Revue de la littérature

Les notions de « revue de la littérature » (ou « revue de littérature » ou d’« analyse de la littérature ») désignent à la fois une méthode de recherche de documentation scientifique et une « catégorie » d’études scientifiques. Le produit de cette méthode de recherche est un souvent un article dit « article de synthèse » ou « article de revue » ou « article de revue de littérature » par les francophones (traduction de l'anglais Review article). Il existe des types d'article de revue plus spécifiques, contenant une importante part de revue de la littérature, tels que les revues systématiques, les examen de la portée ou les méta-analyses. Le premier objectif d’une revue de la littérature est de résumer l'état de l'art ou de la connaissance dans un domaine et pour une période ou un territoire. Précautions sémantiques

La notion de « revue de la littérature » ne doit pas être confondue avec celle de « revue par les pairs » ou « peer review », qui désigne généralement l'exam

Contributions to Likelihood-Based Modelling of Extreme Values

Léo Raymond-Belzile

xtreme value analysis is concerned with the modelling of extreme events such as floods and heatwaves, which can have large impacts. Statistical modelling can be useful to better assess risks even if, due to scarcity of measurements, there is inherently very large residual uncertainty in any analysis. Driven by the increase in environmental databases, spatial modelling of extremes has expanded rapidly in the last decade. This thesis presents contributions to such analysis. The first chapter is about likelihood-based inference in the univariate setting and investigates the use of bias-correction and higher-order asymptotic methods for extremes, highlighting through examples and illustrations the unique challenge posed by data scarcity. We focus on parametric modelling of extreme values, which relies on limiting distributional results and for which, as a result, uncertainty quantification is complicated. We find that, in certain cases, small-sample asymptotic methods can give improved inference by reducing the error rate of confidence intervals. Two data illustrations, linked to assessment of the frequency of extreme rainfall episodes in Venezuela and the analysis of survival of supercentenarians, illustrate the methods developed. In the second chapter, we review the major methods for the analysis of spatial extremes models. We highlight the similarities and provide a thorough literature review along with novel simulation algorithms. The methods described therein are made available through a statistical software package. The last chapter focuses on estimation for a Bayesian hierarchical model derived from a multivariate generalized Pareto process. We review approaches for the estimation of censored components in models derived from (log)-elliptical distributions, paying particular attention to the estimation of a high-dimensional Gaussian distribution function via Monte Carlo methods. The impacts of model misspecification and of censoring are explored through extensive simulations and we conclude with a case study of rainfall extremes in Eastern Switzerland.

EPFL2019

Operando XAS insight in the redox dynamics of VOx species and reducible supports involved in oxidative dehydrogenation of alcohols

Anna Zabilska

Supported vanadia (VOx) belongs to some of the most versatile selective oxidation and reduction catalysts applied for many reactions in the chemical industry and pollution control. Among them, the oxidative dehydrogenation (ODH) of alcohols is particularly attractive since it is one of the main industrial methods of formaldehyde production and a possible route for the transformation of renewable bioethanol to value-added products, such as acetaldehyde and acetic acid. Despite many spectroscopic methods used to investigate the mechanism of this reaction, the details about the redox involvement of VOx species and promoting supports (CeO2 and TiO2) remain debated. In this study, we used an element-specific operando X-ray absorption spectroscopy (XAS) to probe the redox transformations of active sites in vanadia-titania and vanadia-ceria catalysts during ethanol and methanol ODH. By carefully designing the steady-state and transient operando XAS experiments and by applying advanced chemometric methods, we could discriminate specifically and often quantitatively, which role plays each redox couple during the alcohol ODH cycle and uncover hidden structure activity-relationships.Chapter 1 introduces the relevant literature and summarizes the goals and the scope of the thesis.In Chapter 2, we investigate the redox dynamics of active sites in a bilayered VOx/TiOx/SiO2 catalyst (an analog of a widely used VOx/TiO2 catalyst with comparable activity) during ODH of ethanol. Operando time-resolved V and Ti K-edge XAS coupled with a transient experimental strategy quantitatively showed that the formation of acetaldehyde over VOx/TiOx/SiO2 catalyst is kinetically coupled to the formation of a V4+ intermediate, while the formation of V3+ is delayed and its rate is 10-70 times lower. The only very weak redox activity of the Ti4+/Ti3+ couple was detected, which suggests that TiOx species promote the redox activity of VOx indirectly, either via the fast electron transport between VOx species or by changing the electronic structure of VOx species.In Chapter 3, we report on possible difficulties, which can occur during in situ XAS studies of supported vanadia (VOx) catalysts at synchrotron beamlines related to X-ray-induced photochemical reduction of vanadium. We rigorously tested this phenomenon and suggest approaches, which can help to identify and mitigate vanadium photoreduction interfering chemical speciation.In Chapter 4, we focused on the structure-activity relationships in VOx/CeO2 system. We prepared a series of VOx/CeO2 catalysts using high-surface-area CeO2 Using time-resolved operando quick XAS at V K- and Ce L3-edges, we demonstrated that during oxygen cut-off experiments vanadium and cerium change their oxidation states in concert with each other and with the production of acetaldehyde. It suggests that both reducible vanadium and cerium are parts of the same active sites. The maximum VOx/CeO2 activity per mass of catalyst observed at ca. 3 V/nm2 coincides with the maximal amount of cerium atoms, which reversibly change their oxidation state during oxygen cut-off experiments.In Chapter 5, we prove that the mechanistic findings described in Chapter 4 for ethanol ODH over VOx/CeO2 catalysts are also valid for methanol ODH. Moreover, we confirm that the VOx surface density is the main descriptor of the activity for VOx/CeO2 catalysts in alcohol ODH.

EPFL2022

Contributions to Likelihood-Based Modelling of Extreme Values

Léo Raymond-Belzile

EPFL2019

Operando XAS insight in the redox dynamics of VOx species and reducible supports involved in oxidative dehydrogenation of alcohols

Anna Zabilska

EPFL2022

Contributions to Likelihood-Based Modelling of Extreme Values

Operando XAS insight in the redox dynamics of VOx species and reducible supports involved in oxidative dehydrogenation of alcohols

Artificial Neural Networks for Power Systems - A Literature Survey

Contributions to Likelihood-Based Modelling of Extreme Values

Operando XAS insight in the redox dynamics of VOx species and reducible supports involved in oxidative dehydrogenation of alcohols

Artificial Neural Networks for Power Systems - A Literature Survey