Les travaux de cette thèse sont centrés sur le développement de systèmes moléculaires en solution homogène pour la production photocatalytique de dihydrogène dans l'eau utilisant des catalyseurs de cobalt à ligands pentadentate tétrapyridinique ou tétra- et pentaaza macrocycliques. Associés au photosensibilisateur et à l’ascorbate comme donneur d’électron sacrificiel, les complexes à ligands macrocycliques présentent d’excellentes performances pour la production d’H2, bien supérieures à celles des complexes à ligands polypyridiniques en termes d’efficacité et de stabilité, en raison de la grande stabilité de leur état réduit «Co(I)». Enfin, [Ru(bpy)3]2+ a pu être substitué par un colorant organique très robuste du type triazatriangulénium conduisant à un système photocatalytique encore plus performant. Ces résultats démontrent que les colorants organiques sont une alternative viable aux photosensibilisateurs à base de métaux nobles, même en milieu aqueux acide. / The work of this manuscript is focused on the design of molecular systems in homogeneous solution for photocatalytic production of molecular hydrogen in water using cobalt catalysts with pentadentate tetrapyridinic and tetra- and pentaza macrocyclic ligands. In association with [Ru(bpy)3]2+ as photosensitizer and sodium ascorbate as sacrificial electron donor, the macrocycle based catalysts display high performances for H2 production, far exceeding those of the polypyridine based catalysts, both in terms of activity and stability, because of the stability of their reduced state «Co(I)». Finally, [Ru(bpy)3]2+ was successfully substituted with a robust organic dye belonging to the triazatriangulenium family, leading to an even more efficient photocatalytic system. These results demonstrate well that organic dyes are a truly efficient alternative to noble metal based photosensitizers, even in acidic aqueous medium.

No description available.

This Thesis extends our fundamental knowledge of high-oxidation-state chemistry and in particular compounds of Xe(VIII), Xe(VI), and Ir(V). The crystal structure of XeVIIIO4 was obtained and provides important information on this fundamentally interesting endothermic and shock-sensitive compound. Macroscopic amounts of XeO3F2 have been prepared for the first time. Although the low-temperature Raman spectrum of solid XeO3F2 exhibits some frequency shifts and band splittings of the bending modes, the spectrum is similar to the Raman spectrum of the previously reported matrix-isolated compound. The crystal structures of decomposition and byproducts resulting from the syntheses of XeO3F2 have been obtained for [XeF5][HF2]∙XeOF4 and XeF2∙XeO2F2. The solid-state structure of xenon trioxide, XeO3, was reinvestigated by low-temperature single-crystal X-ray diffraction and shown to exhibit polymorphism that is dependent on crystallization conditions. The previously reported α-phase (orthorhombic, P212121) only forms upon evaporation of aqueous HF solutions of XeO3. In contrast, two new phases, β-XeO3 (rhombohedral, R3) and gamma-XeO3 (rhombohedral, R3c) have been obtained by slow evaporation of aqueous solutions of XeO3. The extended structures of all three phases result from Xe=O----Xe bridge interactions among XeO3 molecules that arise from the amphoteric donor-acceptor nature of XeO3. The Xe atom of the trigonal pyramidal XeO3-unit has three Xe---O secondary bonding interactions. The orthorhombic α-phase displays the greatest degree of variation among the contact distances and has a significantly higher density than the rhombohedral phases. The ambient-temperature Raman spectra of solid α- and gamma-XeO3 have also been obtained and assigned for the first time. Xenon trioxide interacts with CH3CN and CH3CH2CN to form O3XeNCCH3, O3Xe(NCCH3)2, O3XeNCCH2CH3, and O3Xe(NCCH2CH3)2. Their low-temperature single-crystal X-ray structures show that the xenon atoms are consistently coordinated to three electron-donor atoms which result in pseudo-octahedral environments around their xenon atoms. The adduct series provides the first examples of a neutral xenon oxide bound to nitrogen bases. Energy-minimized gas-phase geometries and vibrational frequencies were obtained for the model compounds O3Xe(NCCH3)n (n = 1−3) and O3Xe(NCCH3)n∙[O3Xe(NCCH3)2]2 (n = 1, 2). The natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses were carried out to further probe the nature of the bonding in these adducts. Xenon trioxide forms adducts with the polytopic nitrogen base ligands: hexamine, DABCO, 2,2’-bipyridine, 1,10-phenanthroline, and 4,4’-bipyridine. The adducts were conveniently synthesized in aqueous or CH3CN solutions and are stable at room temperature. The crystal structures of hexamine∙2XeO3, hexamine∙XeO3∙H2O, 2,2’-bipyridine∙XeO3, 1,10-phenanthroline∙XeO3, and 4,4’-bipyridine∙XeO3 have been determined by low-temperature single-crystal X-ray diffraction. The structures consist of XeO3 molecules bridged by the ligands to form extended supramolecular networks with Xe---N bonds which range from 2.634(3) to 2.829(2) Å. Raman spectroscopy was used to characterize and probe the room-temperature stabilities of these adducts. The reaction of 1,4-diazabicyclo[2.2.2]octane (DABCO) with XeO3 in aqueous solutions yields thin, plate-shaped crystals which are severely twinned whereas the reaction of DABCO with XeO3 in the presence of HF forms [DABCOH]2[F2(XeO3)2]∙H2O and [DABCOH2][F][H2F3] which were also characterized by low-temperature X-ray crystallography and Raman spectroscopy. A reversible temperature-dependent phase transition occurred for [DABCOH]2[F2(XeO3)2]∙H2O. The structures of 2,2’-bipy∙XeO3 and 1,10-phen∙XeO3 provide the first examples of noble-gas chelates. The structure of hexamine∙XeO3∙H2O provides the first instance in which a noble-gas centre is coordinated by water. These compounds also represent the first examples of sp2- and sp3-hybridized N---Xe(VI) bonds and are rare examples of noble-gas compounds that are air-stable at