Hemilabile and Switchable Metal-Organic Frameworks
Lead Research Organisation:
University of St Andrews
Department Name: Chemistry
Abstract
This grant proposal comes from a team of researchers with expertise spanning synthesis, characterisation and adsorption studies of porous materials. The project is to develop and generalise two new concepts in metal-organic framework (MOF) chemistry that the team have recently published in Nature Chemistry. The overall goal is to provide a step change in the properties of MOFs (including stability of the materials) to enable new types of chemistry that are not currently possible. To do this requires that the preliminary concepts are generalised to maximise their impact in both the academic and, in the long term, commercial worlds (see impact statement). An added feature of the novelty of this work is the application of advanced characterisation techniques, including X-ray pair distribution function analysis and in situ X-ray diffraction and combined adsorption/neutron diffraction to probe the structure and properties of the materials prepared.
Metal-organic frameworks (MOFs) are some of the most exciting and fast-developing materials that have been prepared in the last decade or so. The great versatility of the chemistry of these solids leads to ultra-high porosity, extreme flexibility, post synthetic modification potential and many other interesting and conceivably useful attributes. Because of this wide ranging chemistry and function, potential applications of these solids range from gas storage, separation and delivery, catalysis, and sensing all the way to biology and medicine. In the UK we have great strength in variety of these areas, in highly porous materials and hydrogen storage, chiral and bio-inspired MOFs, post-synthetic modification, computational aspects, crystal growth and several excellent synthetic/materials groups. However, the international competition is great in this rapidly growing area. The importance of developing the synthesis itself as a route to useful attributes has been recognised as a 'Grand Challenge' in the EPSRC-funded network entitled Directed Assembly of Extended Structures with Targeted Properties. The national importance of this area is implicit in its designation as a Grand Challenge. As the field moves on there is a great focus on developing both the fundamental and applied aspects of MOFs.
Metal-organic frameworks (MOFs) are some of the most exciting and fast-developing materials that have been prepared in the last decade or so. The great versatility of the chemistry of these solids leads to ultra-high porosity, extreme flexibility, post synthetic modification potential and many other interesting and conceivably useful attributes. Because of this wide ranging chemistry and function, potential applications of these solids range from gas storage, separation and delivery, catalysis, and sensing all the way to biology and medicine. In the UK we have great strength in variety of these areas, in highly porous materials and hydrogen storage, chiral and bio-inspired MOFs, post-synthetic modification, computational aspects, crystal growth and several excellent synthetic/materials groups. However, the international competition is great in this rapidly growing area. The importance of developing the synthesis itself as a route to useful attributes has been recognised as a 'Grand Challenge' in the EPSRC-funded network entitled Directed Assembly of Extended Structures with Targeted Properties. The national importance of this area is implicit in its designation as a Grand Challenge. As the field moves on there is a great focus on developing both the fundamental and applied aspects of MOFs.
Planned Impact
The overriding goal of this proposal is to develop the fundamental synthesis and potential of MOFs as reactive species in their own right. So there are no specific economic impacts targeted in the proposal.
However the groups involved in the is project are extremely active in developing commercial applications of MOFs and so it is always in our minds that an eventual long-range target of our research is always to have economic impact. In that sense part of our overall group strategy contains the explicit goal of developing a commercialisation plan for our MOF technologies with the aim of exploiting our intellectual property to its fullest extent.
In one area of commercialisation we are looking to develop MOFs towards applications in chemicals processing. It is in this area that the long term economic benefits of this proposal may lie. The development of thermally robust, reactive MOFs has the potential to truly transform the applicability of MOFs in chemicals processing - a major stumbling block in the past has been their lack of stability. However, it should be reiterated that this is primarily a fundamental study and the economic impact is still a long term goal and not short term.
Developing the skills of the personnel involved in the project is an important impact and one that is taken very seriously at both St Andrews and Newcastle. The PDRAs that will be employed on this project are likely to have excellent technical skills already, but these will be added to through the high quality science they will be required to complete. Added value to the training in this project comes from the cross disciplinary (chemistry and chemical engineering) nature of the work and the necessity of the PDRAs to be involved in different aspects. In this way it is likely that they will be exposed to a new audience for their scientific work, and as well as being technically well trained they will also need to develop some understanding of the multidisciplinarity that will stand them in good stead for their future careers in either academic or industrial scientific research and development. As with any innovative research project all members of the team will develop their personal skills.
However the groups involved in the is project are extremely active in developing commercial applications of MOFs and so it is always in our minds that an eventual long-range target of our research is always to have economic impact. In that sense part of our overall group strategy contains the explicit goal of developing a commercialisation plan for our MOF technologies with the aim of exploiting our intellectual property to its fullest extent.
In one area of commercialisation we are looking to develop MOFs towards applications in chemicals processing. It is in this area that the long term economic benefits of this proposal may lie. The development of thermally robust, reactive MOFs has the potential to truly transform the applicability of MOFs in chemicals processing - a major stumbling block in the past has been their lack of stability. However, it should be reiterated that this is primarily a fundamental study and the economic impact is still a long term goal and not short term.
