equilibrium" limitation can be overcome, as we have learned from biology, by controlling interaction of the substrate with not only the metal centre but also its immediate surrounding environment, the so-called secondary and tertiary coordination spheres. In this context, our proposal is to control, understand and utilise these interactions by performing synthesis, reactivity and catalysis entirely in the single crystal, rather than solution. While challenging, this removes the need for solvent (that outcompetes the alkane for binding to the metal) and immediately installs the secondary microenvironment around the active site that encourages alkane coordination. We will achieve this by a combination of "in crystallo" organometallic chemistry (pioneered by Weller) and calculations in the solid-state (usng Macgregor's expertise in computation) which harness the more diffuse interactions between the alkane substrate and the wider environment to both guide and maximise alkane binding. Once the ability to bind these simple alkanes at metal centres is established we will demonstrate our concept in an exemplar, but challenging, catalytic reaction that adds value to methane in an 100% atom efficient manner: the hydromethylation of propene. Our programme thus offers fundamental new opportunities to study the reactivity, and potential use in catalysis, of light alkanes, with a longer term vision for the efficient carbon-management of fossil- or bio-derived alkanes beyond simple burning.

Polymer processing is a multi-billion pound, world-wide industry, manufacturing products used by virtually every person in the developed world (and beyond) on a daily basis. This vital sector of the UK economy will gain a significant competitive advantage from a molecular understanding of how polymers crystallise during processing, as it will enable stronger, lighter, more durable and more easily recycled plastic products. In this proposal we will overcome the key experimental, simulation and numerical issues in understanding polymer crystallisation to deliver a molecular based, predictive platform for the processing of semi-crystalline polymers. We will tightly integrate a family of progressively coarse-grained simulations and models, covering all relevant lengthscales within a single project. This will displace the current sub-optimal semi-empirical approaches in polymer processing and enable molecular design of polymer products, through choice of processing conditions. By facilitating the manufacture of polymer products with tailored properties this program will provide a critical competitive advantage to this important industry. Polymers are long-chain molecules, formed from connecting together a large number of simple molecules. These long-chain molecules are at the heart of the multi-billion pound plastics industry. Semi-crystalline polymers make up a very significant fraction of the worlds production of synthetic polymers. Unlike simple molecules, the connectivity of polymer molecules means they crystallise into a composite structure of crystalline and amorphous regions. The proportion of amorphous and crystalline material, along with the arrangement and orientation of the crystals, is collectively known as the morphology. The crystal morphology strongly influences strength, toughness, permeability, surface texture, transparency, capacity to be recycled and almost any other property of practical interest. Furthermore, polymer crystallisation is radically influenced by the flows that are ubiquitous in polymer processing. Flow drastically enhances the rate at which polymers crystallise and has a profound effect on their morphology. Flow distorts the configuration of polymer chains and this distortion breaks down the kinetic barriers to crystallisation and directs the resulting morphology. Understanding polymer crystallisation is a formidable problem. The huge range of relevant lengthscales ranges from the size of a monomer (nm) up to near macroscopic crystals (micro-metres). The range of timescales is even wider, ranging from the monomer relaxation time (ns) to nucleation (hours at low under-cooling). Our project will involve extensive multiscale modelling, supported at each level by experiments specifically designed to address key modelling issues. Our experiments will involve controlled flow geometries, the systematic variation of molecular weight and the probes of both nucleation and overall crystallisation. Close integration of experiments and all levels of modelling is a key feature. We will develop an interrelated hierarchical family of multiscale models, spanning all relevant lengthscales and delivering results where piecewise approaches have been ineffective. Each technique will be tightly integrated with its neighbours, retaining the molecular basis of the models while progressively addressing increasingly challenging systems. This will cumulate with the low-undercooling and high-molecular weights that are characteristic of polymer processing. Each simulation will use a rare event algorithm to dramatically increase the nucleation rate, the cause of the very long timescales. Insight from the most detailed models will guide the development of faster modelling. At the highest coarse-graining, the program will derive models suitable for computational modelling of polymer processing. Using these models in cutting-edge finite element code, we will compute FIC behaviour in polymer processing geometries.

