The influence of water on the redox properties of ceria is pivotal to its widespread exploitation spanning a variety of applications. Ab initio simulation techniques based on DFT-GGA+U are used to investigate the water–ceria system including associative (H2O) and dissociative (−OH) adsorption/desorption of water and the formation of oxygen vacancies in the presence of water vapor on the stoichiometric and reduced low index surfaces of ceria at different water coverages. Our calculations address the controversy concerning the adsorption of water on the CeO2{111}, and new results are reported for the CeO2{110} and {100} surfaces. The simulations reveal strong water coverage dependence for dissociatively (−OH) adsorbed water on stoichiometric surfaces which becomes progressively destabilized at high coverage, while associative (H2O) adsorption depends weakly on the coverage due to weaker interactions between the adsorbed molecules. Analysis of the adsorption geometries suggests that the surface cerium atom coordination controls the strong adhesion of water as the average distance Ce–OW is always 10% greater than the Ce–O distance in the bulk, while the hydrogen bonding network dictates the orientation of the molecules. The adsorption energy is predicted to increase on reduced surfaces because oxygen vacancies act as active sites for water dissociation. Crucially, by calculating the heat of reduction of dry and wet surfaces, we also show that water promotes further reduction of ceria surfaces and is therefore central to its redox chemistry. Finally, we show how these simulation approaches can be used to evaluate water desorption as a function of temperature and pressure which accords well with experimental data for CeO2{111}. We predict desorption temperatures (T D) for CeO2{110} and CeO2{100} surfaces, where experimental data are not yet available. Such an understanding will help experiment interpret the complex surface/interface redox processes of ceria, which will, inevitably, include water.

The employment of spectroscopically-resolved NMR techniques as analytical probes have previously been both prohibitively expensive and logistically challenging in view of the large sizes of high-field facilities. However, with recent advances in the miniaturisation of magnetic resonance technology, low-field, cryogen-free "benchtop" NMR instruments are seeing wider use. Indeed, these miniaturised spectrometers are utilised in areas ranging from food and agricultural analyses, through to human biofluid assays and disease monitoring. Therefore, it is both intrinsically timely and important to highlight current applications of this analytical strategy, and also provide an outlook for the future, where this approach may be applied to a wider range of analytical problems, both qualitatively and quantitatively.

The thermoelectric properties, including ZT, of stoichiometric and reduced phases of the orthorhombic perovskite CaMnO3 were evaluated using DFT.

Atomistic simulations reveal that the chemical reactivity of ceria nanorods is increased when tensioned and reduced when compressed promising strain-tunable reactivity; the reactivity is determined by calculating the energy required to oxidize CO to CO2 by extracting oxygen from the surface of the nanorod. Visual reactivity “fingerprints”, where surface oxygens are colored according to calculated chemical reactivity, are presented for ceria nanomaterials including: nanoparticles, nanorods, and mesoporous architectures. The images reveal directly how the nanoarchitecture (size, shape, channel curvature, morphology) and microstructure (dislocations, grain-boundaries) influences chemical reactivity. We show the generality of the approach, and its relevance to a variety of important processes and applications, by using the method to help understand: TiO2 nanoparticles (photocatalysis), mesoporous ZnS (semiconductor band gap engineering), MgO (catalysis), CeO2/YSZ interfaces (strained thin films; solid oxide fuel cells/nanoionics), and Li-MnO2 (lithiation induced strain; energy storage).

The interactions between water and the actinide oxides UO2 and PuO2 are important both fundamentally and when considering the long-term storage of spent nuclear fuel. However, experimental studies in this area are severely limited by the intense radioactivity of plutonium, and hence, we have recently begun to investigate these interactions computationally. In this paper, we report the results of plane-wave density functional theory calculations of the interaction of water with the {111}, {110}, and {100} surfaces of UO2 and PuO2, using a Hubbard-corrected potential (PBE + U) approach to account for the strongly correlated 5f electrons. We find a mix of molecular and dissociative water adsorption to be most stable on the {111} surface, whereas the fully dissociative water adsorption is most stable on the {110} and {100} surfaces, leading to a fully hydroxylated monolayer. From these results, we derive water desorption temperatures at various pressures for the different surfaces. These increase in the order {111} < {110} < {100}, and these data are used to propose an alternative interpretation for the two experimentally determined temperature ranges for water desorption from PuO2.