ambient temperatures. Adducts between XeO3 and three molar equivalents of the nitrogen bases, pyridine and 4-dimethylaminopyridine (4-DMAP), have been synthesized and characterized. The crystal structures of (C5H5N)3XeO3, {(CH3)2)2NC5H4N}3XeO3∙H2O have been determined by low-temperature single-crystal X-ray diffraction. The reaction of hydrolyzed XeF6 in acetonitrile with pyridine or 4-DMAP afforded [C5H5NH]4[HF2]2[F2(XeO3)2] and [(CH3)2NC5H4NH][HF2]∙XeO3 which were characterized by low-temperature X-ray crystallography and Raman spectroscopy. The structures contain pyridinium cations that are hydrogen bonded to the fluoride coordinated to XeO3 and can be viewed as pyridinium fluoroxenates. The structure of (CH3)2NC5H5N∙XeO3∙H2O contains a water molecule that is hydrogen bonded to two oxygen atoms of two adjacent XeO3 molecules. The pyridine adduct, (C5H5N)3XeO3, was found to be relatively insensitive to shock, whereas the 4-DMAP adduct was extremely shock sensitive. The number of isolable compounds which contain different noble-gas−element bonds is limited for xenon and even more so for krypton. Examples of Xe−Cl bonds are rare and prior to this work, no definitive evidence for a Xe−Br bonded compound existed. The syntheses, isolation, and characterization of the first compounds to contain Xe−Br bonds ([N(C2H5)4]3[Br3(XeO3)3] and [N(CH3)4]4[Br4(XeO3)4]) and their chlorine analogues are described. The bromo- and chloroxenate salts are stable in the atmosphere at room temperature and were characterized in the solid state by Raman spectroscopy, low-temperature single-crystal X-ray diffraction, and in the gas phase by quantum-chemical calculations. They are the only known examples of cage anions that contain a noble-gas element. The Xe−Br and Xe−Cl bonds are weakly covalent and can be viewed as σ-hole interactions, similar to halogen bonds. Xenon trioxide reacts with alkali metal fluorides and chlorides to form a variety of room-temperature stable fluoro- and chloroxenate salts. The reaction of XeO3 with various ratios of KF in water afforded three new compounds. The crystal structures of α-K[F(XeO3)2], β-K[F(XeO3)2], α-K[FXeO3], K2[F2(XeO3)] have been determined. The reaction of XeO3 with aqueous CsF resulted in Cs3[F3(XeO3)2]. The XeVI−F bond lengths range from 2.3520(18) to 2.5927(17) Å. No stable product was isolated when [N(CH3)4]F was the fluoride source, but in the presence of HF, crystals of [N(CH3)4]3[HF2]2[H2F3]∙2XeO3 were obtained. The reaction of KCl with XeO3 in equimolar amounts resulted in the formation of K[ClXeO3] whereas the analogous reaction with CsCl yielded Cs3[Cl3(XeO3)4]. Attempts to synthesize Xe–P and Xe–S bonded compounds were unsuccessful and instead resulted in adducts between XeO3 and O-bases such as the phosphine oxide adduct, {(C6H5)3PO}2XeO3 and dimethylsulfoxide (DMSO) adduct {(CH3)2SO}3(XeO3)2. Although DMSO was found to be resistant to oxidation by XeO3, no significant Xe---S bonding interactions were observed. Acetone was found to be highly resistant to oxidation by XeO3 and forms {(CH3)2CO}3XeO3 at low temperatures. The reaction of pyridine-N-oxide yielded large crystals of (C5H5NO)3(XeO3)2 in which the structure contains short chains in contrast with ((CH3)2SO)3(XeO3)2 whose structure consists of discrete dimers. The reaction of XeO3 with the oxidatively resistant main-group oxide anion source, [N(CH3)4][OTeF5] in CH3CN solvent afforded [N(CH3)4][F5TeOXeO3(CH3CN)2]. Xenon trioxide reacts with potassium hydroxide to form the previously known K4[XeO6]∙2XeO3 salt which was characterized by Raman spectroscopy and low-temperature X-ray crystallography. The reaction of MgO with XeO3 yielded single crystals of [Mg(OH2)6]4[XeO6(XeO3)12O2]∙12H2O, which also contains perxenate-XeO3 interactions. Alkali metal carbonates also incorporate XeO3 into their crystal lattices. Raman spectra of M2[CO3(XeO3)n]∙xH2O (M = Na, K, Rb) were recorded and contain intense bands assigned to the XeO3 stretching modes and very weak bands assigned to the [CO3]2− modes. The reaction of dilute aqueous solutions of XeO3 with RbOH and atmospheric CO2 afforded single crystals of Rb2[CO3(XeO3)2]∙2H2O which were characterized by low-temperature X-ray crystallography. Attempts to incorporate XeO3 into other polyatomic anion salts such as KMnO4, NaClO3, and NaNO3 were unsuccessful. The reaction of IrO2 with XeF6 in aHF provided [Xe2F11][IrF6], whereas the reaction of IrO2 with KrF2 with ClF3 in anhydrous HF solvent provided [ClO2][Ir2F11] and [ClO2][(μ-OIrF4)3]. The structure of [(μ-OIrF4)3]− consists of a six membered Ir3O3 ring with four terminal fluorine atoms on each Ir atom. It was also found that ClF3 forms an adduct with [Xe2F11][HF2] in which the structural parameters of ClF3 are very similar to that of solid ClF3. The [ClO2][Ir2F11] salt provides the first structural information on the [Ir2F11]− anion and the [(μ-OIrF4)3]− anion represents the first isolated iridium oxide fluoride species. / Thesis / Doctor of Philosophy (PhD) / Xenon is a noble-gas element which is located in the far right-hand column of the periodic table and was previously thought to be chemically unreactive and incapable of forming compounds. In 1962, it was shown that xenon reacts with the most reactive compounds, such as elemental fluorine, but the resulting xenon compounds are themselves highly reactive. This Thesis extends the chemistry of some of the most unstable and chemically reactive xenon compounds that are currently known. One such compound, xenon trioxide, tends to easily detonate unless carefully handled. Methods of stabilizing xenon trioxide were developed and its behaviour with compounds which resulted in formation of new xenon compounds was studied. The molecular structures of these compounds were investigated in the solid with particular emphases on their chemical bonding. Iridium is one of the most chemically resistant metals known. Highly reactive xenon and krypton compounds were used synthesize new iridium compounds.

