Since its commercial introduction three-quarters of a century ago, fluid catalytic cracking has been one of the most important conversion processes in the petroleum industry. In this process, porous composites composed of zeolite and clay crack the heavy fractions in crude oil into transportation fuel and petrochemical feedstocks. Yet, over time the catalytic activity of these composite particles decreases. Here, we report on ptychographic tomography, diffraction, and fluorescence tomography, as well as electron microscopy measurements, which elucidate the structural changes that lead to catalyst deactivation. In combination, these measurements reveal zeolite amorphization and distinct structural changes on the particle exterior as the driving forces behind catalyst deactivation. Amorphization of zeolites, in particular, close to the particle exterior, results in a reduction of catalytic capacity. A concretion of the outermost particle layer into a dense amorphous silica–alumina shell further reduces the mass transport to the active sites within the composite.

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Accurate prediction of atmospheric boundary layer (ABL) flow and its interaction with urban surfaces is critical for understanding the transport of momentum and scalars within and above cities. This, in turn, is essential for predicting the local climate and pollutant dispersion patterns in urban areas. Large-eddy simulation (LES) explicitly resolves the large-scale turbulent eddy motions and, therefore, can potentially provide improved understanding and prediction of flows inside and above urban canopies. This study focuses on the validation and the use of a recently-developed LES framework to simulate a turbulent boundary layer flow through idealized urban canopies represented by uniform arrays of cubes. The LES framework is first validated with wind tunnel experimental data. Good agreement between the simulation results and the experimental data are found in the vertical and spanwise profiles of mean velocities and velocity standard deviations at different streamwise locations. Next, the model is used to simulate ABL flows over surface transitions from a flat homogeneous terrain to aligned and staggered arrays of cubes with height h. For both configurations, five different frontal area densities (λ f ), equal to 0.028, 0.063, 0.111, 0.174 and 0.250, are considered. Within the arrays, the flow is found to adjust quickly and shows similar structure of the wake of the cubes after the second row. Above the arrays, an internal boundary layer (IBL) is identified. No significant difference in the depth of the IBL among different cases is observed. The drag exerted by the cubes on the flow (D f ) and the drag coefficients of the cubes (C d ) are calculated explicitly using the LES results. For the downstream cubes, D f is found to increases with decreasing density for both configurations, and larger values of C d are found for the cubes of staggered arrays than those of the aligned arrays with the same λ f . At a downstream location where the flow immediately above the cube array is already adjusted to the surface, the spatially averaged velocity is found to have a logarithmic profile for all the cases. The values of the displacement height (d) are found to increase roughly from 0.65h to 0.9h as λ f increases from 0.028 to 0.25 for both configurations. For the aerodynamic roughness (z 0 ), a maximum value at λ f =0.11 is observed for both configurations. For all the cube densities tested, larger values of z 0 are obtained for the staggered arrays than for the aligned ones. The results of z 0 are discussed and compared with existing theoretical expressions proposed in the literature. The effective mixing length (l m ) within and above different cube arrays are also calculated using the LES results. A local maximum of l m within the canopy is found in all the cases, with values ranging from 0.2h to 0.4h. These patterns are different from those used in existing urban canopy models.

Three scenarios of large-eddy simulation (LES) were performed to examine the characteristic flow and pollutant dispersion in urban street canyons under neutral, unstable and stable thermal stratifications. Street canyons of unity aspect ratio with ground-heating or-cooling are considered. In the LESs of the thermal stabilities tested, a large primary recirculation is developed in the center core and the turbulence production is dominated at the roof level of the street canyon. The current LES results demonstrate that unstable stratification enhances the mean wind, turbulence and pollutant removal of street canyons. On the other hand, in stable stratification, which has been less investigated in the past, the ground-level mean wind and turbulence are substantially suppressed by the large temperature inversion. Whereas, the weakened recirculating wind in the street canyon results in a larger velocity gradient that increases the turbulence production at the roof level. It also slows down the turbulence being carried from the roof down to the lower street canyon. Therefore, a higher level of turbulent kinetic energy (TKE) is retained at the mid-level of the windward side in the stably stratified street canyon.

A large-eddy simulation (LES) model, using the one-equation subgrid-scale (SGS) parametrization, was developed to study the flow and pollutant transport in and above urban street canyons. Three identical two-dimensional (2D) street canyons of unity aspect ratio, each consisting of a ground-level area source of constant pollutant concentration, are evenly aligned in a cross-flow in the streamwise direction x. The flow falls into the skimming flow regime. A larger computational domain is adopted to accurately resolve the turbulence above roof level and its influence on the flow characteristics in the street canyons. The LES calculated statistics of wind and pollutant transports agree well with other field, laboratory and modelling results available in the literature. The maximum wind velocity standard deviations σ i in the streamwise (σ u ), spanwise (σ v ) and vertical (σ w ) directions are located near the roof-level windward corners. Moreover, a second σ w peak is found at z ≈ 1.5h (h is the building height) over the street canyons. Normalizing σ i by the local friction velocity u * , it is found that σ u /u * ≈ 1.8, σ v /u * ≈ 1.3 and σ w /u * ≈ 1.25 exhibiting rather uniform values in the urban roughness sublayer. Quadrant analysis of the vertical momentum flux u w shows that, while the inward and outward interactions are small, the sweeps and ejections dominate the momentum transport over the street canyons. In the x direction, the two-point correlations of velocity R v,x and R w,x drop to zero at a separation larger than h but R u,x (= 0.2) persists even at a separation of half the domain size. Partitioning the convective transfer coefficient T of pollutant into its removal and re-entry components, an increasing pollutant re-entrainment from 26.3 to 43.3% in the x direction is revealed, suggesting the impact of background pollutant on the air quality in street canyons.

We present a detailed investigation of the electrical properties of epitaxial La 0.7 Sr 0.3 MnO 3 / SrTi 0.98 Nb 0.02 O 3 Schottky junctions. A fabrication process that allows reduction of the junction dimensions to current electronic device size has been employed. A heavily doped semiconductor has been used as a substrate in order to suppress its series resistance. We show that, unlike standard semiconductors, high-quality oxide-based Schottky junctions maintain a highly rectifying behavior for doping concentration of the semiconductor larger than 10 20 cm −3 . Moreover, the junctions show hysteretic current-voltage characteristics.

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