Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity?

Ionic conductivity is ubiquitous to many industrially important applications such as fuel cells, batteries, sensors, and catalysis. Tunable conductivity in these systems is therefore key to their commercial viability. Here, we show that geometric frustration can be exploited as a vehicle for conductivity tuning. In particular, we imposed geometric frustration upon a prototypical system, CaF2, by ball milling it with BaF2, to create nanostructured Ba1-xCaxF2 solid solutions and increased its ionic conductivity by over 5 orders of magnitude. By mirroring each experiment with MD simulation, including "simulating synthesis", we reveal that geometric frustration confers, on a system at ambient temperature, structural and dynamical attributes that are typically associated with heating a material above its superionic transition temperature. These include structural disorder, excess volume, pseudovacancy arrays, and collective transport mechanisms; we show that the excess volume correlates with ionic conductivity for the Ba1-xCaxF2 system. We also present evidence that geometric frustration-induced conductivity is a general phenomenon, which may help explain the high ionic conductivity in doped fluorite-structured oxides such as ceria and zirconia, with application for solid oxide fuel cells. A review on geometric frustration [ Nature 2015 , 521 , 303 ] remarks that classical crystallography is inadequate to describe systems with correlated disorder, but that correlated disorder has clear crystallographic signatures. Here, we identify two possible crystallographic signatures of geometric frustration: excess volume and correlated "snake-like" ionic transport; the latter infers correlated disorder. In particular, as one ion in the chain moves, all the other (correlated) ions in the chain move simultaneously. Critically, our simulations reveal snake-like chains, over 40 Å in length, which indicates long-range correlation in our disordered systems. Similarly, collective transport in glassy materials is well documented [for example, J. Chem. Phys. 2013 , 138 , 12A538 ]. Possible crystallographic nomenclatures, to be used to describe long-range order in disordered systems, may include, for example, the shape, length, and branching of the "snake" arrays. Such characterizations may ultimately provide insight and differences between long-range order in disordered, amorphous, or liquid states and processes such as ionic conductivity, melting, and crystallization.

Liquid crystal seed nucleates liquid-solid phase change in ceria nanoparticles.

Molecular dynamics (MD) simulation was used to explore the liquid-solid (crystal) phase change of a ceria nanoparticle. The simulations reveal that the crystalline seed, which spontaneously evolves and nucleates crystallisation, is a liquid rather than a solid. Evidence supporting this concept includes: (a) only 3% of the total latent heat of solidification had been liberated after 25% of the nanoparticle had (visibly) crystallised. (b) Cerium ions, comprising the (liquid) crystal seed had the same mobility as cerium ions comprising the amorphous regions. (c) Cerium ion mobility only started to reduce (indicative of solidification) after 25% of the nanoparticle had crystallised. (d) Calculated radial distribution functions (RDF) revealed no long-range structure when 25% of the nanoparticle had (visibly) crystallised. We present evidence that the concept of a liquid crystal seed is more general phenomenon rather than applicable only to nanoceria.

Visualizing the enhanced chemical reactivity of mesoporous ceria; simulating templated crystallization in silica scaffolds at the atomic level.

Unique physical, chemical, and mechanical properties can be engineered into functional nanomaterials via structural control. However, as the hierarchical structural complexity of a nanomaterial increases, so do the challenges associated with generating atomistic models, which are sufficiently realistic that they can be interrogated to reliably predict properties and processes. The structural complexity of a functional nanomaterial necessarily emanates during synthesis. Accordingly, to capture such complexity, we have simulated each step in the synthetic protocol. Specifically, atomistic models of mesoporous ceria were generated by simulating the infusion and confined crystallization of ceria in a mesoporous silica scaffold. After removing the scaffold, the chemical reactivity of the templated mesoporous ceria was calculated and predicted to be more reactive compared to mesoporous ceria generated without template; visual "reactivity fingerprints" are presented. The strategy affords a general method for generating atomistic models, with hierarchical structural complexity, which can be used to predict a variety of properties and processes enabling the nanoscale design of functional materials.