[ES] En este trabajo estudiamos dos reacciones catalíticas relevantes para la industria y la localización del anión fluoruro en la zeolita RTH, sintetizada en medio fluoruro. El capítulo 3 es el primer capítulo de resultados, donde se estudia la reducción quimioselectiva del nitroestireno en las superficies Ni(111), Co(111), Cu(111) y Pd(111). El mecanismo generalmente aceptado de esta reacción está basado en el esquema propuesto por Haber en 1898, en el que la reacción puede transcurrir por dos rutas, la directa y la de condensación. En este capítulo exploramos ambas rutas, y observamos que la ruptura de los enlaces N-O y la consecuente formación de enlaces metal-O está más favorecida que la formación de enlaces N-H en las superficies Ni(111) y Co(111), debido al carácter oxofílico de ambos metales. Las etapas más lentas involucran la formación de enlaces N-H. En las superficies de metales nobles como Pt(111) y Pd(111) se observa el comportamiento contrario. La superficie Cu(111) es un caso intermedio comparado con los metales nobles y no nobles. Además, el nitroestireno interactúa con los átomos de Cu de la superficie solo a través de grupo nitro, con lo cual es un candidato ideal para alcanzar selectividades cerca del 100%. Sin embargo, la superficie Cu(111) no es capaz de activar la molécula de H2. En este sentido, proponemos un catalizador bimetálico basado en Cu, dopado con otro metal capaz de activar al H2, tales como el Pd o el Ni. En los capítulos 4 y 5 se ha estudiado la reducción catalítica selectiva de los óxidos de nitrógeno (SCR, en inglés) con amoníaco. Usando métodos de DFT, hemos encontrado rutas para la oxidación de NO a NO2, nitritos y nitratos con energías de activación relativamente bajas. También, hemos encontrado que la reducción de Cu2+ a Cu+ requiere la participación simultánea de NO y NH3. Posteriormente, hemos estudiado la influencia del NH3 en este sistema con métodos de dinámica molecular. El NH3 interacciona fuertemente con el Cu+ de forma que dos moléculas de este gas son suficientes para romper la coordinación del catión Cu+ con los oxígenos del anillo 6r, y formar el complejo lineal [Cu(NH3)2]+. Además, los cationes Cu2+ pueden ser estabilizados fuera de la red mediante la formación del complejo tetraamincobre(II). Debido a la presencia de los cationes Cu+ y Cu2+ coordinados a la red de la zeolita, aparecen bandas en la región entre 800-1000 cm-1 del espectro infrarrojo. El análisis de las frecuencias IR de varios modelos con Cu+ y Cu2+ coordinados al anillo 6r, o formando complejos con amoniaco indica que cuando los cationes Cu+ y Cu2+ están coordinados a los oxígenos del anillo 6r aparecen vibraciones entre 830 y 960 cm-1. Frecuencias en esta zona también se obtienen en los casos en que NO, NO2, O2 y combinaciones de dos de ellos están adsorbidos en Cu+ y Cu2+. Sin embargo, cuando los cationes Cu+ y Cu2+ están fuera del anillo (no hay enlaces entre los cationes de cobre y los oxígenos del anillo 6r) no se obtienen vibraciones de IR en esta región del espectro. Estos resultados indican que con el seguimiento del espectro IR durante la reacción SCR es posible determinar si los cationes Cu+ y Cu2+ están coordinados o no al anillo de 6r en las etapas de oxidación y reducción. Por último, hemos simulado el desplazamiento químico de 19F, δiso,, en la zeolita sintetizada RTH. El análisis del δiso de los distintos modelos utilizados nos ha permitido reconocer la simetría del material sintetizado, el cual pertenece al grupo espacial P1 y la nueva celda unidad ha sido confirmada experimentalmente por difracción de rayos X. Finalmente, hemos asignado la señal experimental que aparece en el espectro de 19F a -67.2_ppm, al F- localizado en un sitio T2, el cual es a su vez la posición más estable. Además, la señal a -71.8 ppm se ha asignado al anión F- localizado en un sitio T4. / [CA] En aquest treball estudiem dues reaccions catalítiques rellevants per a la indústria i la localització de l'anió fluorur en la zeolita RTH, sintetitzada al mig fluorur. El capítol 3 és el primer capítol de resultats, on s'estudia la reducció quimioselectiva del nitroestireno en les superfícies Ni(111), Co(111), Cu(111) i Pd(111). El mecanisme generalment acceptat d'aquesta reacció està basat en l'esquema proposat per Haver-hi en 1898, en el qual la reacció pot transcórrer per dues rutes, la directa i la de condensació. En aquest capítol explorem totes dues rutes, i observem que la ruptura dels enllaços N-O i la conseqüent formació d'enllaços metall-O està més afavorida que la formació d'enllaços N-H en les superfícies Ni(111) i Co(111), a causa del caràcter oxofílico de tots dos metalls. Les etapes més lentes involucren la formació d'enllaços N-H. En les superfícies de metalls nobles com Pt(111) i Pd(111) s'observa el comportament contrari. La superfície Cu(111) és un cas intermedi comparat amb els metalls nobles i no nobles. A més, el nitroestireno interactua amb els àtoms de Cu de la superfície sol a través de grup nitre, amb la qual cosa és un candidat ideal per a aconseguir selectivitats prop del 100%. No obstant això, la superfície Cu(111) no és