Evolution of the active species of homogeneous Ru hydrodeoxygenation catalysts in ionic liquids.

This work establishes structure-property relationships in Ru-based catalytic systems for selective hydrodeoxygenation of ketones to alkenes by combining extensive catalytic testing, in situ X-ray absorption spectroscopy (XAS) under high pressures and temperatures and ex situ XAS structural characterization supported by density functional theory (DFT) calculations. Catalytic tests revealed the difference in hydrogenation selectivity for ketones (exemplified by acetone) or alkenes (exemplified by propene) upon changing the reaction conditions, more specifically in the presence of CO during a pretreatment step. XAS data demonstrated the evolution of the local ruthenium structure with different amounts of Cl/Br and CO ligands. In addition, in the absence of CO, the catalyst was reduced to Ru0, and this was associated with a significant decrease of the selectivity for ketone hydrogenation. For the Ru-bromide carbonyl complex, selectivity towards acetone hydrogenation over propene hydrogenation was explained on the basis of different relative energies of the first intermediate states of each reaction. These results give a complete understanding of the evolution of the Ru species, used for the catalytic valorization of biobased polyols to olefins in ionic liquids, identifying the undesired deactivation routes as well as possibilities for reactivation.

Revisiting the Extended X-ray Absorption Fine Structure Fitting Procedure through a Machine Learning-Based Approach.

A novel approach for the analysis of extended X-ray absorption fine structure (EXAFS) spectra is developed exploiting an inverse machine learning-based algorithm. Through this approach, it is possible to explore and account for, in a precise way, the nonlinear geometry dependence of the photoelectron backscattering phases and amplitudes of single and multiple scattering paths. In addition, the determined parameters are directly related to the 3D atomic structure, without the need to use complex parametrization as in the classical fitting approach. The applicability of the approach, its potential and the advantages over the classical fit were demonstrated by fitting the EXAFS data of two molecular systems, namely, the KAu (CN)2 and the [RuCl2(CO)3]2 complexes.

Inspection of deteriorating asbestos cement force mains with georadar technique.

Several breaks on asbestos cement force mains indicated a problem with these kind of force mains. An inspection technique that could give a good idea about the state of asbestos cement pipes was searched for. A georadar technique already existed to inspect drinking water mains and gravity sewers. The technique measures the wall thickness of cement containing materials and it can differentiate between 'healthy' and deteriorated material. The technique was applied on four wastewater force mains in Flanders. The results indicated a rapid deterioration of the asbestos cement. A deterioration mechanism called 'calcium leaching' was known from asbestos cement drinking water mains. Further it was known that H(2)S is produced in force mains and that it can attack concrete containing materials by mains of biogenic sulphuric acid attack. This research checked if both deterioration mechanisms cause the measured rapid deterioration of the asbestos cement force mains. Finally deterioration speeds and minimum required wall thickness were calculated. With the results the residual lifetimes of the force mains were calculated and these could be applied in an asset management program.