ISIS Impact Awards

​The winner of the science award is Dr Minu Kim from the Max Planck Institute for Solid State Research, for their work investigating a new class of superconductor.

Superconducting materials are able to transfer electrons without any resistance to their flow of motion. This property has applications across a huge range of industries, but superconducting materials tend to only have these exotic properties at extremely low temperatures.

Ba_0.6K_0.4BiO₃ exhibits superconductivity up to a relatively high temperature. Although its high T_c of 30 K is widely reported, the cause of this is still a subject of debate, with multiple models suggested. Minu’s research aims to not only discover new superconducting materials with a higher T_c, but also to uncover the mechanisms behind these unusual properties.

One prevailing model involves the electron orbitals from the oxygen ions in the structure interacting with those from the bismuth (Bi) ions, causing charge density transfer and creating new energy levels and accessible oxygen ligand holes for resistance-free electron transfer. To investigate this model further, Minu and his team decided to try making the same material but with antimony (Sb) rather than bismuth. The relative energy levels of the antimony orbitals would cause the charge density transfer to be in the opposite direction to the bismuth-containing compound.

In their quest to create this material, the team took their inspiration from geoscience. Recreating conditions deep within the Earth’s mantle by using pressures of over 20 GPa and temperatures of 1900°C, they were able to synthesise a series of compounds with the formula Ba_1-xK_xSbO₃.

By looking at the Sb-O bond lengths in BaSbO_3-δ, measured using neutron diffraction on WISH, they could see that there was strong covalency between the antimony and oxygen ions, leading to a stronger interaction than in the bismuth equivalent. Further neutron diffraction experiments enabled them to create a phase diagram for the Ba_1-xK_xSbO₃ series, from which they identified a particular phase that may exhibit superconductivity.

The highest T_c, of 15 K, was observed for Ba_0.35K_0.65SbO₃. Although lower than the T_c of Ba_0.6K_0.4BiO₃, it is higher than the bismuth-equivalent at a similar potassium doping level. This suggests that, if it could be possible to stabilise the structure of an antimony equivalent at the same potassium level, the T_c could be even higher.

Crucially for the field of superconductivity, this research indicates that the direction of charge transfer may not be critical for the mechanism, as the opposite correlation is observed for these two series of materials. These findings sparked renewed interest in exploring similar high Tc materials, which could potentially lead to the development of novel superconductors.

Associated publication: Superconductivity in (Ba,K)SbO₃.​

The winner of the economic award is Timothy Johnson from Johnson Matthey, for their work demonstrating the viability of a scalable route to synthesising gas storage materials.

Sustainable technologies company, Johnson Matthey​, used neutron scattering to track the synthesis of a commercially relevant porous material, suitable for gas storage and catalysis. The results provided insights to develop a more economic, sustainable and scalable production pathway.

Zeolitic imidazolate frameworks (ZIFs) are porous materials with many potential applications, including gas separation, catalysis, electronic devices and drug delivery. For ZIFs to be used industrially, large-scale production routes are needed. Where conventional, small-scale syntheses often use large quantities of expensive and toxic solvents, such as methanol, large-scale production requires economic and environmentally friendly alternatives.

Researchers from Johnson Matthey wanted to investigate the feasibility of preparing ZIF-8 by first synthesising a different material, ZIF-L, and then transforming this into ZIF-8, as this novel route uses much less water and organic solvent. The team used several techniques, including neutron scattering at ISIS Neutron and Muon Source, to track the transformation of ZIF-L into ZIF-8 and demonstrate a scalable route to synthesise ZIF-8.

By using neutron spectroscopy, Johnson Matthey gained better understanding of the chemistry of their production process and showed that the synthesis of ZIF-8 was successful. The study also demonstrated that neutron spectroscopy could be used to track the reaction in real time, which would be beneficial in material scale-up to determine when the transformation of ZIF-L to ZIF-8 is complete.

On scaling production, Johnson Matthey successfully synthesised one kilogram of ZIF-8, with the potential to increase industrial production to 15 tonnes per year. The pilot formed the basis of an economic analysis that showed this synthesis route could produce over six times more ZIF-8 than direct methods.

The results will aid Johnson Matthey in developing larger-scale processes that produce more material at a lower cost, whilst also reducing environmental and safety concerns​.

“INS spectroscopy conducted on the TOSCA beamline at ISIS allowed scientists at Johnson Matthey to probe the structure of ZIF-8 and its polymorph ZIF-L. Data collected on TOSCA gave our scientists high confidence when working towards an accurate and predictive cost model with the ultimate aim of Metal-organic Framework commercialisation.”
Timothy Johnson, ​Senior Scientist, Johnson Matthey

Royal Holloway’s Professor Martin King has been awarded the societal impact award by the UK Science and Technology Facilities Council’s ISIS neutron and muon source for his work investigating real-world atmospheric pollutants using neutron reflectometry.

​The effect of pollutants on the atmosphere is still not fully understood and, although model systems have been used as a predictor, they are still a long way from knowing what happens in the real world. To bridge that gap, a research team led by Professor Martin King from Royal Holloway, University of London, studied atmospheric pollutant particles taken from real-world environments. Unlike model systems, these samples contained different mixtures of molecules, depending on where they came from.

All cloud droplets start as a particle in the atmosphere. Pollution leads to these atmospheric particles being covered in a thin film, with the thickness and lifetime of these films determining how much of an effect they have on cloud formation and the climate.

The group used neutron reflectometry to look at samples from Antarctica, a remote Atlantic Island near Canda, and UK rural and urban areas. During this process, neutrons are reflected from the thin films, enabling the team to measure the thickness of the films on the particles, and how fast they react with other molecules that would be present in the atmosphere. The thickness is critical to understand how they may cool the planet and the speed at which this cooling may occur.

To carry out these experiments, they went to the STFC ISIS Neutron and Muon Source, the UK’s leading centre for neutron and muon research.

They used the hydroxyl radical OH (one of the most reactive molecules found in the atmosphere) and followed its reaction with the natural thin films as a function of time. Once they had measured both the film thickness and the way the film reacts with the OH radical, they could input these data into a multi-layer model.

Using this model, they were able to show that the atmospheric particles remain in the atmosphere for long enough that they need inclusion in meteorological models. Their work highlights key differences between the way pollutants behave and break down in ‘real’ atmospheric conditions compared to the way they behave in the laboratory.

Alongside the STFC Central Laser Facility and the other partners of this ongoing project, funded through a grant from UKRI’s Natural Environment Research Council (NERC), Martin and his collaborators from the University of Birmingham, University of Uppsala, and British Antarctic Survey continue to investigate the impact of atmospheric pollutants on our health and the climate.

Awarded for the first realization of a quantum spin liquid on a triangular spin lattice with dominant Ising antiferromagnetic exchange interaction using WISH, MARI and MuSR.

A significant obstacle to the realisation of quantum computing is the fragility of the qubit, where information would be stored. Developing a system that can store information and remain robust to interference is key to having fault-tolerant quantum computations.

Quantum spin liquids (QSLs) occur when the magnetic moments of a material become entangled but remain disordered even at absolute zero. They can form stable complex topologies, making them a potential candidate for quantum computing materials.

Dr Andrej Zorko has been awarded the Science Impact Award this year for his work on one particular QSL found in neodymium heptatantalate, NdTa7O19. This compound was anticipated to behave as a QSL, after a theoretical prediction made seventy years ago, but, until recently, this had not been experimentally confirmed.

Using a combination of muon spectroscopy on MuSR, inelastic neutron scattering (INS) on MARI and neutron diffraction on WISH, as well as other experimental techniques in the laboratory and at large-scale facilities around the world, the team were able to show for the first time that a QSL is formed in NdTa7O19.

