Three-dimensional laccase electrodes for miniaturised fuel cell power sources

Lead Research Organisation: University of Manchester
Department Name: Materials

Abstract

Laccase is a protein excreted by white-rot fungi that works as well or better than precious metals at catalysing the reduction of oxygen to water. This chemical reaction is central to almost all low-temperature fuel cells that work in air.Fuel cells are devices that convert chemical energy from a fuel like methanol or hydrogen directly and efficiently into electrical energy. In contrast, when fuel is burned in a generator, the fuel's chemical energy is converted into thermal energy (hot gases) and mechanical energy (moving pistons) before it becomes electrical energy. Each energy conversion step has losses from heat loss and friction and from inescapable inefficiencies governed by the laws of thermodynamics; fuel cells, on the other hand, can have greater efficiencies by bypassing these intermediate stages.In most fuel cells the oxygen reduction reaction takes place on the surface of particles of expensive precious metals (usually platinum). Laccase catalyses the same reaction using only four copper atoms per enzyme molecule. Laccase catalysis is more energetically efficient, nearly as rapid, and more selective against catalyst-killing gaseous impurities.There are two key problems with using laccase in fuel cells. The first is stability: enzymes are complex and often fragile biological polymers that need to be properly oriented to work in a fuel cell. However, I have developed a technique that extends the working lifetime of laccase in a fuel cell from hours to several months. The second is the amount of electric current that is generated from a given area or volume. The platinum surface can host thousands of reactions at once while the each laccase molecule can only react one oxygen molecule at a time. To compensate for this, I am proposing introducing laccase into porous, three-dimensional electrode materials, essentially taking laccase from working on a open plain and moving it to a multi-storey office complex. For laccase to function as efficiently as possible, it needs to have its reaction needs met: a good supply of oxygen (fast gas diffusion), a constant concentration of hydrogen ions (buffered pH), and a well-connected electrical supply. Designing and building this infrastructure requires a thorough understanding of the interactions between the enzyme's surface and the surface to which it is attached and careful control of how material flows through the pores. Extending the surfaces into the third dimension lets us make more compact power sources that are suitable, for example, for small electronics like portable music players and mobile phones.Most of the surface area of porous materials is on the inside of the structure and probing an interior surface is always a challenge. I will use small gaseous molecules explore the interior, high-energy beams of metal ions to cut open the structure, high-resolution electron microscopy to examine it, and electronic and spectroscopic methods that can interrogate the interaction between the enzyme and a surface.This work is supported by an active, ongoing collaboration with experts in fungal biology. They are currently working on understanding the molecular biology behind laccase, first to mass produce the enzyme, followed by genetic engineering to change laccase's catalytic behaviour, selectivity and surface interactions.In addition to portable fuel cells that work at ambient temperatures, we may also discover more efficient, less expensive catalysts and learn how enzymes are able to carry out the oxygen reduction reaction with copper, a common metal from the first row of the transition metals, rather than platinum, a rare and expensive metal from the third row.
 
Description In addition to discoveries noted in EP/G00434X/1, which is this grant before transferring to U. Manchester:
1. We found that there is a fundamental issue in the application of enzymes as fuel cell catalysts when they are directly immobilised on an electrode surface. Changing the driving force, equivalent to drawing variable amounts of current from a fuel cell, causes the enzymatic electrocatalyst to degrade much more rapidly than when used with a continual current load (minutes versus months).
2. We found that our technique for monitoring the efficient use of enzyme electrocatalysts has a lucrative application in industrial biotechnology: creating fine chemicals in through enzymatically catalysed chemical transformations.
3. We found evidence of two new enzymatic states that affect the short-term performance of technological devices based on multicopper oxidases.
4. We developed a new technique that combines electrochemistry and modelling to quantify the rates of all the sub-steps in enzymatically catalysed oxygen reduction.
Exploitation Route This will greatly affect the design of any fuel cells based on enzymes. Our method development should have an impact on aspects of industrial biotech in terms of more efficient enzyme use and in biosensor design, in terms of improving long-term performance, especially for those used for continuous monitoring.
Sectors Chemicals

Energy

Healthcare

Pharmaceuticals and Medical Biotechnology

 
Description We trialled our enzyme electrodes on a commercial fuel cell rig with our industrial partner C-Tech in membrane-free alcohol oxidation fuel cells using nanoparticles from a Brazilian collaborator.
First Year Of Impact 2016
Sector Energy
Impact Types Societal

 
Description ALERT14
Amount £491,200 (GBP)
Funding ID BB/M011658/1 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 05/2014 
End 07/2015
 
Description BBSRC
Amount £354,495 (GBP)
Funding ID BB/M007316/1 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 01/2015 
End 12/2017
 
Description BBSRC IAA
Amount £11,817 (GBP)
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 08/2015 
End 07/2016
 
Description DTA studentship
Amount £61,000 (GBP)
Organisation Higher Education Funding Council for England 
Sector Public
Country United Kingdom
Start 09/2012 
End 04/2016
 
Description Electricity generation from biofuels using hybrid inorganic-enzymatic fuel cells
Amount £44,367 (GBP)
Funding ID Internal: 111879 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 08/2016 
End 03/2017
 
Description Graphene Bioscience Interdisciplinary Grand Challenge
Amount £23,133 (GBP)
Organisation University of Manchester 
Sector Academic/University
Country United Kingdom
Start 04/2013 
End 09/2013
 
Description Graphene NowNano studentship
Amount £65,000 (GBP)
Organisation Imperial College London 
Department EPSRC Centres for Doctoral Training
Sector Academic/University
Country United Kingdom
Start 09/2014 
End 09/2018
 
Description Industrial applicability of blue multicopper oxidases to direct methanol fuel cells
Amount £10,000 (GBP)
Funding ID Project Ref: 111321 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 08/2016 
End 02/2017
 
Description Nownano DTP
Amount £74,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 09/2013 
End 09/2017
 
Description Nownano DTP
Amount £74,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 09/2010 
End 09/2014
 
Description Reynaud's & Scleroderma Association
Amount £111,268 (GBP)
Organisation Raynaud's & Scleroderma Association 
Sector Charity/Non Profit
Country United Kingdom
Start 07/2015 
End 07/2017
 
Title Method for modelling multicopper oxidase electrochemistry 
Description An experimental and computational methodology to fully quantify the kinetics of electrocatalytic reduction of O2 catalysed by multicopper oxidases. 
Type Of Material Technology assay or reagent 
Year Produced 2012 
Provided To Others? Yes  
Impact Too early to say. 
URL http://dx.doi.org/10.1039/C2SC00632D
 
Title Code associated with "A sensitivity metric and software to guide the analysis of soft films measured by a quartz crystal microbalance" 
Description MATLAB code with a graphical user inter- face to enable other QCM users to employ this analysis. The current software can be applied to any single, homogeneous adlayer that obeys a Kelvin-Voigt viscoelastic model and sits under a semi-infinite Newtonian fluid. 
Type Of Technology Software 
Year Produced 2016 
Open Source License? Yes  
Impact None to date 
 
Title Matlab code for modelling electrocatalytic oxygen reduction in multicopper oxidases 
Description A set of Matlab routines, linked to and described in the associated Chem. Sci. article, that allows one to convert enzyme responses to electrochemical stimuli and turn them into catalytic rate constants. 
Type Of Technology Software 
Year Produced 2012 
Open Source License? Yes  
Impact Too soon to tell. 
URL http://dx.doi.org/10.1039/C2SC00632D