Programmable Molecular Metal Oxides (PMMOs): From Fundamentals to Application
Lead Research Organisation:
University of Glasgow
Department Name: School of Chemistry
Abstract
Metal oxide based technology is worth over a trillion dollars per year with applications in microchips, hard disks, displays, glass coatings, sun screen, chemical catalysts, and superconductors. In almost all instances the metal oxide based materials are comprised of 'solid-state' infinite materials which require high temperature processing and can be difficult to modify systematically. We have been working on a class of molecular metal oxides called polyoxometalates (POMs). Research in molecular metal oxides or polyoxometalate clusters (POMs) provides an unrivalled structural diversity of molecules, displaying a wide range of properties. During the past 5 years we have transformed the area demonstrating how to control the assembly of the clusters, including the precise design of host-guest systems that are intrinsically electronically active. Now, due to our researcher critical mass and expertise, and state of the art single crystal X-ray diffraction using microsource and area detectors, cryospray and ion mobility mass spectrometry, spectroscopy, flow systems, microsystems, and electrochemical measurements we are the leading group worldwide capable of developing designed approaches to producing clusters and building blocks that can link the molecular with the nanoscale, microscale and device / system level using a programmable approach in the following areas: (i) electronic materials; (ii) hybrid organic inorganic molecules and materials; (iii) emergent materials and structures; (iv) continuous flow discovery, processing and scale up nanoscale clusters. Platform funding will allow us to maintain critical mass, embark on risky cross-cutting projects that are not normally possible using responsive mode funding, allow continuity. These aspects are particularly important here since during the last few years the group has demonstrated a unique research philosophy developing new synthetic areas, fundamental ideas, techniques, and unique research approaches including embracing important disciplines needed to advance the chemical research (e.g. chemical engineering, optical physics, electrical engineering and so on). Although these projects are highly focussed on specific areas, the group has become highly integrated and more successful as a result of this integration but there is a limit to which individual projects can be used to integrate the group. The key aspect of the Platform grant will be the additional integration, adding value way beyond what would be possible through standard responsive mode funding of smaller grants, as well as helping a highly integrated and large research group funded by many different grants remain integrated, responsive, and dynamic. We will also use the Platform mechanism to develop the people funded within the group encouraging them to think critically, develop independence, a new ideas and approaches that exploit the unique mix of projects, expertise developing their careers as academics, industrialists and experts able to link fundamental with applied aspects.
Planned Impact
Who will benefit from this research?
The inorganic materials / coatings / energy / microfluidic / semi-conductor / nano-fabrication industries will be the major beneficiaries of this research at all levels from multi-nationals to SMEs and spin out companies. In addition UK HEIs, students and the general public will also be beneficiaries as well as the UK-PLC as a whole.
How will they benefit from this research?
Industry: The inorganic materials / coatings / energy / microfluidic / semi-conductor / nano-fabrication industries will benefit from the new technologies generated in this research since it will provide, new paradigms in materials, devices and systems for application across a range of sectors with the possibility of delivering breakthroughs that could result in disruptive technologies (e.g. microfluidic systems that do not need lithographic fabrication or solar fuel cells that do not need precious metals). These benefits will be of great interest also to SMEs and spin-outs that develop niche applications that will directly utilize and develop some of the technology in other directions developing 'niche' high value applications. The interactions between Chemists, Physicists, Engineers, and Biosciences proposed in this grant will also yield great potential teaching and research benefits for the students and the University. This is because undergraduate, ERASMUS, and PhD students will get the chance to take part in research that crosses the interface of this project and it may also be possible to develop a research masters based on this area that will train the next generation of researchers and engineers. General Public: The general public will benefit from this research from the increase in wealth that will be developed and the public understanding and promotion of science activities planned through public lectures at Glasgow / Edinburgh Science Weeks, Café Scientifique. e.g. The PI gave a TED talk on 'inorganic biology' which was watched by over 160,000 in just one week after release on the web.