Although a few other QSL candidates have been characterised, this compound is the first of its kind: a triangular spin lattice with dominant Ising antiferromagnetic nearest-neighbour spin correlations.

Using INS, they were able to confirm that the magnetic species had effective spin 1/2 at low temperatures. They then used neutron diffraction to characterise the ground state, finding that there was no magnetic ordering even down at the lowest experimental temperature while spin correlations were found to develop. Following up these studies with experiments on MuSR meant they were able to confirm the absence of magnetic order, and show that there were spin dynamics present in the ground state, revealing the quantum nature of the ground state.

His group’s results show the community that the family of rare-earth heptatantalates is a potential source of candidate materials for quantum computing applications.

Related publication: The Ising triangular-lattice antiferromagnet neodymium heptatantalate as a quantum spin liquid candidate, Nature Materials, 21, 416–422 (2022), DOI: 10.1038/s41563-021-01169-y

Awarded for his work on the in-silico design of safer energetic materials

The economic impact award recognises research into the effect of impact in the other sense of the word. Energetic materials that release energy when a force is applied are widely used across a range of industries from defence and demolition to fireworks and Christmas crackers. However, some of the materials that are commonly used are toxic, with others causing environmental damage, and so there is a drive to find alternatives that are less damaging.

Despite these materials having been used for many years, there is little understanding of what causes mechanical impact to prompt the chemical reaction behind an explosion. Knowing what is happening on the atomic scale is key to developing new, more environmentally-friendly energetic materials.

Dr Adam Michalchuk and his collaborators aim to address this issue using computers. He has developed a computational model, based on vibrational spectra, that predicts the properties of energetic materials. To ensure their model was giving realistic answers, they needed to benchmark it against experimental results.

After attending the ISIS neutron training course, Dr Michalchuk realised that neutrons could provide critical information that cannot be gathered using laboratory-based techniques. Using the results of inelastic neutron scattering to validate their model, they have been able to show that their method is able to accurately describe the properties of a diverse range of energetic materials.

As well as using spectroscopy, he has expanded his work to using neutron diffraction on the PEARL beamline to study the crystal structure of these materials, and how they behave under high pressures. This will help him understand how mechanical force influences the activity.

The next stage of his research will see Dr Michalchuk collaborate with experimental chemists to design the energetic materials of the future. In addition, the understanding of how mechanical force can drive a chemical reaction is not only useful for this area of chemistry but can also be applied more widely.

Related publications:

Michalchuk et al. (2019) J Mater. Chem. A 7, 19539

Michalchuk et al (2018) J. Phys. Chem. C, 122, 19395

Michalchuk et al (2021) J. Chem. Phys., 154, 064105

Michalchuk et al (2021) Chem. Commun. 57, 11213

Michalchuk et al (2018) PhysChemChemPhys, 20, 29061

Awarded for her work on developing smarter materials by tuning physio-chemical properties using TOSCA and IRIS

Dr Heloisa Nunes Bordallo uses neutrons and other complementary techniques to study a range of materials that are relevant to our daily lives including dental cements, food, drug molecules and hair bleach. The common theme that runs through these examples is the presence of water confined in porous polymer frameworks. She uses a range of spectroscopy techniques to study the dynamics of hydrogen bonding in these frameworks, and how the polymers that are held together by these bonds change under different conditions.

In a dental cement, a glassy component is mixed with an aqueous solution, forming a mixture in which strong hydrogen bonds form. Using Quasielastic Neutron Scattering (QENS) on the IRIS instrument at ISIS, Dr Bordallo was able to study the hydrogen bonding network as it formed. To study faster reactions, down to the femtosecond timescale, she uses the TOSCA beamline. Combining the results from experiments on different spectrometers, she can study how a framework behaves over a large range of timescales.

Another feature of TOSCA that Dr Bordallo has used is the ability to do simultaneous Raman spectroscopy. She applied this during a study of psychotic drugs, which meant she was able to define more clearly the peaks caused by the vibrations in the complex drug molecules. This knowledge of the way the individual drug molecules move could be used in the future by those developing new medicines.

By using complex sample environments, her group studies porous polymers in the presence of different gases. This includes the investigation of a material that can capture the toxic gas ammonia from the atmosphere, with potential applications in face masks. By combining neutron spectroscopy experiments with DFT calculations using the STFC computing clusters, she was able to determine exactly how the ammonia was binding to the polymer framework. This understanding will inform the design of future materials with tuneable functionality.

As well as progressing her own research, Dr Bordallo has also introduced many students to the benefits of neutron scattering. These students then take their knowledge of neutrons with them into academia, industry, or teaching.

She is a vocal advocate of using neutrons and continues to raise awareness of the uniqueness of neutron spectroscopy to communities that would otherwise not use the technique, such as cosmetic scientists, dental researchers and, more recently, food scientists.

Related publications:

C.R.R. de Castro Lima, R.J.S. Lima, L.D.B. Machado, M.V.R. Velasco, L. Lakic, M.S. Nordentoft, L. Machuca-Beier, S. Rudić, M.T.F. Telling, V. Garcia-Sakai, C.L.P. de Oliveira, H.N. Bordallo (2020) Human hair: subtle change in the thioester groups dynamics observed by combining neutron scattering, X-ray diffraction and thermal analysis. Eur. Phys. J. Special Topics 229, 2825-2832.

R. J. S. Lima, D. V. Okhrimenko, S. Rudić, M. T. F. Telling, V. Garcia Sakai, D. Hwang, G. N Barin, J. Eckert, J-W.Lee, and H. N. Bordallo (2020) Ammonia Storage in Hydrogen Bond-Rich Microporous Polymers. ACS Appl. Mater. Interfaces 12, 58161–58169

The winner of the ISIS Science Impact Award is Prof Serena Corr for her work applying muon spin relaxation spectroscopy to investigating ion diffusion in battery materials

​Professor Corr and her team have advanced the application of muon spin relaxation spectroscopy (µSR) to investigating ion diffusion across a range of industrially-relevant battery materials. This included the first in-situ µSR study of a functioning battery cell permitting the study of diffusion processes occurring within individual battery components at different states of charge, and most recently in developing a protocol for studying real batteries in operation using µSR.

The team, in collaboration with ISIS Instrument Scientist Dr Peter Baker, began with investigations into olivine cathodes, the positive electrode materials recently introduced in Tesla’s Model 3, for which existing lithium diffusion property measurements spanned orders of magnitude. These studies, in good agreement with first principles studies, illustrated the benefit of applying µSR to interrogate ion diffusion across a breadth of these materials.

The team then investigated ceramic candidate solid electrolytes, safer alternatives to traditional liquid electrolytes, developing novel microwave chemistry methods to prepare the samples. Again using µSR, the results demonstrated the critical importance of applying multiple techniques to holistically probe diffusion properties. The next step was applying both µSR and neutron total scattering methods to a new class of safer solid electrolyte double perovskite materials, which the team synthetically realised and characterised using lattice-matching approaches to deliver a novel candidate solid state battery.

Having developed this extensive expertise, the team then turned its attention to successfully demonstrating the application of µSR to determining ion transport properties in polyatomic anionic cathodes containing fluoride ions. These were previously unexplored using muons due to potential muon-fluoride interactions making ion diffusion study difficult. Work then followed to uncover ion transport properties in next-generation cathodes, including doped high-nickel and disordered rock salt high-energy-density cathodes. Most recently, the team has developed a new cell and testing protocol for µSR investigations of materials within operating batteries for the first time. This technique provides new insights on crucial diffusion properties including ion diffusion in solid electrolytes and interfaces during operation.

