Catalysis is a core area of science that lies at the heart of the chemicals industry - an immensely successful and important part of the overall UK economy, where in recent years the UK output has totalled over £50B annually and is ranked 7th in the world. This position is being maintained in the face of immense competition worldwide. For the UK to sustain its leading position it is essential that innovation in research is maintained, to achieve which the UK Catalysis Hub was established in 2013; and has succeeded over the last four years in bringing together over 40 university groups for innovative and collaborative research programmes in this key area of contemporary science. The success of the Hub can be attributed to its inclusive and open ethos which has resulted in many groups joining its network since its foundation in 2013; to its strong emphasis on collaboration; and to its physical hub on the Harwell campus in close proximity to the Diamond synchrotron, ISIS neutron source and Central Laser Facility, whose successful exploitation for catalytic science has been a major feature of the recent science of the Hub. The next phase of the Catalysis Hub will build on this success and while retaining the key features and structure of the current hub will extend its programmes both nationally and internationally. The core activities to which the present proposal relates include our coordinating activities, comprising our influential and well attended conference, workshop and training programmes, our growing outreach and dissemination work as well as the core management functions. The core catalysis laboratory facilities within the research complex will also be maintained and developed and two key generic scientific and technical developments will be undertaken concerning first sample environment and high throughput capabilities especially relating to facilities experimentation; and secondly to data management and analysis. The core programme will coordinate the scientific themes of the Hub, which in the initial stages of the next phase will comprise: - Optimising, predicting and designing new catalysts - Water - energy nexus - Catalysis for the Circular Economy and Sustainable Manufacturing - Biocatalysis and biotransformations The Hub structure is intrinsically multidisciplinary including extensive input from engineering as well as science disciplines and with strong interaction and cross-fertilisation between the different themes. The thematic structure will allow the Hub to cover the major areas of current catalytic science

Aldehydes are important intermediates for the preparation of a large variety of fine- and bulk-chemicals. Applications of these compounds are found in the pharmaceutical industry, aroma and flavour industry, and in the production of agrochemicals and detergents. Many of these products are currently prepared via stoichiometric reactions which often results in large amounts of chemical waste. There is an increasing demand for new production methods based on mild and selective reactions with a very high atom efficiency , thus reducing the chemical waste problem. The rhodium catalysed hydroformylation of alkenes is an example of such a mild and clean process for the production of high-quality aldehydes, using only CO and H2 as reagents and therefore producing no waste products at all.In this project we will develop a new generally applicable catalyst system capable of converting both internal alkenes and conjugated dienes into high value-added aldehydes and / or esters. Atom economic and clean hydroformylation technology of butadiene to the intermediate 1,6-hexanedial would create a major contribution to the sustainable production of polyamides. Many industries and academic researchers, however, have studied the rhodium-catalyzed hydroformylation of butadiene, but generally the reported selectivity for the desired product 1,6-hexanedial is very low. This is caused by the formation of deleterious Rh allyl and enolate complexes, which can be suppressed by simultaneous activation of both alkene functions using properly designed bimetallic catalysts.Therefore, we will develop well-defined tetraphosphine ligand systems for the formation of bimetallic complexes capable of activating otherwise unreactive substrates by mutual interactions with functional groups by both metals. Starting point will be a successful class of bidentate ligands, already developed by the PI, which will be modified in such a way that they can be bridged straightforwardly by condensation with diacids. The resulting tetraphosphines will provide novel bimetallic complexes that will be applied in the hydroformylation of conjugated dienes. In a later stage the novel ligands systems will be explored in different reactions like palladium catalyzed alkoxycarbonylation of dienes. The exact ligand structures can be optimized by subtle changes in steric, electronic and bite-angle properties. In another approach we will aim at coupling of two different ligand backbones which opens the possibility of the formation of heterobimetallic complexes. Differences in the structure of the ligand backbone will have impact on the complexation constants of different transition metals. It is anticipated that this can be employed to influence the preferential coordination of one transition metal over another. It will be investigated if this will lead to the selective formation of heterobimetallic complexes based on rhodium and palladium without interference of homometallic binuclear compounds. We will explore the use of these rhodium palladium heterobimetallic complexes as catalyst for one-pot hydroformylation / methoxycarbonylation of dienes. The formation of these alpha,omega-aldehyde esters via a two-step process has been investigated intensively by DSM/DuPont.The design of the new chiral catalysts will be supported by fundamental spectroscopic (including kinetic) studies of the catalytic species present under actual reaction conditions. HP-NMR will be used to study the structure of the bimetallic complexes under static conditions. The effect of the metal-metal distance on the interaction with bifunctional substrates will be investigated. HP-IR will be used to study these complexes under actual catalytic conditions.

