The invention of new materials with useful properties is essential to meet global challenges, such as generating energy cleanly and using it efficiently. The invention of Porous Liquids (PLs), recently reported jointly by the investigators in this project [Nature 2015, 527, 216], is an important advance with broad implications for future technologies. PLs are liquids which have permanent holes (micropores) within them, and as such are hybrids of two well-known and widely-used classes of material, specifically microporous solids and liquid solvents. Each of these classes of material provide the basis for many current industries globally. PLs bring together the ability to selectively absorb large amounts of gas (as with microporous solids) with the ability to flow (as with liquids). With development, they are expected to become the basis of a range of new technologies in the coming years. The vision of this proposal is that through greater basic understanding and application-driven development, PLs will ultimately provide the basis for new technologies in the areas of clean energy, chemical separations and as 'super solvents' - advances that would not be possible with porous solids or conventional liquid solvents alone. This project has been designed as a critical step toward reaching this goal. Initially, we will obtain better basic understanding of these material by studying how they absorb, transport and release various industrially important gases, under a range of conditions. We will also synthesise new types of PLs with a range of different compositions and structures to understand better the full scope of this new class of materials, and how the structure and composition may ultimately be used to design the materials for a specific application. Computational modelling will be used to provide accurate molecular-scale models of these PLs which will help in understanding their observed properties. Based upon these findings we will begin to explore possible future applications for PLs, such as in more energy-efficient industrial gas separation processes, safer chemical processes and more efficient battery technology. Overall the project will be a key step in realizing technical and commercial benefits to the UK from the invention of this new class of materials. The project is multidisciplinary, involving experts in materials synthesis, computational modelling and chemical engineering and will provide a first rate training for three early-career scientists in this exciting new field.

Climate Change is the single biggest threat to present and future generations: to meet the ambitious targets for net zero CO2 set out by the UK government and in line with Paris Climate Agreement requires technological mobilization on an unprecedented scale - with action required in rapid development and deployment of new approaches. A paradigm shift in the UK's research and development capabilities is needed to reduce time to market for novel and sustainable solutions for energy production and consumption. Successful rapid translation requires partnership between academia and industry, with a shared vision and commitment. Proposed technological strategies for CO2 reduction - either at source (you don't produce it) or post combustion mitigation (you capture and use it) - have limitations in efficiency, stability or lifetime associated with the behaviour of material interfaces in the systems, and how these interfaces change with time in the operating environments. Examples of such dynamic systems range from geological carbon capture and storage, to interfaces in new electric vehicles, to nanoscale materials for catalysts or energy harvesting. If we were able to understand and control such interfaces it would provide a transformation in our ability to create, optimize and deploy radical technological solutions to both combat climate change and create clean energy systems. In this joint programme between Shell, Imperial College London and the UK National Synchrotron Facility - Diamond Light Source - we aim to develop entirely new capabilities to study the behaviour of interfaces under complex real world conditions - such as high temperature, flow, stress, electric fields etc. and to be able to correlate the measurements in time and across length-scales so that we build up a complete picture of interface properties and how they change. We will combine these experiments with state-of-the-art computational techniques to provide new insights into interfacial behaviour. This mechanistic platform represents the foundation that will underpin the rational design of new materials and processes with reduced energy demand, better lifetime or more robust integrity.

Cellular instability and self-acceleration of premixed flames are commonly observed in fuel combustion, due to the thermal-diffusive and hydrodynamic instability. Cellar instability significantly influences the flame structure and speed, and the resultant self-acceleration has been widely observed in spherical flame studies, with high influences on the turbulent burning velocity of various combustion systems and causing higher fire and explosion hazards. Mapping the regimes of cellular instability and self-acceleration could help improve combustion modelling which is widely used in design of combustion systems and investigation of fire and explosion hazards. The project is divided into two main work packages, in which the research is moving from basic dada acquirement to the cause of instability and in the end of the consequence of self-acceleration. The flame cellular structure will be mathematically characterised and quantified by the microscopic photography and image processing technique rather than traditionally by measuring burning velocity through calculation of flame size or pressure history. A newly defined Cellularity Factor is introduced to represent the flame cellular structure characteristics, and the variation regularity of flame front cells is firstly calculated and analysed by measuring the cellular structure parameters, which are the primary parameters to quantitatively determine the critical point of the fully developed cellular flame and to describe the self-acceleration. Present work will develop a new burning velocity model for flame acceleration. Improved correlations are proposed, incorporating transient and multidimensional effects, as finite rate chemistry, which are crucial for the predictive engineering model developments.