µSR has emerged as an invaluable tool for the microscopic investigation of ionic motion in crystalline solids, e.g. in the study of intrinsic ionic conduction in electrode or solid electrolyte materials. The scientific impact delivered by the team’s efforts is in determining diffusion and local structure properties of energy storage materials and in developing new in-situ methods to interrogate ion diffusion in these during operation. Their new battery cell for in-situ muon investigations was developed through an ISIS Facility Development Studentship held by Mr Innes McClelland and co-supervised by Corr, Baker and Dr Eddie Cussen, which has provided a new capability now available to (and being taken up by) the research community, for example, researchers at the Faraday Institution.

The team led by Professor Corr has demonstrated how non-destructive µSR will pave the way for following transport behaviour across emerging interfaces and provide insights to those researchers tailoring interfaces for optimising ion transport. These insights and the capability developed through her work has benefited both facility technique development and the wide community of international researchers working on next-generation battery materials.

Evidence of Impact

Media coverage

Mar 2021 – “Call for a vision to translate UK battery research to industrial outcomes“, Science Business

Nov 2019 – “Lithium-ion batteries remade the world – they need to change“, OneZero,

Nov 2019 – Filmed for Electric Vehicles piece on ITV news

Sep 2019 – “FutureCat plugs into next generation of lithium-ion batteries“, The Engineer,

November 2018 “Everything you need to know about lithium-ion batteries“, The Telegraph

Jul 2018 – “How long will an electric car’s battery last?“, The Telegraph

Science Communication and Public Engagement

Royal Institution lecture, “The Hunt for New Batteries“, Oct 2020 (>32K YouTube views)

“The Battery Inside Out“, Jun 2019 (>109K YouTube views)

Nov 2018 – Featured in Royal Albert Hall exhibition on “Illuminating atoms” celebrating the 2014 International Year of Crystallography

Policy contributions

House of Lords Science and Technology Select Committee, gave evidence for its inquiry into the Role of batteries and fuel cells in achieving Net-Zero,

Mar 2021 – Royal Society Net Zero Aviation workshop,

Dec 2020 – ISCF battery challenge Cross-government workshop

Sep 2020 – Faraday Institution Masterclass on Synthesis and Operando Characterisation,

Jun 2020 – 2nd China-UK Policy Dialogue on Energy Storage,

Jan 2019 – Roundtable discussion with UK Committee on Climate Change,

Scientific impact

Over 60 invited/plenary/keynote talks at (inter)national conferences and seminars.

Publications include:

• In Situ Diffusion Measurements of a NASICON-Structured All-Solid-State Battery Using Muon Spin Relaxation, McClelland, Booth, El-Shinawi, Johnston, Clough, Guo, Cussen, Baker, Corr, ACS Applied Energy Materials, 2021, 1527
• Li_1.5La_1.5MO₆ (M = W⁶⁺, Te⁶⁺) as a new series of lithium-rich double perovskites for all-solid-state lithium-ion batteries, Amores, El-Shinawi, McClelland, Yeandel, Baker, Smith, Playford, Goddard, Corr, Cussen, Nature Communications, 2020, 6392
• Muon Spectroscopy for Energy Storage Materials, McClelland, Johnston, Baker, Amores, Cussen, Corr, Annu. Rev. Mater. Sci., 2020, 371.
• Na1.5La1.5TeO6: Na+ conduction in a novel Na-rich double perovskite, Amores, Baker, Cussen, Corr, Chem Commun., 2018, 10040
• Structure-property insights into nanostructured electrodes for Li-ion batteries from local structural and diffusional probes, Vidal Laveda, Johnston, Paterson, Baker, Tucker, Playford, Jensen, Billinge, Corr, J. Mater. Chem. A, 2018, 127
• Fast microwave-assisted synthesis of Li-stuffed garnets and insights into Li diffusion from muon spin spectroscopy, Amores, Ashton, Baker, Cussen, Corr, J. Mater. Chem. A, 2016, 1729
• Muon studies of Li+ diffusion in LiFePO4 nanoparticles of different polymorphs, Ashton, Vidal Laveda, MacLaren, Baker, Porch, Jones, Corr, J. Mater. Chem. A, 2014, 6238

The winner of the ISIS Economic Impact Award is Prof David Lennon for his work on probing the interactions of atoms and molecules with the surfaces of catalysts.

David Lennon’s research involves applying a variety of spectroscopic techniques to probe the interaction of atoms and molecules with catalyst surfaces. Over the last two decades he has studied processes as varied as methane reforming to produce syngas (CO + H2), Fischer-Tropsch synthesis to generate fuel and chemicals, the production of methyl chloride (an intermediate in polydimethylsiloxanes), understanding the formation, and the mitigation, of by-products in isocyanate synthesis (the monomers for polyurethane manufacture) and selective hydrogenation for fine chemical synthesis.

He has made a major contribution to the study of methanol-to-hydrocarbons (MTH) reaction, a reaction first commercialised in the 1970s. The reaction uses a zeolite catalyst, and while there is general agreement that the pores of the zeolite act as a microreactor, key details of what is happening inside the zeolite and how it deactivates are still debated.

The process reacts methanol, which is widely available from a variety of sources, including biomass, to a mixture of low molecular weight alkenes (mainly ethene, propene and butenes) and methylated aromatic molecules, i.e. gasoline. David’s group used neutron scattering to observe the “vibrational fingerprint” of the hydrocarbon pool for the first time – that is, to see what is present in an active catalyst as it reacts. It also provided insight into the nature of the carbon that causes the catalyst to deactivate, which was surprisingly well-structured, resembling glassy carbon.

This project has produced fundamental insights into the process with direct industrial relevance, as demonstrated by two EPSRC industrial CASE awards provided by global science and chemicals company, Johnson Matthey, who also provided the catalysts and analytical characterisation.​

David’s group also applied neutron scattering to investigate how the same catalyst can be used to crack long chain alkenes to propene (propylene). This is a valuable commodity chemical that is the monomer for the vast range of products made from polypropylene. This showed that the MTH and the alkene cracking reactions are strongly related, and both go by similar mechanisms, which had not been generally recognised. The work also studied the same catalyst after it had been steam de-aluminated – a process where steam at ~700 °C is passed through a zeolite, greatly reducing the number of active sites by removing the aluminium. The resulting material is much more like that used in working industrial reactors and the reactivity is correspondingly modified. Surprisingly, these materials have been little studied academically and this new understanding helps explain why this is the material of choice industrially.

In addition to the specific knowledge gained about this reaction, this project has raised awareness within Johnson Matthey of the capabilities of neutron scattering and contributed to the creation of the Johnson Matthey – ISIS fellowship, which is about to be renewed for a further three years.

Separately, the wider ISIS user community have benefitted from a collaboration between David’s group, the ISIS Pressure and Furnace section and the Molecular Spectroscopy Group. The Glasgow/ISIS catalysis rig has been developed over a number of years to prepare the large catalyst samples needed for neutron scattering (typically these are 100-1000 larger than used in conventional micro-reactor lab-based studies). Recent major improvements to the rig include on-line quantitative analysis by gas chromatography and the ability to handle liquid products. The rig is heavily used by a variety of academic and industrial users and the recently enhanced capabilities are already popular with the user community. ​

Evidence of impact
This particular project has been highly productive: both students have successfully submitted their PhD theses, 13 publications and at least a dozen presentations have resulted. David is the author of over 55 published ISIS papers, and he has supervised 14 students whose PhD projects have involved the use of neutrons. Commencing in 2021, he also has two students sponsored by Johnson Matthey whose projects will involve the use of neutrons.

