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J. Scilipoti, M. Cismondi, and E. A. Brignole, Prediction of physical properties for molecular design of solvents, Fluid Phase Equilibria, vol.362, pp.74-80, 2014.

J. Li, L. Xia, and S. Xiang, A new method based on elements and chemical bonds for organic compounds critical properties estimation, Fluid Phase Equilibria, vol.417, pp.1-6, 2016.

L. Speyer, Elaboration de mousses de graphène par voie solvothermale et modification de leurs propriétés physicochimiques, 2016.

S. Rönsch, Review on methanation -From fundamentals to current projects, Fuel, vol.166, pp.276-296, 2016.

K. Ghaib, K. Nitz, and F. Ben-fares, Chemical Methanation of CO 2 : A, Review. ChemBioEng Rev, vol.3, pp.266-275, 2016.

V. Kaiser, E. Filippi, H. D. Léger, and P. Lesur, Calcul des réacteurs catalytiques -Synthèse d'ammoniac, vol.18, 1999.

L. Speyer, S. Fontana, S. Ploneis, and C. Hérold, Influence of the precursor alcohol on the adsorptive properties of graphene foams elaborated by a solvothermal-based process, Microporous Mesoporous Mater, vol.243, pp.254-262, 2017.

A. Rubo, R. Kellens, J. Reddy, N. Steier, and W. Hasenpusch, Alkali Metal Cyanides, Ullmann's Encyclopedia of Industrial Chemistry, 2006.

M. F. Ray and M. Rajchel, Method of cyanide salt production, 2003.

K. W. Greenlee, A. L. Henne, and W. C. Fernelius, Sodium Amide. in Inorganic Syntheses, pp.128-135, 1946.

E. Formentin and C. Schafer, Procédé de production d'acide cyanhydrique, 2011.

M. J. Sole and A. D. Yoffe, Decomposition of the inorganic cyanamides, Proc. R. Soc. Lond. Ser. Math. Phys. Sci, vol.277, pp.523-539, 1964.

M. S. Dresselhaus, A. Jorio, and R. Saito, Characterizing graphene, graphite, and carbon nanotubes by Raman spectroscopy, Annu. Rev. Condens. Matter Phys, vol.1, pp.89-108, 2010.

L. P. Wolters, Y. Ren, and F. M. Bickelhaupt, Understanding E2 versus SN2 Competition under Acidic and Basic Conditions, ChemistryOpen, vol.3, pp.29-36, 2014.

, Références bibliographiques du chapitre IV

L. Speyer, S. Fontana, S. Ploneis, and C. Hérold, Influence of the precursor alcohol on the adsorptive properties of graphene foams elaborated by a solvothermal-based process, Microporous Mesoporous Mater, vol.243, pp.254-262, 2017.

M. A. Lillo-rodenas, D. Cazorla-amoros, and A. Linares-solano, Understanding chemical reactions between carbons and NaOH and KOH An insight into the chemical activation mechanism, Carbon, vol.41, pp.267-275, 2003.

L. Speyer, Elaboration de mousses de graphène par voie solvothermale et modification de leurs propriétés physicochimiques, 2016.

E. Raymundo-piñero, KOH and NaOH activation mechanisms of multiwalled carbon nanotubes with different structural organisation, Carbon, vol.43, pp.786-795, 2005.

A. Eckmann, Probing the Nature of Defects in Graphene by Raman Spectroscopy, Nano Lett, vol.12, pp.3925-3930, 2012.

J. Schwan, S. Ulrich, V. Batori, H. Ehrhardt, and S. R. Silva, Raman spectroscopy on amorphous carbon films, J. Appl. Phys, vol.80, pp.440-447, 1996.

M. Thommes, Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report), Pure Appl. Chem, vol.87, pp.1051-1069, 2015.
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F. Addou, Metallization of carbon fiber reinforced polymers: Chemical kinetics, adhesion, and properties, Surf. Coat. Technol, vol.308, pp.62-69, 2016.
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S. Kaciulis, Spectroscopy of carbon: from diamond to nitride films: Spectroscopy of carbon: from diamond to nitride films, Surf. Interface Anal, vol.44, pp.1155-1161, 2012.

