96 research outputs found
Operando chemical tomography of packed bed and membrane reactors for methane processing
Heterogeneous functional materials, like catalytic solids, batteries and fuel cells tend to usually possess complex structures where the 3D spatial distribution of the various components of these materials is rarely uniform. Such materials are known to change with time under operating conditions. In order to gain an insight into the structure-function relationships, it is essential to study them in situ with spatially-resolved techniques. The work presented in this thesis focuses on the development and application of synchrotron X-ray tomographic imaging methods to study various catalytic materials in real time and under real process conditions. The main X-ray tomographic imaging technique used in this study is X-ray diffraction computed tomography (XRD-CT) which couples powder diffraction with âpencilâ beam computed tomography. Chapters 3 and 4 of this thesis outline some of the technical achievements accomplished in this work. More specifically, Chapter 3 outlines the development of a new data processing strategy used to remove line or âstreakâ artefacts generated in reconstructed XRD-CT images due to the presence of large crystallites in the sample; a common problem in XRD-CT measurements. Chapter 4 introduces a new data collection strategy, termed interlaced XRD-CT, which allows, post experiment, choice between temporal and spatial resolution. This data collection strategy can in principle be applied to all pencil beam CT techniques. The results from the first multi-length scale chemical imaging experiments of an unpromoted and a La-promoted Mn-Na-W/SiO2 catalyst for the oxidative coupling of methane are presented in Chapter 5. The spatially-resolved chemical signals obtained from these operando experiments provided new chemical information that can lead to the rational design of improved OCM catalysts. In Chapter 6, the results from, the first ever reported, XRD-CT experiments of working catalytic membrane reactors are presented. It is shown that the pertinent changes in the physicochemical state of these integrated reactor systems can be spatially-resolved. The results from Rietveld analysis of a 5D diffraction imaging (>106 diffraction patterns) redox experiment of a Ni-Pd/CeO2-ZrO2/Al2O3 catalyst and the first XRD-CT study of this catalyst during partial oxidation of methane are presented in Chapter 7
Recent developments in X-ray diffraction/scattering computed tomography for materials science
X-ray diffraction/scattering computed tomography (XDS-CT) methods are a non-destructive class of chemical imaging techniques that have the capacity to provide reconstructions of sample cross-sections with spatially resolved chemical information. While X-ray diffraction CT (XRD-CT) is the most well-established method, recent advances in instrumentation and data reconstruction have seen greater use of related techniques like small angle X-ray scattering CT and pair distribution function CT. Additionally, the adoption of machine learning techniques for tomographic reconstruction and data analysis are fundamentally disrupting how XDS-CT data is processed. The following narrative review highlights recent developments and applications of XDS-CT with a focus on studies in the last five years. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'
Removing multiple outliers and single-crystal artefacts from X-ray diffraction computed tomography data
This paper reports a simple but effective filtering approach to deal with single-crystal artefacts in X-ray diffraction computed tomography (XRD-CT). In XRD-CT, large crystallites can produce spots on top of the powder diffraction rings, which, after azimuthal integration and tomographic reconstruction, lead to line/streak artefacts in the tomograms. In the simple approach presented here, the polar transform is taken of collected two-dimensional diffraction patterns followed by directional median/mean filtering prior to integration. Reconstruction of one-dimensional diffraction projection data sets treated in such a way leads to a very significant improvement in reconstructed image quality for systems that exhibit powder spottiness arising from large crystallites. This approach is not computationally heavy which is an important consideration with big data sets such as is the case with XRD-CT. The method should have application to two-dimensional X-ray diffraction data in general where such spottiness arises
Recent developments in X-ray diffraction/scattering computed tomography for materials science
X-ray diffraction/scattering computed tomography (XDS-CT) methods are a non-destructive class of chemical imaging techniques that have the capacity to provide reconstructions of sample cross-sections with spatially resolved chemical information. While X-ray diffraction CT (XRD-CT) is the most well-established method, recent advances in instrumentation and data reconstruction have seen greater use of related techniques like small angle X-ray scattering CT and pair distribution function CT. Additionally, the adoption of machine learning techniques for tomographic reconstruction and data analysis are fundamentally disrupting how XDS-CT data is processed. The following narrative review highlights recent developments and applications of XDS-CT with a focus on studies in the last five years. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'
Interlaced X-ray diffraction computed tomography
An X-ray diffraction computed tomography data-collection strategy that allows, post experiment, a choice between temporal and spatial resolution is reported. This strategy enables time-resolved studies on comparatively short timescales, or alternatively allows for improved spatial resolution if the system under study, or components within it, appear to be unchanging. The application of the method for studying an MnâNaâW/SiO2 fixed-bed reactor in situ is demonstrated. Additionally, the opportunities to improve the data-collection strategy further, enabling post-collection tuning between statistical, temporal and spatial resolutions, are discussed. In principle, the interlaced scanning approach can also be applied to other pencil-beam tomographic techniques, like X-ray fluorescence computed tomography, X-ray absorption fine structure computed tomography, pair distribution function computed tomography and tomographic scanning transmission X-ray microscopy