The inorganic materials / coatings / energy / microfluidic / semi-conductor / nano-fabrication industries will be the major beneficiaries of this research at all levels from multi-nationals to SMEs and spin out companies. In addition UK HEIs, students and the general public will also be beneficiaries as well as the UK-PLC as a whole.
How will they benefit from this research?
Industry: The inorganic materials / coatings / energy / microfluidic / semi-conductor / nano-fabrication industries will benefit from the new technologies generated in this research since it will provide, new paradigms in materials, devices and systems for application across a range of sectors with the possibility of delivering breakthroughs that could result in disruptive technologies (e.g. microfluidic systems that do not need lithographic fabrication or solar fuel cells that do not need precious metals). These benefits will be of great interest also to SMEs and spin-outs that develop niche applications that will directly utilize and develop some of the technology in other directions developing 'niche' high value applications. The interactions between Chemists, Physicists, Engineers, and Biosciences proposed in this grant will also yield great potential teaching and research benefits for the students and the University. This is because undergraduate, ERASMUS, and PhD students will get the chance to take part in research that crosses the interface of this project and it may also be possible to develop a research masters based on this area that will train the next generation of researchers and engineers. General Public: The general public will benefit from this research from the increase in wealth that will be developed and the public understanding and promotion of science activities planned through public lectures at Glasgow / Edinburgh Science Weeks, Café Scientifique. e.g. The PI gave a TED talk on 'inorganic biology' which was watched by over 160,000 in just one week after release on the web.
Publications
Chen W
(2013)
0D to 1D Switching of Hybrid Polyoxometalate Assemblies at the Nanoscale by Using Molecular Control.
in ChemPlusChem
Zalesskiy S
(2019)
3D designed and printed chemical generators for on demand reagent synthesis
in Nature Communications
Chisholm G
(2014)
3D printed flow plates for the electrolysis of water: an economic and adaptable approach to device manufacture
in Energy Environ. Sci.
Kitson PJ
(2016)
3D printing of versatile reactionware for chemical synthesis.
in Nature protocols
Fielden J
(2012)
[Co(x)Cu(1-x)(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(II) by solid solution 'network mismatch'.
in Dalton transactions (Cambridge, England : 2003)
Cereda A
(2014)
A bioelectrochemical approach to characterize extracellular electron transfer by Synechocystis sp. PCC6803.
in PloS one
Baker ML
(2012)
A classification of spin frustration in molecular magnets from a physical study of large odd-numbered-metal, odd electron rings.
in Proceedings of the National Academy of Sciences of the United States of America
Grizou J
(2020)
A curious formulation robot enables the discovery of a novel protocell behavior.
in Science advances
Richmond CJ
(2012)
A flow-system array for the discovery and scale up of inorganic clusters.
in Nature chemistry
Fielden J
(2012)
A fluorophosphate-based inverse Keggin structure.
in Dalton transactions (Cambridge, England : 2003)
Zhan C
(2017)
A metamorphic inorganic framework that can be switched between eight single-crystalline states.
in Nature communications
Salley DS
(2020)
A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates.
in ACS central science
Salley D
(2020)
A nanomaterials discovery robot for the Darwinian evolution of shape programmable gold nanoparticles.
in Nature communications
Glatzel S
(2016)
A Portable 3D Printer System for the Diagnosis and Treatment of Multidrug-Resistant Bacteria
in Chem
Kirkaldy N
(2018)
A practical, organic-mediated, hybrid electrolyser that decouples hydrogen production at high current densities.
in Chemical science
Marshall SM
(2017)
A probabilistic framework for identifying biosignatures using Pathway Complexity.
in Philosophical transactions. Series A, Mathematical, physical, and engineering sciences
Parrilla-Gutierrez JM
(2020)
A programmable chemical computer with memory and pattern recognition.
in Nature communications
Doran D
(2017)
A recursive microfluidic platform to explore the emergence of chemical evolution.
in Beilstein journal of organic chemistry
Long DL
(2013)
A redox-triggered structural rearrangement in an iodate-templated polyoxotungstate cluster cage.
in Chemical communications (Cambridge, England)
Asche S
(2021)
A robotic prebiotic chemist probes long term reactions of complexifying mixtures.
in Nature communications
Sans V
(2015)
A self optimizing synthetic organic reactor system using real-time in-line NMR spectroscopy.
in Chemical science
Mehr SHM
(2020)
A universal system for digitization and automatic execution of the chemical synthesis literature.
in Science (New York, N.Y.)
