Mikhail Feygenson

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.

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.

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.

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.

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.

Effect of poling on nanodomains and nanoscale structure in A-site disordered lead-free piezoelectric Na0.5Bi0.5TiO3–BaTiO3

This paper establishes the nanoscale poling mechanism operating in A-site disordered lead-free piezoelectric ceramics. Nanoscale domain maps and quantitative structural changes were obtained by deploying high-resolution transmission electron microscopy, dielectric spectroscopy, Raman spectroscopy and neutron scattering. Based on these results a microscopic model is proposed that provides insight into the E-field induced structural transformation. The stripe-like nanodomains in the unpoled system transformed into lamellar tetragonal domains with a reduced degree of displacement disorder during poling. It is proposed that the synergic effect of change in octahedral tilt disorder and cation displacement disorder leads to this transformation under an E-field. The criterion for achieving superior functional response includes stabilization of the long range order and reduction in the tilt disorder through compositional adjustments. Understanding of the poling mechanism in lead-free piezoelectric materials has been mostly limited to the behavior of domains under an applied field. However, this work provides an in-depth understanding of the changes in the local structure along with domain morphology under an applied field.

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.

Bivalence Mn5O8 with hydroxylated interphase for high-voltage aqueous sodium-ion storage

Aqueous electrochemical energy storage devices have attracted significant attention owing to their high safety, low cost and environmental friendliness. However, their applications have been limited by a narrow potential window (∼1.23 V), beyond which the hydrogen and oxygen evolution reactions occur. Here we report the formation of layered Mn5O8 pseudocapacitor electrode material with a well-ordered hydroxylated interphase. A symmetric full cell using such electrodes demonstrates a stable potential window of 3.0 V in an aqueous electrolyte, as well as high energy and power performance, nearly 100% coulombic efficiency and 85% energy efficiency after 25,000 charge–discharge cycles. The interplay between hydroxylated interphase on the surface and the unique bivalence structure of Mn5O8 suppresses the gas evolution reactions, offers a two-electron charge transfer via Mn2+/Mn4+ redox couple, and provides facile pathway for Na-ion transport via intra-/inter-layer defects of Mn5O8.

In-situ study of crystallization kinetics in ternary bulk metallic glass alloys with different glass forming abilities

In-situ transmission electron microcopy and time-resolved neutron diffraction were used to study crystallization kinetics of two ternary bulk metallic glasses during isothermal annealing in the supercooled liquid region. It is found that the crystallization of Zr56Cu36Al8, an average glass former, follows continuous nucleation and growth, while that of Zr46Cu46Al8, a better glass former, is characterized by site-saturated nucleation, followed by slow growth. Possible mechanisms for the observed differences and the relationship to the glass forming ability are discussed.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g−1 in half-cells at a scan rate of 5 mV s−1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g−1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.