Small metal nanoparticles that are also highly crystalline have the potential for showing enhanced catalytic activity. We describe the preparation of single nanocrystals of platinum that are 2 to 3 nanometers in diameter. These particles were generated and immobilized on spherical polyelectrolyte brushes consisting of a polystyrene core (diameter of approximately 100 nanometers) onto which long chains of a cationic polyelectrolyte were affixed. In a first step, a nanoalloy of gold and platinum (a solid solution) was generated within the layer of cationic polyelectrolyte chains. In a second step, the gold was slowly and selectively dissolved by cyanide ions in the presence of oxygen. Cryogenic transmission electron microscopy, wide-angle x-ray scattering, and high-resolution transmission electron microscopy showed that the resulting platinum nanoparticles are faceted single crystals that remain embedded in the polyelectrolyte-chain layer. The composite systems of the core particles and the platinum single nanocrystals exhibit an excellent colloidal stability, as well as high catalytic activity in hydrogenation reactions in the aqueous phase.

In vapor-liquid-solid (VLS) growth, the liquid phase plays a pivotal role in mediating mass transport from the vapor source to the growth front of a nanowire. Such transport often takes place through the liquid phase. However, we observed by in situ transmission electron microscopy a different behavior for self-catalytic VLS growth of sapphire nanowires. The growth occurs in a layer-by-layer fashion and is accomplished by interfacial diffusion of oxygen through the ordered liquid aluminum atoms. Oscillatory growth and dissolution reactions at the top rim of the nanowires occur and supply the oxygen required to grow a new (0006) sapphire layer. A periodic modulation of the VLS triple-junction configuration accompanies these oscillatory reactions.

Calcite, aragonite, and vaterite are the three anhydrous polymorphs of calcium carbonate, in order of decreasing thermodynamic stability. Although vaterite is not commonly found in geological settings, it is an important precursor in several carbonate-forming systems and can be found in biological settings. Because of difficulties in obtaining large, pure, single crystals, the crystal structure of vaterite has been elusive for almost a century. Using aberration-corrected high-resolution transmission electron microscopy, we found that vaterite is actually composed of at least two different crystallographic structures that coexist within a pseudo-single crystal. The major structure exhibits hexagonal symmetry; the minor structure, existing as nanodomains within the major matrix, is still unknown.

In contrast to synthetic materials, materials produced by organisms are formed in ambient conditions and with a limited selection of elements. Nevertheless, living organisms reveal elegant strategies for achieving specific functions, ranging from skeletal support to mastication, from sensors and defensive tools to optical function. Using state-of-the-art characterization techniques, we present a biostrategy for strengthening and toughening the otherwise brittle calcite optical lenses found in the brittlestar This intriguing process uses coherent nanoprecipitates to induce compressive stresses on the host matrix, functionally resembling the Guinier-Preston zones known in classical metallurgy. We believe that these calcitic nanoparticles, being rich in magnesium, segregate during or just after transformation from amorphous to crystalline phase, similarly to segregation behavior from a supersaturated quenched alloy.

The work reported herein is an important continuation of our recent experimental and computational studies on Li­[Ni x Co y Mn z ]­O2 (x + y + z = 1) cathode materials for Li-ion batteries, containing minor amounts of multivalent cationic dopants like Al3+, Zr4+, W6+, Mo6+. On the basis of DFT calculations for LiNi0.8Co0.1­Mn0.1O2, it was concluded that Mo6+ cations preferably substitute Ni cations in the layered structure due to the lowest substitution energy compared to Li, Co, and Mn. It was established that the electrochemical behavior of LiNi0.8Co0.1­Mn0.1O2 as a positive electrode material for Li-ion batteries can be substantially improved by doping with 1–3 mol % of Mo6+, in terms of lowering the irreversible capacity loss during the first cycle, increasing discharge capacity and rate capability, decreasing capacity fade upon prolonged cycling, and lowering the voltage hysteresis and charge-transfer resistance. The latter is attributed to the presence of additional conduction bands near the Fermi level of the doped materials, which facilitate Li-ions and electron transfer within the doped material. This is expressed by a lower charge-transfer resistance of Mo-doped electrodes as shown by impedance spectroscopy studies. We also discovered unique segregation phenomena, in which the surface concentration of the transition metals and dopant differs from that of the bulk. This near surface segregation of the Mo-dopant seems to have a stabilization effect on these cathode materials.

Since its inception, research of cavity quantum electrodynamics (CQED) 1,2 has greatly extended our understanding of light-matter interactions and our ability to utilize them. Thus far, all the work in this field has been focused on light interacting with bound electron systems -such as atoms, molecules, quantum dots, and quantum circuits. In contrast, markedly different physical phenomena and applications could be found in free-electron systems, the energy distribution of which is continuous and not discrete, implying tunable transitions and selection rules. In addition to their uses for electron microscopy 3,4 , the interaction of free electrons with light gives rise to important phenomena such as Cherenkov radiation, Compton scattering, and free-electron lasing 5,6 . Advances in the research of ultrafast electron-light interactions have also enabled the development of powerful tools for exploring femtosecond dynamics at the nanoscale 7,8 . However, thus far, no experiment has shown the integration of free electrons into the framework of CQED, because the fundamental electron-light interaction is limited in strength and lifetime. This limit explains why many phenomena have remained out of reach for experiments with free electrons. In this work, we developed the platform for studying CQED at the nanoscale with free electrons and demonstrated it by observing their coherent interaction with cavity photons for the first time. To demonstrate this concept, we directly measure the cavity photon lifetime via a free electron probe and show more than an order of magnitude enhancement in the electron-photon interaction strength. These capabilities may open new paths toward using free electrons as carriers of quantum information, even more so after strong coupling between free electrons and cavity photons will have been demonstrated.Efficient electron-cavity photon coupling could also allow new nonlinear phenomena of cavity opto-electro-mechanics and the ultrafast exploration of soft matter or other beam-sensitive materials using low electron current and low laser exposure.

Understanding the nature of solid-liquid interfaces is important for many processes of technological interest, such as solidification, liquid-phase epitaxial growth, wetting, liquid-phase joining, crystal growth, and lubrication. Recent studies have reported on indirect evidence of density fluctuations at solid-liquid interfaces on the basis of x-ray scattering methods that have been complemented by atomistic simulations. We provide evidence for ordering of liquid atoms adjacent to an interface with a crystal, based on real-time high-temperature observations of alumina-aluminum solid-liquid interfaces at the atomic-length scale. In addition, crystal growth of alumina into liquid aluminum, facilitated by interfacial transport of oxygen from the microscope column, was observed in situ with the use of high-resolution transmission electron microscopy.

▪ Abstract  Interfaces between solids and liquids are important for a range of materials processes, including soldering and brazing, liquid-phase sintering, crystal growth, and lubrication. There is a wealth of fundamental studies on solid-liquid interfaces in materials, primarily focused on thermodynamics (relative interface energies and segregation effects) from high-temperature wetting experiments, which is often applied to processing design. Less is known about the atomistic structure at solid-liquid interfaces, mainly because of the difficulty involved in obtaining such information experimentally. This work reviews both theoretical and experimental studies of atomistic configurations at solid-liquid interfaces, focusing on the issue of ordering in the liquid adjacent to crystalline solids.