Inversion in Mg1-xNixAl2O4 Spinel: New Insight into Local Structure.

A wide variety of compositions adopt the isometric spinel structure (AB2O4), in which the atomic-scale ordering is conventionally described according to only three structural degrees of freedom. One, the inversion parameter, is traditionally defined as the degree of cation exchange between the A- and B-sites. This exchange, a measure of intrinsic disorder, is fundamental to understanding the variation in the physical properties of different spinel compositions. Based on neutron total scattering experiments, we have determined that the local structure of Mg1-xNixAl2O4 spinel cannot be understood as simply being due to cation disorder. Rather, cation inversion creates a local tetragonal symmetry that extends over sub-nanometer domains. Consequently, the simple spinel structure is more complicated than previously thought, as more than three parameters are needed to fully describe the structure. This new insight provides a framework by which the behavior of spinel can be more accurately modeled under the extreme environments important for many geophysics and energy-related applications, including prediction of deep seismic activity and immobilization of nuclear waste in oxides.

Probing disorder in isometric pyrochlore and related complex oxides.

There has been an increased focus on understanding the energetics of structures with unconventional ordering (for example, correlated disorder that is heterogeneous across different length scales). In particular, compounds with the isometric pyrochlore structure, A2B2O7, can adopt a disordered, isometric fluorite-type structure, (A, B)4O7, under extreme conditions. Despite the importance of the disordering process there exists only a limited understanding of the role of local ordering on the energy landscape. We have used neutron total scattering to show that disordered fluorite (induced intrinsically by composition/stoichiometry or at far-from-equilibrium conditions produced by high-energy radiation) consists of a local orthorhombic structural unit that is repeated by a pseudo-translational symmetry, such that orthorhombic and isometric arrays coexist at different length scales. We also show that inversion in isometric spinel occurs by a similar process. This insight provides a new basis for understanding order-to-disorder transformations important for applications such as plutonium immobilization, fast ion conduction, and thermal barrier coatings.

Realistic molecular model of kerogen's nanostructure.

Despite kerogen's importance as the organic backbone for hydrocarbon production from source rocks such as gas shale, the interplay between kerogen's chemistry, morphology and mechanics remains unexplored. As the environmental impact of shale gas rises, identifying functional relations between its geochemical, transport, elastic and fracture properties from realistic molecular models of kerogens becomes all the more important. Here, by using a hybrid experimental-simulation method, we propose a panel of realistic molecular models of mature and immature kerogens that provide a detailed picture of kerogen's nanostructure without considering the presence of clays and other minerals in shales. We probe the models' strengths and limitations, and show that they predict essential features amenable to experimental validation, including pore distribution, vibrational density of states and stiffness. We also show that kerogen's maturation, which manifests itself as an increase in the sp(2)/sp(3) hybridization ratio, entails a crossover from plastic-to-brittle rupture mechanisms.

Bi4TaO8Cl Nano-Photocatalyst: Influence of Local, Average, and Band Structure.

The average structure, local structure, and band structure of nanoparticles of photocatalyst Bi4TaO8Cl, an Aurivillius-Sillen layered material, has been studied by powder neutron Rietveld refinement, neutron pair distribution function technique, Raman scattering, and density functional theory calculations. A significant local structural deviation of nano-Bi4TaO8Cl was established in contrast to the local structure of bulk-Bi4TaO8Cl. Local structure was further supported by Raman scattering measurements. Through DFT calculations, we identify specific features in the electronic band structure that correlate lower secondary structural distortions in nano-Bi4TaO8Cl. Increased distortion of TaO6, decreased Ta-O-Ta bond angle, and increased octahedral tilt in the local structure of nano-Bi4TaO8Cl influence the band structure and the electron hole pair migration. Therefore, in addition to morphology and size, the local structure of a nanomaterial contributes to the photocatalytic performance. Trapping experiments confirm the role of superoxide radical in the photocatalysis mechanism of this material. Such studies help in developing new functional materials with better photocatalytic efficiency to address energy and environmental issues.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.

