Chemical Synthesis of Transformative Extended Materials

Lead Research Organisation: University of Liverpool
Department Name: Chemistry


Our 10-15 year research vision is: chemical synthesis of advanced functional materials with properties that will challenge contemporary understanding of the physical and chemical behavior of extended systems, achieved with the precision that is now customary in small molecule chemistry. It is important to realize this vision because the synthesis of new functional materials is of strong societal and economic importance to the UK in priority areas such as energy and healthcare, and because access to materials with unprecedented properties opens up new scientific horizons. Realization of the vision requires strong links to the materials science, condensed matter physics, chemical engineering and life science collaborators who form the Programme Grant (PG) partnership.The proposal has a single 5-year thematic target: the development of synthetic methodologies for modular materials with domains of function. The target is addressed in three coupled Themes because the scientific challenges and the skills necessary to tackle them successfully are strongly linked, as reflected in the forecast deployment of 25% of the PG resource in activity that cuts across the themes.Theme 1 targets porous materials with incompatible or contraindicated chemical functional groups that can deploy flexibly to produce unique molecular separations and catalytic reactivity, producing new paradigms for the efficient use of limited natural resources. In Theme 2, optimally controlled interfaces in oxide materials will produce enhanced ionic transport for application in fuel cells and generate contraindicated scientifically challenging physical properties (e.g., ferromagnetism and ferroelectricity in a single material). The properties and functions accessed in Themes 1 and 2 on the molecular scale will be translated into the nano- to mesoscale in Theme 3 by chemical control of the statistical assembly processes which produce nanostructured assemblies. This provides a linked and integrated approach to the contraindicated chemical reactivity and physical property challenges and enables interaction with the more complex environments in living systems.The theme goals will be achieved by the fusion of synthesis, measurement and modeling in a cross-disciplinary, cross-sector, cross-institution international partnership. The partnership is constructed to allow the development of new methodology for the rapid evaluation of materials for properties of interest and subsequent detailed studies of the resulting promising lead examples by expert collaborators. The close thematic links and the opportunity for breakthroughs in competitive areas require a flexible resource deployment strategy, managed by a small leadership team with an experienced project mentor and reporting to an internationally-leading Steering Group. Resource is allocated to allow the building of further partnerships during the PG. The PG team have demonstrated research exploitation and outreach leadership via the formation of the award-winning spin-out, Iota NanoSolutions and the establishment of the Centre for Materials Discovery (with Europe's largest suite of capital equipment for accelerated extended materials discovery). Outreach to industry will be taken to a new level here via the concurrent NWDA-funded Knowledge Centre for Materials Chemistry.The PG activity is focused in an area where global competition is characterised by a strong geographical focus of resources. This is recognised by the University of Liverpool who have consistently reinvested in materials chemistry. This is demonstrated here again by the commitment of 1.22M cash and 276K in-kind support in addition to the normal 20% FEC contribution, which adds value to the EPSRC investment as part of a true long-term partnership with the funding body. 10 dedicated DTA studentships are committed to the grant for cross-disciplinary and cross-institution activity.


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Algara-Siller G (2014) Triazine-based graphitic carbon nitride: a two-dimensional semiconductor. in Angewandte Chemie (International ed. in English)

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Bojdys MJ (2011) Supramolecular engineering of intrinsic and extrinsic porosity in covalent organic cages. in Journal of the American Chemical Society

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Bojdys MJ (2012) Porous organic cage crystals: characterising the porous crystal surface. in Chemical communications (Cambridge, England)

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Bradley KA (2014) Reported and predicted structures of Ba(Co,Nb)(1-d)O3 hexagonal perovskite phases. in Physical chemistry chemical physics : PCCP