The future sustainable production of bulk and fine chemicals is an ever-increasing global challenge that requires a transformative scientific approach. We must develop new ways of efficiently exploiting valuable fossil-fuel resources and tools to exploit renewable resources such as CO2 and lignin. Catalytic methods, the heart of this CDT, are key to these transformations, offering the single most powerful and broadly applied technology for the reduction of energy demand, cost, environmental impact and toxicity. This CDT will drive forward a sustainable and resource-rich culture. This CDT in Critical Resource Catalysis (CRITICAT) combines the catalysis research collective of St. Andrews, Edinburgh, and Heriot-Watt Universities to create a new and unique opportunity in PhD training and research. CRITICAT will allow 80+ bright minds to be challenged in a comprehensive and state-of-the-art PhD training regime in the broad remit of catalytic science, transforming them into future scientific researchers, business leaders, entrepreneurs, and policy makers. These will be people who make a difference in a technologically-led society. Our critical mass in critical resource catalysis will accelerate training, discovery, understanding, and exploitation within catalytic chemistry. We will focus our efforts on the future of catalysis, driving new advances for environmentally sustainable economic growth and underpinning current growth in the UK chemicals sector. The economic impact in this area is huge: in 2010, an EPSRC/RSC jointly commissioned independent report showed that the UK's "upstream" chemicals industry and "downstream" chemistry-using sector contributed a combined total of £258 billion in added value to the economy in 2007, equivalent to 21% of UK GDP, and supported over 6 million UK jobs. Sustained investment in PhD training within this area will provide the highest quality employees for this sector. The CRITICAT PhD students will be exposed to a unique training and research environment. Extensive taught courses (delivered by CRITICAT PIs and industrial collaborators) will offer fundamental insight into homogeneous, heterogeneous, industrial and biocatalysis coupled with engineering concepts and essential techniques to showcase cutting-edge catalysis. The CRITICAT partners will develop these core courses into a foundational textbook for graduate training across catalysis using critical resources as its cornerstone that will serve as a legacy for this programme. We will expand our pedagogical innovation to all PhD graduate students at our three partner universities, providing region-wide enhanced academic provision. Continuous growth and peer-to-peer learning throughout their research efforts will create graduates who are keen to continue learning. They will be equipped with business, management, entrepreneurial and communication skills synergistic with core science knowledge and research undertakings. In this way, we will ensure that our CRITICAT students will be able to innovate, think critically, and adapt to change in any technological career. We will prepare the next generation of scientists, managers and innovators for key roles in our future society. To support this broad developmental approach, industry and business leaders will contribute widely to CRITICAT. Industries will (i) provide scientific ideas and objectives, (ii) deliver new competencies through targeted courses ranging from entrepreneurship to intellectual property rights and (iii) provide laboratory placements to consolidate learning and exploit any scientific advances. Furthermore, our extensive collaboration with leading international academic institutions will engender PhD student mobility, expand impact and allow experiential learning. We will build on our existing public engagement frameworks to enable our students to deliver their research, impact and scientific understanding to a wide audience, exciting others and driving new scientific policy.

