As formulações de eletrocatalisadores Pt:(Ce0,9Y0,1O2)+Pt/C Etek, Pt:(Ce0,9Ru0,1O2)+Pt/C Etek, Pt:Ce0,9Y0,1O2/C e Pt:Ce0,9Ru0,1O2+RuO2/C foram preparados pelo método da redução por álcool e caracterizados por difração de raios X (DRX) e microscopia eletrônica de transmissão (MET). A tolerância ao CO foi estudada utilizando o stripping de CO e medidas de curvas de polarização em células unitárias alimentadas com misturas de H2/CO no ânodo e oxigênio no cátodo, na temperatura de 80ºC e pressão absoluta de 2 bar para ânodo e cátodo. Os testes em células a combustível tipo PEMFC mostraram que a oxidação do CO adsorvido a CO2 na superfície da platina ocorre em potenciais menos positivos quando comparado com o catalisador comercial, Pt/C Etek, mostrando tolerância ao CO adsorvido nos eletrocatalisadores de Pt:Ce0,9Y0,1O2/C e Pt:(Ce0,9Ru0,1O2+RuO2)/C. / Pt:(Ce0,9Y0,1O2)+Pt/C Etek, Pt:(Ce0,9Ru0,1O2)+Pt/C Etek, Pt:Ce0,9Y0,1O2/C e Pt:Ce0,9Ru0,1O2+RuO2/C electrocatalysts, were prepared by an alcohol reduction process. The electrocatalysts were characterized by X-Ray Difratometry (XRD) end Transmission Electronic Microscopy (TEM). the CO tolerance was studied using CO stripping and measurements of polarization curves single-cell fed with H2/CO mixture at the anode and oxygen at the cathode, at a temperature of 85ºC and absolute pressure of 2 bar for anode and cathode. The results showed that the oxidation of CO adsorbed to CO2 on the surface of platinum occur at less positive potentials compared to Pt/C Etek showing the tolerance to CO adsorbed on these Pt:Ce0,9Y0,1O2/C e Pt:(Ce0,9Ru0,1O2+RuO2)/C electrocatalysts.

As formulações de eletrocatalisadores Pt:(Ce0,9Y0,1O2)+Pt/C Etek, Pt:(Ce0,9Ru0,1O2)+Pt/C Etek, Pt:Ce0,9Y0,1O2/C e Pt:Ce0,9Ru0,1O2+RuO2/C foram preparados pelo método da redução por álcool e caracterizados por difração de raios X (DRX) e microscopia eletrônica de transmissão (MET). A tolerância ao CO foi estudada utilizando o stripping de CO e medidas de curvas de polarização em células unitárias alimentadas com misturas de H2/CO no ânodo e oxigênio no cátodo, na temperatura de 80ºC e pressão absoluta de 2 bar para ânodo e cátodo. Os testes em células a combustível tipo PEMFC mostraram que a oxidação do CO adsorvido a CO2 na superfície da platina ocorre em potenciais menos positivos quando comparado com o catalisador comercial, Pt/C Etek, mostrando tolerância ao CO adsorvido nos eletrocatalisadores de Pt:Ce0,9Y0,1O2/C e Pt:(Ce0,9Ru0,1O2+RuO2)/C. / Pt:(Ce0,9Y0,1O2)+Pt/C Etek, Pt:(Ce0,9Ru0,1O2)+Pt/C Etek, Pt:Ce0,9Y0,1O2/C e Pt:Ce0,9Ru0,1O2+RuO2/C electrocatalysts, were prepared by an alcohol reduction process. The electrocatalysts were characterized by X-Ray Difratometry (XRD) end Transmission Electronic Microscopy (TEM). the CO tolerance was studied using CO stripping and measurements of polarization curves single-cell fed with H2/CO mixture at the anode and oxygen at the cathode, at a temperature of 85ºC and absolute pressure of 2 bar for anode and cathode. The results showed that the oxidation of CO adsorbed to CO2 on the surface of platinum occur at less positive potentials compared to Pt/C Etek showing the tolerance to CO adsorbed on these Pt:Ce0,9Y0,1O2/C e Pt:(Ce0,9Ru0,1O2+RuO2)/C electrocatalysts.

