The main objective in DEMO is to provide high-level hands-on, computational and transferable skill training to 13 Doctoral Candidates (DC) through a Joint Doctorate Program and to create a new generation of experts in hybrid catalysis. DEMO uses light (C1-C4) alkanes as example to study the conversion of a sustainable molecule (biomethane) into a relevant chemical in industry (methanol). This project combines 9 world-class research groups, experts in chemical engineering, organic chemistry, catalysis, modelling and spectroscopy from 7 countries. The 9 partners in academic (3), research centre (3), SME (2) and industrial (1) fields will provide recruited DCs with unique perspectives, preparing DCs for their personal career in research with specific skillsets. DEMO will integrate machine learning, organic chemistry, ab initio modelling, high-throughput and reactor engineering and in situ spectroscopy to discover enzyme-like species in Metal Organic Frameworks (MOFs). Specifically, DEMO will follow an interconnected strategy to discover optimal catalyst candidates: a) virtually generate a dataset with active species in MOFs and screen via Machine Learning; b) test the dataset value of a large sample dataset via experimental high-throughput engineering and modelling; c) understand testing outputs through in situ spectroscopy, titration kinetics and modelling; d) optimise protocols for synthetic materials towards biological analogies and engineer reaction conditions to search solvation phenomena. This way, DEMO expects to have a broad impact on the scientific community, EU industry and society by providing high-quality training in hybrid catalysis.

With potential widespread uptake of fuel cell technologies in many areas of energy conversion, there is an increasing need to address new ways to reclaim the significant value associated with end-of-life fuel cell stacks. The term fuel cell can be applied to a wide range of electrochemical devices which use a variety of materials; however, the type with potentially the largest market penetration is the polymer electrolyte membrane fuel cell (PEMFC). Although there has been much research into alternatives, the usual electrocatalyst combinations are based on Pt and Ru, both of which are extremely costly. There are several models such as metal leasing which can help address this, but clearly in all cases to facilitate broad market uptake, efficient and effective means of recovery of these metals by a scalable route needs to be developed. Traditional techniques for recovery of these metals, such as pyrometallurgical routes (smelting) has some particular energy and environmental problems as well as constraints which would make large scale recovery of Pt and Ru by these routes impossible. The research proposed here intends to provide the fundamental knowledge required for the development of a process which addresses the following important requirements: 1) Low process cost and complexity 2) Low environmental impact - direct and in terms of emissions from energy input 3) Safe process An electrochemical based closed loop process is proposed which short cuts a lot of the extraction steps to give selective recovery of each metal constituent in turn. The idealised process consists of two coupled reactors, the leach reactor in which the metals are dissolved selectively and a membrane divided electrochemical reactor, in which the metals are deposited sequentially from solution whilst the oxidant is regenerated simultaneously. This process in conjunction chemical systems to be investigated to facilitate it will produce a much safer and more energy efficient process which could significantly reduce the lifecycle costs of fuel cells. However, there are some real challenges that have to be addressed before a practical process could be deployed. The project will explore in detail: 1) The leaching kinetics and mechanisms for these metals and how intimate lamination of the catalyst layers into the membrane affects recovery rates. 2) Whether there is sufficient access to the precious metal through the pore structures of the carbons used when the catalyst has been laminated without the need for a membrane dissolution or partial dissolution process 3) Selective and sequential recovery of each metal component which will require detailed investigation into the deposition kinetics of each metal and design of a suitable cathode for the electrochemical reactor Fuel cells promise to be a significant part of the future energy conversion market, playing a key role in the decentralisation and diversification of UK electricity generation, finding application in remote and combined heat and power (CHP) systems. The UK has some significant interests in the complete supply chain from raw materials to system integrators with range from small SMEs such as Intelligent Energy and Acal Energy, to large multinationals such as Centrica and Johnson Matthey. If the example is taken of a fuel cell micro-CHP system, to displace the current condensing boiler technology, then the UK market is worth around 1.5 M units per year. To support this shift in technology, complementary supply and reclamation routes clearly need to be established now to help the most efficient and successful uptake of the technology. If successful this research, by reducing life-cycle costs, could quicken the introduction of Fuel Cells in many applications.

