Energy and the Physical Sciences: Hydrogen Production using a Proton Electron Buffer
Lead Research Organisation:
University of Glasgow
Department Name: School of Chemistry
Abstract
We propose to develop 'proton-electron-buffers' (PEBs) using redox-active polyoxometalate (POM) clusters that will be able, for the first time, to address the problem of simultaneous oxygen and hydrogen production during the electrolysis of water. It is anticipated that the use of a PEB in the water-splitting reaction will allow new catalysts, electrodes, and device architectures to be employed in electrolysers, and we will investigate both these new designs and the use of PEBs with exisiting electrolyser technology. Using a PEB in an electrolyser could also bring significant advantages with regards to intermittent power supplies (such as renewables) by reducing the instantaneous voltages required for electrolysis to occur. There could also be significant advantages In addition to exploring water splitting through the paradigm of the proton-electron-buffer, we will also explore the use of reduced polyoxometalate clusters as an intermediate "fuel source", by reacting the reduced PEBs with reducible chemical substrates to produce storable fuels. Thus this work could pave the way to a totally new route to 'clean' low-carbon H2 production temporally separated from the production of oxygen, as well as reducing energy consumption through technological advances informed by a whole system understanding as highlighted by the RCUK Energy Programme.
Planned Impact
In 2011, total worldwide hydrogen production exceeded 31 million metric tons, making hydrogen the world's most produced chemical in terms of number of moles made (> 15.5 trillion moles). Over 80% of this was used in the Haber-Bosch process to make ammonia (and thus the fertilisers upon which the earth's population rely) and the majority of the balance was used in the petro-chemicals industry. However, these already large hydrogen production figures will be dwarfed if and when the "hydrogen economy" becomes a reality, or if the production of fuel-stuffs such as methanol from hydrogen and CO2 becomes economical. A hydrogen and/or methanol economy would make sense from the point of view of both energy security and the environmental impact of continued fossil fuel use. However, both of these arguments are only true if the hydrogen can be sourced in disparate locations and in a renewable fashion. Currently, well over 90% of the world's supply of hydrogen actually comes from fossil fuels in the first place, and so can be considered neither environmentally friendly nor "secure". One route that can deliver hydrogen renewably and almost anywhere is the electrolysis of water. This produces hydrogen and oxygen, and when the hydrogen is subsequently burnt in air or in a fuel cell the only products are water and energy. Hence there is no chemical pollution in this energy storage cycle, provided that the power input used to initially electrolyse the water came from a renewable source. Proton-electrolyte-membrane electrolysers (PEMEs) are favoured for this renewable-driven water electrolysis, because they respond well to the variable and intermittent power delivered by renewable power sources (wind, solar, etc.). During the electrolysis, water is oxidised to give oxygen in one half of the cell and hydrogen in the other half. PEMEs tend to use precious metal electrodes and, in order to offset the costs involved, they tend to operate in fairly compact formats with both gases made at high current densities and high pressures in their respective sides of the cell. Although the two cell compartments are separated by an ostensibly gas-impermeable membrane (typically Nafion), at the high pressures reached (200 bar), hydrogen can permeate through the membrane, with attendant membrane degradation, efficiency losses due to parasitic hydrogen oxidation at the anode and ultimately requiring the electrolyser to be shut down to prevent explosive oxygen/hydrogen mixtures forming in the cell head-space. Despite these drawbacks, the US DOE believes high-pressure electrolysis to be amongst the most promising candidates for low-cost and sustainable hydrogen production for the hydrogen economy, if the issues surrounding gas-mixing and concomitant electrolyser degradation can be surmounted. In this research we propose to address the problems described above by developing a 'proton-electron-buffers' (PEBs) using redox-active polyoxometalate (POM) clusters that will be able to address the problem of simultaneous oxygen and hydrogen production during the electrolysis. It is anticipated that the use of a PEB in the water-splitting reaction will allow new catalysts, electrodes, and device architectures to be employed in electrolysers, and we will investigate both these new designs and the use of PEBs with exisiting electrolyser technology. In addition to exploring water splitting through the paradigm of the proton-electron-buffer, we will also explore the use of reduced polyoxometalate clusters as an intermediate "fuel source", by reacting the reduced PEBs with reducible chemical substrates to produce storable fuels. We therefore think the impact of this research could be large in both academia, industry, and the development of new electrolyzer technologies and we describe the routes to maximise impact in our pathways to impact document including our collaboration with ACAL energy, who are already using Polyoxometalates in next generation fuel cells.
