The aim of this proposal is to expand the capability base that solid state NMR community has at its disposal so that more materials and chemistry systems can be effectively studied with this technique. Solid state NMR usually confines itself to the study of diamagnetic materials and compounds; i.e. systems that do not possess unpaired electrons in their electronic structure. Many modern materials and chemical systems being developed possess transition metals and/or rare earth species as part of the elemental composition; these introduce unpaired electrons into these systems and thus promote paramagnetic characteristics which are incompatible with the conventional NMR methodology. Our traditional mindset of how we approach the typical NMR measurement needs to be adjusted as our typical drive to higher external magnetic field strengths is counterproductive in this case. The electron polarisation that gives rise to paramagnetic anisotropies and shifts scales linearly with magnetic field, and these effects greatly detract from conventional NMR data thus masking the information that is normally sought. Severe cases of paramagnetism can preclude the NMR measurement of some systems completely. The most direct way to address this solid state NMR challenge is to attempt measurements in a much reduced (rather than increased) magnetic field, and to spin the sample at very high MAS frequencies. This low field/fast MAS methodology maximises the chance for NMR data to be elucidated from these systems, however these types of NMR spectrometers are very rare commodities worldwide. While many thousand NMR instruments exist throughout the world at fields of 7.05 T (300 MHz for 1H) and above, only a handful of operational low field spectrometers exist to undertake these type of measurements; furthermore, the UK is not well catered for in this field of spectroscopy apart from very limited proof-of-concept pilot studies that have demonstrated this idea. This new capability will be as easy to operate as conventional solid state NMR instrumentation and no specific additional training is required to enable its usage for data acquisition. The impact of this methodology is expected to influence the fields of catalysis and energy materials (battery materials, solid oxide and H conduction fuel cells, hydrogen storage materials, supported metal nanoparticles systems, zeolites, nuclear waste glasses etc.), general organometallc and inorganic chemistry, and the emerging field of medical engineering (rare earth doped biomaterials for oncology and blood vessel growth stimulation applications). It is also expected that this methodology will bridge across to established techniques such as EPR, and emerging technologies such as DNP, both of which employ different strategies for the manipulation of the paramagnetic interaction. These relationships are expected to stimulate a more vibrant magnetic resonance community that will be capable of collaboratively tackling the challenging research issues that confront the UK. Academic collaborators at Cambridge, Birmingham, Imperial, Queen Mary, Kent, UCL and Lancaster, and industrial partners such as Johnson Matthey and Unilever are all acutely aware of these new solid state NMR possibilities and flexibility that this methodology offers, and they eagerly await the improvements to the measurement technology that a low field/fast MAS combination can offer. The specific objectives that shape this proposal are: (a) to deliver a shared low-field/fast MAS solid state NMR resource to the UK magnetic resonance community that will augment the current UK suite of solid state NMR instrumentation in existence, (b) to put in place a state-of-the-art solid state NMR console and appropriate fast MAS probe technology capable of delivering the most modern experiments, (c) to align this methodology with established characterisation technologies such as EPR and emerging experimental initiatives such as DNP.

The collaborative project EcoFuel addresses the Topic “Development of next generation renewable fuel technologies from CO2 and renewable energy (Power and Energy to Renewable Fuels)” under the call Building a low-carbon, climate resilient future: Secure, clean and efficient energy. EcoFuel develops and demonstrates a novel thorough process chain that significantly improves the energy efficiency for production of synthetic fuel out of CO2 and water using renewable energy. The process chain comprises a) the supply of CO2 from the atmosphere via a novel direct air capture approach, b) direct electro-catalytic reduction of CO2 to C2/C3 alkenes at close to ambient temperatures, and c) thermo-catalytic liquefaction of alkenes, upgrading and fractionation into transport fuels. The direct electro-catalytic CO2 reduction to hydrocarbons offers greatly enhanced efficiency potentials compared to Power-to-X technologies downstream of water electrolysis and at the same time, reduces process pathway steps. Process performance will be validated by in-depth impact assessment. The EcoFuel approach will bring together chemists, physicists, engineers and dissemination and exploitation experts from 4 universities/research institutions, 2 SMEs and 3 industries, innovatively joining their key technologies to develop and exploit a novel complete process chain, based on the power of electrochemistry to deliver truly green (CO2 neutral) fuels with an unprecedented overall energy efficiency. Within 36 months project duration, the EcoFuel technology will undergo a thorough material and component R&D programme and together with its significant industry involvement this project will be set on unique path toward new technology developments up to TRL 4 that will have lasting impact on the European renewable energy system.