Intricate short-range ordering and strongly anisotropic transport properties of Li(1-x)Sn(2+x)As2.

A new ternary compound, Li(1-x)Sn(2+x)As2, 0.2 < x < 0.4, was synthesized via solid-state reaction of elements. The compound crystallizes in a layered structure in the R3̅m space group (No. 166) with Sn-As layers separated by layers of jointly occupied Li/Sn atoms. The Sn-As layers are comprised of Sn3As3 puckered hexagons in a chair conformation that share all edges. Li/Sn atoms in the interlayer space are surrounded by a regular As6 octahedron. Thorough investigation by synchrotron X-ray and neutron powder diffraction indicate no long-range Li/Sn ordering. In contrast, the local Li/Sn ordering was revealed by synergistic investigations via solid-state (6,7)Li NMR spectroscopy, HRTEM, STEM, and neutron and X-ray pair distribution function analyses. Due to their different chemical natures, Li and Sn atoms tend to segregate into Li-rich and Sn-rich regions, creating substantial inhomogeneity on the nanoscale. The inhomogeneous local structure has a high impact on the physical properties of the synthesized compounds: the local Li/Sn ordering and multiple nanoscale interfaces result in unexpectedly low thermal conductivity and highly anisotropic resistivity in Li(1-x)Sn(2+x)As2.

Mechanical Properties of Nanoscopic Lipid Domains.

The lipid raft hypothesis presents insights into how the cell membrane organizes proteins and lipids to accomplish its many vital functions. Yet basic questions remain about the physical mechanisms that lead to the formation, stability, and size of lipid rafts. As a result, much interest has been generated in the study of systems that contain similar lateral heterogeneities, or domains. In the current work we present an experimental approach that is capable of isolating the bending moduli of lipid domains. This is accomplished using neutron scattering and its unique sensitivity to the isotopes of hydrogen. Combining contrast matching approaches with inelastic neutron scattering, we isolate the bending modulus of ∼13 nm diameter domains residing in 60 nm unilamellar vesicles, whose lipid composition mimics the mammalian plasma membrane outer leaflet. Importantly, the bending modulus of the nanoscopic domains differs from the modulus of the continuous phase surrounding them. From additional structural measurements and all-atom simulations, we also determine that nanoscopic domains are in-register across the bilayer leaflets. Taken together, these results inform a number of theoretical models of domain/raft formation and highlight the fact that mismatches in bending modulus must be accounted for when explaining the emergence of lateral heterogeneities in lipid systems and biological membranes.

Average and Local Crystal Structures of (Ga(1-x)Znx)(N(1-x)Ox) Solid Solution Nanoparticles.

We report a comprehensive study of the crystal structure of (Ga(1-x)Znx)(N(1-x)Ox) solid solution nanoparticles by means of neutron and synchrotron X-ray scattering. In our study, we used four different types of (Ga(1-x)Znx)(N(1-x)Ox) nanoparticles, with diameters of 10-27 nm and x = 0.075-0.51, which show energy band gaps from 2.21 to 2.61 eV. Rietveld analysis of the neutron diffraction data revealed that the average crystal structure is hexagonal wurtzite (space group P63mc) for the larger nanoparticles, while the crystal structure of smaller nanoparticles is disordered hexagonal. Pair-distribution-function analysis found that the intermediate crystal structure retains a "motif" of the average one; however, the local structure is more disordered. The implications of disorder on the reduced energy band gap are discussed.

Synthesis, Structure, and Pressure-Induced Polymerization of Li3Fe(CN)6 Accompanied with Enhanced Conductivity.

Pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal-carbon network composite, thus providing a new route to synthesize inorganic/organic conductors with tunable composition and properties. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li3Fe(CN)6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutron diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. The conductivity of the polymer is above 10(-3) S · cm(-1), which reaches the range of conductive polymers. This investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping and heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.