The development of the Haber Bosch Process for the synthesis of ammonia on an industrial scale was one of the major achievements of the 20th Century. It can be directly credited with sustaining the global population through the provision of an accessible route to synthetic fertilizers. The process is based upon the reaction of pure N2 and H2 feedstreams over a promoted iron based catalyst. It is operated at high pressure (>100 atmospheres) and moderate temperature and the process as a whole currently accounts for a significant proportion of global energy demand (>1%). In this research, we are attempting to develop alternative catalysts which will contribute to energy savings by facilitating the reaction at lower reaction temperatures (where there is a thermodynamic advantage.) The approach to be taken will involve a mixture of computational design and experimental testing and is based upon previous studies of metal nitride catalysts which exhibit interesting activity for ammonia synthesis. Metal nitrides potentially contain "activated" nitrogen within their structure and it is the reactivity of this lattice nitrogen which which could be the key to their high activity. Using computational modelling, understanding of experimental results will be obtained and will be extended to the identification of nitride materials of potential high catalytic activity. In parallel laboratory experiments, the identified materials will be synthesised and tested and the results fed back into the computational modelling to provide improved understanding. In this way, optimal catalyst formulations will be identified and these will be prepared and tested under industrially relevant ammonia synthesis conditions and the results will be compared to those from conventional industrially applied iron based catalysts.

Strong solid acids have found various applications as environmentally benign heterogeneous acid catalysts for chemical and petrochemical processes, proton conductive membranes in fuel cells, selective adsorbents of basic impurities in separation and purification technologies, etc. The efficiency of solid acids in such applications depends primarily on their acid strength and thermal stability. The choice of effective solid acids possessing strong acid sites as well as high stability is limited, hence strong demand for such materials in many fields of application. Following promising preliminary experiments, we propose a collaborative programme bringing together experts in heterogeneous catalysis, materials chemistry and solid-state NMR to develop the capability for the synthesis of novel functionalised materials possessing strong acidity and high thermal stability based on polyoxometalates. The acidic forms of typical polyoxometalates, known as heteropoly acids, are very strong protonic acids, however their stability is relatively low. The proposed programme aims at the preparation of solid acid materials by a transformation of multicomponent oxidic systems. Preliminary experiments indicate the formation of a highly stable and strongly acidic two-dimensional heteropoly acid phase in such systems, which could potentially be effective in catalytic and other applications. In the proposed work, the fundamental blending and mounting procedures will be used to prepare the acidic materials. The structure of materials thus made will be thoroughly characterised at different levels. Structural understanding will be essential for the elaboration of the general strategy towards the synthesis of novel materials. We also wish to establish the relationship between the structural features of these materials and their acidity, catalytic activity and ionic conductivity. The catalytic performance of materials will be studied in detail using model reactions in comparison with standard solid acid catalysts. The materials will also be tested in a range of acid-catalysed reactions of commercial interest. The novel strong solid acids derived from multicomponent oxidic systems will have important advantages over the conventional solid acids (mixed oxides, zeolites) and typical heteropoly acids. They will have stronger acidity compared to mixed oxides and zeolites. As compared to the typical soluble heteropoly acids, they will have higher thermal stability and stability towards leaching into liquid phase, allowing effective use of these materials as regenerable green solid acid catalysts, conductive membranes and reusable selective adsorbents in polar solvents.

The drive towards more sustainable technologies relies on developing improved catalytic materials; greater activity and selectivity to desired products with ever decreasing amounts of expensive catalyst metals. Supported metal nanoparticles are a cornerstone within the field of heterogeneous catalysis; the metal support interaction aids the stability of the catalyst and promotes chemical reactions. Controlling the interface of composite structures is a key part of this synergy between metal nanoparticle and metal oxide support. Supported metal nanoparticles are most commonly prepared by the impregnation of metal oxide hosts, followed by a thermal activation. The concept of the project is to use metal nanoparticles supported on MOFs as templates. The intention is to remove the organic linkers through chemical means, i.e. by introducing strong reductants such as NaBH4, producing tailored nanocomposites. Indeed, we have recently performed a proof-of-concept study where we were able to prepare PdCu/Cu2O nanocomposites from Pd/Cu-BTC templates. The programme of work will: (i) Show how systematic variations to preparation conditions influences the composite structure. (ii) Demonstrate their importance for emerging catalytic applications in sustainable energy generation (i.e formic acid decomposition). (iii) Use advanced characterisation under process conditions to understand the formation of the composite structure and how the structures evolve during catalysis.