Publications
Granda JM
(2018)
Controlling an organic synthesis robot with machine learning to search for new reactivity.
in Nature
Grizou J
(2020)
A curious formulation robot enables the discovery of a novel protocell behavior.
in Science advances
Gromski P
(2019)
How to explore chemical space using algorithms and automation
in Nature Reviews Chemistry
Henson A
(2018)
Designing Algorithms To Aid Discovery by Chemical Robots
in ACS Central Science
Kandasamy B
(2021)
Exploring the Geometric Space of Metal-Organic Polyhedrons (MOPs) of Metal-Oxo Clusters.
in Inorganic chemistry
Kirkaldy N
(2018)
A practical, organic-mediated, hybrid electrolyser that decouples hydrogen production at high current densities.
in Chemical science
Kitson PJ
(2016)
The digital code driven autonomous synthesis of ibuprofen automated in a 3D-printer-based robot.
in Beilstein journal of organic chemistry
Kitson PJ
(2016)
3D printing of versatile reactionware for chemical synthesis.
in Nature protocols
Kowalski Daniel J.
(2023)
Automated Library Generation and Serendipity Quantification Enables Diverse Discovery in Coordination Chemistry
in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Kowalski DJ
(2023)
Automated Library Generation and Serendipity Quantification Enables Diverse Discovery in Coordination Chemistry.
in Journal of the American Chemical Society
Kulikov V
(2017)
Spontaneous Assembly of an Organic-Inorganic Nucleic Acid Z-DNA Double-Helix Structure.
in Angewandte Chemie (International ed. in English)
Lei J
(2019)
Tuning Redox Active Polyoxometalates for Efficient Electron-Coupled Proton-Buffer-Mediated Water Splitting.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Lin CG
(2021)
Elucidating the paramagnetic interactions of an inorganic-organic hybrid radical-functionalized Mn-Anderson cluster.
in Dalton transactions (Cambridge, England : 2003)
Lockey D
(2022)
Investigating the autocatalytically driven formation of Keggin-based polyoxometalate clusters
in Matter
MacDonald L
(2018)
Selective hydrogenation of nitroarenes using an electrogenerated polyoxometalate redox mediator.
in Chemical communications (Cambridge, England)
MacDonald L
(2017)
Using earth abundant materials for the catalytic evolution of hydrogen from electron-coupled proton buffers
in Sustainable Energy & Fuels
Martin-Sabi M
(2018)
Redox tuning the Weakley-type polyoxometalate archetype for the oxygen evolution reaction.
in Nature catalysis
Martin-Sabi M
(2016)
Rearrangement of {a-P2W15} to {PW6} moieties during the assembly of transition-metal-linked polyoxometalate clusters.
in Chemical communications (Cambridge, England)
MartÃn S
(2019)
Integrated Synthesis of Gold Nanoparticles Coated with Polyoxometalate Clusters.
in Inorganic chemistry
McAllister J
(2019)
Tuning and mechanistic insights of metal chalcogenide molecular catalysts for the hydrogen-evolution reaction
in Nature Communications
McGlynn JC
(2019)
The rapid electrochemical activation of MoTe2 for the hydrogen evolution reaction.
in Nature communications
McHugh P
(2020)
Decoupled Electrochemical Water Splitting: From Fundamentals to Applications
in Advanced Energy Materials
Mehr SHM
(2020)
A universal system for digitization and automatic execution of the chemical synthesis literature.
in Science (New York, N.Y.)