Description The original vision for this was project was "chemical synthesis of advanced functional materials with properties that will challenge contemporary understanding of the physical and chemical behaviour of extended systems, achieved with the precision that is now customary in small molecule chemistry". We have produced, published and patented materials based on this vision with properties spanning photocatalysis and selective sorption to lead-free replacements of piezoelectric materials and new fuel cell electrodes.
The delivery of this vision is exemplified by the development of molecular cage solids as a new class of porous materials with function arising from their solid state structures but controlled by molecular synthesis. These materials have remarkable sorption properties, for example, they are the best known materials for separating the commercially important noble gases krypton and xenon. These materials were commercialised by Sigma Aldrich. A fundamental breakthrough was the use of crystal structure prediction (CSP) to predict the assembly of these cages in the solid state - this was the first example of using CSP outside of the pharmaceutical area to design new organic functional porous solids. At the time of publication, these organic cages were by far the largest molecules to have been tackled using CSP. Unlike zeotype approaches for metal-organic frameworks, this CSP method involves no assumptions about topology and it is therefore applicable to hypothetical candidate molecules about which nothing is known experimentally. Similarly, by using chemical design criteria, we have grown in an atomic layer-by-atomic layer manner two oxide materials with quite different crystal structures on top of each other, opening up new generations of materials combinations of functional interfaces by revealing the principles needed to fuse different oxide lattices.
The combination of different skills and perspectives within the project team has allowed us to develop new approaches to the identification of functional materials, for example by blending approaches involving inorganic and organic synthesis. By integrating our knowledge of porous, nanostructured and oxide materials in a manner that was quite unanticipated at the start of the project, we identified a new approach to the synthesis of solid oxide fuel cell cathodes based on the self-organisation of ordered regions within an extended structural scaffold - this sort of "emergent" behaviour is common in soft matter, such as polymers, but rare in "hard" materials such as oxides. The resulting material performs well as a cathode and is a candidate for next-generation systems that is currently under development.
One of the most striking scientific developments is the first report of a ferromagnetic ferroelectric bulk material that operates at room temperature - the combination of the two long-range ordered states of ferroelectricity (electrical dipoles) and ferromagnetism (magnetic dipoles or spins) has proved very challenging because the basic chemical bonding requirements of these two states had been thought to be contradictory and in competition with each other. We identified this material by first understanding the structure of related materials that contained only one of the two ground states over a range of length scales, not solely the long-range average view that diffraction gives us, and then designing new systems to favour both states simultaneously. The resulting material displays both switchable magnetisation and electrical polarisation at room temperature, together with magnetoelectric coupling.
Exploitation Route The specific materials reported will contribute to the design of enhanced functional systems across the areas of selective sorption (for example low-energy separations, removal of toxic chemicals), catalysis, ion transport, fuel cell electrodes, lead-free piezoelectrics and multiferroics. The design approaches, for example self-organisation in hard materials, creation of epitaxial non-isostructural oxide interfaces and the control of extended function by local chemical modification, will be used by researchers aiming to create functional materials across a range of materials classes and sectors.
Sectors Aerospace, Defence and Marine,Chemicals,Digital/Communication/Information Technologies (including Software),Electronics,Energy,Environment,Healthcare

Description A new class of porous materials have been created that are now commercially available (see Sigma Aldrich catalogue: New fuel cell electrode design approaches have led to a patented material acquired by a company and are being taken forward partly with EPSRC Impact Acceleration Account funding. Materials with very high sorption capacities for toxic industrial chemicals have been developed and are informing the development of materials for applications at partner organisations. Materials with high selectivities, for example for separating isomers of organic molecules or for separating radioactive gases, are being developed with partner organisations, partly via EPSRC impact acceleration account funding. We have identified the first magnetoelectric ferroelectric ferromagnet, which is a class of material important for low-energy information storage and processing, and are engaging with partners about this material.
First Year Of Impact 2014
Sector Aerospace, Defence and Marine,Chemicals,Digital/Communication/Information Technologies (including Software),Electronics,Energy,Environment
Impact Types Economic

