In situ oxidation and reduction of triangular nickel nanoplates via environmental transmission electron microscopy.

Understanding the oxidation and reduction mechanisms of transition metals, such as nickel (Ni), is important for their use in industrial applications of catalysis. A powerful technique for investigating the redox reactive species is in situ environmental transmission electron microscopy (ETEM), where oxidation and reduction can be tracked in real time. One particular difficulty in understanding the underlying reactions is understanding the underlying morphology of the starting structure in a reaction, in particular the defects contained in the material, and the exposed surface facets. Here-in, we use a colloidal nanoparticle synthesis in a continuous flow reactor to form nanoplates of nickel coated with oleylamine as a capping agent. We utilise an in situ heating procedure at 300 °C in vacuum to remove the oleylamine ligands, and then oxidise the Ni nanoparticles at 25 °C with 2 Pa oxygen, and follow the nanoparticles initial oxidation. After that, the nanoparticles are oxidised at 200 and 300 °C, making the size of the oxide shell increase to ∼4 nm. The oxide shell could be reduced under 2 Pa hydrogen at 500 °C to its initial size of ∼1 nm. High temperature oxidation encouraged the nanoparticles to form pure NiO nanoparticles, which occurred via the Kirkendall effect leading to hollowing and void formation.

Direct observations of dynamic PtCo interactions in fuel cell catalyst precursors at the atomic level using E(S)TEM.

Reduction reactions in practical bimetallic platinum-cobalt electrode catalyst precursors containing platinum, cobalt and cobalt oxides in hydrogen at 200, 450 and 700 °C for 6 h have been studied in situ using an aberration corrected environmental (scanning) transmission electron microscope (AC E(S)TEM). Little difference was observed in reduction at 200 °C but during and after reduction at 450 °C, small nanoparticles less than 3 nm in diameter with tetragonal PtCo structures were observed and limited Pt3 Co ordering could be seen on the surfaces of larger nanoparticles. During and after reduction at 700 °C, fully ordered Pt3 Co and PtCo nanoparticles larger than 4 nm were produced and the average nanoparticle size almost trebled relative to the fresh precursor. After reduction at 450 and 700 °C, most nanoparticles were disordered platinum/cobalt alloys with fcc structure. After reduction at 700 °C many of the smallest nanoparticles disappeared suggesting Ostwald ripening had occurred. Mechanisms concerning the thermal transformation of mixed cobalt and platinum species are discussed, offering new insights into the creation of bimetallic platinum-cobalt nanoparticles in fuel cell catalysts.

Structural elucidation of microporous and mesoporous catalysts and molecular sieves by high-resolution electron microscopy.

Twenty years ago, one of us embarked (Bursill, L. A.; Lodge, E. A.; Thomas, J. M. Zeolitic structures as revealed by high-resolution electron microscopy. Nature 1980, 286, 111-113) on the study of zeolites (renowned for their electron-beam sensitivity) by high-resolution transmission electron microscopy (HRTEM). In the ensuing years, high-resolution imaging aided by optical diffractometry has yielded details of the open framework structures of a number of new aluminosilicate and aluminophosphate molecular sieves and catalysts. The nature of intergrowth and recurrently twinned structures, as well as new types of structural imperfection in hitherto uncharacterized materials, has also been elucidated. With continued improvements in instrumental development, encompassing higher accelerating voltages, better objective lenses and vacua, computational advances, and the arrival of slow-scan CCD detectors, electron crystallographic methods and HRTEM imaging now enable the ab initio three-dimensional structures of micro- and mesoporous solids, with their occluded structure-directing organic species, to be determined. High-resolution scanning transmission electron microscopy using subnanometric probes provides supplementary structural and ultramicro analytical information and electron spectroscopic imaging (at the attogram level). In its high-angle annular dark-field mode, it is capable of locating and determining the composition of individual nanoparticle catalysts (consisting of just a few atoms) supported on porous hosts.

Solid-state defect mechanism in vanadyl pyrophosphate catalysts: implications for selective oxidation.

High-resolution and in situ electron microscopy of vanadyl pyrophosphate catalysts reacted in alkane (n-butane) and other reducing environments have shown evidence for surface structure modifications accompanied by two sets of symmetry-related extended defects. Defect analysis reveals that the defects are formed by pure (glide) shear mechanism. The defect mechanism suggests the presence of basal (coplanar) anion vacancies, associated with Lewis acid centers, at oxygen sites linking corner-sharing phosphorus tetrahedra and vanadyl octahedra in the active plane. These in-plane defect sites may be key to the activation of the alkane, especially in the dehydrogenation.

Direct Observation and Analysis of CuO2 Shear Defects in La2-xSrxCuO4.

Direct observations of CuO(2) sheet defect structures in superconducting La(2-x)Sr(x)CuO(4), with x in the range 0.05 crystallographic directions, by a pure shear mechanism along the edge of the octahedral copper-oxygen units. The line defects are partial screw dislocations, with characteristic displacement vectors of the type <(a/2), 0, (c/6)>, bounding the stacking faults. The existence of this type of defect demonstrates that there is an oxygen deficiency within the CuO(2) layers. However, unlike the open ReO(3) type-related structures, the packing density of the K(2)NiF(4) structure necessarily requires that anion defects be accompanied by the loss of cations of the A type (lanthanum, strontium). Under identical synthesis conditions, no defects are observed in the parent compound La(2)CuO(4).

Submicrometer Superconducting YBa2Cu3O6+x Particles Made by a Low-Temperature Synthetic Route.

Evidence suggests that superconducting, orthorhombic YBa(2)Cu(3)O(6+x)+ (x greater, similar 0.5) is always produced by oxidation of the oxygen-deficient, tetragonal form (x less, similar 0.5) of this phase (commonly referred to as 123). A synthetic route whereby solution-derived, carbon-free precursors are decomposed at 650 degrees to 700 degrees C in inert atmosphere to yield tetragonal 123 is now available. Appropriate precursors include hydrated oxides derived from the hydrolysis of organometallic solutions and aqueous solution-derived hyponitrites. Subsequent oxidation of the tetragonal phase at 400 degrees C results in submicrometer particles of orthorhombic 123. Superconductivity (T(c) onset approximately 87 K) has been confirmed in these materials by both Meissner effect and specific-heat measurements.

Bulk Superconductivity up to 122 K in the Tl-Pb-Sr-Ca-Cu-O System.

New high-temperature superconductors based on oxides of thallium and copper, but not containing barium, have been prepared. A transition temperature (T(c)) of about 85 K is found for (Tl(0.5)Pb(0.5)) Sr(2)CaCu(2)O(7) whereas (Tl(0.5)Pb(0.5))Sr(2)Ca(2)Cu(3)O(9) has a T(c) of about 120 K. Both materials possess tetragonal symmetry with a = 3.80 A, c = 12.05 A for (Tl(0.5)Pb(0.5))Sr(2)CaCu(2)O(7), and a = 3.81 A, c = 15.23 A for (Tl(0.5)Pb(0.5))Sr(2)Ca(2)Cu(3)O(9). A structure refinement of the latter phase has been carried out with single-crystal x-ray diffraction data.