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Мемристивный эффект в сэндвич-структуре металл/полупроводник/металл на основе анодированного диоксида титана : магистерская диссертация / Memristive effect in metal/semiconductor/metal sandwich structure based on anodized titaniaДорошева, И. Б., Dorosheva, I. B. January 2016 (has links)
Объектом исследования являются структуры металл/полупроводник/металл на основе анодированных слоев диоксида титана толщиной от 60 до 500 нм с диаметром нанотрубок от 30 до 60 нм, полученных во фторсодержащем растворе.
Цель работы – исследование влияния толщины оксидного слоя, материала электрода и его площади на процессы резистивного переключения сэндвич-структур Ti/TiO2/Ме на основе нанотубулярного диоксида титана.
Синтезированы сэндвич-структуры Ti/TiO2-НТ/Au и Ti/TiO2-НТ/Ag с диаметрами мемристивных элементов ≈ 100 мкм и ≈ 5,5 мм. Аттестация образцов проведена методами растровой электронной и оптической микроскопии, рентгенофазового анализа и спектроскопии комбинационного рассеяния. Исследованы ВАХ сфабрикованных структур в полных циклах резистивного переключения и в процессах, симулирующих многократное считывание информации. Получено, что микромемристор Ti/TiO2-НТ/Au с толщиной оксидного слоя 160 нм имеет наилучшие характеристики биполярного переключения среди исследованных. Продемонстрирована работоспособность структуры на протяжении 17 тыс. циклов переключения. Сделан вывод о возможности использования микромемристоров Ti/TiO2-НТ/Au в качестве перспективных элементов резистивной памяти. / The object of investigation of metal/semiconductor/metal structures based on the anodized layer of titanium dioxide. Ones are 60 – 500 nm thick with 30 – 60 nm diameter of nanotubes obtained in fluorine-containing solution.
The goal of this paper is to investigate the effect of oxide layer thickness, its electrode material and the area on resistive switching processes in sandwich Ti/TiO2/Me nanotubular structures based on titanium dioxide.
Sandwich structures of Ti/TiO2-NT/Au and Ti/TiO2-NT/Ag with diameters of memristive elements about 5.5 mm and 100 µm have been synthesized. Characterization of samples was carried out by scanning electron and optical microscopy, X-ray diffraction and Raman spectroscopy. CVC fabricated structures in the full cycle of the resistive switching and processes simulating multiple reading of information were studied. It was found that Ti/TiO2-NT/Au micromemristor with a thickness of the oxide layer about 160 nm has the best bipolar switching characteristics among studied samples. Structure performance within 17 thousands switching cycles was demonstrated. It is concluded that Ti/TiO2-NT/Au micromemristors were proved to be promising resistive memory elements.
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[pt] NANOHÍBRIDOS SENSÍVEIS À LUZ VISÍVEL À BASE DE NANOFOLHAS DE FERRITITANATO ESFOLIADAS E UM COMPLEXO DE TRANSFERÊNCIA DE CARGAS: EFEITO DE DIFERENTES RAZÕES MOLARES DE TI ANATÁSIO TI FERRITITANATO E DISTINTAS ROTAS DE SÍNTESE / [en] VISIBLE LIGHT SENSIBLE NANOHYBRIDS BASED ON FERRITITANATE EXFOLIATED NANOSHEETS AND A CHARGE TRANSFER COMPLEX: EFFECT OF DIFFERENT MOLARS RATION OF TI ANATASE TI FERRITITANATE AND DISTINCT SYNTHESIS ROUTESLUCAS ARAUJO LIMA ALMEIDA 09 December 2021 (has links)
[pt] Os semicondutores à base de TiO2 atualmente em desenvolvimento na área de fotodegradação de poluentes apresentam limitações para viabilização comercial. Os desafios encontrados são, i) tornar mais eficiente a absorção de luz na faixa visível para fotogeração dos pares elétrons livres e buracos, ii) elevação da área superficial e iii) redução da taxa de recombinação elétrons livres-buracos. Este estudo focou na síntese e caracterização de um novo nanohíbrido, sensível a luz visível à base de nanofolhas de ferrititanato esfoliadas e de nanopartículas de TiO2 (anatásio) conjugadas com