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.

Our CDT in Inorganic Materials for Advanced Manufacturing (IMAT) will provide the knowledge, training and innovation in Inorganic Chemistry and Materials Science needed to power large-scale, high-growth, current and future manufacturing industries. Our cohort-centred programme will build the skills needed to understand, transform and discover better products and materials, and to tackle the practical challenges of manufacturing, application and recycling. IMAT CDT addresses the 'Meeting a user need' CDT focus area, while also addressing 3 EPSRC strategic priorities: 'Physical Sciences Powerhouse', 'Engineering Net Zero' and 'Quantum Technologies'. 'Inorganics' are essential to many industries, from fuel cells to electronics, from batteries to catalysts, from solar cells to medical imaging. These materials are made by technically skilful chemical transformations of elements from across the breadth of the Periodic Table: success is only achievable via in-depth understanding of their properties and dynamic behaviour, requiring systems-thinking across the boundaries of Chemistry and Materials Science. The sector is characterized by an unusually high demand for high-level (MSc/PhD) qualified employees. Moreover, wide-ranging synergies in manufacturing challenges for 'inorganics' mean significant added value is attached to interdisciplinary training in this area. For example, understanding ionic/electronic conductivity is relevant to thermo-electric materials, photo-voltaics, batteries and quantum technologies; replacing heavy metals with earth-abundant alternatives is relevant to chemical manufacturing from plastics to fragrances to speciality chemicals; and methods to manufacture starting from 'natural molecules' like water, oxygen, nitrogen and CO2 will impact nearly every sector of the chemical industry. IMAT will train graduates to navigate interconnected supply chains and meet industry technology/sustainability demands. To invent and propel future industries, graduates must have a clear understanding of scientific fundamentals and be able to quickly apply them to difficult, fast-changing challenges to ensure the UK's leadership in high-tech, high-growth industries. A wide breadth of technical competence is essential, given the sector dominance of small enterprises employing <50 people. The 'inorganic' sector must also meet challenges associated with resource sustainability, manufacturing net zero, pollution minimisation and recycling; our cohorts will be trained to think broadly, with awareness of environmental, societal, legal and economic factors. Our creative and highly skilled graduates will transform sectors as diverse as energy generation, storage, electronics, construction materials, consumer goods, sensing/detection and healthcare. IMAT builds upon the successful EPSRC 'inorganic synthesis' CDT (OxICFM) and (based on extensive end-user/partner feedback) expands its training portfolio to include materials science, physics, engineering and other areas needed to equip graduates to tackle advanced materials challenges. It addresses local, national and international skills gaps identified by our partners, who include companies spanning a wide range of business sizes/sectors, together with local enterprise partnerships and manufacturing catapults. IMAT offers a unique set of training goals in 'inorganic' chemistry and materials - a key discipline encompassing everything made which is not an organic molecule: from salts to composites, from acids/bases to ceramics, from organometallics to (bio)catalysts, from soft-matter to the toughest materials known, and from semi-conductors to super-conductors. A unifying training spanning this breadth is made possible through the strength of expertise across Oxford Chemistry and Materials, and our national partner network. Our goal is to empower future graduates by equipping them with this critical knowledge ready to apply it to new manufacturing sectors.

Humanity faces critical global challenges in supplying clean energy, food, medicines and materials for a population forecast to reach 10 billion by 2050. Chemical synthesis will play a central role in addressing these challenges, as organic molecules are the fundamental building blocks of drugs, agrochemicals, and materials. However, the synthesis of most chemicals remains energy intensive, requiring fossil fuel feedstocks and endangered metal catalysts, and produces huge levels of waste - far from what is needed for a net-zero future. The essential transition to a circular chemistry economy will materialise only with a total re-think of organic synthesis: a 'Chemical Revolution' is urgently needed, for which Industry users will require a 'next generation' of suitably trained graduates. Without such change, the chemical industry will not be able to sustain the necessary pace of innovation in new chemical technologies, in the face of rapidly changing chemical regulation and policy, thus rendering this CDT crucial for the future of UK PLC. The Oxford-York ESPRC CDT in Chemical Synthesis for a Healthy Planet will deliver world-leading, ground-breaking training to a next generation of synthetic chemists, developing a sustainable, innovative chemistry culture that equips them to address major emerging and future global challenges in Human Health, Energy and Materials, and Food Security. In doing so, we meet a critical User Need, by supplying the workforce that is essential to create the innovative solutions UK chemical industries urgently require. Our overarching objective is to train students to supersede current practices for the synthesis of functional organic molecules by developing sustainable, field-advancing synthetic pathways to the complex targets needed in drug discovery, agrochemistry, and materials development. Our student cohorts will work together in a training period at both Oxford and York, before engaging with industry co-supervised projects in four research fields that develop innovative, sustainable transformations and synthetic strategies, and apply them in pharma, agro and materials chemistry contexts. With around a third of projects supervised jointly at Oxford and York, we will ensure a strong cross-institute connection; whole programme meetings and research field seminars will enable students across multiple cohorts to contribute to and elevate each others' science. Our association with the Eur1.25bn Center for the Transformation of Chemistry brings a unique connection for our students to a major initiative that is aiming to revolutionise chemical synthesis, as well its >140 chemical organisations across Europe. Our partnership with >10 SMEs and their Entrepreneurs-in-Residence will develop entrepreneurial skills and ensure students are exposed to the cutting-edge of chemical innovation in UK PLC. The applications and benefits from the CSHP CDT are many: Primarily, we will develop a UK-wide network of sustainably-minded, innovative chemists ready to meet the urgent User Needs of the UK chemical industry, bolstering this major sector of UK PLC. The scientists graduating from the CSHP CDT, the high-level science they produce, along with the related tools and technologies, will all contribute to the UK's ambitions as a Physical and Mathematical Sciences Powerhouse. We will set new benchmarks for graduate training by ensuring sustainability is embedded and visible in all research and its outputs, as well as influencing and connecting to graduates across the UK through biennial symposia. Our cohorts' work as Sustainability Ambassadors will permeate our exciting discoveries and the message of the future role of synthetic chemistry throughout society - from school to the general public. Above all, we believe this rigorous and inspirational programme is utterly essential if the UK is to remain globally competitive in the rapidly evolving chemistry landscape.