Peter A. Crozier

Brown carbon spheres in East Asian outflow and their optical properties.

Atmospheric aerosols play a substantial role in climate change through radiative forcing. Combustion-produced carbonaceous particles are the main light-absorbing aerosols; thus, quantifying their optical properties is essential for determining the magnitude of direct forcing. By using the electron energy-loss spectrum in the transmission electron microscope, we quantified the optical properties of individual, submicrometer amorphous carbon spheres that are ubiquitous in East Asian–Pacific outflow. The data indicate that these common spheres are brown, not black, with a mean refractive index of 1.67 – 0.27i (where i = \batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(\sqrt{1}\) \end{document}) at a wavelength of 550 nanometers. The results suggest that brown carbon aerosols should be explicitly included in radiative forcing models.

Vibrational spectroscopy in the electron microscope

Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample—that is, for ‘aloof’ spectroscopy that largely avoids radiation damage.

Stabilized Gold Nanoparticles on Ceria Nanorods by Strong Interfacial Anchoring

Au/CeO(2) catalysts are highly active for low-temperature CO oxidation and water-gas shift reaction, but they deactivate rapidly because of sintering of gold nanoparticles, linked to the collapse or restructuring of the gold-ceria interfacial perimeters. To date, a detailed atomic-level insight into the restructuring of the active gold-ceria interfaces is still lacking. Here, we report that gold particles of 2-4 nm size, strongly anchored onto rod-shaped CeO(2), are not only highly active but also distinctively stable under realistic reaction conditions. Environmental transmission electron microscopy analyses identified that the gold nanoparticles, in response to alternating oxidizing and reducing atmospheres, changed their shapes but did not sinter at temperatures up to 573 K. This finding offers a new strategy to stabilize gold nanoparticles on ceria by engineering the gold-ceria interfacial structure, which could be extended to other oxide-supported metal nanocatalysts.

SSZ-26 and SSZ-33: Two molecular sieves with intersecting 10- and 12-ring pores

The framework structures of two closely related molecular sieves, SSZ-26 and SSZ-33, are described. These materials possess a previously missing but desired structural feature in a group of industrially significant zeolites. They contain a three-dimensional pore system that provides access to the crystal interior through both 10- and 12-rings. This property is a consequence of the organic structure—directing agents used in the synthesis of these materials. These materials are examples of the purposeful design of a micropore architecture. Both SSZ-26 and SSZ-33 contain the 4=4–1 building unit that had been previously found only in natural zeolites.

Synthesis of ternary SiGeSn semiconductors on Si(100) via SnxGe1−x buffer layers

Single-phase Si1−x−yGexSny alloys with random diamond cubic structures are created on Si(100) via ultrahigh vacuum chemical vapor deposition reactions of SnD4 with SiH3GeH3 at 350 °C. Commensurate heteroepitaxy is facilitated by Ge1−xSnx buffer layers, which act as templates that can conform structurally and absorb the differential strain imposed by the more rigid Si and Si–Ge–Sn materials. The crystal structure, elemental distribution and morphological properties of the Si1−x−yGexSny/Ge1−xSnx heterostructures are characterized by high-resolution electron microscopy, including electron energy loss nanospectroscopy, x-ray diffraction (rocking curves) and atomic force microscopy. These techniques demonstrate growth of perfectly epitaxial, uniform and highly aligned layers with atomically smooth surfaces and monocrystalline structures that have lattice constants close to that of Ge. Rutherford backscattering ion channeling shows that the constituent elements occupy random substitutional sites in the same ave...

Oxygen vacancy migration in ceria and Pr-doped ceria: A DFT+U study

Oxygen vacancy formation and migration in ceria (CeO(2)) is central to its performance as an ionic conductor. It has been observed that ceria doped with suitable aliovalent cationic dopants improves its ionic conductivity. To investigate this phenomenon, we present total energy calculations within the framework of density functional theory to study oxygen vacancy migration in ceria and Pr-doped ceria (PDC). We report activation energies for oxygen vacancy formation and migration in undoped ceria and for different migration pathways in PDC. The activation energy value for oxygen vacancy migration in undoped ceria was found to be in reasonable agreement with the available experimental and theoretical results. Conductivity values for reduced undoped ceria calculated using theoretical activation energy and attempt frequency were found in reasonably good agreement with the experimental data. For PDC, oxygen vacancy formation and migration were investigated at first, second, and third nearest neighbor positions to a Pr ion. The second nearest neighbor site is found to be the most favorable vacancy formation site. Vacancy migration between first, second, and third nearest neighbors was calculated (nine possible jumps), with activation energies ranging from 0.41 to 0.78 eV for first-nearest-neighbor jumps. Overall, the presence of Pr significantly affects vacancy formation and migration, in a complex manner requiring the investigation of many different migration events. We propose a relationship illuminating the role of additional dopants toward lowering the activation energy for vacancy migration in PDC.