capaç d'activar la molècula d'H2. En aquest sentit, proposem un catalitzador bimetàl·lic basat en Cu, dopat amb un altre metall capaç d'activar a l'H2, com ara el Pd o el Ni. En els capítols 4 i 5 hem estudiat la reducció catalítica selectiva dels òxids de nitrogen (SCR, en anglés) amb amoníac. Usant mètodes de DFT, hem trobat rutes per a l'oxidació de NO a NO2, nitrits i nitrats amb energies d'activació relativament baixes. També, hem trobat que la reducció de Cu2+ a Cu+ requereix la participació simultània de NO i NH3. Posteriorment, hem estudiat la influència del NH3 en aquest sistema amb mètodes de dinàmica molecular. El NH3 interacciona fortament amb el Cu+ de manera que dues molècules d'aquest gas són suficients per a trencar la coordinació del catió Cu+ amb els oxígens de l'anell 6r, i formar el complex lineal [Cu(NH3)2]+. A més, els cations Cu2+ poden ser estabilitzats fora de la xarxa mitjançant la formació del complex tetraamincobre(II). A causa de la presència dels cations Cu+ i Cu2+ coordinats a la xarxa de la zeolita, apareixen bandes a la regió entre 800-1000 cm-1 de l'espectre infraroig. L'anàlisi de les freqüències IR de diversos models amb Cu+ i Cu2+ coordinats a l'anell 6r, o formant complexos amb amoníac indica que quan els cations Cu+ i Cu2+ estan coordinats als oxígens de l'anell 6r apareixen vibracions entre 830 i 960 cm-1. Freqüències en aquesta zona també s'obtenen en els casos en què NO, NO2, O2 i combinacions de dues d'ells estan adsorbidos en Cu+ i Cu2+. No obstant això, quan els cations Cu+ i Cu2+ estan fora de l'anell (no hi ha enllaços entre els cations de coure i els oxígens de l'anell 6r) no s'obtenen vibracions d'IR en aquesta regió de l'espectre. Aquests resultats indiquen que amb el seguiment de l'espectre IR durant la reacció SCR és possible determinar si els cations Cu+ i Cu2+ estan coordinats o no a l'anell de 6r en les etapes d'oxidació i reducció. Finalment, hem simulat el desplaçament químic de 19F, δiso, en la zeolita sintetitzada RTH. L'anàlisi del δiso dels diferents models utilitzats ens ha permés reconéixer la simetria del material sintetitzat, el qual pertany al grup espacial P1 i la nova cel·la unitat ha sigut confirmada experimentalment per difracció de raigs X. Finalment, hem assignat el senyal experimental que apareix en l'espectre de 19F a -67.2 ppm, al F- localitzat en un lloc T2, el qual és al seu torn la posició més estable. A més, el senyal a -71.8 ppm s'ha assignat a l'anió F- localitzat en un lloc T4. / [EN] In this work, we have studied two heterogeneous catalytic reactions and the localization of the fluoride anion in the as-made RTH framework, synthesized in fluoride medium. The first results, included in chapter 3, correspond to the chemoselective reduction of nitrostyrene on different metal surfaces, i.e, Ni(111), Co(111), Cu(111) and Pd(111). Until very recently, the reduction of the nitro group was explained on the basis of the general mechanism proposed by Haber in 1898 where the reaction can follow two routes, the direct and condensation route. We have explored the relevant elementary steps of both routes and found that because of the oxophilic nature of Ni and Co, the steps involving the dissociation of N-O bonds and formation of metal-O bonds are significantly favored compared with the other steps on both metal surfaces. In addition, the most demanding steps in terms of energy involve the formation of N-H bonds. These findings are in contrast to those of noble metals such as Pt and Pd, where the opposite behavior is observed. The behavior of Cu(111) lies in between the aforementioned cases, and also no chemical bonds between the carbon atoms of the aromatic ring of nitrostyrene and the Cu(111) surface is formed. For this reason, it might be an ideal candidate to achieve nearly 100 % selectivity. However, the Cu(111) surface does not seem to activate the H2 molecule. In this regard, we propose a bimetallic Cu-based catalyst whose surface is doped with atoms of a H2-activating metal, such as Ni or Pd. On another matter, we have also investigated the selective catalytic reduction of nitrogen oxides (SCR-NOx) and the main results are presented in the following two chapters, 4 and 5. By using static DFT methods, we found pathways for the oxidation of NO to NO2, nitrites and nitrates with relatively low activation energies. We also found, in agreement with experimental reports, that the reduction of Cu2+ to Cu+ requires the simultaneous participation of NO and NH3. Later, molecular dynamics simulations allowed us to assess the influence of NH3. The strong interaction of NH3 with the Cu+ cation is evidenced by its ability to detach Cu+ from the zeolite framework and form the mobile linear complex [Cu(NH3)2]+. Cu+ is no longer coordinated to the zeolite framework in the presence of two NH3 molecules. This observation and the fact that the T-O-T vibrations of the framework produce bands in the 800-1000 cm-1 region of the IR spectrum when perturbed by the coordination of Cu+ and Cu2+ cations, indicate that bands in the 800-1000 cm-1 regions should be observed when both copper cations are bonded to