Minato T
(2021)
Robotic Stepwise Synthesis of Hetero-Multinuclear Metal Oxo Clusters as Single-Molecule Magnets.
in Journal of the American Chemical Society
Title | Brainwaves |
Description | Prof Cronin has appeared on the BBC Radio Scotland "Brainwaves" program, in which he discusses his work, the origin of life, and his development as a scientist. (link below for a limited time only) |
Type Of Art | Film/Video/Animation |
Year Produced | 2016 |
Impact | Scottish audience (but also available on-line) |
URL | http://www.bbc.co.uk/programmes/b070d3yb |
Title | Disruptive Interview |
Description | In an interview for the 3D printing magazine "Disruptive", Lee Cronin discusses his approach of using 3D printing technology for drug discovery and pharmaceuticals, and the digitalisation of the chemical world. |
Type Of Art | Film/Video/Animation |
Year Produced | 2015 |
Impact | target audience |
URL | http://www.disruptivemagazine.com/opinion/disruptive-interview-lee-cronin-regius-chair-chemistry-uni... |
Title | People Behind the Science |
Description | Prof Cronin has appeared on the "People Behind the Science" podcast, where he shared his views on the Origin of Life, and on how chemistry gets complicated, as well as discussing his life as a scientist. |
Type Of Art | Film/Video/Animation |
Year Produced | 2015 |
Impact | inspiration |
URL | http://www.peoplebehindthescience.com/dr-lee-cronin/ |
Title | TED Talk |
Description | The idea is to make a device that could download plans for molecules and create them, in exactly the way that 3D printers can download plans and create objects. He would have a universal set of software, hardware and inks, and he believes all of them, including the ink, could be fantastically cheap. The software would be the product; the materials would be commodities. |
Type Of Art | Film/Video/Animation |
Year Produced | 2012 |
Impact | What would this mean? It would mean that you could print your own medicine. First, his team going to look at drug discovery and manufacturing. If drugs could be manufactured easily, they could be distributed anywhere - even printed at the point of need. If a new super-bug emerges, you could print a treatment right where it breaks out. Ultimately, Cronin says, "For me the cool bit, going into the future, is the idea of taking your own stem cells with your own genes and environment and printing your own medicine." Quickly delivered, cheap, personalized medicine. Does that sound like enough? If not, in the long long run, "You could make a matter fabricator. Beam me up, Scotty!" |
URL | http://blog.ted.com/lee-cronin-at-tedglobal2012/ |
Title | Through the Wormhole |
Description | Lee Cronin and Cronin group research were featured on the latest episode of Through the Wormhole. Lee explained his theory of chemical evolution that pre-dates biological evolution without genes. The episode was broadcast on the Science Channel, and the Cronin Group research can be seen in the first section of the 1-hour episode. (with Morgan Freeman) |
Type Of Art | Film/Video/Animation |
Year Produced | 2015 |
Impact | Large audience. |
URL | http://www.dailymotion.com/video/x2qd2qu |
Description | This work could pave the way to a totally new route to 'clean' low-carbon H2 production temporally separated from the production of oxygen, as well as reducing energy consumption through technological advances informed by a whole system understanding as highlighted by the RCUK Energy Programme. This grant set the group work for our recent patent filing on USE OF POLYOXOMETALATE MEDIATORS This invention provides methods for producing hydrogen using a mediator that is capable of reversibly donating and accepting four or more electrons. A method of the invention comprises the steps of reducing a mediator by four or more electrons to yield a reduced mediator, and oxidising a reduced mediator to yield a mediator, and reducing protons to yield hydrogen. |
First Year Of Impact | 2017 |
Sector | Electronics,Energy,Environment |
Impact Types | Cultural,Societal,Economic,Policy & public services |
Title | Decoupled Electrolysis using a Silicotungstic Acid Electron-Coupled-Proton Buffer in a Proton Exchange Membrane Cell |