The winner of the ISIS Society Impact Award is Dr Mariela Martins Nolasco for her work characterising polymer structure and dynamics.

​Mariela Martins Nolasco (University of Aveiro, Portugal) has developed the ability to characterise polymer structure and dynamics, embracing both natural polymers (e.g. cellulose and bacterial cellulose) and bio-based synthetic polymers. This knowledge is critical in developing new functionalized or composite materials for use in emerging technologies such as medical devices or fuel cells.

Her approach took advantage of inelastic neutron scattering (INS) combined with discrete and periodic density functional theory (DFT) calculations to delve deeper into the structure−property correlations in polymeric materials. This combination is ideal either to assist the elucidation of measured data or, conversely, as method of validating theoretical models. The scientific impact of these projects arises from the recognition of the potential of INS spectroscopy to give answers to the questions relating the micro-structure and dynamics of polymer chains and the macroscopic properties of polymeric materials, including nano-structured and composite materials.

One class of polymers studied using INS was bio-based synthetic polymers (furandicaboxylate polyesters). These polymers are a new class of sustainable materials derived from renewable resources which are intended to gradually phase out their petrochemical counterparts. They could replace poly(ethylene terephthalate) (PET), a petro-based high performance polyester widely used as packaging material, offering good mechanical performance, comparable thermal stability, and increased barrier properties (ca. 10 times less permeable to oxygen and 20 times less permeable to carbon dioxide). Their industrial and commercial potential is already being implemented by industry stakeholders.

In addition, her comprehensive study of celluloses – in which the periodic-DFT calculations provide a detailed description of the vibrational spectra of bacterial and vegetal cellulose with different wet contents – set the grounds for the understanding of subtle interactions in cellulose-based composites and to assist the characterization of bacterial cellulose membranes in microbial fuel cells. The comprehensive character and clarifying nature concerning the vibrational spectra of celluloses makes it possible to assess not only domains within the supramolecular structure, but also to identify the sample origin (bacterial, kraft pulp, etc), with high accuracy, a result of the resolution power of the INS technique.

Evidence of impact
Hydrogen Bond Dynamics of Cellulose through Inelastic Neutron Scattering Spectroscopy, Biomacromolecules, 19 (2018) 1305-1313
Inside PEF: Chain Conformation and Dynamics in Crystalline and Amorphous Domains Macromolecules, 51 (2018) 3515–3526
Asymmetric Monomer, Amorphous Polymer? Structure–Property Relationships in 2,4-FDCA and 2,4-PEF, Macromolecules, 53 (2020) 1380-1387
Understanding the Structure and Dynamics of Nanocellulose-Based Composites with Neutral and Ionic Poly(methacrylate) Derivatives Using Inelastic Neutron Scattering and DFT Calculations, Molecules, 25 (2020) 1689;
Poly(4-styrene sulfonic acid)/bacterial cellulose membranes: Electrochemical performance in a single-chamber microbial fuel cell, Bioresource Technology Reports, 9 (2020) 100376.

The winner of the ISIS Science Impact Award is Professor Jin-Chong Tan, for his group’s work on lattice dynamics in Metal-Organic Frameworks, and how this effects the way they absorb and release gases and drug molecules.

The winner of the Science Award is Professor Jin-Chong Tan from the University of Oxford, who leads the Multifunctional Materials & Composites Laboratory in the Department of Engineering Science. Since 2012, Jin-Chong’s research group has used neutron vibrational spectroscopy at ISIS to investigate the distortions of Metal-Organic Framework (MOF) materials that enable them to absorb and release target molecules.

MOFs are open-framework materials that combine metal nodes and organic linkers to create crystalline frameworks that have unique chemical and physical properties, which cannot be achieved in purely inorganic or organic compounds. These unique properties can be altered by changing the composition of the MOF, leading to the intelligent design of different MOF systems with applications in technologies from gas separation to drug delivery, and from photonics to sensors.

The way that the framework distorts to enable the adsorption and release of molecules is important to understand, as controlling this could lead to a greater ability to direct the functionality. By studying the vibrational spectra of the MOFs using inelastic neutron scattering, and combining this with computational studies, Jin-Chong and his research group have been able to determine the behaviour of the MOF structure under low-frequency terahertz (THz) vibrations.

Their work revealed that the vibrational modes in the THz range are linked to the “gate opening” and pore “breathing” mechanisms of the framework, paving the way to an expanding area of research towards understanding of the role of THz vibrations in framework materials. This understanding has helped to identify ways the material could collapse under mechanical stress, and to develop new materials that are less prone to this kind of detrimental distortions. A deeper understanding of the THz modes also reveals opportunities for engineering new molecular sensors.

Building on this work, the group have investigated the low-frequency lattice vibrations of MOFs that have a molecule inside them, known as guest-encapsulated systems, including those containing anti-cancer drugs. The work has also led to the development of smart luminescent sensors that can detect toxic chemical compounds non-invasively, and sense changes in physical stimuli such as temperature and pressure.

Media and Publications
Oxford Science Blog (21 Nov 2014): “Vibrations reveal how material takes a breath”
Diamond Annual Review 2014/15: “Good vibrations: Terahertz modes and lattice dynamics in metal-organic frameworks”
BBC Radio 4 – Science in Action Broadcast (9 Feb 2018)
Oxford University News (9 Jan 2018): “Smart sensor could revolutionise crime and terrorism prevention”
Invited lectures and seminars on the emerging topic of “MOF terahertz dynamics”. Invited speakers at the CECAM International Workshop (Zaragoza, 2016); the UK Neutron and Muon Science User Meeting (2015) and the MOF2014 Conference (Kobe). Plenary Speaker in the CCP5 International Summer School 2016 (Lancaster) and Keynote Speaker in the 7th International Zeolite Membrane Meeting (Dalian, 2016).
B.E. Souza, A.F. Möslein, K. Titov, J.D. Taylor, S. Rudic, and J.C. Tan, “Green Reconstruction of MIL‑100 (Fe) in Water for High Crystallinity and Enhanced Guest Encapsulation”, ACS Sustainable Chemistry & Engineering, 8, 8247-8255 (2020). DOI: 10.1021/acssuschemeng.0c01471
B.E. Souza, S. Rudić, K. Titov, A.S. Babal, J.D. Taylor and J.C. Tan, “”Guest‑Host Interactions of Nanoconfined Anti-Cancer Drug in Metal‑Organic Framework Exposed by Terahertz Dynamics””, ChemComm, 55, 3868–3871 (2019). DOI: 10.1039/C8CC10089F
K. Titov, D.B. Eremin, A.S. Kashin, R. Boada, B.E. Souza, C.S.Kelley, M.D. Frogley, G. Cinque, D. Gianolio, G. Cibin, S. Rudić, V.P. Ananikov, and J.C. Tan, “”OX‑1 Metal-Organic Framework Nanosheets as Robust Hosts for Highly Active Catalytic Palladium Species””, ACS Sustainable Chemistry & Engineering, 7, 5875–5885 (2019). DOI: 10.1021/acssuschemeng.8b05843
M.R. Ryder, B. Van de Voorde, B. Civalleri, T.D. Bennett, S. Mukhopadhyay, G. Cinque, F. Fernandez-Alonso, D. De Vos, S. Rudic, and J.C. Tan, “”Detecting Molecular Rotational Dynamics Complementing the Low-Frequency Terahertz Vibrations in a Zirconium-Based Metal-Organic Framework””, Physical Review Letters, 118, 255502 (2017). DOI: 10.1103/PhysRevLett.118.255502
M.R. Ryder, B. Civalleri, T.D. Bennett, S. Henke, S. Rudić, G. Cinque, F. Fernandez-Alonso, J.C. Tan, “Identifying the Role of Terahertz Vibrations in Metal-Organic Frameworks: From Gate-Opening Phenomenon to Shear-Driven Structural Destabilization” Physical Review Letters 113, 215502 (2014). DOI: 10.1103/PhysRevLett.113.215502​

The winner of the ISIS Economic Impact Award is Peter Albers, for his work over the last thirty years using neutrons alongside other methods to investigate materials with commercial applications, including catalysis.