the framework oxygens. Finally, we have also studied NMR properties of the as-made pure silica RTH framework, aiming at locating the compensating fluoride anion. The calculation of the 19F chemical shift in different T sites and comparison with the experimental NMR spectra shows that the as-made RTH belongs to the P-1 space group with 16 Si, 32 O atoms, one fluoride anion and one OSDA cation. These results have been confirmed experimentally by XRD. In addition, we have assigned the experimental signal of 19F at -67.2 ppm to the fluoride anion in a T2 site, which in turn is the most stable location found, and the signal of -71.8 ppm to a fluoride anion sitting in a T4 site. / My acknowledgements to “La Caixa foundation” for the financial support through “La Caixa−Severo Ochoa” International PhD Fellowships (call 2015), to the Spanish Supercomputing Network (RES), to the Centre de Càlcul de la Universitat de València, to the Flemish Supercomputer Center (VSC) of Ghent University for the computational resources and technical support, and to the Spanish Government through the MAT2017-82288-C2-1-P programme / Millan Cabrera, R. (2021). Computational study of heterogeneous catalytic systems. Kinetic and structural insights from Density Functional Theory [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/161934

Both Temple and Tomb is a dissertation in two parts. The first part is an examination and analysis of a collection of 'colonial' sculptures on permanent display in the Royal Museum of Central Africa in Tervuren Belgium. The second part is a reflection on the author's own paintings, drawings and film and an examination of the critical potential of these images in challenging the colonial narratives of the RMCA. Part I presents two arguments. The first is that European aesthetic codes have been used to legitimize the conquest of the Congo and to award sanction to a voyeuristic gaze. The second is that the organization of the sculptures of Africans (and European females) into carefully managed spaces and relationships results in the creation of erotically-charged formations that are intended to afford pleasure to male European spectators. Part II examines the strategies used in Re-Turning the Shadows to disrupt (neo)colonial patterns of viewing that have become ritual and 'naturalized'. Against RMCA narratives that pay homage to the objectivity of science and research, the paintings and film present images that explore multiple subjectivities, mythologizing impulses, and metaphoric allusions. / Art History, Visual Arts & Musicology / M.A. (Visual Arts)

「人觀」注重「人」與「社會」、「自然」與「自我」之間的互動關係，以及依據不同脈絡下，如何思考「人」的意義與定位，進以建構「社會人」、「自然人」或「自由人」命題，形成「人觀」的理論體系。當中特別凸顯「人」所具道德、藝術、宗教、文化的多向度事實，注重諸向度間的相互作用，抉發「人」於此關係迴環下呈現的「形象」蘊涵，依此可作為體現人物豐富生命義蘊的方法。 　　在儒家「人觀」視域下，「好學進德」的顏回形象，可視作「君子之學」典範，豁顯「仁」「禮」修身的「具體實踐」內涵。《莊子》則建構「心齋坐忘」的「體道」顏回形象，內容多與「至人」身心修養和主體轉化相關，故顏回實為深入莊子「人觀」的「思想符號」。漢代揚雄、王充依「用氣言性」態度，創構「氣化大賢」的顏回形象，由是發展出「潛心學聖未至」的說法，又用「未達一間」詮釋孔顏聖賢位階之分，甚至將顏回短命早亡視作「性善命凶」、「以才自殺」的必然結果。魏晉南朝綰合「玄理思辨」與「人物品鑒」，如講求天資、智愚、識量、言語的觀人識鑒情境，對照「本末」、「形神」、「言意」概念的玄學《論語》詮釋，反映出會通儒道、玄化孔顏的聖賢觀，故有「玄化顏回」的特殊形象面目。就「玄化顏回」現象的實踐面觀，如黃憲「顏子復生」或謝尚「年少一坐之顏回」稱譽，背後便以「淵粹玄遠」、「天才神悟」的顏回形象為品鑒依據。待及唐宋，退之、習之、伊川皆據《中庸》、《易傳》立義，闡發「體道學聖」的顏回形象命題和「聖學」理論。如濂溪將「顏回之學」提升至「體天明誠」的「證體」超越層次。「顏學」與「顏樂」互相包含，「聖學」踐履以「學顏回」、「求至樂」為目標。明道則匯流「識仁」與「觀氣象」命題，塑造「體之而樂，反身而誠」的顏回形象，發揚濂溪「尋顏樂」的體道美學與聖賢觀，「體道」即含「樂道」，更是「觀聖人氣象」和「觀天地生物氣象」前提，也是探討明道孔顏觀的關鍵線索。 　　要之，本文認為，顏回「好學進德」、「心齋坐忘」、「氣化」、「玄化」、「樂道」、「學聖」諸「形象」，彼此相互作用與轉化之際，組織成儒道「人觀」體系圖像的運行圓周，「形象」與「人觀」猶如珠網牽連相即的共生關係。依此脈絡，不管是如詩劇美趣的玄化顏回觀到向上超拔的理學「體天樂道」顏回觀，當中包含身體與社會間的關係互動，名教與自然間的調和抗爭，道德相與超道德相的工夫分際，都是學者試圖還原與建構顏回形象的珍貴線索。故本文所論，實與採取「類型化」或概念結構理解模式的顏回形象研究有別，望藉此對顏回於儒道思想、身體觀、工夫論及人物品鑒學具有的關鍵意義，提出不同的理解視域和詮釋路徑。 / The “idea of the person” is a concept that centers on the interrelationship between “man” and his interaction with “society” and “the self” and its relation to “nature”. Different philosophical thought systems have differing definitions of “man”`, and use their specific definition of “man” as a basis for the development of their unique concepts of “man in society” and “natural man” or “free man”. These concepts together construct the philosophical system for the “idea of the person”. These philosophical systems place a strong emphasis on the interaction between virtue, art, religion, culture and the multiple aspects of man’s existence. Through the interaction between these different aspects of life, thus emerges the significance of the classical “images” or paradigms that serve as a concrete example of how these concepts are used in life. In the Confucian “idea of the person” the “virtue through learning” portrayal of Yanhui conveys the Confucian paradigm of “learning to be a man of noble character” and through this it can be known that Yanhui in the Confucian tradition is portrayed as a concrete personification of the cultivation of the self through “ren” and “li”. In Zhuang zi ,Yanhui is portrayed as the model of Zhuang zi’s “purification of the mind” and having done so portrays Yanhui as an exemplar of the Zhuang zi’s”the perfect person”. Through this it can be known that Zhuang zi uses Yanhui as a symbol for the “idea of the person”, thus highlighting