Uranium-Ligand Multiple Bonds: From Molecules to Materials

Lead Research Organisation: University of Manchester
Department Name: Chemistry


Since the 2011 Fukushima disaster, a major priority for the nuclear sector has been to develop accident tolerant fuels (ATFs). A very promising ATF is uranium-nitride (UN). UN has a high thermal conductivity, enabling heat to be transferred efficiently so the fuel is meltdown-resistant. UN has a high fissile content, so more power can be generated than with existing oxide fuels for the same enrichment level. Mixed UN/PuN is a fuel option for Generation IV reactors breeding fissile material and producing less long-lived radioactive waste. So, UN is a safer, more environmentally friendly, and sustainable nuclear fuel. For similar reasons uranium-carbides are also attractive ATFs.

However, preparing uranium-nitrides and -carbides by traditional routes presents challenges. An attractive approach is to use molecular uranium-nitride and -carbyne precursors and decompose them to binary nitrides and carbides. Sadly, for decades there were few molecular uranium-nitrides so a molecules-to-materials approach was not realistic. The situation for uranium-carbynes is worse; there are only two spectroscopic reports of uranium-carbynes at ~10 Kelvin. Recently, we prepared the first molecular uranium-nitride triple bonds (Science, 2012, 337, 717; Nature Chemistry, 2013, 5, 482). Metal-ligand multiple-bonding is fundamentally important in chemistry and we have made a number of contributions in this area (e.g. J. Am. Chem. Soc. 2014, 136, 5619; Angew. Chem. Int .Ed. 2014, 53, 4484) and preliminary results show that our molecular nitrides can be controllably decomposed to binary nitrides which opens up a molecules-to-materials approach.

This Proposal aims to apply our recent coordination chemistry to the preparation of materials for energy in Grand Challenge and Priority Areas. We will develop a new range of uranium precursors to generate a platform to expand the range of nitrides. This exploits a blend of steric and electronic properties uniquely suited to stabilising uranium-ligand multiple bonds. Using these precursors we have identified four routes to maximise our chance of success to prepare high-value uranium-carbynes which have no precedent. With an expanded range of molecular uranium-nitrides and new uranium-carbynes we will build on preliminary results and investigate their decomposition to binary materials. The availability of new precursors leads to the possibility of exploring high pressure phase transitions to give new polymorphs. This is directly relevant to understanding fuels under extreme conditions in nuclear reactors and these metallic polymorphs are interesting to study as their itinerant vs localised 5f electron behaviour is magnetically fascinating and crucial to designing better ATFs.

We will combine synthetic, structural, and materials studies with interdisciplinary magnetometric, computational, and spectroscopic studies with collaborators to give a comprehensive understanding of uranium-nitrogen and -carbon bonding, reactivity, and materials applications. A Fellowship will provide the best opportunity to oversee this complex programme of research, manage an intensive array of collaborations, and make the time to engage with the nuclear industry and translate academic advances on to the next level into industrially relevant applications. The researchers on this project will develop a range of skills in a recognised strategic skills shortage area. Our molecules provide unique opportunities to probe the nature and extent of covalency in uranium bonding; this issue is long-running, still hotly debated, and important because of the nuclear waste legacy in the UK. Spent nuclear fuel is ~96% uranium and the official Nuclear Decommissioning Authority figure for nuclear waste clean-up bill is 70 billion pounds. If we can better understand the chemistry of uranium this may in the future contribute to ameliorating the UK's nuclear waste legacy and provide new routes to ATFs to be developed with the Nuclear Industry.

Planned Impact

The 2009 EPSRC International Chemistry Review stated: "The resurgence in radiochemistry is a potentially important development given rising interest worldwide in nuclear power. There are obvious needs for better understanding the chemistry related to radioisotopes and for educating a new generation of personnel trained to deal with these materials. This presents an opportunity to explore the fundamentals of compounds rarely accessed in academia".

We therefore believe this Fellowship will have major impact, as evidenced by our prior outputs, collaborations, and industrial potential. Furthermore, the proposed research addresses two Grand Challenges identified by EPSRC and will deliver the following outcomes and inventions:

1. Delivery of a better understanding of a strategically important area internationally;
2. Materials synthesis and small molecule activation and conversion into value-added products;
3. Fundamental scientific knowledge and understanding of academic and technological merit;
4. Maximise knowledge-exchange, -transfer, and -impact in exploitation, and commercialisation;
5. Early career researchers available for the UK economy, coupled to significant outreach.
6. A consolidated and enhanced internationally leading position and profile for the PI.