Elucidating the Lithiation Process in Fe3-δO4 Nanoparticles by Correlating Magnetic and Structural Properties.

Due to their high potential energy storage, magnetite (Fe3O4) nanoparticles have become appealing as anode materials in lithium-ion batteries. However, the details of the lithiation process are still not completely understood. Here, we investigate chemical lithiation in 70 nm cubic-shaped magnetite nanoparticles with varying degrees of lithiation, x = 0, 0.5, 1, and 1.5. The induced changes in the structural and magnetic properties were investigated using X-ray techniques along with electron microscopy and magnetic measurements. The results indicate that a structural transformation from spinel to rock salt phase occurs above a critical limit for the lithium concentration (xc), which is determined to be between 0.5< xc ≤ 1 for Fe3-δO4. Diffraction and magnetization measurements clearly show the formation of the antiferromagnetic LiFeO2 phase. Upon lithiation, magnetization measurements reveal an exchange bias in the hysteresis loops with an asymmetry, which can be attributed to the formation of mosaic-like LiFeO2 subdomains. The combined characterization techniques enabled us to unambiguously identify the phases and their distributions involved in the lithiation process. Correlating magnetic and structural properties opens the path to increasing the understanding of the processes involved in a variety of nonmagnetic applications of magnetic materials.

Probing spin waves in Co3O4 nanoparticles for magnonics applications.

The magnetic properties of spinel nanoparticles can be controlled by synthesizing particles of a specific shape and size. The synthesized nanorods, nanodots and cubic nanoparticles have different crystal planes selectively exposed on the surface. The surface effects on the static magnetic properties are well documented, while their influence on spin waves dispersion is still being debated. Our ability to manipulate spin waves using surface and defect engineering in magnetic nanoparticles is the key to designing magnonic devices. We synthesized cubic and spherical nanoparticles of a classical antiferromagnetic material Co3O4 to study the shape and size effects on their static and dynamic magnetic proprieties. Using a combination of experimental methods, we probed the magnetic and crystal structures of our samples and directly measured spin wave dispersions using inelastic neutron scattering. We found a weak, but unquestionable, increase in exchange interactions for the cubic nanoparticles as compared to spherical nanoparticle and bulk powder reference samples. Interestingly, the exchange interactions in spherical nanoparticles have bulk-like properties, despite a ferromagnetic contribution from canted surface spins.

Structure and stability of SnO2 nanocrystals and surface-bound water species.

The structure of SnO2 nanoparticles (avg. 5 nm) with a few layers of water on the surface has been elucidated by atomic pair distribution function (PDF) methods using in situ neutron total scattering data and molecular dynamics (MD) simulations. Analysis of PDF, neutron prompt gamma, and thermogravimetric data, coupled with MD-generated surface D2O/OD configurations demonstrates that the minimum concentration of OD groups required to prevent rapid growth of nanoparticles during thermal dehydration corresponds to ~0.7 monolayer coverage. Surface hydration layers not only stabilize the SnO2 nanoparticles but also induce particle-size-dependent structural modifications and are likely to promote interfacial reactions through hydrogen bonds between adjacent particles. Upon heating/dehydration under vacuum above 250 °C, nanoparticles start to grow with low activation energies, rapid increase of nanoparticle size, and a reduction in the a lattice dimension. This study underscores the value of neutron diffraction and prompt-gamma analysis, coupled with molecular modeling, in elucidating the influence of surface hydration on the structure and metastable persistence of oxide nanomaterials.

A reverse Monte Carlo algorithm to simulate two-dimensional small-angle scattering intensities.