Bagchi V
(2014)
A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations.
in Journal of the American Chemical Society
Parrilla-Gutierrez JM
(2017)
Adaptive artificial evolution of droplet protocells in a 3D-printed fluidic chemorobotic platform with configurable environments.
in Nature communications
Points LJ
(2016)
An all-inorganic polyoxometalate-polyoxocation chemical garden.
in Chemical communications (Cambridge, England)
Dragone V
(2017)
An autonomous organic reaction search engine for chemical reactivity.
in Nature communications
Zheng Q
(2019)
Anisotropic Polyoxometalate Cages Assembled via Layers of Heteroanion Templates.
in Journal of the American Chemical Society
Turk-MacLeod R
(2018)
Approach to classify, separate, and enrich objects in groups using ensemble sorting.
in Proceedings of the National Academy of Sciences of the United States of America
Zhao T
(2023)
Aqueous solutions of super reduced polyoxotungstates as electron storage systems.
in Energy & environmental science
Points LJ
(2018)
Artificial intelligence exploration of unstable protocells leads to predictable properties and discovery of collective behavior.
in Proceedings of the National Academy of Sciences of the United States of America
Molina PI
(2014)
Assembly and core transformation properties of two tetrahedral clusters: [Fe(III)13P8W60O227(OH)15(H2O)2]30- and [Fe(III)13P8W60O224(OH)12(PO4)4]33-.
in Dalton transactions (Cambridge, England : 2003)
De La Oliva AR
(2012)
Assembly of a gigantic polyoxometalate cluster {W200Co8O660} in a networked reactor system.
in Angewandte Chemie (International ed. in English)
Zang HY
(2016)
Assembly of inorganic [Mo2S2O2]2+ panels connected by selenite anions to nanoscale chalcogenide-polyoxometalate clusters.
in Chemical science
Gao J
(2012)
Assembly of molecular "layered" heteropolyoxometalate architectures.
in Angewandte Chemie (International ed. in English)
Zang HY
(2013)
Assembly of thiometalate-based {Mo16 } and {Mo36 } composite clusters combining [Mo2O2S2 ](2+) cations and selenite anions.
in Advanced materials (Deerfield Beach, Fla.)
Zhan C
(2015)
Assembly of Tungsten-Oxide-Based Pentagonal Motifs in Solution Leads to Nanoscale {W 48 }, {W 56 }, and {W 92 } Polyoxometalate Clusters
in Angewandte Chemie
Zhan CH
(2015)
Assembly of Tungsten-Oxide-Based Pentagonal Motifs in Solution Leads to Nanoscale {W48}, {W56}, and {W92} Polyoxometalate Clusters.
in Angewandte Chemie (International ed. in English)
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
Taylor JW
(2017)
Autonomous model protocell division driven by molecular replication.
in Nature communications
Xuan W
(2016)
Back Cover: Self-Templating and In Situ Assembly of a Cubic Cluster-of-Clusters Architecture Based on a {Mo 24 Fe 12 } Inorganic Macrocycle (Angew. Chem. Int. Ed. 41/2016)
in Angewandte Chemie International Edition
Li F
(2012)
Cation induced structural transformation and mass spectrometric observation of the missing dodecavanadomanganate(IV).
in Dalton transactions (Cambridge, England : 2003)
Ruiz De La Oliva A
(2017)
Coding the Assembly of Polyoxotungstates with a Programmable Reaction System.
in Inorganic chemistry
Kitson P
(2013)
Combining 3D printing and liquid handling to produce user-friendly reactionware for chemical synthesis and purification
in Chem. Sci.
