Propene and 1-Octene Hydroformylation with Silica-Supported, Ionic Liquid-Phase (SILP) Rh-Phosphine Catalysts in Continuous Fixed-Bed Mode

Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], on a silica support. The catalysts were active in continuous gas- and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h^-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.     

Creating geometrically robust designs for highly sensitive problems using topology optimization

Resonance and wave-propagation problems are known to be highly sensitive towards parameter variations. This paper discusses topology optimization formulations for creating designs that perform robustly under spatial variations for acoustic cavity problems. For several structural problems, robust topology optimization methods have already proven their worth. However, it is shown that direct application of such methods is not suitable for the acoustic problem under consideration. A new double filter approach is suggested which makes robust optimization for spatial variations possible. Its effect and limitations are discussed. In addition, a known explicit penalization approach is considered for comparison. For near-uniform spatial variations it is shown that highly robust designs can be obtained using the double filter approach. It is finally demonstrated that taking non-uniform variations into account further improves the robustness of the designs.     

Combining the triangle method with thermal inertia to estimate regional evapotranspiration — Applied to MSG-SEVIRI data in the Senegal River basin

Spatially distributed estimates of evaporative fraction and actual evapotranspiration are pursued using a simple remote sensing technique based on a remotely sensed vegetation index (NDVI) and diurnal changes in land surface temperature. The technique, known as the triangle method, is improved by utilizing the high temporal resolution of the geostationary MSG-SEVIRI sensor. With 15 min acquisition intervals, the MSG-SEVIRI data allow for a precise estimation of the morning rise in land surface temperature which is a strong proxy for total daytime sensible heat fluxes. Combining the diurnal change in surface temperature, dT_s with an interpretation of the triangular shaped dT_s − NDVI space allows for a direct estimation of evaporative fraction. The mean daytime energy available for evapotranspiration (R_n − G) is estimated using several remote sensors and limited ancillary data. Finally regional estimates of actual evapotranspiration are made by combining evaporative fraction and available energy estimates. The estimated evaporative fraction (EF) and actual evapotranspiration (ET) for the Senegal River basin have been validated against field observations for the rainy season 2005. The validation results showed low biases and RMSE and R² of 0.13 [−] and 0.63 for EF and RMSE of 41.45 W m^− 2 and R² of 0.66 for ET.     

Photocatalytic Valorization of Plastic Waste over Zinc Oxide Encapsulated in a Metal–Organic Framework

The conversion of waste plastic into high-value-added chemicals is regarded as a promising approach for relieving global plastic pollution and contributing to the circular economy. Herein, a partial calcination strategy is developed to fabricate a zinc oxide/UiO66-NH₂ (ZnO/UiO66-NH₂) heterojunction, in which ZnO is encapsulated in porous UiO66-NH₂ for the photocatalytic valorization of plastic. This strategy preserves the framework structure of UiO66-NH₂, thus enabling the formation of ZnO with ultra-small size distributed inside the skeleton. The synergistic effect of the obtained ZnO/UiO66-NH₂ heterojunction facilitates providing an efficient channel for carrier/mass transfer and guarantees structural stability. As a result, ZnO/UiO66-NH₂ exhibits high activity for converting polylactic acid (PLA) and polyvinyl chloride (PVC) into acetic acid, coupled with H₂ production. This work provides a feasible strategy for rationally designing heterojunction photocatalysts, as well as an insight into understanding the process of photocatalytic valorization of plastic.     

Utility of an image-based canopy reflectance modeling tool for remote estimation of LAI and leaf chlorophyll content at the field scale

This paper presents a physically-based approach for estimating critical variables describing land surface vegetation canopies, relying on remotely sensed data that can be acquired from operational satellite sensors. The REGularized canopy reFLECtance (REGFLEC) modeling tool couples leaf optics (PROSPECT), canopy reflectance (ACRM), and atmospheric radiative transfer (6SV1) model components, facilitating the direct use of at-sensor radiances in green, red and near-infrared wavelengths for the inverse retrieval of leaf chlorophyll content (C_ab) and total one-sided leaf area per unit ground area (LAI). The inversion of the canopy reflectance model is constrained by assuming limited variability of leaf structure, vegetation clumping, and leaf inclination angle within a given crop field and by exploiting the added radiometric information content of pixels belonging to the same field. A look-up-table with a suite of pre-computed spectral reflectance relationships, each a function of canopy characteristics, soil background effects and external conditions, is accessed for fast pixel-wise biophysical parameter retrievals. Using 1 m resolution aircraft and 10 m resolution SPOT-5 imagery, REGFLEC effectuated robust biophysical parameter retrievals for a corn field characterized by a wide range in leaf chlorophyll levels and intermixed green and senescent leaf material. Validation against in-situ observations yielded relative root-mean-square deviations (RMSD) on the order of 10% for the 1 m resolution LAI (RMSD = 0.25) and C_ab (RMSD = 4.4 μg cm^− 2) estimates, due in part to an efficient correction for background influences. LAI and C_ab retrieval accuracies at the SPOT 10 m resolution were characterized by relative RMSDs of 13% (0.3) and 17% (7.1 μg cm^− 2), respectively, and the overall intra-field pattern in LAI and C_ab was well established at this resolution. The developed method has utility in agricultural fields characterized by widely varying distributions of model variables and holds promise as a valuable operational tool for precision crop management. Work is currently in progress to extend REGFLEC to regional scales.     

A divide-and-conquer approach for analysing overlaid data structures

We present a static program analysis for overlaid data structures such that a node in the structure includes links for multiple data structures and these links are intended to be used at the same time. These overlaid data structures are frequently used in systems code, in order to impose multiple types of indexing structures over the same set of nodes. Our analysis implements two main ideas. The first is to run multiple sub-analyses that track information about non-overlaid data structures, such as lists. The second idea is to control the communication among the sub-analyses using ghost states and ghost instructions. The purpose of this control is to achieve a high level of efficiency by allowing only necessary information to be transferred among sub-analyses and at as few program points as possible. Our analysis has been successfully applied to prove the memory safety of the Linux deadline IO scheduler and AFS server.     

Point or pointless – quality of ground data

A method for measuring continuously the inherent optical properties of water together with the salinity and the temperature values was developed and tested at the Division of Geophysics, University of Helsinki. The flow‐through system operates from a moving boat and has been used to collect parameters for optical modelling, coastal zone and inland water studies and to track the path of the fresh water spreading into sea areas. The system was also used in Lake Vänern, Sweden, to calculate the radiance reflectance, R _r, and total back‐scattering efficiency, b _{b eff}, along a transect. An example from the Gulf of Finland is presented, which shows how the spectral behaviour of light changes when moving away from a fresh water source. Data collected from the River Kymijoki estuary showed that the details in a rapidly changing environment were strongly smoothed in a Moderate Resolution Imaging Spectroradiometer (MODIS) data image. The correlation for continuously measured scattering values and MODIS channel 1 data varied between 0.70 and 0.85, n?=?126. Flow‐through measurement datasets can be used to obtain representative sites for vertical profiles or calibration measurements.