acetilacetona (ACAC), controlando a razão molar de titânio nos dois componentes, além de abordar diferentes rotas de síntese do nanohíbrido e estudar os componentes separadamente. Os nanohíbridos foram sintetizados pelas rotas de mistura física e de química branda sendo nomeados como MF e HM-1 respectivamente, considerando as razões molares de [Ti]anatásio/[Ti]ferrititanato de 10, 5 e 2. Todos os nanohíbridos apresentaram elevada área superficial (superior a 100 m2/g) e restauração parcial da estrutura pilarizada. Os nanohíbridos com maior razão molar de [Ti]anátasio/[Ti]ferrititanato apresentaram maior eficiência de foto-oxidação dos gases poluentes NOx, bem como a MF apresentou maior eficiência que a HM-1. O nanohíbrido com melhor desempenho, a MF de razão 10, obteve uma conversão após 5 min de aproximadamente 80 por cento e apresentou redução gradativa de conversão até 25 por cento após 2h. Contudo, o componente isolado TiO2-ACAC calcinado a 300 graus C promoveu a sensibilização do anatásio em todo o espectro visível, tendo área superficial de 137 m2/g e uma conversão do NOx superior a 95 por cento, com redução gradativa da conversão até 38,5 por cento após 2h. Os resultados do anatásio modificado podem ser compreendidos pela combinação da estrutura nanométrica, da elevada área superficial e, principalmente, pela presença de ligações de titânia com acetilacetona superficiais em monocamadas
maximizando e estabilizando a fotogeração de pares elétrons/buracos. Enquanto odesempenho inferior dos nanohíbridos pode ser atribuído a presença devacâncias de oxigênio e íons de Fe3+ atuando como centros de recombinação reduzindo a formação de radicais oxidantes. / [en] Currently, the development of TiO2-based semiconductors carry out drawback at photocatalytic commercial applications for photodegradation of pollutants gases. The photocatalytic limitations are i) inefficient absorption of visible light that inhibits the photogeneration of free electron and hole pairs, ii) small surface area and iii) high rate of electron to hole recombination. The aim of this study was the synthesis and characterization of a new visible light sensitive nanohybrids based on ferrititanate exfoliated nanosheets and a charge transfer complex (TiO2-ACAC) by controlling the [Ti] anatase/[Ti] ferrititanate molar ratio and applying two different synthesis route. Besides, it was studied the individual components. The nanohybrids were synthesized through physical mixture route and soft chemical route, named respectively as MF and HM-1. The molar ratios used in this work were 10, 5 and 2. All of the heterostructures presented high surface area (higher than 100m2/g) and partial restacking of lamellar structure. The nanohybrids with higher molar ratio and synthesized through physical mixture showed the greatest photocatalytic activity with more efficient photo-oxidation of gas NOx than the nanohybrids synthesized through soft chemical route. The nanohybrid with better performance, the MF with ratio 10, obtained a NO conversion of approximately 80 percent after 5min and gradual reduction of conversion to 25 percent after 2h. Nevertheless, the TiO2-ACAC nanoparticles component calcined at 300 C degrees presented total sensitivity at the range of visible light, surface area of 137m2/g and conversion higher than 95 percent with partial photocatalytic deactivation to 38.5 percent after 2h. The results of TiO2-ACAC system studied can be described due to its nanometric structure, high surface area and, mainly, for the presence of strongly interacting between acetylacetone with Ti ions from anatase surface, while maximized and stabilized the photogeneration of electron-hole pairs and reactive oxidizing species (ROS), .O2 -. However, the lower performance of the nanohybrids ascribed to the oxygen vacancies and Fe3+ ions that acting as electron trapping center reducing the formation of ROS.