the fact that the image of Yanhui is deeply engrained in the symbolism contained in Zhuang zi, During the Han dynasty, Yang Xiong and Wang Chong’s thought incorporated “qi” and used “qi” in particular in describing “nature”. In light of this, thus developing the idea of using “qi” to describe the image of Yanhui, as being the paradigm for the man of virtue. They also gave commentary and description of the difference between the levels of Confucius and Yanhui, describing Yanhui as having a”partial actualization of sagelypotential” and being ”slightly lower than a sage”. Lastly viewing Yanhui’s early death as the eventual result of a man having a “good nature but bad fate” and his practice of “self sacrifice”. During the Han dynasty Yang Xiong and Wang Chong’s usage of “qi” in describing “nature” thus developing the idea of using “qi” to describe the image of Yanhui as the paradigm for the man of virtue. They also gave commentary and description of the difference between the levels of Confucius and Yanhui, describing Yanhui as having a”partial actualization of sagely potential” and being “slightly lower than a sage”. Lastly viewing Yanhui’s early death as the eventual result of a man having a “good nature but bad fate”and “self-sacrifice”. The WeiJin and Southern Dynasty philosophers combined “Speculative Mystical Philosophy”with the “Examination of the character of cultural Figures”. They used natural endowment, wisdom/ignorance, capacity to use one’s abilities and language to analyze a historical figure. Also using these idea in concert with ideas such as: “beginning/end”, “Form/Spirit” and “language/meaning” , which then formed the essential concepts used in Xuan Xue’s commentary on The Analects. In using Daoist concepts to comment on The Analects, they combined Confucian and Daoist thought and through this mergence, the images of Confucuis and became mystified and through this creating the “Mystical Yan Hui」portrayal of Yanhui. The practical aspect of the “Mystical Yan Hui” is portrayed in the praise given to Huang Hui and Xie Xiang. Huang Hui was praised as being “Yanhui Resurrected” and Xie Xiang was said to be a “young Yanhui”, using the “mystical” and “gifted student” Yanhui as the basus for the praise given to these two philosophers. During the Tang and Song dynasties the philosopher Yi Chuan used The Doctrine of the mean and Yi Zhuan to develop the philosophical treatise for the “Practice of Dao and learning to be a sage”, and in this treatise thus using the image of Yanhui to signify these concepts. He then used this treatise to develop the “Learning to be a sage” philosophical system. For example, Lian xi elevated the idea of “The learning of Yanhui” to “actualizing the way of heaven in the self”, giving the image of Yanhui a transcendental aspect which can be specifically seen in Yi Chuan ’s concept of the “actualizing the essence of all”. Thus in his philosophy he merged the ideas of the “learning of Yanhui” and the “contentment of Yanhui” and used them both in concert, making the “learning of Yanhui” and the “pursuit of contentment” the goals of one who seek to learn to be a sage. Ming Dao used the topics of “understanding ren” and “observation of the disposition of the sages ”, two ideas that in antiquity are associated with Yanhui, to construct his image of Yanhui. He portrays Yanhui as the paradigm of “using practice to find contentment, internalize this practice and actualizing virtue”. Thus developing Lian xi’s “pursuing the contentment possessed by Yanhui” and its aesthetic description of the practice of dao and the concept of the sage and the man of virtue. In his thought, the “learning of Yanhui” encompasses the “Dao of contentment” and serves as the basis for the “observation of the disposition of the sages” and “observing the qi of heaven, earth and all things” , which serves as the quintessence of Ming Dao's treatise on Confucius and Yanhui. “Virtue through learning”, “purification of the mind”, “qi approach” ,“mystical approach” , “dao of contentment”, “Learning to be a sage” are the major portrayals of Yanhui. Through the inter use and melding of these ideals they became the structure of the Confucian “idea of the person” , thus melding the relationship between “image” and the “idea of the person”. From the artistic and mystical Yanhui to the transcendental "actualization of heaven and contentment in Dao" Yanhui of the li xue philosophers and in between, all conceptions of Yanhui incorporate a few major themes: the body and its interaction with society, the harmonizing of the relationship between ethics and nature , the differentiation between the practice of virtue and transcendental virtue . These are all the attempts of philosophers to construct the importance of the image of Yanhui. Therefore this paper discusses the difference between the historical Yanhui and the conceptualized Yanhui portrayal in the hopes of offering a new research direction and a deeper understanding of Yanhui's role in Confucian and Daoist thought, philosophical treatises on the body, treatises on practice and the character analyses of ancient figures.