Georgiev V
(2015)
Comparison Between Bulk and FDSOI POM Flash Cell: A Multiscale Simulation Study
in IEEE Transactions on Electron Devices
Hutin M
(2013)
Comprehensive Inorganic Chemistry II
Description | The Platform will link in with the Cronin-group website (www.Croninlab.com) which will be expanded to have significant resources that explain the research of the team and its significance, and then this will be established as a stand-alone site; 'metal-oxide-technology'. We already have some teaching and public awareness resources through our other projects and these will be harmonized and brought together during the period of the Platform to increase impact and utilize synergies. We will also explain the links to other areas such as energy and health with some case studies (Note, this links with a Royal Society Wolfson Merit Award to Lee Cronin in June 2009 which provides some funding for a public-science website). We will also have a section called the 'researchers'-blog' in which leading scientists around the world will spend one month blogging about their experiences, ambitions, and ideas. In addition we will give lectures at Glasgow Science week and Café Scientifique as well as other media outlets. One example is Cronin's TED talk entitled 'inorganic biology' (http://www.ted.com/talks/lee_cronin_making_matter_come_alive.html) which was watched by over 160,000 viewers within one week of release on the web. |
Exploitation Route | As a result of this cross-departmental collaboration, new approaches to molecular and engineering sciences will be developed. In synergy with the project, the team has developed a lecture / workshop module to address the interdisciplinary aspects; three modules are planned from a chemical, engineering, and physics perspective. It is envisaged that as the Platform develops and expands that the training element could expand into a MSc., with courses in applications of metal oxides in catalysis, energy, engineering, and hybrid materials as well as microsystem devices One of the key value-added aspects of the Platform funding model is that our researchers can be exposed to a variety of projects, disciplines, techniques, and methodologies. This feature will be of considerable benefit for their careers and we will engage with our academic and industrial stakeholders to ensure that the combination of expertise is desirable. |
Sectors | Aerospace, Defence and Marine,Chemicals,Creative Economy,Digital/Communication/Information Technologies (including Software),Electronics,Energy,Pharmaceuticals and Medical Biotechnology |
URL | http://www.ted.com/talks/lee_cronin_making_matter_come_alive.html |
Description | This platform grant has helped to incorporate a technology transfer element that will allow 'real-time' technology transfer and knowledge transfer to industry including multi-nationals, SMEs, and spin-outs. Glasgow already has extensive contacts and either present or previous research contracts with many of the potential companies including FujiFilm, BP Chemicals, Unilever, P&G, Pilkington's, Worldmark, Johnson Matthey and so on. This technology transfer element will interact directly with the EPSRC funded Knowledge Training Account (KTA) awarded to the University of Glasgow, as well as the Glasgow University Research and Enterprise officer (Lynne Brown). The KTA is a key element that we will exploit to give this work visibility, interact with end-users, and develop a forum of interested parties that will receive information and progress updates about the project as it proceeds. Indeed the group to be funded by the Platform has already received KTA funding to work with two companies to develop highly focused aspects of metal oxide technology. One unique aspect of the Platform is the provision for funding of an 'embedded' technologist within the group for direct interactions with various companies to help transfer the fundamental aspects to allow application under 'real-world' circumstances. The steering group of the Platform will include Prof. Chick Wilson (Bath), Dr. Michael Duncan (P&G), Prof. Alexi Lapkin (Warwick), Prof. Duncan Graham (Strathclyde) and this team has a formidable range of expertise ranging from innovation in industry (MD), interactions with the chemicals industry (AL), big facilities (CW) as well as setting up spin-out companies and licensing (DG). Finally, the IPGroup, technology investors who have a partnership with Glasgow University, have been interacting with the Cronin group and have been evaluating the overall portfolio with a view to developing a range of investments with the aim of developing exploitable technology, know-how, and product innovations. |
First Year Of Impact | 2012 |
Sector | Chemicals,Creative Economy |
Impact Types | Cultural,Societal,Economic,Policy & public services |
Title | The Chemputer |
