Combining Frustrated Lewis Pair (FLP) and Solid State Molecular Organometallic (SMOM) Catalysis

Lead Research Organisation: University of Oxford


This project falls within the EPSRC "Manufacturing the future" research theme, with a focus on catalysis.
Performing chemical processes, such as making plastics and refining fuels, takes a great deal of energy. Catalysts reduce this energy requirement and, in some cases, allow these processes to happen at all. Current catalyst technology is based on precious metals, such as platinum and palladium. These are not only expensive but display toxicity towards humans and the environment. When designing future catalysts we must move away from the expensive and toxic precious metals and move towards more sustainable elements.
My work focuses on using non-metals, such as phosphorus and boron, from the p block of the periodic table to perform catalysis. In order to move away from traditional metal-based catalyst systems I will use bulky Lewis acid and base systems to perform metal free catalysis. Lewis bases are compounds with a lone pair of electrons and Lewis acids are compounds that accept a lone pair of electrons. When a Lewis acid and base are brought together an adduct normally is formed from the lone pair on the Lewis base being donated to the Lewis acid. However, in a frustrated Lewis pair (FLP), bulky Lewis acids and bases prevent adduct formation leading to a system which can donate and accept electrons much like traditional metal catalysts. FLPs have been shown to be active hydrogenation catalysts, which is the process in which hydrogen atoms are added to a compound. These systems are not used widely in industry due to lower activity than the current metal-based systems and lack of compatibility with industrial chemistry. The purpose of this project is to develop a FLP system that may be compatible with, and, provide activities that rival the current industrial processes.
Much of the current work in this field is done in solution with reactants, products and catalyst all being dissolved in solution and thus being in the same phase. This is described as a homogenous system; however, the unique aspect of my research is heterogenous reactivity. This means using a solid catalyst with reactants and products that are either in the gas or solution phase. The catalyst existing in a different phase allows for continuous reactivity as reagents flow across the catalyst, rather than having to work in batches. This allows for no down time between batches, increasing the efficiency of the process. Further to this, no additional separation of the catalyst, reactants and products is required. These factors together save on cost and energy, with benefits to both the consumer and the environment. In order to achieve heterogenous catalytic activity I will be employing the solid-state molecular organometallic (SMOM) approach used by Prof. Weller et al. using a BArF anion, a bulky negatively charged ion, to facilitate reactivity of the FLP as a single crystal. Through my project I will be collaborating with Prof Weller at the University of York.

Planned Impact

The primary impact of the OxICFM CDT will be the highly-trained world-class scientists that it delivers. This impact will encompass both the short term (during their doctoral studies), the medium term (subsequent employment) and ultimately the longer timescale defined by their future careers and consequent impact on science, engineering and policy in the UK.

The impact of OxICFM students during their doctoral studies will be measured by the culture change in graduate training that the Centre brings about - in working at the interface between inorganic synthesis and manufacturing, and fostering cross-sector industry/academia working practices. By embedding not only from larger companies, but also SMEs, we have developed a training regime that has broader relevance across the sector, and the potential for building bridges by fostering new collaborations spanning enormous diversity in scientific focus and scale. Moreover, at a broader level, OxICFM offers to play a unique role as a major focus (and advocate) for manufacturing engagement with academic inorganic synthetic science in the UK.

From a scientific perspective, OxICFM will be uniquely able to offer a broad training programme incorporating innovative and challenging collaborative projects spanning all aspects of fundamental and applied inorganic synthesis, both molecular and materials based (40+ faculty). These will address key challenges in areas such as energy provision/storage, catalysis, and resource provision/renewal necessary to enhance the capability and durability of UK plc in the medium term. To give some idea of perspective, the output from previous CDTs in Oxford's MPLS Division include two start-up companies and in excess of 30 patents.

It is not only in the industrial and scientific realms that students will have impact during their timeframe of their doctorate. Part of the training programme will be in public engagement: team-based challenges in resource development/training and outreach exercises/implementation will form part of the annual summer school. These in turn will constitute a key part of the impact derived from the CDT by its engagement with the public - both face-to-face and through electronic/web-based media. As the centre matures, our aspiration is that our students - from diverse backgrounds - will act as ambassadors for the programme and promote even higher levels of inclusion from all parts of society.

For our partners, and businesses both large and small in the manufacturing sector, it will be our students who are considered the ultimate output of the OxICFM CDT. Our programme has been shaped by the need of such companies (frequently expressed in preliminary discussions) to recruit doctoral graduates who can apply themselves to a broad spectrum of multi-disciplinary challenges in manufacturing-related synthesis. OxICFM's cohort-based training programme integrates significant industry-led training components and has been designed to deliver a much broader skill set than standard PhD schemes. The current lack of CDT training at the interface of inorganic chemistry and manufacturing (and the relevance of inorganic molecules/materials to numerous industrial sectors) heightens the need for - and the potential impact of - the OxICFM CDT. Our students will represent a tangible and valuable asset to meet the long-term skills demand for scientists to develop new materials and nanotechnology identified in the UK Government's 2013 Foresight report.

In the longer term, the broad and relevant training delivered by OxICFM, and the uniquely wide perspective of the manufacturing sector it will deliver, will allow our graduates to obtain (and thrive in) positions of significant responsibility in industry and in research facilities/institutes. Ultimately we believe that many will go on to be future research leaders, driving innovation and changing research culture, and thereby making a lasting contribution to the UK economy.


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Studentship Projects

Project Reference Relationship Related To Start End Student Name
EP/S023828/1 31/03/2019 29/09/2027
2329320 Studentship EP/S023828/1 30/09/2019 31/03/2024 Agamemnon Crumpton