INSPIRE: Robust Biocatalysis for Energy Solutions(2)

Lead Research Organisation: University of Oxford
Department Name: Oxford Chemistry


Enzymes are highly selective and efficient catalysts for a range of energy cycling reactions, including H2 production and oxidation and the interconversion of CO2 and CO. However, existing strategies for controlling enzyme catalysis electrochemically have not transferred well to device development, largely due to instability of the proteins themselves and of their attachment to electrode surfaces. We therefore bring together innovative ideas and expertise in each building block of this process, to create a step change in the development of robust biocatalytic systems for energy technologies.

Planned Impact

Direct academic impacts will arise from the innovative aspects of this project as outlined in the Case for Support. Each of these innovations represents an entirely new direction of research which will have significant impact on a range of academic communities from colloid science to energy research. The work will be published in high impact journals across the biological, chemical, physical and materials sciences and presented at conferences across the span of our fields. The highly interdisciplinary nature of this ambitious project means that results will have transformative impact across a diverse range of scientific fields.

Collaboration: This work represents a new collaboration bringing together 5 early-career researchers from very different disciplines. The opportunity to work together and also to explore subsequent many-directional projects, will have positive impacts on each of our research careers. Although we each bring substantial expertise to the project, the project itself represents an entirely new direction for each of us and thus opens up many new possibilities. This project will have significant impact in each of the individual research areas, adding value and extending our existing funded projects in new directions, in particular through the working visits to one another's laboratories.

Training: This project will provide MSci, MPhys and PhD students, as well as PDRAs, from all five research groups the opportunity to work in collaboration with another research group and learn interdisciplinary skills. The PI and CoIs on the project will also gain knowledge and exposure to techniques outside their own fields.

Industrial connections and commercialisation: The end goal of our research - to design components for new energy-cycling devices - would have significant financial impacts if carried through to production. We have a strong track-record of collaboration with industry and exploitation of research, including links with the following companies: Infineum UK, Nanotecture Ltd, Johnson Matthey, EON, British Energy and National Nuclear Laboratories, Solvay, and BayerTechonologies. We have the skills to interact with industry in order to maximize the impact and exploitation of our discoveries and strong links with technology transfer offices at our respective institutions.

Device development: Advanced catalysts for energy cycling reactions are essential, and enzymes offer cheap, renewable and highly efficient alternatives to precious metals such as platinum and palladium. This project transforms enzyme catalysis from the laboratory scale into robust electrode devices that will eventually be used in clean production of H2, fuel cells and carbon capture.

Public engagement: Through school talks and workshops, the PI and CoIs will educate young people in energy science and issues surrounding sustainable energy.


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Britton J (2014) A graphene surface force balance. in Langmuir : the ACS journal of surfaces and colloids

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McPherson I (2014) Electrocatalysis by Hydrogenases: Lessons for Building Bio-Inspired Devices in Journal of the Brazilian Chemical Society

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Smith A (2013) Monolayer to Bilayer Structural Transition in Confined Pyrrolidinium-Based Ionic Liquids in The Journal of Physical Chemistry Letters

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Smith AM (2013) Quantized friction across ionic liquid thin films. in Physical chemistry chemical physics : PCCP

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Thompson LA (2020) Biocatalytic hydrogenations on carbon supports. in Methods in enzymology

Description The project has led to development of a range of carbon materials as supports for enzyme adsorption for bioelectrocatalysis. These have allowed us to develop new high surface-area electrodes for enzyme electrocatalysis, particularly for oxidation of dihydrogen by hydrogenases. We have incorporated these carbon materials into an approach for studying enzyme active site chemistry, in which we combine Infrared spectroscopic detection with electrochemical control. The materials have proved very successful in these experiments. The materials are also likely to be useful in leading to high enzyme-loading electrodes for applications of enzyme electrocatalysis in fuel cells or fuel production.

Ionic liquids, salts that are liquid at room temperature, have attracted attention relatively recently. We have examined electrocatalysis by sub-monolayer enzyme films on carbon electrodes in ionic liquid electrolytes and established an ionic liquid concentration range over which enzyme films tolerate different ionic liquids in the electrolyte.
Exploitation Route High surface area enzyme electrodes are necessary for applications of enzymes in fuel cells, sensing, and fuel production. The materials and approaches developed by the Grobert and Vincent groups are therefore likely to be useful in these areas. High surface area carbon materials identified as suitable enzyme supports have also proved useful in a new approach to biocatalysis for chemical synthesis developed in the Vincent group, and Vincent and Grobert have initiated a new project on flow biocatalysis using carbon materials developed on this project.