In order to maximise the impact of our work, we will communicate and engage with private and public sectors, academia, the public, and stakeholders through a series of activities with well-defined milestones and timelines.

Outreach: The PI has a strong record of science communication through university open days, school visits, the Royal Society MP/Scientist Pairing Scheme, the 2012 Royal Society Summer Science Exhibition ('The Wonder of Chemistry' 9 lecture series), the Sunday Times Magazine, Periodic Videos and EPSRC funded MolVids. We will build on our approach by building a new website, producing new videos on nitrides and carbides, and use our public lecture experience to culminate with a Royal Society Summer Science Exhibition stand in Year 5.

Industry and Commerce: The Business Partnership Unit, which is uniquely embedded in chemistry at Nottingham, maintains an excellent awareness of industrial needs and will manage potential exploitation of research outputs. Progress will be regularly monitored and contact with end-users will be made as exploitable outputs are identified. As demonstrated by the letters of support the team already established contacts with the nuclear industry and will develop them as appropriate following the establishment of a collaboration following an EPSRC IAA fKTS grant which seeded this proposal. Through departmental advisory boards we have access to industrial representatives. Knowledge exchange will be exploited using standard protocols as collaborative opportunities are identified. The BPU has extensive experience of negotiating contracts covering collaboration, confidentiality, material transfer, and licenses and all necessary arrangements are in place with partners.

EU: Although the PI's COST Action finishes in 2015 he orged enduring links with COST so has a communications line to that office and thus to the EU to increase the impact of this work. An application for a new f-block Action will be submitted. Activities will then include training schools and conferences within the Action and independently though COST science fairs.

Training: The PDRAs working on this research will gain a comprehensive background in uranium-handling (a rare skill), synthesis, spectroscopy, magnetism, computation, materials chemistry, and hands-on experience with collaborators kit. They will receive UoN and external RPS and NNL radiochemical training, attend conferences and exhibitions, and acquire a host of transferable skills. This will enhance their careers, make them very attractive, valuable candidates for scientific careers, and help restructure UK science and the nuclear industry.


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Brown JL (2016) Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold. in Chemical communications (Cambridge, England)

Description We have delivered several landmark results in uranium chemistry which can be found in the list of publications.
Exploitation Route We have developed the fundamental base of knowledge and understanding of the area, others may well make advances based on this but impossible to predict this.
Sectors Chemicals,Education,Energy

Description Some of our work has been featured in YouTube videos on our CAMERA outreach project, e.g. https://www.youtube.com/watch?v=BghAC7XSuFI, https://www.youtube.com/watch?v=3m3CbQct0pM, and https://www.youtube.com/watch?v=g1_HHwJqhzs. Total views ~28,000.
First Year Of Impact 2018
Sector Chemicals,Other
Impact Types Cultural

Description EPSRC Established Career
Amount £1,422,792 (GBP)
Funding ID EP/M027015/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 10/2015 
End 09/2020
Description High Intensity High Sensitivity X-ray Diffraction Equipment
Amount £1,100,000 (GBP)
Funding ID EP/P001386/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 10/2016 
End 10/2021
Description Magnetic Properties Measurement System for Manchester and National EPR Facility
Amount £732,000 (GBP)
Funding ID EP/S033181/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 09/2019 
End 08/2024
Description National Nuclear User Facility at the Centre for Radiochemistry Research (CRR)
Amount £4,420,000 (GBP)
Funding ID EP/T011289/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 11/2019 
End 05/2022
Description Presidents Doctoral Scholarship
Amount £80,000 (GBP)
Organisation University of Manchester 
Sector Academic/University
Country United Kingdom
Start 10/2016 
End 09/2021
Description EPSRC UK EPR Service 
Organisation Engineering and Physical Sciences Research Council (EPSRC)
Department National EPR Research Facility and Service Home
Country United Kingdom 
Sector Academic/University 
PI Contribution We provide materials to be measured.
Collaborator Contribution The EPR service measures the EPR spectra of our compounds.
Impact Please see outputs associated with the grant.
Start Year 2012
Description CAMERA 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact YouTube channel presenting videos on research done at chemistry in manchester, majority of videos feature research funded by EPSRC, BBPSRC. See: https://www.youtube.com/channel/UCXf3CFkyGpa2eIeT5wz_Prw/videos. At 09-02-2018 >24k views from a standing start 4 months ago.
Year(s) Of Engagement Activity 2017
URL https://www.youtube.com/channel/UCXf3CFkyGpa2eIeT5wz_Prw/videos