Structural information about “traditional”, crystalline coordination complexes is typically obtained from single crystal XRD. This source of information is not available for LCCs, therefore the liquid-phase speciation is elucidated by combining several spectroscopic techniques, such as Raman and NMR spectroscopies (Figure 1), but also more advanced techniques, such as EXAFS (extended X-ray absorption fine structure). Furthermore, in contrast to solid phase, in the liquid there are often not one, but several species in a dynamic equilibrium with each other, which further complicates the characterisation.

Figure 1. Speciation of liquid coordination complexes based on aluminium and gallium.

In this work, the focus will be on the development and characterisation of entirely new liquid coordination complexes with non-chloride ligands, and the measurement of their Lewis acidity and physico-chemical properties. There will be ample opportunities to train and practice lab skills, especially inorganic synthesis (including air-sensitive synthesis using Schlenk techniques and glovebox) and analytical techniques (NMR, Raman and FT-IR spectroscopies, in addition to differential scanning calorimetry and thermogravimetric analysis).

Project Duration: 12 weeks, from July to September (indicative).

Moreover concentrated solutions of lithium salts with glymes can form highly coordinated liquid complexes that contain only low concentrations of free glyme and can be considered as solvate ionic liquids (J Phys Chem C, 2015, 119, 3957; ACS Appl Mater Interfaces, 2017, 9, 6014) inheriting many useful characteristics of conventional ionic liquids (reduced vapour pressure, high thermal stability, wide electrochemical potentials).

This project will complete studies on novel glycerol-derived polyethers that are (i) non-toxic and biodegradable (in contrast to glymes that can induce reproductive toxicity) and (ii) derived from waste bio-resources (cf industrial glyme production from dimethylether and ethylene oxide).  The research will include optimisation of an ionic liquid catalysed procedure for synthesis of new glycerol-glymes, and investigation of their phase behaviour in mixtures with lithium bistrifylimide to examine the potential formation of highly conductive concentrated electrolyte solutions and new solvate ionic liquids using DSC, rheometry, conductivity and linear sweep voltametry.

Project Duration: 12 weeks, from July to September (indicative).

The first aim of this project is to perform ¹H, ¹³C and 2D NMR of solutes such as CO₂ and small hydrocarbons (gases and liquids such as CH₄, ethane, ethene, hexane, hexene) in a variety of common laboratory solvents. These small molecules will serve as probes of the liquid environment. Since the solvents have different environments in terms of polarity, hydrogen bond ability and basicity they will provide a calibration for the chemical shifts expected for the “probes”.

The same experiments will then be performed with the probe molecules in a variety of ILs and DES. By comparison with the calibration, we aim to understand better the environment felt by each solute in the ILs and DES.

This understanding will help us with the second aim of this project, the design, synthesis and testing of ILs and DES that promote stronger interactions between the gas and the liquid phase.

This work will help validate NMR and the use of small molecules as NMR probes as tools for the understanding of the liquid environment and interactions in ILs and DES.

Project Duration: up to 12 weeks, between June and August.

There are opportunities to unlock and obtain fine control to tune the behaviour and properties of inorganic salt hydrate/solvate eutectics through selection of the appropriate solvate donor components. This project will build on, and complete studies initiated originally as a L4 research project in 2020/21 on the influence of changing the degree of hydrogen-bond sites available in the solvate donors of SAT-urea eutectics by systematically replacing urea N-H groups with N-alkyl functions, to complete detailed thermophysical characterisation of the phase behaviour of these new SAT/functional-urea mixtures using differential scanning calorimetry and polarising optical microscopy in the laboratory, and also studying the liquid structure of the SAT/urea eutectic using Empirical Potential Structure Refinement (EPSR) modelling with experimental neutron scattering data that is due for collection at the ISIS Neutron and Muon Source in May 2021 giving insight into potential competition between urea and water as hydrogen-bonding components in the molten mixed hydrate/solvate eutectics.

Project Duration: 12 weeks, from July to September (indicative).

The novelty of our approach is the use of hybrid nanocatalysts, which allow for the efficient one-step CO₂ hydrogenation to DME by combining the methanol synthesis with the de-hydration in a single reactor. This approach represents a breakthrough over the conventional two-step process, leading to a higher conversion of the CO₂ and a significantly simplified process.

DME is considered a “future fuel”, particularly as a diesel substitute. DME has a high cetane number of 55 similar to that of diesel fuel from petroleum (40–53), then only moderate modifications are needed to convert a diesel engine to burn dimethyl ether. In comparison to other synthetic fuels, DME has a very high thermal efficiency, equivalent to that of traditional fuels. It also does not emit sulphur oxides or soot; and there is a considerable reduction of nitrous oxides in the exhaust gases. DME can be used as fuel for diesel engines, for running turbines in a power generation facility and as H₂ carrier for electric vehicles with a direct DME fuel cell (DDMEFC). As such, DME is placed to become an important next-generation clean fuel and will contribute to the effective management of energy resources in the future. Dimethyl ether is used widely in the chemical industry and established storage and distribution infrastructure can easily be adapted.

Project Duration: 12 weeks, from June to August.

Lithium (Li) mining requires high energy, and water consuming processing. Therefore, from both economic and environmental perspectives, recycling of spent LIBs is worthwhile (see Figure 1), considering the need for a sustainable use of these resources.

Figure 1. Components of a lithium-ion battery given as approximate average mass percentages.

While most previously reported processes mainly focus on recovering valuable metals such as cobalt and nickel via hydrometallurgical and pyrometallurgical processes, these processes are not necessarily sustainable. In this project, we envisage the development of a strategy for a novel clean, highly efficient, low cost, and pollution-free recycling process for LIBs, involving ‘green’ leaching and solvometallurgical refinement processes using ionic liquids. These ILs have a great potential for selective high-tech metal extraction, separation and processing to create greener and environmentally benign solvents to achieve significant process intensification.

Project Duration: 12 weeks, from July to September (indicative).

This opens up new possibilities with accelerated flexibility and reduced development time in the design cycle. This project will focus on the design of electrochemical devices for versatile applications, starting from nanocomposite materials for 3D printing of multifunctional electrodes. This allows improving a variety of properties such as surface area, electron transfer and porosity along with reducing cost and weight. These materials will be fabricated and characterised, and thereby improve the performance of a fully 3D printed energy storage cell (see example for prototype in Figure 1) with the goal to create well-structured battery devices with superior energy & power density thereby meeting the sustainable development goals (SDGs) towards a zero-carbon future.

Figure 1. 3D printed energy storage cell.

The candidate should have an interest in synthesis, electrochemistry, polymers and working at the interface between Chemistry and Material Science.

Project Duration: 12 weeks, from July to September (indicative).