En m'appuyant sur des mesures atmosphériques et à l'aide de la modélisation, je propose une nouvelle estimation du bilan du dihydrogène troposphérique (H2). Pendant mon stage de master, j'ai installé un chromatographe en phase gazeuse pour analyser les concentrations de H2 et CO sur les échantillons du réseau RAMCES. L'analyse des mesures in-situ à Gif-sur-Yvette permet d'estimer le dépôt de H2 dans le sol de cette région (0.027 cm s−1) et le ratio H2/CO (0.5) provenant des émissions dues au transport automobile. La haute tour de Trainou située près de la forêt d'Orléans (100 km au sud-ouest de Paris) a été instrumentée en octobre 2008 pour H2 et CO à trois hauteurs de prélèvement (50, 100 et 180 m), en mai 2009 pour 222Rn à 180 m et en avril 2010 pour 222Rn à 50 m. Avec trois hauteurs de prélèvement, les masses d'air locales à régionales sont échantillonnées. L'infl uence du traffi c n'est pas visible mais pendant l'hiver on observe des évènements pendant lesquels les concentrations de H2 et CO sont fortement corrélées. La vitesse moyenne de dépôt estimée avec la même méthode qu'à Gif-sur-Yvette atteint 0.026 cm s−1. Dans la partie modélisation, les mesures de la concentration de H2 au sein des réseaux RAMCES et EUROHYDROS ont été utilisées dans le système LMDz-SACS-PYVAR. Ce système permet d'optimiser l'estimation quantitative du bilan de H2 : le modèle de transport atmosphérique LMDz est couplé avec le système de chimie simpli fiée SACS et intégré dans le système d'inversion PYVAR. Plusieurs scénarios, impliquant la séparation progressive des sources et puits de H2 ont été testés pour optimiser les flux de H2 à l'échelle globale et européenne. La meilleure estimation du dépôt global de H2 atteint 59 ± 5 Tg an−1.

The use of carbon from fossil-based resources result in changes in the earth’s climate due to emissions of greenhouse gases. Biomass is the only renewable source of carbon that may be converted to transportation fuels and chemicals, markets now fully dominated by traditional oil supply. The biorefinery concept for upgrading and refinement of biomass feedstocks to value-added end-products has the potential to mitigate greenhouse gas emissions and replace fossil products. Most biorefineries use biochemical conversion processes and may have by-product streams suitable as feedstocks for thermal conversion and production of syngas. Further synthesis to value-added products from the syngas could increase the product output from the biorefinery. The application of thermal conversion processes integrated into an existing biorefinery concept has been evaluated in this licentiate thesis work. Two by-product streams; hydrolysis (lignin) residue from an ethanol plant and biogas from wastewater treatment, have been investigated as gasification/reforming feedstocks. Also, the pre-treatment method torrefaction has been evaluated for improved gasification fuel characteristics and integration aspects. A new process and system concept (Bio2Fuels) with potential carbon negative benefits has been suggested and evaluated as an alternative route for syngas production by separating biomass into a hydrogen rich gas and a carbon rich char product. The evaluation demonstrated that hydrolysis residue proved a suitable feedstock for gasification with respect to syngas composition. Biogas can be further reformed to syngas by combined biomass gasification and methane reforming, with promising results on CH4 conversion rate and increased H2/CO ratio at temperatures ≥1000°C. The pre-treatment method torrefaction was demonstrated to improve fuel qualities and may thus significantly facilitate entrained flow gasification of biomass residue streams. Also, integration of a torrefaction plant at a biorefinery site could make use of excess heat for drying the raw material before torrefaction. The Bio2Fuels concept was evaluated and found feasible for further studies. The application of thermal conversion processes into an existing biorefinery, making use of by-products and biomass residues as feedstocks, has significant potential for energy integration, increased product output as well as for climate change mitigation.