Materials Chemistry

Our research is in the area of material design, synthesis and characterisation for applications such as battery and hydrogen storage/fuel cell materials, functional polymers, porous solids for catalysis, gas storage and nuclear waste remediation, nanoscience, drug delivery, recycling and sustainability. We make extensive use of synchrotron and neutron diffraction techniques and have strong links to these central facilities.

Research unit leader

Areas of interest

Nanoscale Science; Noncovalent Bonding; Self-Assembly; Self-Organisation; C60; Electron Beam Resists; Liquid Crystals; Self-Assembled Monolayers; Nano-Tribology

Representative paper: Novel polystyrene sulfonate-silica microspheres as a carrier of a water soluble inorganic salt (KCl) for its sustained release, via a dual-release mechanism

C. Sui, J.A. Preece, Z. Zhang, RSC Advances2017, 7, 478-481.

Novel polystyrene sulfonate-silica microspheres as a carrier of a water soluble inorganic saltThis paper reports for the first time the encapsulation of a water soluble inorganic salt in a hybrid organic-inorganic microcapsule.  By careful tuning of the microcapsule chemistry it proved possible to modulate the release of the salt, which we propose involves two stages: initially by leaching out as complex with an encapsulated polyanion, and subsequently as the free salt.  The work has been patented, and industry has shown an interest.

Research unit members

Areas of interest

lithium- and sodium-ion batteries, ion-exchangers, electrochemistry, recycling, solid-state materials synthesis, synchrotron-based characterization, in situ studies of functional behaviour.

Representative paper: Tracking Sodium-Antimonide Phase Transformations in Sodium-Ion Anodes: Insights from Operando Pair Distribution Function Analysis and Solid-State NMR Spectroscopy

Phoebe K. Allan, John M. Griffin, Ali Darwiche, Olaf J. Borkiewicz, Kamila M. Wiaderek, Karena W. Chapman, Andrew J. Morris, Peter J. Chupas, Laure Monconduit, and Clare P. Grey. Journal of the American Chemical Society, 2016, 138 , 7  2352, DOI: 10.1021/jacs.5b13273

Tracking Sodium-Antimonide Phase Transformations in Sodium-Ion AnodesAntimony is a promising high-capacity anode material for sodium-ion batteries.  However, many of the (dis)charge products are amorphous, meaning that the way in which sodium is stored in the material is not well understood.  This paper uses solid-state NMR and (X-ray) pair distribution function analysis - methods which are sensitive to the local structure - to shed light upon the amorphous discharge products and hence the reasons for the excellent electrochemical performance of antimony anodes.  

Areas of interest

Critical materials, endangered elements, hydrogen storage materials, metal-organic frameworks, microporous materials, materials for energy storage and conversion, non-oxide solid electrolytes, zeolites

Representative paper: Synthesis and Characterization of Two New Amide Chloride Compounds: Potential H2 Storage Materials

R. A. Davies, D. R. Hewett and P. A. Anderson, Int. J. Hydrogen Energy, 2015, 40, 3001–3005. DOI: 10.1016/j.ijhydene.2014.12.044Synthesis and Characterization of Two New Amide Chloride Compounds: Potential H2 Storage MaterialsDespite the promising volumetric and gravimetric hydrogen storage capacities of many complex hydrides, reaction kinetics remain too slow for on-board hydrogen storage in automotive applications. Previously we showed that a range of amide halide compounds exhibited both improved kinetics of hydrogen release/reabsorption and elimination of ammonia release, but at the cost of a reduction in gravimetric capacity through the incorporation of halide. This paper reports the identification of two new amide chloride phases in which the chloride content has effectively been halved. For both new phases, this gravimetric gain was achieved with improvements in both desorption and rehydrogenation properties.

Areas of interest

Zeolites, ion exchange, nuclear waste treatment, nuclear wasteforms, metal silicates, synchrotron X-ray studies, neutron diffraction

Representative paper: A potential wasteform for Cs immobilisation: synthesis, structure determination, and aqueous durability of Cs2TiNb6O18

T.-Y. Chen, E. R. Maddrell, N. C. Hyatt and J. A. Hriljac, Inorg. Chem. 55, 12686 (2016). DOI: 10.1021/acs.inorgchem.6b01826 A potential wasteform for Cs immobilisationIn this paper we characterise a caesium titanium niobate phase as a good wasteform for long term sequestration of radioactive caesium.  We previously showed that this is the main ceramic caesium-containing phase that forms when used IONSIV ion exchange is hot isostatically pressed. The aqueous durability is shown to be excellent and so the material does fulfil the requirements for a good wasteform.