Peter’s work combining neutron scattering, electron microscopy and surface science (XPS, SIMS) to investigate materials of commercial relevance spans three major areas: carbons, silica and catalysts.

Peter’s work on carbons spans fundamental studies on C60 to tyre reinforcement agents. The use of neutrons enables the development of a better understanding of the hydrogen in the materials and its distribution. His use of inelastic scattering to study the hydroxyls present in silica materials used in products including toothpastes has developed the knowledge around their reactions and interaction with water.

Both carbons and silica materials have applications in catalysis, and this is where they link in with his other area of expertise. Peter has contributed significantly to the knowledge of the surface behaviour of precious metal catalysts, particularly platinum and palladium based materials. As an industrial user, his studies are carried out on commercial carbon supported palladium and platinum catalysts and the metal blacks that are used in industry every day, not model systems. The aim of his catalysis work has been to characterise the nature of hydrogen present on, or in, these catalysts.

Palladium (Pd) is well-known for absorbing hydrogen gas to form PdH, with the structure dependant on the concentration of hydrogen in the material. At low H-contents (<5%) it forms a solid solution with a random distribution of hydrogen atoms (α phase) and above this it forms an ordered structure (β phase). It was this β phase that was of interest: although it had been studied extensively, the details of the surface interactions, behaviour at low hydrogen contents and low palladium particle sizes were yet to be determined.

Using TOSCA and IN1-Lagrange, confirmed by density functional theory, Peter was able to observe an additional subsurface site for the hydrogen atoms, which was previously unreported. They found that the surface sites are occupied first; only when these are fully occupied are subsurface sites occupied. As more hydrogen is added, the H atoms move into the bulk to minimise interactions forming the α phase, until it becomes favourable to form β PdH. At hydrogen levels above PdH0.7, the hydrogen at the surface also occupies the newly identified on-top site, where it is bonded to a single palladium surface atom.

To detect hydrogen on this site for the first time, Peter used direct geometry spectrometry on MAPS and MERLIN. This work, alongside further experiments on SANDALS, enabled Peter and his research group to determine the mechanism of the hydrogen absorption by palladium. As this is the last site to be populated, it is likely they are the most reactive, and provide easy access for reactants.

As with palladium, platinum readily dissociates hydrogen gas into its atoms at room temperature, but the solubility of hydrogen in platinum is extremely low; therefore, all of the adsorbed hydrogen is at the surface. The techniques usually used (infrared and Raman spectroscopy) to observe the bonding of the hydrogen atoms to the surface are restricted by selection rules caused by the behaviour of light, which leave some bonding modes unobserved. Inelastic neutron scattering (INS) is the only technique that enables scientists to study all of the modes.

When hydrogen adsorbs onto platinum, it can bond in a number of ways. These are described as on-top, twofold, threefold and fourfold coordination, depending on how many platinum atoms the hydrogen is connected to. Peter and his collaborators used INS experiments on TOSCA and on Lagrange at the ILL, combined with computational modelling, to investigate platinum nanoparticles loaded with hydrogen.

They found that, for adsorbed hydrogen on platinum nanoparticles in general, most of the hydrogen is in twofold coordination sites whereas, in previous reports, the spectra were generally assigned to mostly threefold hydrogen. These twofold sites are proposed to be the most active sites for the hydrogen oxidation reaction, and therefore their dominance may be one of the reasons as to why platinum is the preferred material in fuel cells.

Peter’s well-established work at ISIS has provided the scientific community with the most detailed understanding currently available of the surface of palladium and platinum-based catalysts. By using ISIS, his employer Evonik gains a commercial advantage by being able to show that they have cutting-edge technical support for their products. Their continued use of neutron scattering for over twenty years is an illustration of its importance.

The winner of the Society Award was Paolo Rech, Associate Professor at the Institute of Informatics of the Federal University of Rio Grande do Sul, for his work investigating the effect of neutrons on the computing behind autonomous vehicles, and developing ways to improve its reliability.

Atmospheric neutrons are known to generate faults in computing devices, and these failures are extremely dangerous when the devices are an integral part of a cyber-physical system such as an autonomous vehicle. The detection of objects is the most computationally demanding task for these vehicles, and is the task where the presence of errors causes the majority of accidents.

Until the hardware/software frameworks for object detection are compliant with industry requirements, the full potential of the use of autonomous vehicles in transportation, space and deep sea exploration cannot be realised. It will also take proven reliability for the general public to accept their widespread use.

For a vehicle to detect objects such as pedestrians or other cars, images need to be processed in real-time. This requires cutting-edge hardware computing platforms that Paolo and his research group have found, through experiments on ChipIr, to have a failure rate of hundreds to thousands of times higher than the limit imposed by industry dependability standards.

The traditional solutions to these errors, such as hardware or software replication, are costly and disfavoured by the competitive automotive market. Paolo has worked with advanced devices designed by NVIDIA, AMD, ARM, Intel, and Xilinx using ChipIr to identify the errors that changed the computing behind the vehicle behaviour: the artificial neural networks.

By redesigning the artificial intelligence (AI) software that is used in object detection, Paolo and his group have managed to significantly reduce the probability of incorrect identification and detection. They have introduced a mechanism to compare the decision made from an object detection image with previous and subsequent images, as an equivalent of a “sense check” for the software, at much lower cost than established techniques. Additionally, they have exploit redundant hardware in modern computing systems to run error detection procedures. Testing their AI software on ChipIr, they found a reduction of more than 90% of errors with an overhead lower than 20% (0.01% in the best case).

As well as a long-standing relationship with NVIDIA, Paolo’s engagement with ARM, a leading computing devices designer company based in the UK, has led to a collaborative project between them and ChipIr, including a co-funded PhD position.

Besides the automotive industry, their work has also had an impact on the space industry through a collaboration with the European Space Agency and NASA’s Jet Propulsion Laboratory in the USA, using ChipIr to investigate the use of autonomous vehicles for space exploration.

Recently, Paolo has extended his studies of the effect of neutrons on electronic equipment by using ALF at ISIS to monitor the effect of thermal neutrons.

​Awards and Related Publications​
2020 Marie Skłodowska-Curie Fellowship from the European Union
Winner of the 2019 Rosen Scholar Fellowship at the Los Alamos National Laboratory, USA
“Evaluation and Mitigation of Radiation-Induced Soft Errors in Graphics Processing Units”, IEEE Transactions on Computers
“Analysing and Increasing the Reliability of Convolutional Neural Networks on GPUs”, IEEE Transactions on Reliability
“Selective Hardening for Neural Networks in FPGAs”, Transactions on Nuclear Science
“Evaluation of Histogram of Oriented Gradients Soft Errors Criticality for Automotive Applications”, in Transaction on Architecture and Code Optimization
“Demystifying Soft Error Assessment Strategies on ARM CPUs: Microarchitectural Fault Injection vs. Neutron Beam Experiments”, International Conference on Dependable Systems and Networks – Best Paper candidate
“Reliability Evaluation of Mixed-Precision Architectures”, International Symposium on High- Performance Computer Architecture
“Identifying the Most Reliable Collaborative Workload Distribution in Heterogeneous Devices”, Design, Automation & Test in Europe Conference
“Code-Dependent and Architecture-Dependent Reliability Behaviors”, International Conference on Dependable Systems and Networks – Best Paper candidate
“Evaluation and Mitigation of Soft-Errors in Neural Network-based Object Detection in Three GPU Architectures”, presented at Silicon Errors in Logic System Effects – Best Paper

The winner of the Science Award is Dr Sihai Yang from the University of Manchester, for his work using neutrons to investigate a wide range of porous materials based on metal-organic frameworks, metal oxides and phosphates, and zeolites.