Description | A universal modular robotic synthesiser which can undertake ca. 60% of the batch reactions in the chemical literature. This also includes the XDL language and ontology for translating chemical procedures into universally readable actionable code which can potentially be implemented in any robotic system. |
Type Of Material | Improvements to research infrastructure |
Year Produced | 2017 |
Provided To Others? | Yes |
Impact | 19 News outlets have reported on this discovery. Plans are underway to setup a spinout and patent aspects of the discovery. https://www.altmetric.com/details/45198487/news https://www.altmetric.com/details/51967737/news |
URL | http://www.chem.gla.ac.uk/cronin/chemify/ |
Description | Collaboration with Burns Group (Princeton) - Calorimetry |
Organisation | Princeton University |
Country | United States |
Sector | Academic/University |
PI Contribution | We have synthesised POMs for calorimetry testing by our collaborator. We established synthetic methods for interconversion of POMs which backed up the conclusions of their measurements. |
Collaborator Contribution | The Burns group performed calorimetry studies on both our and their own POMs. This work resulted in a JACS paper in 2021 |
Impact | https://pubs.acs.org/doi/10.1021/jacs.0c10133 |
Start Year | 2019 |
Description | Programmable Molecular Metal Oxides (PMMOs): From Fundamentals to Application |
Organisation | University of Glasgow |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Metal oxide based technology is worth over a trillion dollars per year with applications in microchips, hard disks, displays, glass coatings, sun screen, chemical catalysts, and superconductors. In almost all instances the metal oxide based materials are comprised of 'solid-state' infinite materials which require high temperature processing and can be difficult to modify systematically. We have been working on a class of molecular metal oxides called polyoxometalates (POMs). Research in molecular metal oxides or polyoxometalate clusters (POMs) provides an unrivalled structural diversity of molecules, displaying a wide range of properties. During the past 5 years we have transformed the area demonstrating how to control the assembly of the clusters, including the precise design of host-guest systems that are intrinsically electronically active. Now, due to our researcher critical mass and expertise, and state of the art single crystal X-ray diffraction using microsource and area detectors, cryospray and ion mobility mass spectrometry, spectroscopy, flow systems, microsystems, and electrochemical measurements we are the leading group worldwide capable of developing designed approaches to producing clusters and building blocks that can link the molecular with the nanoscale, microscale and device / system level using a programmable approach in the following areas: (i) electronic materials; (ii) hybrid organic inorganic molecules and materials; (iii) emergent materials and structures; (iv) continuous flow discovery, processing and scale up nanoscale clusters. Platform funding will allow us to maintain critical mass, embark on risky cross-cutting projects that are not normally possible using responsive mode funding, allow continuity. These aspects are particularly important here since during the last few years the group has demonstrated a unique research philosophy developing new synthetic areas, fundamental ideas, techniques, and unique research approaches including embracing important disciplines needed to advance the chemical research (e.g. chemical engineering, optical physics, electrical engineering and so on). Although these projects are highly focussed on specific areas, the group has become highly integrated and more successful as a result of this integration but there is a limit to which individual projects can be used to integrate the group. The key aspect of the Platform grant will be the additional integration, adding value way beyond what would be possible through standard responsive mode funding of smaller grants, as well as helping a highly integrated and large research group funded by many different grants remain integrated, responsive, and dynamic. We will also use the Platform mechanism to develop the people funded within the group encouraging them to think critically, develop independence, a new ideas and approaches that exploit the unique mix of projects, expertise developing their careers as academics, industrialists and experts able to link fundamental with applied aspects. |
Collaborator Contribution | as above |
Impact | All publications tagged to EP/J015156/1 |
Start Year | 2012 |
Title | Use of Polyoxometalate Mediators |
Description | The present 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. |
IP Reference | US2021032762 |
Protection | Patent application published |
Year Protection Granted | 2021 |
Licensed | No |
Impact | No impact yet. Early stages. |