Mechanical properties of mesoporous ceria nanoarchitectures.

Architectural constructs are engineered to impart desirable mechanical properties facilitating bridges spanning a thousand meters and buildings nearly 1 km in height. However, do the same 'engineering-rules' translate to the nanoscale, where the architectural features are less than 0.0001 mm in size? Here, we calculate the mechanical properties of a porous ceramic functional material, ceria, as a function of its nanoarchitecture using molecular dynamics simulation and predict its yield strength to be almost two orders of magnitude higher than the parent bulk material. In particular, we generate models of nanoporous ceria with either a hexagonal or cubic array of one-dimensional pores and simulate their responses to mechanical load. We find that the mechanical properties are critically dependent upon the orientation between the crystal structure (symmetry, direction) and the pore structure (symmetry, direction).

Reduced graphene oxide conjugated Cu2O nanowire mesocrystals for high-performance NO2 gas sensor.

Reduced graphene oxide (rGO)-conjugated Cu(2)O nanowire mesocrystals were formed by nonclassical crystallization in the presence of GO and o-anisidine under hydrothermal conditions. The resultant mesocrystals are comprised of highly anisotropic nanowires as building blocks and possess a distinct octahedral morphology with eight {111} equivalent crystal faces. The mechanisms underlying the sequential formation of the mesocrystals are as follows: first, GO-promoted agglomeration of amorphous spherical Cu(2)O nanoparticles at the initial stage, leading to the transition of growth mechanism from conventional ion-by-ion growth to particle-mediated crystallization; second, the evolution of the amorphous microspheres into hierarchical structure, and finally to nanowire mesocrystals through mesoscale transformation, where Ostwald ripening is responsible for the growth of the nanowire building blocks; third, large-scale self-organization of the mesocrystals and the reduction of GO (at high GO concentration) occur simultaneously, resulting in an integrated hybrid architecture where porous three-dimensional (3D) framework structures interspersed among two-dimensional (2D) rGO sheets. Interestingly, "super-mesocrystals" formed by 3D oriented attachment of mesocrystals are also formed judging from the voided Sierpinski polyhedrons observed. Furthermore, the interior nanowire architecture of these mesocrystals can be kinetically controlled by careful variation of growth conditions. Owing to high specific surface area and improved conductivity, the rGO-Cu(2)O mesocrystals achieved a higher sensitivity toward NO(2) at room temperature, surpassing the performance of standalone systems of Cu(2)O nanowires networks and rGO sheets. The unique characteristics of rGO-Cu(2)O mesocrystal point to its promising applications in ultrasensitive environmental sensors.

Amorphization and recrystallization study of lithium insertion into manganese dioxide.

Various polymorphs of MnO(2) are widely used as electrode materials in Li/MnO(2) batteries. Electrolytic manganese dioxide (EMD) is the most electrochemically active form of MnO(2) and is very difficult to characterize. Their structural details are still largely unknown owing to the poor quality of X-ray diffraction (XRD) patterns obtained from most MnO(2) samples. Simulated amorphisation and crystallization technique was used to derive microstructural models for Li-MnO(2) which included most microstructural details that one would expect to find in the real material. Specifically, pyrolusite-MnO(2), comprising about 25,000 atoms, was amorphised (strain-induced) under molecular dynamics (MD) and different concentrations of lithium ions were inserted. Each system was then crystallized under MD simulation. The resulting models conformed to the pyrolusite polymorph, with microstructural features including: extensive micro-twinning and more general grain-boundaries, stacking faults, dislocations and isolated point defects and defect clusters. Molecular graphical images, showing the atom positions for the microstructural features together with simulated XRD patterns they give rise to, are presented and compared with measured XRD. The calculated XRD are in accord with experiment thus validating the structural models.

Nanopolycrystalline materials; a general atomistic model for simulation.