Enzyme catalysis in ionic liquids is of interest in industrial biotechnology where enzymes are used to help with difficult steps in chemical synthesis, but solubility of the substrates or products in water is often a limiting factor. The information we have established about stability of enzyme electrodes in ionic liquids will inform future developments in this area. For example, we have patented a system for recycling biological cofactors NADH and NADPH involving enzymes on carbon beads, and application of these beads will require tolerance to a range of solution conditions. The carbon materials we have developed during this project look very promising for new approaches we are establishing for biological spectroscopy combined with electrochemistry and have allowed us to detect adsorbed hydrogenase on the carbon surface. We hope that this will lead to powerful new approaches for studying enzyme chemistry under fast catalytic turnover conditions.

The Grobert and Perkin groups developed a novel use of chemical vapour deposition (CVD) grown graphene as a material to produce conducting substrates for surface force balance (SFB) experiments. Consequently, they developed an "ultra-flat" transfer technique for graphene sheets of ~cm2 area that avoids polymer contamination and has shown an improved roughness of around 5 nm.

The Dougan group have tested the feasibility of completing single molecule force spectroscopy experiments on protein folding in ionic liquids, showing that it is possible to have folded proteins in ionic liquids, and to record a clean unfolding trace.

Rachel Edwards established an Ultrasonic Force Microscopy (UFM) setup at Warwick and carried out preliminary tests CNT samples from the Grobert group; this approach may now be useful in materials characterisation.
Sectors Chemicals,Energy,Manufacturing, including Industrial Biotechology

Description Insight into binding of enzymes to different forms of carbon has been valuable in developing a technology for the industrial biocatalysis area involving enzymes immobilised on carbon supports. This has resulted in a new industrial collaboration (with Dr Reddy's and with Thales Nano) and we are seeking to commercialise this technology.
First Year Of Impact 2016
Sector Chemicals
Description Biocatalysis for Sustainable Chemistry - Understanding Oxidation/Reduction of Small Molecules by Redox Metalloenzymes via a Suite of Steady State and Transient Infrared Electrochemical Methods
Amount € 2,980,000 (EUR)
Funding ID ERC-2018-COG 819580 
Organisation European Research Council (ERC) 
Sector Public
Country Belgium
Start 03/2019 
End 02/2023
Title Protein Film Infrared Electrochemistry 
Description The method couples direct electrochemical control over electrode-immobilised redox enzymes ('protein film electrochemistry') with infrared spectroscopy to study aspects of the mechanistic of redox enzymes under catalytic turnover conditions. 
Type Of Material Improvements to research infrastructure 
Year Produced 2015 
Provided To Others? Yes  
Impact We have been able to employ this in a series of related publications to understand aspects of the mechanism of NiFe hydrogenases. 
Title Ultrasonic force microscopy 
Description An AFM has been adapted to include the ability to do ultrasonic force microscopy, a technique which has been shown to be highly beneficial for fragile samples, including nanotubes. Several further adaptions have been developed to also include e.g. conductivity measurements. 
Type Of Material Improvements to research infrastructure 
Year Produced 2012 
Provided To Others? Yes  
Impact This offers an adaptable microscopy technique. We are currently investigating its potential. 
Description School visits 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact K Vincent gave a number of talks in schools:

5/7/2012: Sixth Form College, Farnborough Moving On Day

1/2/2013: Claremont High School, London, talk to year 11 and 12 students

2/2/2013: Chemistry subject day for Chemistry teachers

25/2/2013: Hodge Hill School for Girls lunchtime careers event.
Year(s) Of Engagement Activity 2011,2012,2013
Description Schools outreach talks 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? Yes
Geographic Reach Local
Primary Audience Schools
Results and Impact Kylie Vincent regularly speaks in schools to promote chemistry careers, and has spoken about her research into enzyme catalysis on carbon materials in this context.

9/3/2012: Mulberry School for Girl's conference 'What makes a great 'Women of the World' education for 21st Century girls?', speaker and panel member
Year(s) Of Engagement Activity 2012
Description Tutorials at UNIQ Summer School, Oxford 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Schools
Results and Impact K Vincent and her research group presented tutorials at the UNIQ summer school which targets school students from low socio-economic backgrounds and/or from areas with low progression to higher education and aims to encourage these students to participate in higher education.
Year(s) Of Engagement Activity 2010,2011,2012,2013