Afin de préciser l'origine des volatils terrestres et les flux actuels et passés vers l’atmosphère, de nombreuses études s’intéressent à la composition du manteau. Ce réservoir est échantillonné naturellement lors des éruptions volcaniques, mais une grande partie des gaz est alors émise dans l'atmosphère, de sorte que la composition des volatils du manteau reste peu contrainte. Nous cherchons à préciser les mécanismes de dégazage sous les dorsales océaniques afin de corriger ces fractionnements. L'analyse (He-Ne-Ar-CO2) de verres basaltiques issus de la dorsale des Galápagos, dans la zone d'influence du point chaud des Galápagos, montre que la composition en volatils des laves s'explique par distillation de Rayleigh d'une source unique. Cette source est distincte de celle du point chaud (isotopes du néon), impliquant un dégazage en profondeur du panache ou une hétérogénéité spatiale de sa composition.Plusieurs verres volcaniques issus de la dorsale Atlantique et Est Pacifique ont été imagés par micro-tomographie aux rayons X. L'étude met en évidence des mécanismes de nucléation et de croissance des bulles différents sous les deux dorsales. De la convection en périphérie de la chambre magmatique avant l’éruption a été mise en évidence par l’étude pétrologique des verres. Les vésicules imagées ont ensuite été ouvertes individuellement sous vide par ablation laser et analysées (CO2, 4He, isotopes de l'argon). La composition des bulles est hétérogène dans certains échantillons et compatible avec une distillation de Rayleigh. Les tendances de dégazage obtenues permettent d'obtenir localement la composition de la source mantellique, qui est hétérogène.L'étude permet également d'appréhender l'hétérogénéité des rapports 40Ar/36Ar dans les chambres magmatiques par la technique d’ablation laser qui diminue la contamination atmosphérique par rapport à la technique classique de broyage / The composition of mantle volatiles is related to the origin of Earth's volatiles and to the past and present volatile fluxes to the atmosphere. Although this reservoir is naturally sampled during volcanic eruptions, most of the volatiles are lost to the atmosphere during this event, thus the composition of mantle volatiles is still uncertain. We try here to precise the processes of degassing below mid-oceanic ridges to correct the lava compositions for degassing.The He-Ne-Ar-CO2 analyses of basaltic glasses sampled along the Galapagos Spreading Center, in the area of influence of the Galapagos hotspot, show that the volatile composition of lavas is fully explained by a Rayleigh distillation of a unique source distinct from the plume source. These results imply that the plume degasses at depth or is heterogeneous.Several volcanic glasses from Mid-Atlantic ridge and East Pacific Rise have been imaged by X-rays microtomography. The mechanisms of vesicle nucleation and growth appear to be different below the two ridges. A step of convection at the magma body margin has been evidenced by the petrologic study of the glasses. Imaged vesicles have been subsequently opened under vacuum by laser ablation and analysed (CO2, 4He, argon isotopes). We observe, depending on the samples, either a single composition for all bubbles, or variations in composition between bubbles consistent with a trend of equilibrium degassing in an open system. The trends of degassing allow extrapolating locally to the volatile composition of the mantle source, which is heterogeneous. We also studied the heterogeneity of 40Ar/36Ar ratios in magmatic chambers using the laser opening method, which lowers the contribution of atmospheric gases compared to the classical crushing method

This thesis is composed of two parts - research part, focused on field research of occurence and abundance of the Stone Crayfish and the Noble Crayfish in the basin of Zákolanský stream, and a pedagogical part, project Crayfish in the Czech Republic and their protection, aimed for grammar school students. The literature outline summarizes contemporary knowledge about all five species of crayfish in the Czech Republic. Our native species are the Stone Crayfish (Austropotamobius torrentium) and Noble Crayfish (Astacus astacus). The non-native are Narrow-clawed Crayfish (Astacus leptodactylus), Spiny-cheek Crayfish (Orconectes limosus) and Signal Crayfish (Pacifastacus leniusculus). Aside from the chapters concerning the particular species and their determination, the literature outline also contains general information about the life and endangerment of crayfish. I have conducted the field research from April to September 2009. I also noted and evaluated the environmental conditions of the crayfish habitats. Based on the adjusted AOPK ČR methodology, I selected eight 100-meter long brook-sections of the Europe-important locality of Zákolanský stream, with the previously confirmed occurrence of crayfish. From the eight sections, I found crayfish only in three. All the captured specimens were of the...

L’industrie produit de grandes quantités d’effluents aqueux qu’il convient de traiter. Des traitements alternatifs aux procédés biologiques doivent être développés pour certains effluents toxiques et/ou non biodégradables. L’oxydation en voie humide catalytique repose sur l’action de l’oxygène sur les polluants en phase aqueuse à haute température et haute pression. Préalablement à cette étude, des catalyseurs au Ru ou Pt supportés sur ZrO2 ou TiO2très actifs et très stables pour l’OVHC de polluants modèles et de quelques effluents réels ont été développés. Ce travail a examiné ces catalyseurs sur d’autres effluents réels : un effluent provenant d’une unité de production de membranes contenant du glycérol et du DMF, uneffluent de sauce de couchage provenant de l’industrie papetière et un concentrât de lixiviatde décharge. Les catalyseurs se sont révélés très actifs et stables pour la minéralisation du glycérol, mais une forte lixiviation a été observée lors de l’OVHC du DMF du fait de la présence d’amines. L’oxydation de l’effluent de sauce de couchage permet de minéraliser la charge organique, facilitant le recyclage de la charge minérale, avec une amélioration accrue de la biodégradabilité du surnageant en présence des catalyseurs. Enfin, l’ajout de catalyseurs lors de l’OVH du concentrât de lixiviat de décharge permet d’améliorer sa minéralisation et d’éliminer totalement les ions ammonium / Industries produce huge volumes of effluents which need to be treated before disposal.Alternative treatments to the more classical biological techniques are required in the case oftoxic