We present a general strategy for generating full atomistic models of nanopolycrystalline materials including bulk and thin film. In particular, models for oxide nanoparticles were constructed using simulated amorphisation and crystallisation and used to populate a library of oxide nanoparticles (amorphous and crystalline) with different radii. Nanoparticles were then taken from this library and positioned, within a specific volume, using Monte Carlo techniques, to facilitate a tight-packed structure. The grain-size distribution of the polycrystalline material was controlled by selecting particular sized nanoparticles from the library. The (randomly oriented) grains facilitated a polycrystalline oxide, which comprised a network of general grain-boundaries. To help validate the model, gas diffusion through the (polycrystalline) oxide material was then simulated and the activation energy calculated directly. Specifically, we explored He transport in UO(2), which is an important material with respect to both civilian and military applications. We found that He transport proceeds much faster through the grain-boundary and grain-junction network compared with intracrystalline UO(2) regions, in accordance with experiment.

Engineered defects in cerium oxides: tuning chemical reactivity for biomedical, environmental, & energy applications.

Nanocrystalline cerium oxide (nanoceria) is a rare earth oxide with a complex surface chemistry. This material has seen substantial investigation in recent years in both fundamental and applied studies due largely to more precise characterization of the unique surface structures, which mediate its pronounced redox activity. In particular, oxygen storage/buffering capacities have been thoroughly correlated with synthesis and processing condition effects on other material features such as surface (micro-) faceting, reconstruction, and (extent of) hydration. Key material features such as these modulate nanoceria redox performance by changing the crystal microenvironment. In this review, we present nanoengineering methods, which have produced increased nanoceria performance in biomedical, energy, and catalysis applications. The impact of combined/cooperative theoretical and experimental studies are highlighted throughout.

Predicting the electrochemical properties of MnO2 nanomaterials used in rechargeable li batteries: simulating nanostructure at the atomistic level.

Nanoporous beta-MnO2 can act as a host lattice for the insertion and deinsertion of Li with application in rechargeable lithium batteries. We predict that, to maximize its electrochemical properties, the beta-MnO2 host should be symmetrically porous and heavily twinned. In addition, we predict that there exists a "critical (wall) thickness" for MnO2 nanomaterials above which the strain associated with Li insertion is accommodated via a plastic, rather than elastic, deformation of the host lattice leading to property fading upon cycling. We predict that this critical thickness lies between 10 and 100 nm for beta-MnO2 and is greater than 100 nm for alpha-MnO2: the latter accommodates 2 x 2 tunnels compared with the smaller 1 x 1 tunnels found in beta-MnO2. This prediction may help explain why certain (nano)forms of MnO2 are electrochemically active, while others are not. Our predictions are based upon atomistic models of beta-MnO2 nanomaterials. In particular, a systematic strategy, analogous to methods widely and routinely used to model crystal structure, was used to generate the nanostructures. Specifically, the (space) symmetry associated with the nanostructure coupled with basis nanoparticles was used to prescribe full atomistic models of nanoparticles (0D), nanorods (1D), nanosheets (2D), and nanoporous (3D) architectures. For the latter, under MD simulation, the amorphous nanoparticles agglomerate together with their periodic neighbors to formulate the walls of the nanomaterial; the particular polymorphic structure was evolved using simulated amorphization and crystallization. We show that our atomistic models are in accord with experiment. Our models reveal that the periodic framework architecture, together with microtwinning, enables insertion of Li anywhere on the (internal) surface and facilitates Li transport in all three spatial directions within the host lattice. Accordingly, the symmetrically porous MnO2 can expand and contract linearly and crucially elastically under charge/discharge. We also suggest tentatively that our predictions for MnO2 are more general in that similar arguments may apply to other nanomaterials, which might expand and contract elastically upon charging/discharging.

Computer-Aided Design of Nanoceria Structures as Enzyme Mimetic Agents: The Role of Bodily Electrolytes on Maximizing Their Activity.

