Strongly Bound Surface Water Affects the Shape Evolution of Cerium Oxide Nanoparticles

The surface structure and composition of functional materials are well-known to be critically important factors controlling the surface reactivity. However, when doped the surface composition will change, and the challenge is to identify its impact on important surface processes and nanoparticle morphologies. We have begun to address this by using a combination of density functional theory and potential-based methods to investigate the effect of surface dopants on water adsorption and morphology of the technologically important material, CeO$_2$, which finds application as electrolyte in SOFCs, catalyst in soot combustion, and enzyme mimetic agents in biomedicine. We show that by mapping CeO$_2$ surface phase diagrams we can predict nanoparticle morphologies as a function of dopant, temperature, and water partial pressure. Our results show that low-temperature, undoped CeO$_2$ nanocubes with active {100} surface sites are thermodynamically stable, but at the typical high temperature, operating conditions favor polyhedra where {100} surfaces are replaced by less active {111} surfaces by surface ion migration. However, doping with trivalent cations, such as Gd$^{3+}$, will increase binding of water on the {100} surfaces and hence act to preserve the cuboidal architecture by capping the active surfaces. As surfaces tend to be decorated by impurities and dopants it is clear that their role should receive more attention and the approach we describe can be routinely applied to nanomaterials, morphologies, and associated active/inactive surfaces

Controlling the {111}/{110} Surface Ratio of Cuboidal Ceria Nanoparticles

The ability to control size and morphology is crucial in optimizing nanoceria catalytic activity as this is governed by the atomistic arrangement of species and structural features at the surfaces. Here, we show that cuboidal cerium oxide nanoparticles can be obtained via microwave-assisted hydrothermal synthesis in highly alkaline media. HRTEM revealed that the cube edges were truncated by CeO2{110} surfaces and the cube corners by CeO2{111} surfaces. When adjusting synthesis conditions by increasing NaOH concentration, the average particle size increased. Although this was accompanied by an increase of the cube faces, CeO2{100}, the cube edges, CeO2{110}, and cube corners, CeO2{111} remained of constant size. Molecular Dynamics (MD) was used to rationalise this behaviour and revealed that energetically, the corners and edges cannot be atomically sharp, rather they are truncated by {111} and {110} surfaces respectively to stabilise the nanocube; both experiment and simulation agreed a minimum size of ~1.6 nm associated with this truncation. Moreover, HRTEM and MD revealed {111}/{110} faceting of the {110} edges, which balances the surface energy associated with the exposed surfaces, which follows {111}>{110}>{100}, although only the {110} surface facets because of the ease of extracting oxygen from its surface, which follows {111}>{100}>{110}. Finally, MD revealed that the {100} surfaces are ‘liquid-like’ with a surface oxygen mobility 5 orders of magnitude higher than that on the {111} surfaces; this arises from the flexibility of the surface species network that can access many different surface arrangements due to very small energy differences. This finding has implications for understanding the surface chemistry of nanoceria and provides avenues to rationalize the design of catalytically active materials at the nanoscale

Thermoelectric Properties of Pnma and Rocksalt SnS and SnSe

Thermoelectric materials convert waste heat to electricity and are part of the package of technologies needed to limit global warming. The tin chalcogenides SnS and SnSe are promising candidate thermoelectrics, with orthorhombic SnSe showing some of the highest figures of merit ZT reported to date. As for other Group IV chalcogenides, SnS and SnSe can form rocksalt phases under certain conditions, but the thermoelectric properties of these phases are largely unexplored. We have applied a fully ab initio modelling protocol to compare the ZT of the orthorhombic and rocksalt phases of SnS and SnSe. Electronic structures from hybrid density-functional theory were used to calculate the three electrical transport properties, including approximate models for the electron relaxation times, and lattice dynamics calculations were performed to model the phonon spectra and lattice thermal conductivities. We obtained good estimates of the ZT of the well-studied orthorhombic phases. The rocksalt phases were predicted to show larger electrical conductivities and similar Seebeck coefficients to the orthorhombic phases, resulting in higher thermoelectric power factors, but these were offset by larger thermal conductivities. These results therefore motivate further investigation of the recently discovered “π-cubic” phases of SnS and SnSe, which are based on distorted rocksalt supercells, to establish their thermoelectric performance

Structural Dynamics, Phonon Spectra and Thermal Transport in the Silicon Clathrates

The potential of thermoelectric power to reduce energy waste and mitigate climate change has led to renewed interest in “phonon-glass electron-crystal” materials, of which the inorganic clathrates are an archetypal example. In this work we present a detailed first-principles modelling study of the structural dynamics and thermal transport in bulk diamond Si and five framework structures, including the reported Si Clathrate I and II structures and the recently-synthesised oC24 phase, with a view to understanding the relationship between the structure, lattice dynamics, energetic stability and thermal transport. We predict the IR and Raman spectra, including ab initio linewidths, and identify spectral signatures that could be used to confirm the presence of the different phases in material samples. Comparison of the energetics, including the contribution of the phonons to the finite-temperature Helmholtz free energy, shows that the framework structures are metastable, with the energy differences to bulk Si dominated by differences in the lattice energy. Thermal-conductivity calculations within the single-mode relaxation-time approximation show that the framework structures have significantly lower κlatt than bulk Si, which we attribute quantitatively to differences in the phonon group velocities and lifetimes. The lifetimes vary considerably between systems, which can be largely accounted for by differences in the three-phonon interaction strengths. Notably, we predict a very low κlatt for the Clathrate-II structure, in line with previous experiments but contrary to other recent modelling studies, which motivates further exploration of this system