Small-angle scattering (SAS) experiments are a powerful method for studying self-assembly phenomena in nanoscopic materials because of the sensitivity of the technique to structures formed by interactions on the nanoscale. Numerous out-of-the-box options exist for analysing structures measured by SAS but many of these are underpinned by assumptions about the underlying interactions that are not always relevant for a given system. Here, a numerical algorithm based on reverse Monte Carlo simulations is described to model the intensity observed on a SAS detector as a function of the scattering vector. The model simulates a two-dimensional detector image, accounting for magnetic scattering, instrument resolution, particle polydispersity and particle collisions, while making no further assumptions about the underlying particle interactions. By simulating a two-dimensional image that can be potentially anisotropic, the algorithm is particularly useful for studying systems driven by anisotropic interactions. The final output of the algorithm is a relative particle distribution, allowing visualization of particle structures that form over long-range length scales (i.e. several hundred nanometres), along with an orientational distribution of magnetic moments. The effectiveness of the algorithm is shown by modelling a SAS experimental data set studying finite-length chains consisting of magnetic nanoparticles, which assembled in the presence of a strong magnetic field due to dipole interactions.

Nanospheres of a new intermetallic FeSn5 phase: synthesis, magnetic properties and anode performance in Li-ion batteries.

We synthesized monodisperse nanospheres of an intermetallic FeSn(5) phase via a nanocrystal-conversion protocol using preformed Sn nanospheres as templates. This tetragonal phase in P4/mcc space group, along with the defect structure Fe(0.74)Sn(5) of our nanospheres, has been resolved by synchrotron X-ray diffraction and Rietveld refinement. Importantly, FeSn(5), which is not yet established in the Fe-Sn phase diagram, exhibits a quasi-one dimensional crystal structure along the c-axis, thus leading to interesting anisotropic thermal expansion and magnetic properties. Magnetization measurements indicate that nanospheres are superparamagnetic above the blocking temperature T(B) = 300 K, which is associated with the higher magnetocrystalline anisotropy constant K = 3.33 kJ m(-3). The combination of the magnetization measurements and first-principles density functional theory calculations reveals the canted antiferromagnetic nature with significant spin fluctuation in lattice a-b plane. The low Fe concentration also leads Fe(0.74)Sn(5) to enhanced capacity as an anode in Li ion batteries.

Ionothermal synthesis and magnetic studies of novel two-dimensional metal-formate frameworks.

Five novel two-dimensional frameworks containing formate-bridged metal-centered octahedra are synthesized ionothermally from two ionic liquids previously unused as solvents in hybrid synthesis, 2-hydroxyethylammonium (HEA) formate, and 1-hydroxy-3-proplyammonium (HPA) formate. Templating effects of the cation from each ionic liquid drive the formation of different structures. [NH(3)C(2)H(4)OH](2)[M(CHO(2))(4)] (1: M = Co, 2: M = Ni) exhibit the same stoichiometry and connectivity as their manganese analogue (3: M = Mn), but the manganese form exhibits a different topology from 1 and 2. [NH(3)C(3)H(6)OH][M(CHO(2))(3)(H(2)O)] (4: M = Co, 5: M = Mn) were synthesized using the HPA formate ionic liquid with a metal-formate connectivity related to those of 1-3. Canted antiferromagnetic ordering occurs at low temperatures (1: T(N) = 7.0 K, 2: T(N) = 4.6 K, 3: T(N) = 8.0 K, 4: T(N) = 7.0 K, 5: T(N) = 9.2 K), similar to the magnetic properties previously reported for other metal-formate hybrid materials.

Mechanism of magnetization reduction in iron oxide nanoparticles.

Iron oxide nanoparticles are presently considered as main work horses for various applications including targeted drug delivery and magnetic hyperthermia. Several questions remain unsolved regarding the effect of size onto their overall magnetic behavior. One aspect is the reduction of magnetization compared to bulk samples. A detailed understanding of the underlying mechanisms of this reduction could improve the particle performance in applications. Here we use a number of complementary experimental techniques including neutron scattering and synchrotron X-ray diffraction to arrive at a consistent conclusion. We confirm the observation from previous studies of a reduced saturation magnetization and argue that this reduction is mainly associated with the presence of antiphase boundaries, which are observed directly using high-resolution transmission electron microscopy and indirectly via an anisotropic peak broadening in X-ray diffraction patterns. Additionally small-angle neutron scattering with polarized neutrons revealed a small non-magnetic surface layer, that is, however, not sufficient to explain the observed loss in magnetization alone.