Nanoceria, typically used for "clean-air" catalytic converter technologies because of its ability to capture, store, and release oxygen, is the same material that has the potential to be used in nanomedicine. Specifically, nanoceria can be used to control oxygen content in cellular environments; as a "nanozyme", nanoceria mimics enzymes by acting as an antioxidant agent. The computational design procedures for predicting active materials for catalytic converters can therefore be used to design active ceria nanozymes. Crucially, the ceria nanomedicine is not a molecule; rather, it is a crystal and exploits its unique crystal properties. Here, we use ab initio and classical computer modeling, together with the experiment, to design structures for nanoceria that maximize its nanozymetic activity. We predict that the optimum nanoparticle shape is either a (truncated) polyhedral or a nanocube to expose (active) CeO2{100} surfaces. It should also contain oxygen vacancies and surface hydroxyl species. We also show that the surface structures strongly affect the biological activity of nanoceria. Analogous to catalyst poisoning, phosphorus "poisoning", the interaction of nanoceria with phosphate, a common bodily electrolyte, emanates from phosphate ions binding strongly to CeO2{100} surfaces, inhibiting oxygen capture and release and hence its ability to act as a nanozyme. Conversely, the phosphate interaction with {111} surfaces is weak, and therefore, these surfaces protect the nanozyme against poisoning. The atom-level understanding presented here also illuminates catalytic processes and poisoning in "clean-air" or fuel-cell technologies because the mechanism underpinning and exploited in each technology, oxygen capture, storage, and release, is identical.

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

The ability to control the 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. High-resolution transmission electron microscopy (HRTEM) revealed that the cube edges were truncated by CeO2{110} surfaces and the cube corners were truncated 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 rationalize this behavior and revealed that energetically, the corners and edges cannot be atomically sharp, rather they are truncated by {111} and {110} surfaces, respectively, to stabilize the nanocube; both the experiment and simulation showed agreement regarding the 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 and 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 because of 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.

Self-assembly of cerium oxide nanostructures in ice molds.

The formation of nanorods, driven by the physicochemical phenomena during the freezing and after the aging of frozen ceria nanoparticle suspensions, is reported. During freezing of a dilute aqueous solution of CeO2 nanocrystals, some nuclei remain in solution while others are trapped inside micro- and nanometer voids formed within the growing ice front. Over time (2-3 weeks) the particles trapped within the nanometer-wide voids in the ice combine by an oriented attachment process to form ceria nanorods. The experimental observations are consistent with molecular dynamics simulations of particle aggregation in constrained environments. These observations suggest a possible strategy for the templated formation of nanostructures through self-assembly by exploiting natural phenomena, such as voids formed during freezing of water. This research suggests a very simple, green chemical route to guide the formation of one- and three-dimensional self-assembled nanostructures.

Protecting Ceria Nanocatalysts-The Role of Sacrificial Barriers.

Forces acting on a functional nanomaterial during operation can cause plastic deformation and extinguish desirable catalytic activities. Here, we show that sacrificial materials, introduced into the catalytic composite device, can absorb some of the imposed stress and protect the structural integrity and hence the activity of the functional component. Specifically, we use molecular dynamics to simulate uniaxial stress on a ceria (CeO2) nanocube, an important functional material with respect to oxidative catalysis, such as the conversion of CO to CO2. We predict that the nanocube, protected by a "soft" BaO or "hard" MgO sacrificial barrier, is able to withstand 40.1 or 26.5 GPa, respectively, before plastic deformation destroys the structure irreversibly; the sacrificial materials, BaO and MgO, capture 71 and 54% of the stress, respectively. In comparison, the unprotected nanoceria catalyst deforms plastically at only 2.5 GPa. Furthermore, modeling reveals the deformation mechanisms and the importance of microstructural features, insights that are difficult to measure experimentally.

Tuning Antisite Defect Density in Perovskite-BaLiF3 via Cycling between Ball Milling and Heating.