Developing the skills of the personnel involved in the project is an important impact and one that is taken very seriously at both St Andrews and Newcastle. The PDRAs that will be employed on this project are likely to have excellent technical skills already, but these will be added to through the high quality science they will be required to complete. Added value to the training in this project comes from the cross disciplinary (chemistry and chemical engineering) nature of the work and the necessity of the PDRAs to be involved in different aspects. In this way it is likely that they will be exposed to a new audience for their scientific work, and as well as being technically well trained they will also need to develop some understanding of the multidisciplinarity that will stand them in good stead for their future careers in either academic or industrial scientific research and development. As with any innovative research project all members of the team will develop their personal skills.
Organisations
Publications
Brown C
(2013)
Structure and spectroscopy of hydrogen adsorbed in a nickel metal-organic framework
in Chemical Physics
Cattaneo D
(2016)
Crystal structure resolution of two different chlorhexidine salts.
in Journal of molecular structure
Clark L
(2015)
Extending the Family of V(4+) S=(1/2) Kagome Antiferromagnets.
in Angewandte Chemie (International ed. in English)
Clark L
(2015)
Extending the Family of V 4+ S =${ { 1/2 }}$ Kagome Antiferromagnets
in Angewandte Chemie
Duncan M
(2020)
Antibacterial efficacy from NO-releasing MOF-polymer films
in Materials Advances
Hayes O
(2020)
Preventing Undesirable Structure Flexibility in Pyromellitate Metal Organic Frameworks
in European Journal of Inorganic Chemistry
Henkelis S
(2016)
Synthesis and crystallographic characterisation of Mg(H 2 dhtp)(H 2 O) 5 ·H 2 O
in Inorganic Chemistry Communications
Henkelis S
(2018)
Monitoring the assembly-disassembly-organisation-reassembly process of germanosilicate UTL through in situ pair distribution function analysis
in Journal of Materials Chemistry A
Description | We have a developed a new mechanism by which MOFs that were previously expected to be unstable can be made stable |
Exploitation Route | We are exploring the possibilities at the present time. We have Non disclosure agreements with one company who are interested in exploring the technology further. |
Sectors | Chemicals |
Description | We have now been invovled in a collaboration with a company who are exploring commercial use, but nothing concrete has been developed yet. |
First Year Of Impact | 2018 |
Sector | Chemicals |
Title | A single crystal study of CPO-27 and UTSA-74 for nitric oxide storage and release (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
Title | CCDC 1432662: Experimental Crystal Structure Determination |
Description | Related Article: Susan E. Henkelis, Laura J. McCormick, David B. Cordes, Alexandra M.Z. Slawin, Russell E. Morris|2016|Inorg.Chem.Commun.|65|21|doi:10.1016/j.inoche.2016.01.007 |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Controlled Synthesis of Large Single Crystals of Metal-Organic Framework CPO-27-Ni Prepared by a Modulation Approach: In situ Single Crystal X-ray Diffraction Studies (dataset) |
Description | underpinning data for open access publication |
Type Of Material | Database/Collection of data |
Year Produced | 2021 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/controlled-synthesis-of-large-single-crystals-of-... |
Title | Data Underpinning Article: Extending the Family of V4+ S = ½ Kagome Antiferromagnets |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2015 |
Provided To Others? | Yes |
Title | Data Underpinning: Synthesis of 'unfeasible' zeolites |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2015 |
Provided To Others? | Yes |
Title | Data underpinning "Expansion of the ADOR strategy for the synthesis of new zeolites: The synthesis of IPC-12 from zeolite UOV" |
Description | The data files are not yet publicly available. Enquiries and requests for data should be directed to the publication's corresponding authors: Kasneryk, V, Shamzhy, M, Opanasenko, M, Wheatley, PS, Morris, SA, Russell, SE, Mayoral, A, Trachta, M, Cejka, J & Morris, RE 2017, 'Expansion of the ADOR strategy for the synthesis of new zeolites: the synthesis of IPC-12 from zeolite UOV' Angewandte Chemie, vol. 56, no. 15, pp. 4324-4327. DOI: 10.1002/anie.201700590 |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
Title | Data underpinning "In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6" |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Title | High silica zeolites are widely used catalysts; those with different structural topologies being used for different applications. This protocol describes the Assembly-Disassembly-Organization-Reassembly (ADOR) process for preparing new zeolites. (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
Title | In situ flow pair distribution function analysis to probe the assembly-disassembly-organisation-reassembly (ADOR) mechanism of zeolite IPC-2 synthesis (dataset) |
Description | Underpinning data for open access publication |
Type Of Material | Database/Collection of data |
Year Produced | 2021 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/in-situ-flow-pair-distribution-function-analysis-... |
Title | Kinetics and mechanism of the hydrolysis and rearrangement processes within the Assembly-Disassembly-Organization-Reassembly synthesis of zeolites (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
Title | Monitoring the Assembly-Disassembly-Organisation-Reassembly Process of Germanosilicate UTL through in situ Pair Distribution Function Analysis (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2019 |
Provided To Others? | Yes |
Title | Multifaceted Study of the Interactions between CPO-27-Ni and Polyurethane and Their Impact on Nitric Oxide Release Performance (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2020 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/multifaceted-study-of-the-interactions-between-cp... |