Heterogeneous catalysis plays a major role in the synthesis of commodity and fine chemicals, fuels and environmental protection for UK industry and aluminosilicate zeolites are the catalysts of choice for many important reactions in oil refining and petrochemical and automobile emission control. Uniquely among industrial solid catalysts, their performance is directly related to their bulk crystal structure, via important details of their pore structure and the chemical structure of their active sites, but synthesis of new materials has by and large relied on trial-and-error approaches. Our research hypothesis is that enough is now known about the synthesis of zeolites and their action as catalysts to plan and execute the preparation of novel active heterogeneous catalysts for selected expanding catalytic technologies. This ambitious research program spans structural design, hydrothermal synthesis and catalytic performance testing of zeolite catalysts. It will be facilitated by crystallography, atomistic modelling and in situ spectroscopic methods to predict and elucidate details of the mechanisms of crystallisation and of catalysis over targeted zeolites. The program will build on our recent advances in the design of hypothetical zeolite structures and the targeted preparation of novel zeolites, and in the in situ monitoring by solid state NMR, Raman and X-ray spectroscopies of zeolite preparation and of their catalytic reactions. These reactions are important for hydrocarbon generation from oxygenates and for the selective catalytic reduction (SCR) of unwanted nitrogen oxides with ammonia. The designed synthesis of new zeolites will target hypothetical frameworks that, under computational screening, show promise for SCR or for oxygenates-to-hydrocarbons. Initial studies will develop 'retrosynthetic', modelling-led, approaches to templating these structures, while extended studies will aim to extend these to devise upscalable, commercially viable approaches. The work will be performed in close collaboration with the UK's leading commercial catalyst company and will not only prepare novel catalysts with potential advantages of performance and patentability over current materials, but will also develop a fully-connected methodology for the synthesis of new catalysts embedded in a computational and in situ experimental framework for the study of the relationship between structure and catalytic function.

LOTER.CO2M aims to develop advanced, low-cost electro-catalysts and membranes for the direct electrochemical reduction of CO2 to methanol by low temperature CO2-H2O co-electrolysis. The materials will be developed using sustainable, non-toxic and non-critical raw materials. They will be scaled-up, integrated into a gas phase electrochemical reactor, and the process validated for technical and economic feasibility under industrially relevant conditions. The produced methanol can be used as a chemical feedstock or for effective chemical storage of renewable energy. The demonstration of the new materials at TRL5 level, and the potential of this technology for market penetration, will be assessed by achieving a target electrochemical performance > 50 A/g at 1.5 V/cell, a CO2 conversion rate > 60%, and a selectivity > 90% towards methanol production with an enthalpy efficiency for the process > 86%. A significant increase in durability under intermittent operation in combination with renewable power sources is also targeted in the project through several stabilization strategies to achieve a degradation rate of 2-5 Hz) to electrical current fluctuations typical of intermittent power sources and a wide operating range in terms of input power, i.e. from 10% to full power in less than a second. Such aspects are indicative of an excellent dynamic behaviour as necessary to operate with renewable power sources. A life cycle assessment of the CO2 electrolysis system, which will compile information at different levels from materials up to the CO2 electrolysis system including processing resources, will complete the assessment of this technology for large-scale application. Field testing of the co-electrolysis system in an industrial relevant environment will enable to evaluate the commercial competitiveness and the development of a forward exploitation plan.