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Efficient Photocatalytic Degradation of Organic Pollutant in Wastewater by Electrospun Functionally Modified Polyacrylonitrile Nanofibers Membrane Anchoring TiO2 Nanostructured.AlAbduljabbar, Fahad A., Haider, S., Ali, F.A.A., Alghyamah, A.A., Almasry, W.A., Patel, Rajnikant, Mujtaba, Iqbal 28 March 2022 (has links)
Yes / In this study, polyacrylonitrile (PAN_P) nanofibers (NFs) were fabricated by electrospinning. The PAN_P NFs membrane was functionalized with diethylenetriamine to prepare a functionalized polyacrylonitrile (PAN_F) NFs membrane. TiO2 nanoparticles (NPs) synthesized in the laboratory were anchored to the surface of the PAN_F NFs membrane by electrospray to prepare a TiO2 NPs coated NFs membrane (PAN_Coa). A second TiO2/PAN_P composite membrane (PAN_Co) was prepared by embedding TiO2 NPs into the PAN_P NFs by electrospinning. The membranes were characterized by microscopic, spectroscopic and X-ray techniques. Scanning electron micrographs (SEM) revealed smooth morphologies for PAN_P and PAN_F NFs membranes and a dense cloud of TiO2 NPs on the surface of PAN_Coa NFs membrane. The attenuated total reflectance in the infrared (ATR-IR) proved the addition of the new amine functionality to the chemical structure of PAN. Transmission electron microscope images (TEM) revealed spherical TiO2 NPs with sizes between 18 and 32 nm. X-ray powder diffraction (XRD) patterns and energy dispersive X-ray spectroscopy (EDX) confirmed the existence of the anatase phase of TiO2. Surface profilometry da-ta showed increased surface roughness for the PAN_F and PAN_Coa NFs membranes. The adsorption-desorption isotherms and hysteresis loops for all NFs membranes followed the IV -isotherm and the H3 -hysteresis loop, corresponding to mesoporous and slit pores, respectively. The photocatalytic activities of PAN_Coa and PAN_Co NFs membranes against methyl orange dye degradation were evaluated and compared with those of bare TiO2 NPs.The higher photocatalytic activity of PAN_Coa membrane (92%, 20 ppm) compared to (PAN_Co) NFs membrane (41.64%, 20 ppm) and bare TiO2 (49.60%, 20 ppm) was attributed to the synergy between adsorption, lower band gap, high surface roughness and surface area.
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Sol-Gel Derived Titania Films And Their Potential Application As Gas SensorRaval, Mehul Chandrakant 12 1900 (has links)
Today there is a great deal of interest in the development of gas sensors for various applications like monitoring of toxic gases, detection in oil reservoirs, mines, homes etc. Solid-state gas sensors have many advantages over the conventional analytical methods and hence are widely used. Amongst them, semiconducting metal-oxides based sensors are popular due to many advantages like low cost, small size, high sensitivity and long life.
The present thesis reports a detailed work of TiO2 (Titania) thin film fabrication based on sol-gel method, study of their crystallization behavior and surface morphology, and characterizing them for alcohol sensing properties
Sol-gel method is a wet chemical technique with many advantages over the conventional methods and offers a high degree of versatility to modify the film properties. Titania thin films were made with titanium isopropoxide as the precursor and ethanol and isopropanol as the solvents. Also effect of surfactants(PEG and CTAB) on the sol properties and film properties have experimentally examined.
A in-house gas sensor testing setup has been designed and fabricated to characterize the sensors. Sensors with three different electrode configurations and also two different electrode material have been tested. The electrode geometry and material play a significant role on the sensing behavior and results for the same have been discussed.
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Modified track-etched membranes using photocatalytic semiconductors for advanced oxidation water treatment processesRossouw, Arnoux 03 1900 (has links)
Thesis (MScEng)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The purpose of this study was to develop modi ed tract-etched membranes using
nanocomposite TiO2 for advanced water treatment processes. Photocatalytic oxidation
and reduction reactions take place on TiO2 surfaces under UV light irradiation,
therefore sunlight and even normal indoor lighting could be utilised to achieve this effect.
In membrane ltration, caking is a major problem, by enhancing the anti-fouling
properties of photocatalysts to mineralise organic compounds the membrane life and
e ciency can be improved upon.