An application of Systems Science in the context of Greek Environmental Education for planning interventions against volcanic hazards
Schools (amid in secondary and primary education) are installations vulnerable to all kinds of hazards. Because within the last 70 years, at least, there has not been any experience of volcanic activity in Greece, this kind of hazard is not extensively referred to, by official plans, local communities as well as teachers and pupils. In this paper and by using the systemic methodology of Systems Inquiry, the authors make an exploratory analysis of school-units located at the relatively short distances of 2 to 50 Km from volcanoes with registered âVolcanic Explosivity Indexâ (VEI) activity. Data regarding schools, adopted from the official database of the Greek government and Ministry of Education, have been utilized. The results indicate, regarding only the historically registered VEI activity and not the following consequences/phenomena (as for example, a tsunami), that vulnerable schools are located in Sousaki (East Corinth prefecture), Methana, Milos, Santorini, Nisyros and Kos Islands. The possible number of educational personnel, pupils and infrastructures is estimated. New approaches in the context of Greek environmental education are proposed for the presentation of these hazards in the educational personnel
Chemical imaging of Fischer-Tropsch catalysts under operating conditions
Although we often understand empirically what constitutes an active catalyst, there is still much to be understood fundamentally about how catalytic performance is influenced by formulation. Catalysts are often designed to have a microstructure and nanostructure that can influence performance but that is rarely considered when correlating structure with function. Fischer-Tropsch synthesis (FTS) is a well-known and potentially sustainable technology for converting synthetic natural gas (âsyngasâ: CO + H2) into functional hydrocarbons, such as sulfur- and aromatic-free fuel and high-value wax products. FTS catalysts typically contain Co or Fe nanoparticles, which are often optimized in terms of size/composition for a particular catalytic performance. We use a novel, âmultimodalâ tomographic approach to studying active Co-based catalysts under operando conditions, revealing how a simple parameter, such as the order of addition of metal precursors and promoters, affects the spatial distribution of the elements as well as their physicochemical properties, that is, crystalline phase and crystallite size during catalyst activation and operation. We show in particular how the order of addition affects the crystallinity of the TiO2 anatase phase, which in turn leads to the formation of highly intergrown cubic close-packed/hexagonal close-packed Co nanoparticles that are very reactive, exhibiting high CO conversion. This work highlights the importance of operando microtomography to understand the evolution of chemical species and their spatial distribution before any concrete understanding of impact on catalytic performance can be realized
X-ray physico-chemical imaging during activation of cobalt-based Fischer-Tropsch synthesis catalysts
The imaging of catalysts and other functional materials under reaction conditions has advanced significantly in recent years. The combination of the computed tomography (CT) approach with methods such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) now enables local chemical and physical state information to be extracted from within the interiors of intact materials which are, by accident or design, inhomogeneous. In this work, we follow the phase evolution during the initial reduction step(s) to form Co metal, for Co-containing particles employed as FischerâTropsch synthesis (FTS) catalysts; firstly, working at small length scales (approx. micrometre spatial resolution), a combination of sample size and density allows for transmission of comparatively low energy signals enabling the recording of âmultimodalâ tomography, i.e. simultaneous XRFâCT, XANESâCT and XRDâCT. Subsequently, we show high-energy XRDâCT can be employed to reveal extent of reduction and uniformity of crystallite size on millimetre-sized TiO2 trilobes. In both studies, the CoO phase is seen to persist or else evolve under particular operating conditions and we speculate as to why this is observed
In situ X-ray Diffraction Computed Tomography studies examining the thermal and chemical stabilities of working Ba0.5Sr0.5Co0.8Fe0.2O3-δ membranes during oxidative coupling of methane
In this study we present the results from two in situ X-ray diffraction computed tomography experiments of catalytic membrane reactors (CMRs) using Ba0.5Sr0.5Co0.8Fe0.2O3âδ (BSCF) hollow fibre membranes and Na-Mn-W/SiO2 catalyst during the oxidative coupling of methane (OCM) reaction. The negative impact of CO2, when added to the inlet gas stream, is seen to be mainly related to the C2+ yield, while no evidence of carbonate phase(s) formation is found during the OCM experiments. The main degradation mechanism of the CMR is suggested to be primarily associated with the solid-state evolution of the BSCF phase rather than the presence of CO2. Specifically, in situ XRD-CT and post-mortem SEM/EDX measurements revealed a collapse of the cubic BSCF phase, formation of secondary phases, which include needle-like structures and hexagonal Ba6Co4O12, and formation of a BaWO4 layer, the latter being a result of chemical interaction between the membrane and catalyst materials at high temperatures
Planning Educational Activities for Learning âRoad Safetyâ
In this paper, a project of the local sustainability network of schools in the area of Western Attica (Greece) is described. The subject of this project is âRoad Safetyâ, and it was addressed to third grade pupils of junior high-schools. It has been planned as the result of collaboration between the local Secondary Education Directorate, a few voluntary organizations, some private Vehicle Technical Inspection Centers and the local traffic-police department. This educational activity had been mainly implemented through the teaching and learning method of âexperiential learningâ. The pupils were divided into groups and attended six workshops that were designed accordingly. The entire process aims at establishing educational activities that in long-term will deal effectively with the acute problem of road safety
- âŚ