In situ environmental TEM studies of dynamic changes in cerium-based oxides nanoparticles during redox processes.

We apply in situ environmental transmission electron microscopy (ETEM) to study the dynamic changes taking place during redox reactions in ceria and ceria-zirconia nanoparticles in a hydrogen atmosphere. For pure ceria, we find that a reversible phase transformation takes place at 730 degrees C in which oxygen vacancies introduced during reduction order to give a cubic superstructure with a periodicity of roughly twice the basic fluorite lattice. We also observe the structural transformations taking place on the surface during reduction in hydrogen. The (110) ceria surface is initially constructed with a series of low-energy (111) nanofacets. Under strong reduction, the surface slowly transforms to a smooth (110) surface which was not observed to change upon re-oxidation. The surface transformation allows the reduced surface to accommodate a high concentration of oxygen vacancies without creating a strong perpendicular dipole moment. In the ceria-zirconia system, we are able to use ETEM to follow the redox activity of individual nanoparticles and correlate this property with structure and composition. We find considerable variation in the redox activity and interpret this in terms of structural differences between the nanoparticles.

Atomic-Scale Observations of Catalyst Structures under Reaction Conditions and during Catalysis

Heterogeneous catalysis is a chemical process performed at a solid-gas or solid-liquid interface. Direct participation of catalyst atoms in this chemical process determines the significance of the surface structure of a catalyst in a fundamental understanding of such a chemical process at a molecular level. High-pressure scanning tunneling microscopy (HP-STM) and environmental transmission electron microscopy (ETEM) have been used to observe catalyst structure in the last few decades. In this review, instrumentation for the two in situ/operando techniques and scientific findings on catalyst structures under reaction conditions and during catalysis are discussed with the following objectives: (1) to present the fundamental aspects of in situ/operando studies of catalysts; (2) to interpret the observed restructurings of catalyst and evolution of catalyst structures; (3) to explore how HP-STM and ETEM can be synergistically used to reveal structural details under reaction conditions and during catalysis; and (4) to discuss the future challenges and prospects of atomic-scale observation of catalysts in understanding of heterogeneous catalysis. This Review focuses on the development of HP-STM and ETEM, the in situ/operando characterizations of catalyst structures with them, and the integration of the two structural analytical techniques for fundamentally understanding catalysis.

Beam-Induced Damage to Thin Specimens in an Intense Electron Probe

We have investigated the changes produced in single-element and two-layer transmission electron microscope (TEM) specimens irradiated by an intense nanometer-sized electron probe, such as that produced in a field-emission or aberration-corrected TEM. These changes include hole formation and the accumulation of material within the irradiated area. The results are discussed in terms of mechanisms, including electron-beam sputtering and surface diffusion. Strategies for minimizing the effect of the beam are considered.

Dealloying of Noble-Metal Alloy Nanoparticles

Dealloying is currently used to tailor the morphology and composition of nanoparticles and bulk solids for a variety of applications including catalysis, energy storage, sensing, actuation, supercapacitors, and radiation damage resistant materials. The known morphologies, which evolve on dealloying of nanoparticles, include core-shell, hollow core-shell, and porous nanoparticles. Here we present results examining the fixed voltage dealloying of AgAu alloy particles in the size range of 2-6 and 20-55 nm. High-angle annular dark-field scanning transmission electron microcopy, energy dispersive, and electron energy loss spectroscopy are used to characterize the size, morphology, and composition of the dealloyed nanoparticles. Our results demonstrate that above the potential corresponding to Ag(+)/Ag equilibrium only core-shell structures evolve in the 2-6 nm diameter particles. Dealloying of the 20-55 nm particles results and in the formation of porous structures analogous to the behavior observed for the corresponding bulk alloy. A statistical analysis that includes the composition and particle size distributions characterizing the larger particles demonstrates that the formation of porous nanoparticles occurs at a well-defined thermodynamic critical potential.