The Departments of Chemistry (Chem) and Chemical Engineering (Chem Eng) at the University of Bath propose a Doctoral Training Centre (DTC) in Sustainable Chemical Technologies. The 6.9m requested from the EPSRC will be supplemented by 6.0m from the University and a 3.0m industrial contribution to fund a DTC operating at the interface of Chem and Chem Eng. The DTC will place fundamental concepts of sustainability at the core of a broad spectrum of research and training in applied chemical sciences. A dynamic, multidisciplinary research and training environment (the combined current EPSRC portfolio for the two departments is 19.9m) will underpin transformative research and training in Sustainable Chemical Technologies. This will respond to a national and global need for highly skilled and talented scientists and engineers in the area. All students will receive foundation training to supplement their undergraduate knowledge, as well as training in Sustainable Chemical Technologies and transferable skills. They will all conduct high quality and challenging research within the Sustainable Chemical Technologies theme directed by joint Chem and Chem Eng supervisors. The broad research themes encompass the areas of; Renewable Resources, Clean Energy, Clean Processes, Pharmaceuticals and Wellbeing, and Life Cycle Impact Reduction. Participation from key industry partners will address stakeholder needs, and partner institutions in the USA and Germany will provide world-leading international input, along with exciting opportunities for student placements. Detailed management plans have been developed in order to facilitate the smooth running of the centre and to enable excellence in the training and research aspects of the proposal. The Doctoral Training Centre will be supported by the creation of physical and virtual laboratories for the students.This 16m initiative has attracted strong and influential support: I strongly support the objectives you describe...the center is the right idea at the right time. Good luck! (Prof. George Whitesides, Harvard); The proposed initiative...should enable significant impacts to be made in this vital area. (joint letter signed by six Chief Executives of key stakeholders, including David Brown, IChemE and Richard Pike, RSC).

Catalysis is an extremely important branch of science, which is vital in our modern society. It is estimated that about 90% of all processed chemical compounds have, at some stage of their production, involved the use of a catalyst. As a result catalysis is recognized as a key strategic priority area by EPSRC. In general, catalytic reactions are more energy efficient and, at least in the case of highly selective reactions, lead to reduced waste and undesirable compounds, which is an important consideration with dwindling global reserves of raw materials. New catalysts are being developed for use in alternative energy sources and new conversion technologies, for manufacturing of new materials, for synthesis of molecules such as pure drugs, and for the production of chemicals with minimal energy input. The importance of these developments cannot be overstated. In the past 10 years alone the Nobel Prize in Chemistry was awarded on three separate occasions for the outstanding achievement of scientists whose work has a strong bias in catalysis. Their combined work has revolutionized the field of fine chemical synthesis and chiral feedstock production using well defined and discrete homogeneous organometallic catalysts. Despite the phenomenal success of these homogeneous catalysts, further improvements and developments of new asymmetric catalysts, bio-catalysts and indeed heterogeneous catalysts will benefit from a greater understanding of the mechanistic pathways involved in the catalytic cycles. Undoubtedly a greater understanding of the mechanism can lead to enhanced performance, even with well established systems. Therefore this advancement in our mechanistic understanding of how catalysts function and operate will require the application and development of new techniques that can probe the catalytic reaction and reveal the inner workings of the mechanism in unsurpassed detail. One approach to address this is the development of a unique high pressure system enabling advanced Electron Paramagnetic Resonance (EPR) methods to be used for the first time to study catalytic reactions under extreme conditions. In many cases, paramagnetic metal centers or reaction intermediates are involved in catalytic cycles, so that EPR spectroscopy and the related hyperfine techniques, such as ENDOR and ESEEM, are ideal characterization tools to study reactions at high pressures as a means to gain further insights into reaction mechanism. Since pressure is a primary thermodynamic parameter of central importance in reaction kinetics, chemical equilibria, molecular conformations and molecular interactions, it is very important in catalysis, and becomes a crucial and available parameter to study the reaction mechanisms. Since the equilibria, selectivity, population of states, conformations of the catalyst - substrate intermediates, role of solvent interactions, can all be affected, HP-EPR will be able to examine these properties. The structure, redox states, electronic and spin states, dynamics, non-covalent interactions, conformation changes, relaxation behavior, can all be analysed by these advanced EPR techniques, using the high pressure facility as a means of controlling and enhancing mechanistic variables in order to facilitate their investigations. Pressure also influences the outcome of most chemical processes, and therefore the HP-EPR facility developed in this project can also be applied to a range of other problems in chemistry involving free radicals, from organic and inorganic reactions, to electron transfer and activation of small molecules. Specific collaborative projects in heterogeneous catalysis, spin crossover phenomena, and electron spin states in condensed media, will all be explored using this new HP-EPR assembly.