In this study the rst approach in nanocomposite membrane development was to directly
modify the surface of polyethylenetherephthalate (PET) track-etched membranes
(TMs) with titanium dioxide (TiO2) using inverted cylindrical magnetron sputtering
(ICMS) for TiO2 thin lm deposition. The second approach was rst to thermally
evaporate silver (Ag) over the entire TM surface, followed by sputtering TiO2 over
the silver-coated TM. As a result a noble metal-titania nanocomposite thin lm layer
is produced on top of the TM surface with both self-cleaning and superhydrophilic
properties. Reactive inverted cylindrical magnetron sputtering is a physical vapour
deposition method, where material is separated from a target using high energy ions
and then re-assimilated on a substrate to grow thin lms. Argon gas is introduced
simultaneously into the deposition chamber along with O2 (the reactive gas) to form
TiO2. The photocatalytic activity and other lm properties, such as crystallinity can
be in
uenced by changing the sputtering power, chamber pressure, target-to-substrate
distance, substrate temperature, sputtering gas composition and
ow rate. These characteristics
make sputtering the perfect tool for the preparation of di erent kinds of TiO2
lms and nanostructures for photocatalysis.
In this work, the utilisation of ICMS to prepare photocatalytic TiO2 thin lms
deposited on track-etched membranes was studied in detail with emphasis on bandgap
reduction and TM surface regeneration. Nanostructured TiO2 photocatalysts were prepared through template directed deposition on track-etched membrane substrates
by exploiting the good qualities of ICMS. The TiO2-TM as well as Ag-TiO2-TM thin
lms were thoroughly characterised. ICMS prepared TiO2 lms were shown to exhibit
good photocatalytic activities. However, the nanocomposite Ag-TiO2 thin lms were
identi ed to be a much better choice than TiO2 thin lms on their own. Finally a
clear enhancement in the photocatalytic activity was achieved by forming the Ag-TiO2
nanocomposite TMs. This was evident from the band-gap improvement from 3.05 eV
of the TiO2 thin lms to the 2.76 eV of the Ag-TiO2 thin lms as well as the superior
surface regenerative properties of the Ag-TiO2-TMs. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie was om verbeterde baan-ge etste membrane (BMe) met behulp
van nano-saamgestelde titaandioksied (TiO2) vir gevorderde water behandeling
prosesse te ontwikkel. Fotokatalitiese oksidasie- en reduksie reaksies vind plaas op
die TiO2 oppervlaktes onder UV-lig bestraling, en dus kan sonlig en selfs gewone binnenshuise
beligting gebruik word om die gewenste uitwerking te verkry. In membraan
ltrasie is die aanpaksel van onsuiwerhede 'n groot probleem, maar die verbetering
van die self-reinigende eienskappe van fotokatalisators deur organiese verbindings te
mineraliseer, kan die membraan se leeftyd en doeltre endheid verbeter word.
In hierdie studie was die eerste benadering om nano-saamgestelde membraan ontwikkeling
direk te verander deur die oppervlak van polyethylenetherephthalate (PET)
BMe met 'n dun lagie TiO2 te bedek, met behulp van reaktiewe omgekeerde silindriese
magnetron verstuiwing (OSMV).Die tweede benadering was eers om silwer (Ag)
termies te verdamp oor die hele BM oppervlak, gevolg deur TiO2 verstuiwing bo-oor
die silwer bedekte BM. As gevolg hiervan is 'n edelmetaal-titanium nano-saamgestelde
dun lm laag gevorm bo-op die oppervlak van die BM, met beide self-reinigende en
verhoogde hidro liese eienskappe. OSMV is 'n siese damp neerslag metode, waar
materiaal van 'n teiken, met behulp van ho e-energie-ione, geskei word, en dan weer opgeneem
word op 'n substraat om dun lms te vorm. Argon gas word gelyktydig in die
neerslag kamer, saam met O2 (die reaktiewe gas), vrygestel om TiO2 te vorm. Die fotokatalitiese
aktiwiteit en ander lm eienskappe, soos kristalliniteit, kan be nvloed word
deur die verandering van byvoorbeeld die verstuiwingskrag, die druk in die reaksiekamer,
teiken-tot-substraat afstand, substraattemperatuur, verstuiwing gassamestelling
en vloeitempo. Hierdie eienskappe maak verstuiwing die ideale hulpmiddel vir die voorbereiding
van die verskillende soorte TiO2 lms en nanostrukture vir fotokatalisasie. In hierdie tesis word OSMV gebruik ter voorbereiding van fotokatalitiese TiO2
dun lms, wat gedeponeer is op BMe. Hierdie lms word dan in diepte bestudeer,
met die klem op bandgaping vermindering en BM oppervlak hergenerasie. Nanogestruktureerde
TiO2 fotokataliste is voorberei deur middel van sjabloongerigte neerslag
op BM substrate deur die ontginning van die goeie eienskappe van OSMV. Die
TiO2-BM dun lms, sowel as Ag-TiO2-BM dun lms, is deeglik gekarakteriseer. OSMV
