In recent work we have identified a very powerful and extensive phenomenon, the constrained production of nanoparticles that opens up a new field impinging on chemistry, materials science and physics. The dispersion, stability, versatility and coherence with the substrate impart quite significant properties to the emergent nanoparticles opening up a major new topic. The process is driven by the lattice decomposition of a metal oxide under reduction by various means. Conventional thinking considers this as a simple phase separation; however, by careful control of the defect chemistry and reduction conditions, a very different process can be achieved. These nanoparticles emerge from the substrate in a constrained manner reminiscent of fungi emerging from the earth. The emergent nanoparticles are generally dispersed evenly with a very tight distribution often separated by less than one particle diameter. Here we will explore the composition and reaction space conditions necessary to optimise functionality, structure and applocability. We will also seek to better understand this phenomenology relating to correlated diffusion, driving energetics and mechanism of emergence. Further work is necessary to understand the critical dependence of composition in a very extensive domain of composition space depending upon charge and size of the A-site cations, oxygen stoichiometry and transition metal redox chemistry. Of particular importance is to understand the nature of the interaction between the nanoparticle and the substrate addressing the evolution of the nanoparticles from the surface and how the particles become anchored to the substrate. Exolved metals can react to form compounds whilst maintaining the integrity of the nanostructural array and this offers much potential for further elaboration of the concept. We will investigate the important catalytic, electrocatalytic and magnetic physics properties arising at constrained emergent particles, driven by dimensional restriction. Emergent nanomaterials provide very significant surface-particle interactions and promise new dimensions in catalysis. The electrochemical reactions in devices such as batteries and fuel cells are restricted to the domain very close to the electrolyte electrode interface. Emergent materials can be applied in exactly this zone.

Acrylic acid is an essential bulk chemical commodity used for the production of resins, coatings, adhesives, textile, detergents and other consumer products. It is currently manufactured on the commercial using fossil fuel-based routes, in particular from the oxidation of propylene, the latter being a major product of the naphtha and oil cracking process. The global market of acrylic acid is currently growing of 3-5% annually and the UK is responsible of consuming > 25 ktons/y with no local production capacity thus totally relying on imports from EU and Asia. On the other hand, glycerol is an abundant and cheap feedstock with yearly production of 58 tons/y between UK and Ireland. In order to reach the much sought-after goal of a carbon neutral society, the chemical industry must evolve and shift the focus on new and sustainable routes that are still able to meet current demands of key chemicals, such as acrylic acid, but with significant reduction of detrimental effects on the environment. In this context, the main goal of the SPACING project is the demonstration and scale-up of a new process for acrylic acid manufacturing using waste glycerol. This project comprises three interlinked work packages (WPs): - WP1 will involve the design, testing and characterisation of new bi-functional catalytic materials, stability test and kinetic studies, including the scale-up to 200 grams for the subsequent tests. - WP2 will focus on the development and testing of the new integrated fluidised membrane reactor. Both new experimental demonstration and long-term testing under different reactive conditions will be carried out including the benchmark and comparison of different reactor configurations. The experimental results will be used to validate the reactor model. The knowledge gained both from the experimental and numerical activities will be used as guidance for future pilot-scale demonstration of the technology. - In WP3, the SPACING process will be integrated into the acrylic acid process including feedstock pre-treatment and downstream product separation and refining. The techno-economic and environment performance of the process will be compared with commercial state-of-the-art technologies for acrylic acid manufacturing.

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.

The aim is to exploit a recent discovery concerning the production of a new high activity catalyst for use in respiratory protection devices for the removal of toxic carbon monoxide from air. The methodology uses supercritical carbon dioxide as an antisolvent and this prepares a nano-structured material that is the key to the observed activity. Initial results show the new catalyst is over twice as active as the current commercial catalyst. Funding is requested to complete patent exemplification and to ensure commercial exploitation can be achieved.

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