Porous materials containing nano-sized cavities (1-5 nm), the walls of which are decorated with various active sites, can form unique functional platforms to study and re-define the chemistry of guest molecules within confined space and on active sites. Yang’s research group uses neutron scattering techniques with the aim to determine what happens to the guest molecules inside these materials, and find out how and where the guest molecules interact with the walls of the cavities. Such knowledge will allow the design of successive generations of porous materials with enhanced functionality. Their work at ISIS since 2015 has generated 26 joint publications with ISIS scientists.

Toxic gas removal

There is increasing concern over global air quality, with high concentrations of smog posing significant health risks worldwide, particularly in countries with heavy and ageing industries and high population densities. SO2 and NO2 are the most toxic components in the smog, causing not only premature death, but also reacting with tropospheric ozone and forming acid rain. Complete removal of traces of SO2 and NO2 is extremely challenging to achieve.

Dr Yang and his group have made a series of breakthroughs on the development of robust metal-organic materials for highly efficient clean-up of SO2 and NO2. These materials show record-high adsorption capacity and selectivity of SO2 and NO2. More importantly, the captured gases are fully recovered for use in other chemical processes, and the host materials are regenerated for the next cycle of use.

Catalytic biofuel conversion

Catalysis research is fundamental for the sustainability of our society. Catalysts are used in over 80% of manufactured products, such as fuels, chemicals, polymers and pharmaceuticals, translating to 35% of the world GDP being reliant on catalytic processes. Catalysis underpins over £50 billion a year of economic activity through the UK’s chemical industry.

For biomass conversion, it is critical but challenging to develop a detailed mechanistic understanding of how a catalyst functions. Yang’s work has strengthened the links between neutron scattering and catalysis, promoting new discovery and knowledge in a wider range of heterogeneous catalysis. Their recent success has the potential to lead to huge reductions in the energy consumption of bio-refineries by developing new efficient catalysts, and hence reduced costs for biomass-derived materials – promoting their widespread applications.

Collaborators at ISIS: Stewart Parker, Svemir Rudic, Ivan da Silva; Pascal Manuel; Victoria Garcia-Sakai; Ian Silverwood, Samantha K. Callear, Martin Owen, Jones, Ron Smith, Bill David

The winner of the Economic Award is Indri Adilina from the Indonesian Institute of Sciences (LIPI) for her work at ISIS on the use of palm oil biomass waste as an alternative source for biofuel, supported by the UK’s Newton Fund​.

Indonesia is the world’s largest producer of palm oil producing more than 35 million tonnes annually. The industry is hugely wasteful with the oil extracted making up as little as 10% of the total biomass produced – meaning the remaining 90% of that biomass is classified as waste.

​Indri and her group aim to establish a viable method of using palm oil biomass waste in place of the palm oil itself to meet government targets without affecting the local food industry. However, significant advances in catalysis are required to convert the bulky feedstock into high value biofuel. With the unique properties of neutrons, they have been able to understand the interactions between the chemical compounds in biomass waste and the catalyst, which gives important information for the catalyst design and optimisation strategies.

From their work using INS and QENS, they have developed a new catalyst based on bentonite clay, a renewable and abundant resource in Indonesia, which can promote the chemical reactions that convert the heavy palm oil molecules into the lighter hydrocarbon molecules that make up fuels like gasoline and diesel.

The impacts are not just limited to the research itself: most of the members of the research team are early career scientists and having been able to access large-scale facilities such as ISIS at a starting stage of their career has been very beneficial in shaping their scientific development. The Indonesian neutron source is limited and does not have advanced techniques such as INS and QENS that the team have been able to access at ISIS.

Both the knowledge that the team has gained and the networks established in neutron science at ISIS will return with them to Indonesia, opening up research using techniques that were previously unavailable. This project is pioneering for users in Indonesia and the South East Asia region. It has sparked other research groups in LIPI and other Indonesian Universities to collaborate with ISIS, including those working in battery materials. The project has also resulted in discussions with research groups in Thailand working in this field.

Media Coverage:

Chairman of the Indonesian Institute of Sciences – Laksana Tri Handoko: “LIPI aims to unite initiatives where research addressing global challenges also benefits local needs. In the short term the Newton fund has enabled us to access an international facility to understand how we can reduce our reliance on fossil fuels without a negative impact on Indonesian society. In the longer term we have increased the expertise of the Indonesian scientific community allowing us to access the full potential of neutron science.”

British Ambassador for Indonesia – Moazzam Malik​: “Indonesia will need to increase investments in research and innovation, while also fostering partnerships between local and international research institutions to increase the quality and capability of Indonesian research. I believe in working together and succeeding together and this is one such example. The British government is committed to invest and support Indonesia’s development.”

Publications:

Indri B. Adilina, Nino Rinaldi, Sabar P. Simanungkalit, Fauzan Aulia, Ferensa Oemry, Gavin B. G. Stenning, Ian P. Silverwood, Stewart F. Parker “Hydrodeoxygenation of guaiacol as a bio-oil model compound over pillared clay supported nickel-molybdenum catalysts” Journal of Physical Chemistry C, April 2019, to be accepted after revisions.
Indri B. Adilina, Fauzan Aulia,, Muhammad A. Fitriady, Gagus K. Sunnardianto, Ferensa Oemry, Ian P. Silverwood, Stewart F. Parker “Hydrogenolysis of lignin-derived benzyl phenyl ether over nickel-molybdenum clay catalyst” manuscript in preparation.
Indri B. Adilina, Fauzan Aulia, Muhammad A. Fitriady, Ferensa Oemry, Gavin B. G. Stenning, Ian P. Silverwood, Stewart F. Parker “The interaction of bio-oil with pillared clay supported nickel-molybdenum catalysts” manuscript in preparation.
Indri B. Adilina “Clay supported metal catalysts for sustainable chemicals production” University of Glasgow Lecture, Glasgow, 29 February 2019.
Indri B. Adilina, Nino Rinaldi, Sabar Simanungkalit, Fauzan Aulia, Ferensa Oemry, Ian Silverwood, Stewart F. Parker “Hydrodeoxygenation of guaiacol as a lignin model compound over pillared clay supported NiMo catalyst” UK Catalysis Conference, Loughborough, 9-11 January 2019.
Ferensa Oemry, Anna Kroner, Indri B. Adilina, Nino Rinaldi, Elizabeth Shotton “Structural Geometry of Small α-NiMoO4 Nanoclusters Adsorbed on Al-PILC: a Combined EXAFS and DFT Studies” UK Catalysis Conference, Loughborough, 9-11 January 2019.
Upgrading of bio-oil and its derivatives using pillared bentonite clay supported nickel-molybdenum catalyst (Indonesian Patent Application No. P00201806629, filed in 2018

The winner of the Society Award was Professor Maria Paula M. Marques, the co-coordinator of the Molecular Physical-Chemistry R&D Unit of Coimbra University, Portugal. The Unit’s main goal is the development of improved platinum and palladium-based anticancer agents for low prognosis cancers, for which no successful therapeutic strategies are available.