voorbereide TiO2 dun lms toon goeie fotokatalitiese aktiwiteite. Nano-saamgestelde
Ag-TiO2 dun lms is egter ge denti seer as 'n veel beter keuse as TiO2 dun lms. Ten
slotte is 'n duidelike verbetering in die fotokatalitiese aktiwiteit bereik deur die vorming
van die Ag-TiO2 nano-saamgestelde BMe. Dit was duidelik uit die bandgapingverbetering
van 3,05 eV van TiO2 dun lms in vergelyking met die 2,76 eV van Ag-TiO2
dun lms. 'n Duidelike verbetering is behaal in die fotokatalitiese aktiwiteit deur die
vorming van die Ag-TiO2 nano-saamgestelde TMs.
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Fotokatalytický rozklad vody oxidovými polovodiči modifikovanými grafenem/grafenoxidem / Photocatalytic water splitting by oxide semiconductors modified with graphen/graphenoxideMarek, Jiří January 2015 (has links)
This master thesis deals with the topic of alternative production of hydrogen as the energy carrier of the future. The primary focus is on the production of hydrogen based on photocatalytical water splitting in the presence of semiconductor materials (especially modified and unmodified TiO2). The aim of the thesis is a synthesis of nanostructured oxide, graphene/graphene oxide particles and its composites, and a study of its structures and photocatalytical properties regarding photolysis of water. Products of the syntheses are described from the point of view of phase composition, surface area and photocatalytical activity. The main output of the thesis is a discussion of the influence of alkaline complex forming reagents on the hydrothermal low-temperature synthesis of biphasic TiO2, and a study of the influence of graphene/graphene oxide modification on photocatalytical activity of biphasic TiO2.
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Traitement d’eaux huileuses par photocatalyse hétérogène : application à la dépollution des eaux de cales / Treatment of oily water by heterogeneous photocatalysis : application to the bilge water remediationCazoir, David-Alexandre 13 December 2011 (has links)
Afin de réduire la quantité d’hydrocarbures déversés dans le milieu marin, les navires de la flotte marchande et, depuis peu, les navires militaires sont tenus de contrôler leurs rejets huileux. Par exemple, seules les eaux de cales dont la concentration en huile (indice hydrocarbure) est inférieure à 15 ppmv peuvent être déversées en mer (Marpol 73/78). Au-delà de cette teneur, et si le stockage à bord n’est pas envisageable, un traitement avant rejet devient alors inévitable. Cependant, les traitements actuels des eaux de cales se sont avérés jusqu’ici insuffisants. La photocatalyse hétérogène, méthode largement utilisée dans le cas du traitement d’effluents gazeux et liquides, a ainsi été proposée dans ce travail. L’abattement de l’indice hydrocarbure a été suivi par analyse GC-MS. Dès lors, après avoir mis en évidence la faisabilité et les limites du procédé batch, un réacteur photocatalytique à aération diffusée (DAPR) a été développé afin de remédier au manque d’oxygène dissous de l’effluent réel. Comparativement au traitement dans le réacteur batch, une meilleure efficacité de la dégradation a été observée dans le DAPR. Cependant, l’analyse parallèle (ATD-GC-MS) de l’évolution de la composition de la phase gazeuse a montré qu’une quantité non négligeable de composés organiques volatils (COV) y étaient alors émis. Enfin, les nalcanes ont été identifiés comme étant les composés les plus réfractaires au traitement photocatalytique et le pentadécane a alors été choisi comme polluant modèle des eaux de cales pour une analyse cinétique. / In order to reduce the marine oil pollution, ships have to control their hydrocarbon dumping at sea. For example, only bilge water that has a hydrocarbon oil index less than 15 ppmv can be discharged at sea (Marpol 73/78). Otherwise, effluents have to be stored on board or treated. In this study, heterogeneous photocatalysis was proposed as an alternative method to the current treatments that are still not efficient enough. Oil removal was monitored by GC-MS analysis. Then, by demonstrating the feasibility and limitations of the batch process, we developed a diffused aeration photocatalytic reactor (DAPR). In this case, better results were obtained than in the batch reactor because the problem of the lack of dissolved oxygen in the real effluent was solved by supplying air continuously. However, volatile organic compounds were then found by monitoring (ATD-GC-MS) the evolution of the gaseous phase composition. Finally, we showed that linear alkanes were the most resistant compounds to the photocatalytic treatment and thereby, pentadecane was chosen as a model pollutant of bilge water for a kinetic study.