Areas of interest

Energy storage, hydrogen storage, solid state chemistry, metal-nitrogen-hydrogen materials, ammonia synthesis and decomposition, ionic conduction, X-ray and neutron powder diffraction, in situ characterisation.

Representative paper: Ammonia decomposition catalysis using non-stoichiometric lithium imide

JW Makepeace, TJ Wood, HMA Hunter, MO Jones, WIF David, Chemical Science, 2015, 6, 3805-3815
( decomposition catalysis using non-stoichiometric lithium imideAmmonia is an attractive answer to the question of how best to store and transport hydrogen so it can be used as a sustainable fuel. However, the catalytic decomposition of ammonia to release its stored hydrogen using transition metals (ruthenium is the most active metal) typically requires very high temperatures. This paper details a new approach to ammonia decomposition catalysis using lithium imide (Li2NH), showing a decrease in the temperature of 90% conversion of around 50°C compared to ruthenium. In this work, in situ neutron powder diffraction was used to demonstrate that under operating conditions the catalyst adopts a non-stoichiometric mixed amide-imide phase. Furthermore, H-D isotope exchange reactions showed that the entire bulk of the catalyst interacts with the ammonia as it decomposes, in contrast to common surface-only catalytic cycles.

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Areas of interest

Nuclear Materials Modelling, Nuclear Fuel Performance, Nuclear Materials Ageing and storage, atomistic simulation

Representative paper: Derivation of Transferable Pair Potentials and the Calculation of Intrinsic Defect Properties for Xenotime

G. L. Cutts, J. A. Hriljac and M. S. D. Read, J. Phys. Chem. C, 122, 25617−25627, 2018. DOI: 10.1021/acs.jpcc.8b06978

Derivation of Transferable Pair Potentials and the Calculation of Intrinsic Defect PropertiesIn this paper we empirically derive a new force field that is transferable across the YPO4, Y2O3, and P2O5 phases, utilising a reverse Monte Carlo method. These potentials are used to investigate the defect properties of xenotime, where a wide range of intrinsic defects including Schottky, Schottky-like, Frenkel pairs, and anti-site defects have been investigated, both at infinite dilution and as defect clusters. A common feature in the lowest energy defect configurations was the presence of polymerized phosphate tetrahedra, forming P2O7 units. The intrinsic defect calculations presented here have been compared with previous work in zircon to gain insight into differences that may contribute to the disparity in the radiation resistance of the two minerals.

Areas of interest

Polymer synthesis, self-assembly, nanoparticles, catalysis, soft matter and DNA.

Representative paper: Confinement of Therapeutic Enzymes in Selectively Permeable Polymer Vesicles by Polymerization-Induced Self-Assembly (PISA) Reduces Antibody Binding and Proteolytic Susceptibility

Lewis D. Blackman, Spyridon Varlas, Maria C. Arno, Zachary H. Houston, Nicholas L. Fletcher, Kristofer J. Thurecht, Muhammad Hasan, Matthew I. Gibson, and Rachel K. O’Reilly. ACS Central Science, 2018, 4, 718

Confinement of Therapeutic Enzymes in Selectively Permeable Polymer VesiclesThis paper highlights an alternative to PEGylaton through protection of a therapeutic enzyme using a polymer capsule, prepared in a scalable and precise way. This represents a new direction for the growing field of polymerisation induced self-assembly.

Areas of interest

Green Chemistry; Sustainability; Biomass; energy (fuel cells, batteries); water purification 

Representative paper: Mechanistic insights into porous carbons from gelatin

A.E. Danks, M.J. Hollamby, B. Hammouda, D.C. Fletcher; F. Johnston-Banks; S.R. Rogers, Z. Schnepp; J. Mater. Chem. A 5, 11644-11651, 2017.  