Description Leverhulme Research Centres
Amount £10,000,000 (GBP)
Funding ID Leverhulme Centrer for Functional Materials Design 
Organisation The Leverhulme Trust 
Sector Charity/Non Profit
Country United Kingdom
Start 10/2016 
End 10/2026
Description High resolution Electron Microscopy of thin films (Antwerp) 
Organisation University of Antwerp
Country Belgium 
Sector Academic/University 
PI Contribution Preparation and supply of thin film samples
Collaborator Contribution high resolution electron microscopy and analysis
Impact Publication in Nature Chemistry (2016). Publication in Chemical Science (2011), publication in Angewandte Chemie (2007)
Start Year 2018
Title A perovskite structure for solid oxide fuel cell 
Description A perovskite structure comprises a first element X, strontium, iron, cobalt, oxygen and tungsten; where the first element X is barium and/or a lanthanide and wherein the structure comprises a region of single perovskite and a region of double perovskite. The structure may be included in an electrode for a solid oxide fuel cell (SOFC). A method of forming a perovskite structure comprises mixing a first element X, strontium, iron, cobalt, oxygen and tungsten; heating the mixture to a first temperature for a first period of time to form a single perovskite; and heating the mixture to a second temperature for a second period of time to form a double perovskite; where the first element X is barium and/or a lanthanide. Preferably, the first temperature is in the range 650Â C to 750Â C, and the second temperature is in the range 850Â C to 1000Â C. The molar percentage of tungsten may be in the range of 5-10%. Preferably, the structure has the formula (Ba1-xSrx)(Co1-yFey)WbOc, where both x and y are independently in the range 0.1 to 0.9; a+b is equal to 1; and c is in the range 2 to 3. 
IP Reference WO2016083780 
Protection Patent granted
Year Protection Granted 2015
Licensed Yes
Impact Further EPSRC Impact Accelerator Account funding resulting from this technology.
Title Lanthanide-based MOF 
Description The present invention relates to compounds capable of forming metal-organic frameworks (MOFs), particularly f-block metal MOFs which selectively sorb one component (e.g. para-xylene) from a mixture of components (e.g. m-/p-xylene mixture). The invention also relates to methods of producing and using said compounds. 
IP Reference GB1215693.1 
Protection Patent application published
Year Protection Granted 2012
Licensed No
Impact The separation capability of this and related materials, plus the associated concept of guest-driven restructuring, are likely to influence the broad ranging selective sorption field.
Title Layered Perovskites 
Description The present invention relates to a mixed metal oxide exhibiting perovskite-type structural characteristics in which there are cations of Ba, Ca or Sr, a rare earth metal and Fe, Cr, Cu, Co or Mn present in three different coordination sites or a composition thereof, to a cathode composed of the mixed metal oxide or composition thereof and to a solid oxide fuel cell comprising the cathode. 
IP Reference GB1019156.7 
Protection Patent application published
Year Protection Granted 2010
Licensed No
Impact -
Title Multiferroic Materials 
Description The present invention relates to new multiferroic materials. More particularly, the present invention relates to new multiferroic single phase ceramic materials as well as to thin films formed from these materials, methods of preparing these materials and their use as multiferroic materials in electronic components and devices. 
IP Reference GB1504418.3 
Protection Patent application published
Year Protection Granted 2016
Licensed No
Impact Not yet published hence inappropriate to comment further.
Title Removal of Formaldehyde using Amine Cage 
Description Formaldehyde capture using reduced porous organic cages 
IP Reference WO2016174468 
Protection Patent application published
Year Protection Granted 2015
Licensed No
Impact too early to say
Title Separation using solid organic molecular cages 
Description This invention relates to chemical separations using porous materials 
IP Reference GB1411515.8 
Protection Patent application published
Year Protection Granted 2014
Licensed No
Impact We are collaborating with other academics and Public Health England to test properties and applications of the materials
Title Soluble Conjugated Microporous Polymers 
Description Polymers exhibiting solubility, conjugation and microporosity are processable and useful for a variety of applications. The polymers comprise repeating units which are linked together to form rigid macromolecular structures which do not exhibit space-efficient packing. The polymers may comprise aromatic structures, e.g. fused aromatic structures and/or multiply bonded aromatic structures, and may comprise solubilising groups such as for example branched alkyl groups or silyl groups. 
IP Reference GB1219783.6 
Protection Patent application published
Year Protection Granted 2012
Licensed No
Impact -
Title Two-dimensional carbon nitride materials and method of preparation 
Description This invention relates to a two-dimensional carbon nitride material, and the synthesis of said material, The material has inherent semiconductor properties and its of particular use in the field of electronics 
IP Reference WO2016027042 
Protection Patent application published
Year Protection Granted 2014
Licensed No
Impact this material will most probably have impact in the electronics industry and we have been approached by a multinational company
Title synthetic method and materials for ion separation and recovery 
Description Japan patent application Synthetic method and materials for ion separation and recovery T.Nankawa, M.J.Rosseinsky, D.Stewart, A.Katsolidis 
IP Reference JP2016-161059 
Protection Patent application published
Year Protection Granted 2016
Licensed No
Impact -
Company Name Porous Liquid Technologies Ltd 
Description Porous liquids-liquids with permanent holes in them-are a fundamentally new and counterintuitive state of matter, first described in 2015 in a joint Nature paper co-authored by researchers at Queen's University of Belfast and the University of Liverpool. This attracted much interest from academic teams and the media worldwide. Porous Liquid Technologies Ltd (PLT) was formed in July 2017 by the inventors to commercialise these materials ( The first porous liquids were hard to scale up, involving both complex chemistry and toxic solvents. Since 2015, we have solved both of those problems. Our most recent liquids have porosities of around 20%; a huge increase compared to our first-generation materials, opening up a range of applications. PLT has five directors - Prof. Stuart James (Belfast), Prof. Andrew Cooper (Liverpool), Dr Barry Murrer (ex Johnson Matthey), Mr David Moore (QUBIS) and Mr David James. 
Year Established 2017 
Impact The company is in discussion with a number of potential commercial partners in sectors spanning oil and gas, catalysis, and food and drink.
Description Seminar at Physics Department, Imperial College London 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact The project and latest results related to photocatalysis were presented to staff, students and potential collaborators by Dr R.S. Sprick in an invited seminar at Imperial College London. This resulted in a collaboration on ultra-fast spectroscopy with materials made in Liverpool.
Year(s) Of Engagement Activity 2015