The defect density of a material is central to its properties. Here, we show, employing EXAFS measurements and MD simulation, how the Ba-Li antisite defect density of perovskite-structured BaLiF3 nanoparticles can be tuned. In particular, we show that ball milling reduces the defect content. Conversely, thermal annealing increases the defect density. The work represents a first step toward tailoring the properties of a material via defect tuning postsynthesis.

Engineering of nanoscale defect patterns in CeO2 nanorods via ex situ and in situ annealing.

Single-crystalline ceria nanorods were fabricated using a hydrothermal process and annealed at 325 °C-800 °C. As-synthesized CeO2 nanorods contain a high concentration of defects, such as oxygen vacancies and high lattice strains. Annealing resulted in an improved lattice crystalline quality along with the evolution of novel cavity-shaped defects in the nanorods with polyhedral morphologies and bound by e.g. {111} and {100} (internal) surfaces, confirmed for both air (ex situ) and vacuum (in situ) heating. We postulate that the cavities evolve via agglomeration of vacancies within the as-synthesized nanorods.

Origin of electrochemical activity in nano-Li2MnO3; stabilization via a 'point defect scaffold'.

Molecular dynamics (MD) simulations of the charging of Li2MnO3 reveal that the reason nanocrystalline-Li2MnO3 is electrochemically active, in contrast to the parent bulk-Li2MnO3, is because in the nanomaterial the tunnels, in which the Li ions reside, are held apart by Mn ions, which act as a pseudo 'point defect scaffold'. The Li ions are then able to diffuse, via a vacancy driven mechanism, throughout the nanomaterial in all spatial dimensions while the 'Mn defect scaffold' maintains the structural integrity of the layered structure during charging. Our findings reveal that oxides, which comprise cation disorder, can be potential candidates for electrodes in rechargeable Li-ion batteries. Moreover, we propose that the concept of a 'point defect scaffold' might manifest as a more general phenomenon, which can be exploited to engineer, for example, two or three-dimensional strain within a host material and can be fine-tuned to optimize properties, such as ionic conductivity.

Shape of CeO2 nanoparticles using simulated amorphisation and recrystallisation.

Evolutionary simulation has been used to generate full atomistic models for CeO2 nanoparticles, which comprise [100]-truncated [111] octahedra in accord with experiments.

Synthesis, structure and ionic conductivity in nanopolycrystalline BaF2/CaF2 heterolayers.

Atomistic simulations have shown that the calculated conductivity of nano-polycrystalline BaF2/CaF2 heterolayers is considerably higher than the component bulk materials and we predict that grain-boundary diffusion is the key to fast ionic conductivity in these systems.

Environment-mediated structure, surface redox activity and reactivity of ceria nanoparticles.

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.

Morphological Phase Diagram of Biocatalytically Active Ceria Nanostructures as a Function of Processing Variables and Their Properties.

We rationalize how fluorite-structured CeO2 , which is crystallographically isotropic, can grow anisotropically (without templates) to form nanoparticles, rods, and cubes. In particular, single-crystalline and monodispersed cubic CeO2 nanoparticles, nanorods, and nanocubes have been selectively synthesized by a very simple, efficient, and economical hydrothermal process using different NaOH concentrations, and Ce(NO3 )3 as the cerium precursor. High-resolution transmission electron microscopy reveals nanomaterials with differently exposed crystal planes: {111} and {100} for nanoparticles, {110} and {100} for nanorods, and {100} for nanocubes. During the preparation of the CeO2 nanomaterials, the formation of intermediate anisotropic Ce(OH)3 species under basic conditions and their conversion into CeO2 at higher temperature are key factors responsible for the shape evolution. Atomistic computer simulations were used to help rationalize how the synthetic conditions impact upon the morphology of the nanomaterial. The synthesized CeO2 nanoparticles and nanorods demonstrate higher catalase mimetic activities than the nanocubes.