Unravelling Magnetic Nanochain Formation in Dispersion for In Vivo Applications.

Self-assembly of iron oxide nanoparticles (IONPs) into 1D chains is appealing, because of their biocompatibility and higher mobility compared to 2D/3D assemblies while traversing the circulatory passages and blood vessels for in vivo biomedical applications. In this work, parameters such as size, concentration, composition, and magnetic field, responsible for chain formation of IONPs in a dispersion as opposed to spatially confining substrates, are examined. In particular, the monodisperse 27 nm IONPs synthesized by an extended LaMer mechanism are shown to form chains at 4 mT, which are lengthened with applied field reaching 270 nm at 2.2 T. The chain lengths are completely reversible in field. Using a combination of scattering methods and reverse Monte Carlo simulations the formation of chains is directly visualized. The visualization of real-space IONPs assemblies formed in dispersions presents a novel tool for biomedical researchers. This allows for rapid exploration of the behavior of IONPs in solution in a broad parameter space and unambiguous extraction of ​the parameters of the equilibrium structures. Additionally, it can be extended to study novel assemblies formed by more complex geometries of IONPs.

Water-dispersible, multifunctional, magnetic, luminescent silica-encapsulated composite nanotubes.

A multifunctional one-dimensional nanostructure incorporating both CdSe quantum dots (QDs) and Fe(3)O(4) nanoparticles (NPs) within a SiO(2)-nanotube matrix is successfully synthesized based on the self-assembly of preformed functional NPs, allowing for control over the size and amount of NPs contained within the composite nanostructures. This specific nanostructure is distinctive because both the favorable photoluminescent and magnetic properties of QD and NP building blocks are incorporated and retained within the final silica-based composite, thus rendering it susceptible to both magnetic guidance and optical tracking. Moreover, the resulting hydrophilic nanocomposites are found to easily enter into the interiors of HeLa cells without damage, thereby highlighting their capability not only as fluorescent probes but also as possible drug-delivery vehicles of interest in nanobiotechnology.

Electronic and magnetic properties of ultrathin Au/Pt nanowires.

We have reported the synthesis of Au(25)Pt(75) and Au(48)Pt(52) alloyed ultrathin nanowires with average widths of less than 3 nm via a wet chemistry approach at room temperature. Using a combination of techniques, including scanning transmission electron microscopy equipped with X-ray energy dispersive spectroscopy, ultraviolet-visible spectroscopy, and X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopies, we identified the stoichiometry-dependent heterogeneous crystalline structures, as well as electronic structures with respect to the charge transfer between Pt and Au within both nanowires. In particular, we observed d-charge depletion at the Au site and the d-charge gain at the Pt site in Au(48)Pt(52) nanowires, which accounted for its ferromagnetic magnetic behavior, in contrast to the paramagnetism and diamagnetism appearing respectively in bulk Pt and Au.

Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite.

Birnessite is a low-cost and environmentally friendly layered material for aqueous electrochemical energy storage; however, its storage capacity is poor due to its narrow potential window in aqueous electrolyte and low redox activity. Herein we report a sodium rich disordered birnessite (Na0.27MnO2) for aqueous sodium-ion electrochemical storage with a much-enhanced capacity and cycling life (83 mAh g-1 after 5000 cycles in full-cell). Neutron total scattering and in situ X-ray diffraction measurements show that both structural water and the Na-rich disordered structure contribute to the improved electrochemical performance of current cathode material. Particularly, the co-deintercalation of the hydrated water and sodium-ion during the high potential charging process results in the shrinkage of interlayer distance and thus stabilizes the layered structure. Our results provide a genuine insight into how structural disordering and structural water improve sodium-ion storage in a layered electrode and open up an exciting direction for improving aqueous batteries.