Professor Marques and her team use neutron scattering techniques (inelastic and quasi-elastic) to study the changes happening inside the cell as it undergoes drug treatment. Their work focusses on the water inside the cell, and how this ‘intracellular water’ could be used as a target for anticancer drugs.

The water inside the cells has different properties to water outside the body – it maintains the three-dimensional architecture and functional conformation of the molecules required for normal cellular activity. Just small variations in the structure or dynamics of intracellular water could trigger inhibition of cell growth and eventually cell death.

The team used inelastic and quasi-elastic neutron scattering (QENS) techniques as a direct probe of the behaviour of the different types of cellular water, in the presence and absence of a drug. For these experiments, the team developed a new experimental procedure where cells were grown and drug-incubated immediately before neutron data acquisition.

The measurements (QENS with isotope labelling) were very successful in highlighting drug-induced differences in intracellular water mobility. These studies constitute an innovative approach for chemotherapeutic research, aiding the interpretation of a drug´s mode of action within the cell and enabling the identification of alternative therapeutic targets. Looking at water as a promising chemotherapeutic target may pave the way for the development of improved anti-tumour drugs with multiple sites of action, i.e. multi-targeted as opposed to single-targeted agents, leading to an enhanced efficiency and minimised acquired resistance during treatment.​

Media interest:

Several articles in portuguese and spanish newspapers (2015-2018);
live interview for Porto Canal – Mentes que Brilham (23th April 2014) (http://bit.ly/2hRgurU);
interview for the BBC World Service – Science in Action (12th November 2015)
Published articles:

1. Anticancer Drug Impact on DNA – A Study by Neutron Spectroscopy coupled to Synchrotron-based FTIR and EXAFS, A.L.M. Batista de Carvalho, A.P. Mamede, A. Dopplapudi, V. Garcia Sakai, J. Doherty, M. Frogley, G. Cinque, P. Gardner, D. Gianolio, L.A.E. Batista de Carvalho, M.P.M. Marques, Phys.Chem.Chem.Phys. 21 (2019) 4162 (DOI: 10.1039/C8CP05881D).

2. Intracellular Water – an Overlooked Drug Target? Cisplatin´s Impact in Cancer Cells Probed by Neutrons, M.P.M. Marques, A.L.M. Batista de Carvalho, V. Garcia-Sakai, L. Hatter, L.A.E. Batista de Carvalho, Phys.Chem.Chem.Phys. 19 (2017) 2702 (DOI: 10.1039/C6CP05198G). The first article on the drug impact on intracellular water featured on the back cover of Phys.Chem.Chem.Phys. (19 (2017) 2702, DOI 10.1039/C6CP05198G)

The winner of the Science Award was given to Dr. Thomas Douglas Bennett, Hybrid Materials Group Leader at the University of Cambridge, for his work on modelling the structure of metal-organic framework glasses.

Metal-organic frameworks (MOFs) are a highly topical class of nanoporous materials containing inorganic nodes linked by organic ligands. Over 60,000 crystalline structures exist to date, finding commercial uses in a diverse array of applications such as fruit packaging, harmful gas storage and in vehicular H2 storage.

The major benefit of this beamtime was the elucidation of a structure of a melt-quenched metal-organic framework glass – the first example of the new hybrid glass family. Room temperature neutron data were collected and combined with that from I15-1 (XPDF), to aid in producing an atomic configuration for the glass via reverse Monte Carlo modelling. This model was then used with high temperature synchrotron data to produce an atomic configuration for MOF in the liquid state.

The work featured on the front cover of Nature Materials, and was highlighted in both in the same journal and also in Nature Reviews Materials. It was number 1 in the ISIS Neutron and Muon Source’s top 10 most-discussed journal articles of 2017, and also featured in C&EN and Chemistry World.

A follow up work, using the same data collected, aimed at comparing RMC models of amorphous MOFs with the same chemical composition, though formed via different methodologies. This work has just been accepted into PCCP and is titled “Structural Investigations of Amorphous Metal-Organic Frameworks Formed Via Different Routes”. D. A. Keen and T. D. Bennett, Phys Chem Chem Phys, 2018, 20, 7857-7861

A second paper, building on the work, and specifically focusing on the creation and characterisation of a blend of liquid MOFs, has recently been published in Nature Communications . PDF data was again collected, on a liquid mixture of a cobalt MOF and a zinc MOF, finding domain interlocking after quenching from the liquid phase.

More broadly, the work on amorphous MOFs has led to over 40 publications from this group.

Underpinning research

2001-2007: Profs David Keen, Mathew Tucker, Martin Dove and Andrew Goodwin worked on the reverse Monte-Carlo modelling of disordered crystalline compounds [3.1] ad published the RMCProfile software [3.2], which enabled modelling of amorphous compounds.

2008 – 2012: Bennett (PhD student) under the supervision of Prof. Anthony Cheetham FRS and collaborating with Prof. David Keen and Prof. Andrew Goodwin, characterised a solid amorphous MOF [3.3] Other methods to induce amorphisation, including ball-milling and pressurisation, were also uncovered [3.4, 3.5].

2012-2015: Bennett (Research Fellow, Trinity Hall, Cambridge) led work in observing the melting process of a crystalline MOF of composition Zn(C3H3N2)2 [3.6] though no structural characterisation could be done at that time. A review article on the non-crystalline MOF state was produced in efforts to draw more researchers to the under developed field [3.7]. Computational work led by Coudert [3.8, 3.9] confirmed the structural collapse upon solvent removal of some MOFs, and pointed towards generalised metastability amongst MOFs. Melting was also found in the related coordination polymer family by Prof. Satoshi Horike [3.10], and a sol-gel route to hybrid glasses published by Yaghi and Angell [3.11].

​2016-2018: Bennett (Royal Society University Research Fellow) with Prof. David Keen expanded the melting behavior of the ZIF family, drawing structural correlations between the identity of the organic linker used in the crystalline framework, and both melting and glass transition temperatures [3.12]. Positron annihilation lifetime measurements performed with colleagues at CSIRO confirmed the presence of appreciable porosity within the MOF-glass formed from ZIF-4 [3.13]

The winner of the Economic Award was given to Dr. Andrea Lazzarini from the University of Oslo, for their work on activated carbons which are widely employed in industrial catalysis.

Activated carbons are widely employed in industrial catalysis, usually employed as a support for nanoparticle-based catalysts. Heterogeneous catalysis are manufactured by depositing a dispersed active phase (in the form of isolated ions or nanoparticles) on a high-surface-area support, which needs to cheap, inert and stable.

Despite their widespread use, the way in which activated carbons interact with the active phase of the catalyst and/or with the molecules involved in the reaction (reactants and products) is still far from understood. This is mainly due to the strong light-absorbing nature of activated carbons, which makes their investigation with traditional spectroscopic techniques extremely difficult.

Researchers used Inelastic Neutron Scattering (INS), coupled with several light-based spectroscopic techniques, to shed light on the role that the carbonaceous support has in the catalytic processes. The use of INS was fundamental to this study due to the nature of these materials, which are extremely rich in hydrogen terminations on their surface.

Thanks to neutron spectroscopy and to the multi-technique approach, researchers were able to discriminate the type and the behaviour of the different species present on the surface of the catalyst, and to describe how they influence the activity and selectivity of different hydrogenation processes.