Description | The storage of renewably-generated energy as hydrogen via the electrolysis of water is a fundamental cornerstone of a sustainable hydrogen economy. Conventional electrolysers usually require stable power inputs in order to operate effectively and safely and so may be unsuited to harnessing renewable power, which is often intermittent and diffuse. Electrolysis mediated by Electron-Coupled-Proton Buffers has the potential to overcome some of the challenges surrounding electrolysis using low and/or sporadic power inputs (especially those related to gas crossover) as the use of Electron-Coupled-Proton Buffers allows the oxygen and hydrogen evolution reactions to be completely decoupled from one another. Herein, we show that silicotungstic acid can be used as an Electron-Coupled-Proton Buffer in a proton exchange membrane cell, decoupling the hydrogen and oxygen evolution reactions at steady state current densities as high as 500 mA cm-2. O2 and H2 can be produced continuously by this system by cycling a fixed volume of the Electron-Coupled-Proton Buffer solution. Even at current densities as low as 25 mA cm-2, the level of hydrogen in the oxygen stream is <0.4%, whereas a conventional proton exchange membrane electrolyser operating at this current density produces oxygen containing nearly 2% hydrogen (unacceptable for most applications). Furthermore, using silicotungstic acid as an Electron-Coupled-Proton Buffer also confers greater tolerance to non-deionised water inputs and reduces fluoride release from the perfluorosulfonated membrane (a marker for membrane degradation) relative to a conventional proton exchange membrane electrolyser. Together, these results highlight the promise and potential advantages of Electron-Coupled-Proton Buffers (and silicotungstic acid in particular) for the electrolytic production of hydrogen and oxygen over a wide range of current densities, such as might be produced by renewable power inputs. |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
Description | Energy and the Physical Sciences: Hydrogen Production using a Proton Electron Buffer |
Organisation | University of Glasgow |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | We propose to develop 'proton-electron-buffers' (PEBs) using redox-active polyoxometalate (POM) clusters that will be able, for the first time, to address the problem of simultaneous oxygen and hydrogen production during the electrolysis of water. It is anticipated that the use of a PEB in the water-splitting reaction will allow new catalysts, electrodes, and device architectures to be employed in electrolysers, and we will investigate both these new designs and the use of PEBs with exisiting electrolyser technology. Using a PEB in an electrolyser could also bring significant advantages with regards to intermittent power supplies (such as renewables) by reducing the instantaneous voltages required for electrolysis to occur. There could also be significant advantages In addition to exploring water splitting through the paradigm of the proton-electron-buffer, we will also explore the use of reduced polyoxometalate clusters as an intermediate "fuel source", by reacting the reduced PEBs with reducible chemical substrates to produce storable fuels. Thus this work could pave the way to a totally new route to 'clean' low-carbon H2 production temporally separated from the production of oxygen, as well as reducing energy consumption through technological advances informed by a whole system understanding as highlighted by the RCUK Energy Programme. |
Collaborator Contribution | As above |
Impact | Publications are tagged to: EP/K023004/1 |
Start Year | 2013 |
Company Name | Astrea Power |
Description | Astrea Power is an exciting new spin out company that will exploit a novel electrolysis technique invented at the University of Glasgow that will revolutionise hydrogen generation and power to gas. Electrolysis for hydrogen generation is increasingly being recognized as a key enabling technology for the supply of high purity hydrogen for fuel cell vehicles, energy systems and industrial applications. Within these contexts, hydrogen production via electrolysis enables: Maximising grid integration of renewables. Increasing the economic value of renewable assets (energy storage). Creation of a low zero carbon fuel to decarbonize transport, heat and industrial applications (CO2 reduction value). Economic application of ultrapure hydrogen in industrial and laboratory applications. Current electrolytic hydrogen generation systems remain high cost, are not easily coupled to renewable sources and their cost reduction routes other than via economies of scale are limited. The technology Astrea will exploit was developed by a team led by Professor Lee Cronin of the School of Chemistry at the University Of Glasgow. Scottish Enterprise, Scotland's economic development agency, have funded the project since 2013. The technology has resulted in a patented system that has both cost and performance advantages over current current electrolyser and hydrogen storage systems including: increased durability, increased efficiency, low cost high pressure and high purity capability, reduced precious metal usage and low load capability for maximizing solar/wind capture and as a consequence delivers a lower cost of ownership to the end user. |
Year Established | 2015 |
Impact | just started |