In the UK, the plastic industry alone employs >170,000 people and has an annual sale turnover of >£23.5 billion, it is also one of the top 10 UK exports. Worldwide polymer production volumes exceed 300 Mt/annum, with CAGR of 5-10%. Today almost all polymers are sourced from oi/gas and are neither chemically recycled nor biodegradable. Existing polymer manufacturing plants are optimized for a single product and because of the very high capital expenditure required to build plants their lifetimes must be as long as possible. One drawback of existing processes designed for a single product is that they hinder innovation and slow the introduction of step-change products. In this proposal a new manufacturing process allows monomer mixtures to be selectively polymerized to selectively deliver completely new types of sustainable materials. The process requires just one reactor which is re-configured to dial-up multiple combinations of desirable products with controllable structures and compositions. This fellowship allows time for detailed investigation and development of the manufacturing concept as well as new research into product applications in three high-tech, high-value sectors, namely as recyclable and biodegradable thermoplastic elastomers, shape-memory plastics for robotics and delivery agents for biomolecule therapies. The research is underpinned by the efficient use of renewable resources, such as carbon dioxide and bio-derived monomers, and the polymers are designed for efficient end-of-life recycling and biodegradation. By applying existing commodity monomers, such as propene oxide and maleic anhydride, industrialization and translation of the results is accelerated. The fellowship allows the PI to learn new skills and build collaborations which will be realized through regular sabbaticals and secondments. It also allows the close industrial collaboration and oversight to re-configure polymer manufacturing to produce sustainable, high value materials to meet existing and future industrial needs.

The OxICFM CDT, centred in Oxford University's Department of Chemistry, and involving eight key industrial stakeholders, two STFC national facilities, and faculty from Oxford Materials, Physics and Engineering seeks to address a UK-wide need for the training of doctoral scientists in the synthesis of inorganic materials relevant to the future prosperity of the manufacturing sector. Chemical synthesis is a key enabling scientific discipline that allows humanity to maintain and improve its quality of life. Within the UK, the EPSRC's own data show that the chemical/chemistry-using sectors contributed a total of £258B in value-added in 2007 (21% of UK GDP), and supported over 6 million UK jobs. Manufacturing processes and future materials are highlighted as key technologies in the recent UK Industrial Strategy green paper, and the long-term skills demand for scientists to develop new materials and nanotechnology was highlighted in the UK Government's 2013 Foresight report. The EPSRC's prioritisation in the area is highlighted by (among other things) the recent Future Manufacturing Hubs call. Future advances in societally critical areas such as petrochemical utilisation, battery technologies, semiconductors, smart materials, catalysts for chemical manufacturing, carbon capture, solar conversion and water supply/agro-chemicals are all underpinned by the ability to design and make chemical compounds and materials - to order - with custom designed properties. As an example, many technological developments in the last 30 years would not have been possible without Goodenough's fundamental work (carried out in Oxford) leading to the development of cathode materials for rechargeable lithium batteries - and ultimately to a $30B global industry currently growing at 10% per annum. We will exploit the uniquely broad range of excellence, innovation and multi-disciplinarity offered at Oxford by a critical mass of world-class researchers in this area (40+ faculty), to deliver a rigorous, challenging and relevant CDT programme in what is an under-represented area of graduate training. We believe that such a programme is not only timely and complementary to existing EPSRC CDT provision, but will address the national need for resilience, growth and innovation in key manufacturing sectors. The 'art and craft' of inorganic synthesis as applied to manufacturing is necessarily extremely diverse. OxICFM will exploit a cohort model allied to training incorporating faculty-, industry- and peer-led components, to deliver scientists (i) with a broad spectrum training across the interface between inorganic synthesis and manufacturing, and (ii) with in-depth expertise in one specific stream (molecular, nano-scale or extended materials). This model is driven by a strong end-user pull, including a desire expressed on numerous occasions by industrial partners, to recruit doctoral graduates who not only have depth of expertise in one area, but who can also apply themselves to a broad spectrum of inter-disciplinary challenges in manufacturing related synthesis with greater effectiveness than 'standard' doctoral graduates. As expressed by our SME partners and highlighted in Econic's letter of support: '(we do) not need lots more chemistry (post)graduates, we needed better prepared ones who could understand and adapt to working in industry more readily. I see a clear connection with the CDT intent and our own, and other scaling chemical businesses, needs.' With this clear vision in mind, a central component of our approach is the integration of industry-led training from both larger partner companies and SMEs in order to promote a holistic understanding of cross-scale issues relating to different business models. We stress that our aim is not to add significantly to total post-graduate numbers in Oxford Chemistry, but rather to provide a different training package to those currently available.