, Au vu des densités de puissance obtenues, il est toutefois probable que le matériau préparé sous une pression de 200 bar soit plus actif que celui préparé sous seulement 100 bar

, IV. Corrélations avec d'autres grandeurs physiques

, Seuls les échantillons N-Gr/CE-P750, N-Gr/CE-P800, N-Gr/CE-P850 et N-Gr/CE-P900 issus de la partie III.2.1 seront ici étudiés, ces matériaux ayant été complètement caractérisés précédemment. De plus, la comparaison de ces quatre échantillons permettra de tirer des conclusions moins ambigües, Il a été montré dans les paragraphes précédents que les performances catalytiques des matériaux élaborés variaient fortement avec leurs conditions de préparation

, IV.1. Corrélation avec les propriétés texturales

, Les densités de puissance maximales des échantillons N-Gr/CE-P750 -N-Gr/CE-P900 ont été tracées en fonction de leurs surfaces spécifiques (2D-NLDFT), mesurées par adsorption de N2

V. Figure, Evolution de la densité de puissance en fonction de la surface spécifique (2D-NLDFT) des échantillons

, Byambasuren et al. [9] ont montré que dans le cas de matériaux carbonés mésoporeux adjoints de 1,5 wt.% de fer, la surface spécifique et le diamètre des pores jouent un rôle sur le transfert de matière. Dans leur étude, tous les pores sont assez larges pour permettre un transfert de matière (entre 4,13 nm et 4,55 nm), mais les plus petits pores, possédant une surface spécifique plus grande

M. Boudellal, , 2012.

H. A. Gasteiger, S. S. Kocha, B. Sompalli, and F. T. Wagner, Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs, Appl. Catal. B Environ, vol.56, pp.9-35, 2005.

F. Barbir, PEM fuel cells: theory and practice, 2013.

Y. Xia, Carbone fonctionnalisé pour une meilleure performance des piles à combustible, 2014.

O. Antoine, Y. Bultel, and R. Durand, Oxygen reduction reaction kinetics and mechanism on platinum nanoparticles inside Nafion®, J. Electroanal. Chem, vol.499, pp.85-94, 2001.

F. Gloaguen, F. Andolfatto, R. Durand, and P. Ozil, Kinetic study of electrochemical reactions at catalyst-recast ionomer interfaces from thin active layer modelling, J. Appl. Electrochem, vol.24, pp.863-869, 1994.

P. Mani, R. Srivastava, and P. Strasser, Dealloyed Pt?Cu Core?Shell Nanoparticle Electrocatalysts for Use in PEM Fuel Cell Cathodes, J. Phys. Chem. C, vol.112, pp.2770-2778, 2008.

Y. Chatillon, Méthodes électrochimiques pour la caractérisation des piles à combustibles de type PEM en empilement, 2013.

U. Byambasuren, Y. Jeon, D. Altansukh, Y. Ji, and Y. Shul, The particle size effect of N-doped mesoporous carbons as oxygen reduction reaction catalysts for PEMFC, Korean J. Chem. Eng, vol.33, pp.1831-1836, 2016.

Y. Jiang, Significant Contribution of Intrinsic Carbon Defects to Oxygen Reduction Activity, ACS Catal, vol.5, pp.6707-6712, 2015.

, ont été obtenus avec une technique de préparation des assemblages membrane électrodes découlant de l'expérience encore modeste du LRGP en la matière. Ainsi, la préparation des assemblages constitue un point important d'optimisation sur plusieurs aspects : (i) amélioration du procédé de dépôt de l'encre afin de rendre la couche catalytique la plus homogène possible, (ii) optimisation de la quantité de solution de Nafion lors de la préparation de l'assemblage, (iii) conditions de température et de pression pour la réalisation des AME. De telles optimisations pourraient permettre une forte amélioration des performances

L. , électrons), nettement plus stable qu'au voisinage d'une surface de platine, et dont la réduction en eau -au prix de 2 autres électrons -peut être assez lente. La production de ce peroxyde soulève d'importants problèmes de dégradation de la membrane et du catalyseur de la pile : en vue d'un possible développement de notre catalyseur, il convient de vérifier, au moyen par exemple d'une électrode à disque tournant (RDE), ou mieux, d'une électrode à disque et anneau (RRDE), que la réduction du dioxygène implique 4 électrons et non 2. Une étude de la réduction d'oxygène dissous en milieu acide devrait être menée avec de telles électrodes. 1. Optimisation des pics principaux : pour la spectroscopie Raman, il s'agit généralement des bandes D, G et G'

, Les paramètres du(des) pic(s) principal(aux) sont conservés et ne sont pas modifiés lors de cette étape

, Optimisation des intensités et des largeurs de tous les pics en même temps, permettant un dernier ajustement. La position des pics n'est pas modifiée lors de cette étape

, Note : le paramètre ? n'est pas optimisé, il est choisi manuellement et reste le même pour toutes les déconvolutions provenant d'une technique de caractérisation

, Des exemples de tableaux utilisés pour la procédure de déconvolution sont présentés ci-après