Mechanistic insights into porous carbons from gelatinIn this paper we show how the biopolymer gelatin can be utilised to produce functional carbon foams with multimodal porosity. The mechanism of the formation of these foams is assessed through the use of small angle neutron scattering alongside other techniques. We illustrate that the choice of metal nitrate can be exploited to control foam macrostructure, attributed to synergistic interaction of metal ions with the gelatin polypeptide, which changes the viscoelastic properties.

Representative paper Carbonate: an alternative dopant to stabilize new perovskite phases; synthesis and structure of Ba3Yb2O5CO3 and related isostructural phases Ba3Ln2O5CO3 ( Ln = Y, Dy, Ho, Er, Tm and Lu)

Joshua Deakin, Ivan Trussov, Alexandra Gibbs, Emma Kendrick  and Peter R. Slater; Dalton Trans. 47, 12901-12906, 2018Carbonate: an alternative dopant to stabilize new perovskite phasesIn this paper we report the synthesis of the new layered perovskite oxide carbonate, Ba3Yb2O5CO3. This phase is formed when 3BaCO3:1Yb2O3 mixtures are heated in air at temperatures 1000°C, while above this temperature the carbonate is lost and the simple oxide phase Ba3Yb4O9 is observed. The structure of Ba3Yb2O5CO3 was determined from neutron diffraction studies and consists of a tripled perovskite with double Yb-O layers separated by carbonate layers, the first example of a material with such a structure. Further studies showed that analogous Ba3Ln2O5CO3 phases could be formed for other rare earths (Ln = Y, Dy, Ho, Er, Tm and Lu). The results highlight the ability of the perovskite structure to accommodate carbonate groups, and emphasise the need to consider their potential presence particularly for perovskite systems prepared in lower temperature synthesis routes.

Areas of interest

Polymer Synthesis - Nanotechnology - Supramolecular Science - Smart Materials - Antimicrobials - Drug Delivery

Representative paper: In Situ Functionalized Polymers for siRNA Delivery

Angew. Chem., Int. Ed. (2016), 55, 7492–7495

In Situ Functionalized Polymers for siRNA DeliveryA new method is reported herein for screening the biological activity of functional polymers across a consistent degree of polymerization and in situ, that is, under aqueous conditions and without purification/isolation of candidate polymers. In brief, the chemical functionality of a poly(acryloyl hydrazide) scaffold was activated under aqueous conditions using readily available aldehydes to obtain amphiphilic polymers. The transport activity of the resulting polymers can be evaluated in situ using model membranes and living cells without the need for tedious isolation and purification steps. This technology allowed the rapid identification of a supramolecular polymeric vector with excellent efficiency and reproducibility for the delivery of siRNA into human cells (HeLa‐EGFP). The reported method constitutes a blueprint for the high‐throughput screening and future discovery of new polymeric functional materials with important biological applications.

Areas of interest

Functional materials, porous materials, metal-organic frameworks, molecular conductors, crystallography, energetics, in situ X-ray diffraction, crystallisation, formation mechanisms, high pressure, synchrotron techniques.

Representative paper: In-Situ Observation of Successive Crystallisations and Metastable Intermediates in Metal-Organic Framework Formation

H. H.-M. Yeung,* Y. Wu, S. Henke, A. K. Cheetham, D. O’Hare, R. I. Walton
Angewandte Chemie, International Edition 2016 55, 2012-2016.
DOI: 10.1002/ange.201508763

Understanding the driving forces controlling crystallization is essential for the efficient synthesis and design of new materials, particularly metal–organic frameworks (MOFs), where mild solvothermal synthesis often allows access to various phases from the same reagents. Using high‐energy in situ synchrotron X‐ray powder diffraction, we monitor the crystallization of lithium tartrate MOFs, observing the successive crystallization and dissolution of three competing phases in one reaction. By determining rate constants and activation energies, we fully quantify the reaction energy landscape, gaining important predictive power for the choice of reaction conditions. Different reaction rates are explained by the structural relationships between the products and the reactants; larger changes in conformation result in higher activation energies.In-Situ Observation of Successive Crystallisations and Metastable Intermediates in Metal-Organic Framework Formation


Enquiries about specific aspects of their research areas should be addressed to individual research group leaders. For more general enquiries about working with the MC Unit, please contact Professor Jon Preece (MSC Unit Lead). Information on various postgraduate (PhD and Masters) degree opportunities can be found on our postgraduate opportunities page.