The greenhouse gas (GHG) emissions that result from burning fossil fuels are a major contributor to climate change. Energy usage is increasing globally and alternative forms that are renewable and reduce GHG emissions are urgently needed. New forms of liquid transport fuels are particularly important, as the number of vehicles is increasing rapidly worldwide. Plants are 'biological solar panels'. Through photosynthesis, plants capture sunlight energy and use it to convert carbon molecules from atmospheric carbon dioxide to form carbohydrate. Plants use energy from carbohydrates for growth and the production of new dry matter (biomass). They also store carbohydrates in different forms as reserves. Liquid transport biofuels can be produced from plant carbohydrates by biological conversion processes such as fermentation. These enzymatic processes operate best when the carbohydrates are in simple forms, such as sucrose and starch, as these are easily accessed and broken down. In the UK, bioethanol is produced from sugar and starchy food crops such as sugar beet and wheat, respectively. However, growing such crops requires high inputs of nutrients particularly nitrogen (N) fertilisers. As N fertilisers require fossil fuels to make there is little overall energy saving or reduction in GHG emissions. Producing biofuels from arable crops can also conflict with food production. Perennial biomass crops, such as willows and the grass Miscanthus, are fast growing non-food crops which can produce biomass with little N fertiliser. Biofuels from these crops would give higher energy savings and GHG reductions. However, most of the carbon is in the form of lignocellulose which makes up the plant cell wall and complex linkages make it difficult for enzymes to access the carbon in this form. In the BBSRC Sustainable Bioenergy Centre (BSBEC) Perennial Bioenergy Crops Programme, we will bring together leading experts in plant biology, crop breeding, genomics, biochemistry, biomathematics and bioenergy to over come these limitations and thus underpin the improvements needed in willows and Miscanthus to develop biofuels from plant lignocellulose. Our focus will be on: (1) Optimising biomass yield. We will investigate ways of capturing more energy by developing leaf canopies earlier and extending the growing season and by improving the canopy architecture and we will investigate how carbon is partitioned into different parts of the plant e.g. shoots, roots, organs, tissues, cells and cell walls. (2) Optimising the biomass composition (specifically the accessibility of carbon in cell walls) for processing to biofuels. This will be done by first improving our understanding of biomass composition, how it varies naturally in Miscanthus and willow and how this variation influences the processibility of the biomass. We will also use gene discovery techniques to identify genes that affect cell wall composition and accessibility of the carbon. We have over two decades of experience with breeding and improving willow and Miscanthus. We also have exciting scientific leads in both crops. Our industrial partners (Shell and Ceres) have complementary strengths and expertise that will help develop these and new innovation within the programme and bring it to international markets.

The UK plans to undergo a "green industrial revolution" to mitigate global warming and reach net-zero by 2050. Switching to hydrogen, a promising zero-carbon fuel, is part of this plan and requires a massive improvement on the current hydrogen economy and associated technologies. Hydrogen gas, however, is difficult to store and transport, limiting its utility. It is desirable to chemically store hydrogen in ammonia because it is safer and easier to contain and transport and benefits from an established supply chain. However, cracking ammonia back to hydrogen requires catalysts that delicately balances two rate-limiting steps that inhibit the reaction: 1) rapid desorption of ammonia from the catalyst at hot temperatures and 2) inability to reform hydrogen and nitrogen from ammonia bound to the catalyst at cold temperatures. Under fixed operating conditions, this balance creates an optimal temperature for catalyst activity only achieved with rare and expensive elements operating at high temperatures, thus challenging the utility of ammonia as a hydrogen store. Interestingly, this theoretical maximum for static catalysis may be overcome by rapidly switching between operating conditions that favour these opposing rate-limiting steps, i.e., dynamic catalysis. For ammonia cracking, this involves shifting between cold (< 150 C) and hot (> 500 C) temperatures a thousand to a million times per second, which is operationally difficult. Sonochemistry uses sound to create bubbles that expand and contract to enhance chemical reactions and may provide a unique means of rapidly oscillating temperature. As a bubble expands and contracts above its initial size, its temperature remains equal to the ambient temperature whereby ammonia will adsorb onto the catalyst. Below its initial size, the bubble may rapidly shrink, compressing the gas and causing it to heat up to temperatures above 500 C. These hot compressions create a local high-energy microenvironment ideal for catalytic cracking of ammonia. After compression, the bubble expands back to its original size, cooling back to ambient temperatures and starting the cycle again. This approach to sonochemistry requires site-controlled bubble motion around a catalyst. Yet current sonochemical processes do not control bubble dynamics. We have recently shown that nanostructured catalysts that also function as nucleation sites for bubbles vastly improve reaction rates. However, this work used simpler chemistry as a proof-of-concept and did not fully exploit the potential in addressing more challenging heterogenous catalytic reactions. This project seeks to advance our approach to sonochemistry to achieve ammonia cracking. We hypothesize that rapid hot-cold cycles are achievable with bubbles nucleated by nanostructured catalysts and will overcome the conventional kinetic limitations associated with ammonia cracking. We start the project by first developing novel catalytic cavitation agents and study their sonochemistry using simpler chemistries. After, we will advance cavitation metrology and demonstrate that ammonia cracking is possible. These results will then be used in technoeconomic models to assess the potential industrial impact. Our key novelty is the combination of cavitation agents with catalysts to enhance sonochemical processes, which has yet to be done and is a paradigm shift in sonochemistry. As such, Shell, ExxonMobil, NPL, and SENFI UK Ltd. all support our research vision, proposed project, and desire to achieve a sustainable route to clean hydrogen production.