Nanomaterials, with potential application as bio-medicinal agents, exploit the chemical properties of a solid, with the ability to be transported (like a molecule) to a variety of bodily compartments. However, the chemical environment can change significantly the structure and hence properties of a nanomaterial. Accordingly, its surface reactivity is critically dependent upon the nature of the (biological) environment in which it resides. Here, we use Molecular Dynamics (MD) simulation, Density Functional Theory (DFT) and aberration corrected TEM to predict and rationalise differences in structure and hence surface reactivity of ceria nanoparticles in different environments. In particular we calculate reactivity 'fingerprints' for unreduced and reduced ceria nanoparticles immersed in water and in vacuum. Our simulations predict higher activities of ceria nanoparticles, towards oxygen release, when immersed in water because the water quenches the coordinative unsaturation of surface ions. Conversely, in vacuum, surface ions relax into the body of the nanoparticle to relieve coordinative unsaturation, which increases the energy barriers associated with oxygen release. Our simulations also reveal that reduced ceria nanoparticles are more active towards surface oxygen release compared to unreduced nanoceria. In parallel, experiment is used to explore the activities of ceria nanoparticles that have suffered a change in environment. In particular, we compare the ability of ceria nanoparticles, in an aqueous environment, to scavenge superoxide radicals compared to the same batch of nanoparticles, which have first been dried and then rehydrated. The latter show a distinct reduction in activity, which we correlate to a change in the redox chemistry associated with moving between different environments. The reactivity of ceria nanoparticles is therefore not only environment dependent, but is also influenced by the transport pathway or history required to reach the particular environment in which its reactivity is to be exploited.

Uranium trioxide (UO3) is known to adopt a variety of crystalline and amorphous phases. Here we applied the Perdew-Burke-Ernzerhof functional + U formalism to predict structural, electronic, and elastic properties of five experimentally determined UO3 polymorphs, in addition to their relative stability. The simulations reveal that the methodology is well-suited to describe the different polymorphs. We found better agreement with experiment for simpler phases where all bonds are similar (α- and δ-), while some differences are seen for those with more complex bonding (β-, γ-, and η-), which we address in terms of the disorder and defective nature of the experimental samples. Our calculations also predict the presence of uranyl bonds to affect the elastic and electronic properties. Phases containing uranyl bonds tend to have smaller band gaps and bulk moduli under 100 GPa contrary to those without uranyl bonds, which have larger band gaps and bulk moduli greater than 150 GPa. In line with experimental observations, we predict the most thermodynamically stable polymorph as γ-UO3, the least stable as α-UO3, and the most stable at high pressure as η-UO3.

Novel sensing technologies for liquid biopsies offer promising prospects for the early detection of metabolic conditions through omics techniques. Indeed, high-field nuclear magnetic resonance (NMR) facilities are routinely used for metabolomics investigations on a range of biofluids in order to rapidly recognise unusual metabolic patterns in patients suffering from a range of diseases. However, these techniques are restricted by the prohibitively large size and cost of such facilities, suggesting a possible role for smaller, low-field NMR instruments in biofluid analysis. Herein we describe selected biomolecule validation on a low-field benchtop NMR spectrometer (60 MHz), and present an associated protocol for the analysis of biofluids on compact NMR instruments. We successfully detect common markers of diabetic control at low-to-medium concentrations through optimised experiments, including α-glucose (≤2.8 mmol/L) and acetone (25 µmol/L), and additionally in readily accessible biofluids, particularly human urine. We present a combined protocol for the analysis of these biofluids with low-field NMR spectrometers for metabolomics applications, and offer a perspective on the future of this technique appealing to ‘point-of-care’ applications.