and/or non biodegradable effluents. The wet air oxidation (WAO) and catalytic wet airoxidation (CWAO) are based on the reaction of an oxidant (oxygen) with the pollutants in aqueous phase at high temperature and pressure. Ru or Pt catalysts supported on zirconium and titanium oxides were previously shown to be highly active and stable in the CWAO of awide range of model compounds and real complex effluents. These catalysts were evaluated in the CWAO of problematic effluents: one containing glycerol and DMF, one paper coatingslip effluent and one concentrated landfill leachate. The catalysts showed high activity and stability in the CWAO of glycerol, while the metal leached upon DMF CWAO due to the presence of amines. WAO leads to the partial mineralization of the organic load in paper coating slip, allowing an easy separation recycling of mineral pigments, with an improved biodegradability of the supernatant with the use of a catalyst. The use of a catalyst upon landfill leachate WAO leads higher COT conversion and complete ammonia elimination

Le stockage géologique du carbone est l’une des techniques les plus prometteuses pour réduire le taux de CO₂ dans l’atmosphère. La séquestration géologique possède la capacité et la longévité potentielles pour diminuer les émissions de CO₂ vers l’atmosphère. Dans le cadre d’injections à l’échelle industrielle, les réservoirs carbonatés peuvent faire partie des sites aptes à stocker du CO₂. Toutefois, ces injections à grandes profondeurs sont sujettes à des risques de fuites du piège géologique lui-même ou des infrastructures liés à l’exploitation du site de stockage. Ainsi, il existe principalement deux types de fuite : brutale et diffuse. Dans les deux cas, elles sont susceptibles d’entrainer des risques pour l’environnement et de mettre en danger les populations. Il est ainsi nécessaire de développer des outils capables de prévenir une fuite de CO₂ quel que soit son type. Par ailleurs, il est particulièrement indispensable de comprendre les mécanismes de transport réactif qui rentrent en jeu lors de l’arrivée de cette fuite en contexte de proche surface (zone vadose) et ainsi d’essayer d’étudier comment cette fuite peut s’amortir. Ces travaux de thèse traitent donc de la caractérisation, de la quantification et de la modélisation des processus de transferts et des interactions CO₂-H₂O-CaCO₃ dans la zone vadose en contexte de fuite à partir d’un puits de forage. Cette problématique a été d’abord abordée par une approche expérimentale sur un site pilote à Saint-Emilion. Puis, les interactions CO₂-H₂O-CaCO₃ ont été étudiées au travers d’une approche expérimentale à l’échelle de la carotte en laboratoire. L’approche expérimentale a conduit à la réalisation de deux fuites dans la zone vadose du site pilote : une fuite diffuse et une fuite ultra diffuse. Elles furent réalisées dans la continuité des expériences qui avaient déjà eu lieu auparavant. Une comparaison de l’ensemble des fuites a montré la nécessité d’utiliser des gaz nobles comme précurseurs de l’arrivée en surface du CO₂. Selon le type de fuite, l’hélium peut servir de précurseur temporel du CO₂, tandis que le krypton prévient de l’étendue du panache de gaz durant la fuite. Plus la pression d’injection du CO₂ est importante et plus le gaz migre par advection. Par ailleurs, une pression d’injection importante favorise l’existence de passage préférentiel dans la zone vadose. L’utilisation d’isotopes tels que ceux de l’hélium et du carbone permet de mettre en évidence la présence locale de phases aqueuses dans le massif et de déterminer l’origine biologique ou anthropique du CO₂. Les expériences à l’échelle de la carotte permettent d’estimer le pouvoir tampon des calcaires oligocènes en fonction du faciès de la roche. La perméabilité et la porosité de celle-ci conditionnent la dissolution des calcaires. De même, la réactivité des carbonates en contexte de fuite dépend du pH de la phase aqueuse, du débit qui traverse le réseau poreux, de la saturation en eau et des caractéristiques pétro-physiques des carbonates. / Carbon storage is one of the most encouraging methods to decrease CO₂ concentration into the atmosphere. Carbon storage provides the longevity and the capacity needed to decrease CO₂ emissions toward the atmosphere. When dealing with storage on an industrial scale, carbonated reservoirs can be among the most suitable storage sites. However, these high depth injections are subject to leakage risks from the geologic trap itself or from the framework created by the establishment of the site. Two main types of leakage exist: brutal and diffusive leakage. In both cases, they are likely to endanger the environment and the population. Therefore, it is essential to develop tools that are able to anticipate any types of CO₂ leakage. Furthermore, it is also necessary to understand the reactive transport mechanism that take place when the leakage arrives in the shallow subsurface (vadose zone)and to see how the leakage can be buffered. This work deals with the characterization, the quantification and the modelling of transfer processes and CO₂-H₂O-CaCO₃ interactions into the vadose zone in a context of a leakage from a drilling well. This issue was first dealt through field experiment on the site of Saint Emilion. Then, the CO₂-H₂O-CaCO₃ interactions were studied through an experimental approach in laboratory. Two leakage experiments were performed on the site: a diffusive leakage and an ultra-diffusive leakage. They were performed as a sequel of former experiments carried on the pilot site. A comparison of all the leakage experiments revealed the necessity to use noble gases as precursor of the CO₂ arrival at the surface. Depending of the type of the leakage, helium can be a temporal precursor while krypton can anticipate the spread of the CO₂ gas plume. The higher the injection pressure, the more the gas migrates through advective flux. Moreover, a high injection pressure favors the existence of preferential paths in the vadose zone. The use of helium and carbon isotopes makes it possible to reveal the presence of a local aqueous phase within the porous media and to identify the origin of CO₂. The core scale experiments lead to the estimation of the buffering power of Oligocene limestone according to the rock facies. The permeability and the porosity influence the dissolution of the limestone. The reactivity of carbonates during a leakage depends on the pH of the aqueous phase, the flow rate that goes through the porous media, the water saturation and petrophysical characteristics of the carbonates.