This project had a strong impact on two different levels. Firstly, their industrial partner, Chimet S.p.A., provided both financial support and the samples that were investigated. The results achieved had a large impact on researchers understanding of the catalyst, from the support material through to the end of the lifecycle. Our industrial partner therefore has the opportunity to develop more efficient and more durable catalysts in the future.

Secondly, the team developed an exhaustive protocol for the characterization of activated carbons for catalytic purposes and for carbon-based materials in general. The use of inelastic neutron scattering was essential for investigating the state of the hydrogen-rich surface of the support, which interacts with the active phase and reaction’s substrate. Our INS measurements were complemented with other techniques (FT-IR spectroscopy, Raman spectroscopy, XRD, XPS, SEM and catalytic tests), establishing a full characterization protocol able to produce a complete picture of the material under analysis. The team shed light on the behaviour of the catalysts under reaction conditions and the influence that the support (the main target of the study) has during catalyst operation.

Underpinning research

1994-2004. Fillaux, Albers, Parker and their coworkers, extensively studied activated carbons-supported Pd nanoparticles catalysts for hydrogenation reactions. Their INS studies were focused on the H-containing terminations at the edge of graphitic domains of the carbon supports and their dynamical behavior in the presence or without the presence of the metal active phase [3.1-3.5].

2000. Ferrari and Robertson defined a new interpretation of Raman data, based on the intensity ratio between I(D)/I(G) signals, describing the average lateral dimension of the graphitic domains in activated carbons. According to Tuinstra-Koenig law, the larger is the ratio the higher is the structural disorder; however, it has been demonstrated that for domain size smaller than 20Å the I(D)/I(G) ratio follows an opposite behavior with respect to Tuinstra-Koenig law [3.6]. This work was fundamental in the interpretation of the controversial Raman data on our samples.

2005. Centrone and coworkers combined FT-IR spectroscopy and molecular modeling to ascribe to precise C-H species in condensed aromatic rings edges, the vibrations present in IR spectra of activated carbons in the 1000-700 cm−1 region [3.7]. The ratio between those species reflects different levels of size and defectivity at the molecular level of the graphitic domains of the activated carbon supports.

2016: Smith and coworkers improved the deconvolution and interpretation of XPS data by means of molecular modeling. They proposed a 7-peaks fit of the C 1s signal instead of the traditional 6-peaks fit: this allows a better discrimination between structural defectivity of the carbon atoms in the graphene-like structure and the one arising from the presence of oxygenated functional groups, decorating the graphitic platelets edges [3.8].

References to the research

Journal article. F. Fillaux, R.Papoular, A.Lautié, J.Tomkinson, “Inelastic neutron-scattering study of the proton dynamics in carbons and coals”, Carbon, 1994, vol. 32 (7), p. 1325-1331.
Journal article. P. Albers, G. Prescher, K. Seibold, D. K. Ross, F. Fillaux, “Inelastic neutron scattering study of proton dynamics in carbon blacks”, Carbon, 1996, vol. 34 (7), p. 903-908.
Journal article. P. Albers, S. Bösing, H. Lansink Rotgerink, D. K. Ross, S. F. Parker, “Inelastic neutron scattering study on the influence of after-treatments on different technical cokes of varying impurity level and their sp2/sp3 character”, Carbon, 2002, vol. 40 (9), p. 1549-1558.
Journal article. P. Albers, J. Pietsch, J. Krauter, S. F. Parker, “Investigations of activated carbon catalyst supports from different natural sources”, Phys. Chem. Chem. Phys., 2003, vol. 5 (9), p. 1941-1949.
Journal article. P. Albers, M. Lopez, G. Sextl, G. Jeske, S. F. Parker, “Inelastic neutron scattering investigation on the site occupation of atomic hydrogen on platinum particles of different size”, J. Catal., 2004, vol. 223 (1), p. 44-53.
Journal article. A. C. Ferrari, J. Robertson, “Interpretation of Raman spectra of disordered and amorphous carbon”, Phys. Rev. B, 2000, vol. 61 (20), article n. 14095.
Journal article. A. Centrone, L. Brambilla, T. Renouard, L. Gherghel, C. Mathis, K. Müllen, G. Zerbi, “Structure of new carbonaceous materials: The role of vibrational spectroscopy”, Carbon, 2005, vol. 43 (8), p. 1593-1609.
Journal article. M. Smith, L. Scudiero, J. Espinal, J.-S. McEwen, M. Garcia-Perez, “Improving the deconvolution and interpretation of XPS spectra from chars by ab initio calculations”, Carbon, 2016, vol. 110, p. 155-171.

The winner of the Society Award was The Wallace Collection, London for their non-invasive analysis of arms and armour.

The Wallace Collection is a national museum in London which has, inter alia, the largest collection of princely European armour in London, and one of the finest collections of Indo-Persian armour outside the subcontinent (and as yet catalogued). Researchers have undertaken a program of analysis of these arms and armour by neutron techniques at ISIS Neutron and Muon Source for a number of years, with very interesting results. Neutron techniques have proven to be particularly valuable analytical methods for museum objects since they are entirely non-invasive.

The outcomes of these studies will be of vital importance in future decision making regarding the ethical conservation and restoration of the Arms & Armour collection at the Wallace Collection, and will influence future decisions about other historical collections in the UK and beyond.

After a number of swords and other museum items from The Wallace Collection had been successfully analysed, and the results demonstrated to their Conservation department, the Dean and Chapter of Canterbury Cathedral agreed to allow the helmet of the Black Prince (d 1376) to be taken down from where it hangs over his tomb in Canterbury Cathedral and brought to ISIS Neutron and Muon Source for examination. This is probably the oldest helmet in England with a known owner.

Researchers used neutron diffraction on the INES instrument to analyse the helm, and showed that its three plates are made of similar low-carbon steels, with traces of stress in the front plate. These results are consistent with the helm being a local product rather than an import ( the import trade in suits of Italian armour does not develop until the 15th century). The stress in the front plate evidently resulted from being struck, and subsequently straightened out, indicating that the helm was probably worn by the Black Prince in battle.

Underpinning researchers

Dr. Antonella Scherillo (STFC) instrument scientist on INES

Dr Francesco Grazzi (CNR) theoretical physicist

David Edge (Wallace Collection) conservator; author of “Arms and Armour of the Medieval Knight”(1988)

Dr Alan Williams (Wallace Collection) archaeometallurgist; author of “The Knight and the Blast Furnace” (2003)

References to the research

“Phase composition mapping of a 17th century Japanese helmet” (A.Williams, A.Fedrigo, F.Grazzi, S.Kabra & M.Zoppi) Journal of Analytical Atomic Spectrometry, (2015) online

“Characterization of an Indian sword: classic and noninvasive methods of investigation in comparison” (A.Williams, E. Barzagli, F. Grazzi, D. Edge, A. Scherillo, J. Kelleher, M. Zoppi) Applied Physics A , 119, 1 (2015) 97-105.

“Determination of the manufacturing methods of Indian swords through neutron diffraction”. Franceso Grazzi, Alessio De Francesco, Elisa Barzagli, Antonella Scherillo, Alan Williams, David Edge, and Marco Zoppi. Microchemical Journal, 125, (March 2016) 273-278.

“A new method of revealing armourers’ marks” (A.Williams, D.Edge, F.Grazzi, N.Kardjilov) Studies in Conservation (2017) published online 4th April, 2017.

Combined application of imaging techniques for the characterization and authentication of ancient weapons” ( Floriana Salvemini, Francesco Grazzi; Nikolay Kardjilov; Frank Wieder; Ingo Manke; David Edge; Alan Williams; Marco Zoppi) European Physical Journal – Plus, (2017) 132: 228.