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Surfaces fonctionnalisées à base de nanoparticules métalliques pour l'optique et la photonique / Surfaces functionalized with metal nanoparticles for optics and photonicsNadar, Latifa 27 October 2011 (has links)
Ce travail de thèse porte sur l’élaboration et la caractérisation optique et structurale de films de silice ou de titane mésostructurés porteurs de nanoparticules d’argent. Il s’intéresse également aux propriétés photochromiques des films à base de titane. Pour ce travail, des films mésoporeux de SiO2, et de TiO2, amorphe ou anatase, ont été synthétisés par voie sol-gel et caractérisés. Après leur imprégnation par des ions métalliques, trois protocoles de réduction ont été utilisés. La croissance thermique favorise la coalescence des nanoparticules; des bâtonnets d’argent sont obtenus dans les films de silice hexagonaux 2D alors que des agglomérats se forment en surface et dans l’épaisseur des films de TiO2 présentant des pores sphériques. La réduction chimique permet une croissance rapide des nanoparticules d’argent dans les pores; des bâtonnets et sphères de taille et forme contrôlées sont obtenus dans les films de SiO2 et de TiO2, respectivement. La croissance optique des nanoparticules d’argent par photoréduction est aussi un procédé rapide; des nanoparticules avec une plus large distribution de taille que leurs similaires chimiques sont obtenues dans les films de TiO2, mais seulement quelques nanoparticules dans la matrice SiO2 en raison de sa faible réponse à l’UV. L’étude du comportement photochromique des nanoparticules d’argent déposées dans des films de TiO2 a démontré l’influence de la répartition initiale des nanoparticules et de l’intensité incidente sur la couleur du film. Un blanchiment du film optique ou chimique est observé après insolation avec une lumière monochromatique puissante, et un comportement multiphotochromique pour de faibles intensités lumineuses / This study is focused on the elaboration, and the optical and structural characterization of mesostructured silica and titania films incorporating silver nanoparticles. It also deals with the photochromic properties of titania films. For that purpose, mesoporous thin films of silica and amorphous or anatase titania were produced using sol-gel method and characterized. After soaking in a metal salt solution, three kinds of reduction processes were explored. The thermal route promotes coalescence of nanoparticles; silver nanorods are obtained in 2D hexagonal silica films, whereas aggregates are formed on the surface and in the thickness of titania films having spherical pores. Chemical reduction leads to a rapid growth of silver nanoparticles in the pores: silver nanorods and spheres with a controlled size and shape are obtained in the silica and the titania films, respectively. Optical growth of silver nanoparticles by photoreduction is also a fast process: nanoparticles with a larger size distribution than the chemically reduced films are obtained in the titania matrix, but few nanoparticles are obtained in the silica matrix due to their low response to the UV light. The photochromic behavior study of silver nanoparticles deposited in amorphous or anatase titania films shows the influence of the initial nanoparticle distribution inside the film and the irradiance intensities on the photo-induced color changes. A bleaching of the optically and chemically reduced film can be observed after irradiation with monochromatic visible light at high intensities and multiphotochromic behavior at low irradiance values
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Hydrogenation of succinic acid and carbon dioxide over molybdenum carbide catalysts / Carbures de molybdène catalyseurs supportés pour hydrogénation de l'acide succinique et du dioxyde de carboneAbou Hamdan, Marwa 28 May 2019 (has links)