Data for: Thermoelectric Properties of Pnma and Rocksalt SnS and SnSe

This online repository provides additional data to accompany the paper: "Thermoelectric Properties of Pnma and Rocksalt SnS and SnSe" J. M. Flitcroft, I. Pallikara and J. M. Skelton Solids 3 (1), 155-176 (2022) DOI: https://doi.org/10.3390/solids3010011 This article provides a theoretical prediction of the electrical- and thermal-transport properties, and thermoelectric figure of merit ZT, of Pnma and rocksalt SnS and SnSe. This repository makes available raw data from these calculations, including: * Optimised structures; * Input files for determining the phonon spectra and lattice-thermal conductivity; and * Input files for determining the Seebeck coefficient, electrical conductivity and electronic thermal conductivity. For details of how this data was generated, users are referred to the published article and supporting information. Brief details of file formats and links to further documentation are given in the included README file

Composition-dependent morphology of stoichiometric and oxygen deficient PuO2 nanoparticles in the presence of H2O and CO2:A density-functional theory study

Among the most pressing challenges faced by the UK nuclear industry is how to safely handle its large stockpile of plutonium dioxide. In particular, understanding how the exposed surfaces interact with the environment is critical to establishing the chemical reactivity and determining suitable processing and storage conditions. In this work, we apply an ab initio modelling approach to predict the morphology and surface speciation of stoichiometric and oxygen deficient PuO2 nanoparticles as a function of temperature and in the presence of individually- and co-adsorbed H2O and CO2. We find that co-adsorption of the two species has a significant impact on the surface composition, resulting in the equilibrium particle morphology being strongly dependent on the storage conditions. This work provides valuable insight into the behaviour of nanoparticulate PuO2 in the presence of ubiquitous small molecules and marks an important step toward more realistic models extendable to other adsorbates and actinide oxides

The critical role of hydrogen on the stability of oxy-hydroxyl defect clusters in uranium oxide

Despite considerable work applying ab initio techniques to model the role of defects on mechanical, structural and electronic properties of oxides, there has been little on the role of trapped hydrogen, despite it being virtually always present.</p

Composition-dependent morphologies of CeO₂ nanoparticles in the presence of Co-adsorbed H₂O and CO₂: a density functional theory study

Catalytic activity is affected by surface morphology, and specific surfaces display greater activity than others. A key challenge is to define synthetic strategies to enhance the expression of more active surfaces and to maintain their stability during the lifespan of the catalyst. In this work, we outline an ab initio approach, based on density functional theory, to predict surface composition and particle morphology as a function of environmental conditions, and we apply this to CeO2 nanoparticles in the presence of co-adsorbed H2O and CO2 as an industrially relevant test case. We find that dissociative adsorption of both molecules is generally the most favourable, and that the presence of H2O can stabilise co-adsorbed CO2. We show that changes in adsorption strength with temperature and adsorbate partial pressure lead to significant changes in surface stability, and in particular that co-adsorption of H2O and CO2 stabilizes the {100} and {110} surfaces over the {111}. Based on the changes in surface free energy induced by the adsorbed species, we predict that cuboidal nanoparticles are favoured in the presence of co-adsorbed H2O and CO2, suggesting that cuboidal particles should experience a lower thermodynamic driving force to reconstruct and thus be more stable as catalysts for process involving these species

Composition-dependent morphologies of CeO₂ nanoparticles in the presence of Co-adsorbed H₂O and CO₂:a density functional theory study

Catalytic activity is affected by surface morphology, and specific surfaces display greater activity than others. A key challenge is to define synthetic strategies to enhance the expression of more active surfaces and to maintain their stability during the lifespan of the catalyst. In this work, we outline an ab initio approach, based on density functional theory, to predict surface composition and particle morphology as a function of environmental conditions, and we apply this to CeO2 nanoparticles in the presence of co-adsorbed H2O and CO2 as an industrially relevant test case. We find that dissociative adsorption of both molecules is generally the most favourable, and that the presence of H2O can stabilise co-adsorbed CO2. We show that changes in adsorption strength with temperature and adsorbate partial pressure lead to significant changes in surface stability, and in particular that co-adsorption of H2O and CO2 stabilizes the {100} and {110} surfaces over the {111} surface. Based on the changes in surface free energy induced by the adsorbed species, we predict that cuboidal nanoparticles are favoured in the presence of co-adsorbed H2O and CO2, suggesting that cuboidal particles should experience a lower thermodynamic driving force to reconstruct and thus be more stable as catalysts for processes involving these species.</p