Ce travail de thèse porte sur la synthèse de carbures de molybdène sur support afin de tester leurs performances catalytiques dans des réactions d’hydrogénation. Dans ce but, la conversion d'acide succinique en phase aqueuse dans un réacteur discontinu et du dioxyde de carbone en phase gazeuse dans un réacteur à flux continu, ont été effectuées. Les catalyseurs ont été préparés par la méthode de carburation par réduction en température programmée, pendant laquelle des paramètres ont été modifiés conduisant à différents rapports molybdène/carbone. Les différents catalyseurs testés dans cette réaction étaient actifs pour la conversion de l'acide succinique en gamma-butyrolctone et, plus remarquablement, en acide butyrique, ce dernier n'était pas obtenu en quantités significatives avec des catalyseurs à base de métaux précieux. L’augmentation de la conversion d’acide succinique avec une sélectivité plus élevée en acide butyrique a été faite avec les catalyseurs contenant plus de carbone, préparés en augmentant la vitesse spatiale horaire gazeuse. Les intermédiaires ont été ensuite convertis en tétrahydrofurane, butanol, 1,4-butanediol et butane. La désactivation observée lors de recyclage du catalyseur a été principalement attribuée à une diminution de la quantité de molybdène et de carbone carbidique, démontrée par l'analyse XPS. Des essais préliminaires de ces catalyseurs dans l'hydrogénation du dioxyde de carbone ont montré qu'ils fonctionnaient principalement en tant que catalyseurs pour la réaction du gaz à l’eau inverse, et l'excès de carbone entrave l'activité catalytique d'une manière opposée à la réaction en phase aqueuse. Le support semble jouer un rôle dans la réactivité des catalyseurs, la conversion du dioxyde de carbone ainsi que la sélectivité en méthane et méthanol, qui ont augmenté dans l'ordre suivant: carbure de molybdène sur support DT51 TiO2> P25 TiO2 ˜ ZrO2 / This work focuses on the synthesis of supported molybdenum carbides and evaluating their catalytic performance in succinic acid hydrogenation reactions in aqueous phase using batch reactor and carbon dioxide hydrogenation in gas phase using continuous flow reactor. The catalysts were prepared by the temperature programmed reduction carburization method, where the parameters were modified leading to different molybdenum to carbon ratios. The different catalysts tested were active in converting succinic acid to gamma butyrolctone and more remarkably butyric acid which is not reported in significant quantities in this reaction with precious metal based catalysts. The catalysts containing more carbon contents that were prepared by increasing the gas hourly space velocity showed higher activity in converting succinic acid and higher selectivity to butyric acid. The intermediates were then converted to tetrahydrofuran, butanol, 1,4-butanediol and butane gas. The deactivation observed while recycling the catalyst was mainly attributed to a decrease in the amounts of carbidic molybdenum and carbidic carbon, as demonstrated by XPS analysis. Preliminary tests for these catalysts in carbon dioxide hydrogenation showed that they functioned mainly as reverse water gas shift catalysts, and the excess of carbon hinders the catalytic activity in an opposite manner of the reaction in aqueous phase. The support seems playing a role in the reactivity of the catalysts, carbon dioxide conversion as well as methane and methanol selectivity increased in the order: molybdenum carbide supported on DT51 TiO2 > P25 TiO2 ˜ ZrO2
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[en] SYNTHESIS AND CHARACTERIZATION OF THE PHOTOCATALYSTS BASED ON MESOPOROUS MATERIALS FOR PHOTOCATALYTIC PRODUCTION OF H2 FROM WATER / [pt] SÍNTESE E CARACTERIZAÇÃO DE FOTOCATALISADORES BASEADOS EM MATERIAIS MESOPOROSOS PARA A PRODUÇÃO FOTOCATALÍTICA DE H2 A PARTIR DA ÁGUASABRINA GUIMARAES SANCHES 01 July 2014 (has links)
[pt] Neste trabalho foram sintetizados fotocatalisadores baseados em Ti e suportados nas sílicas mesoporosas HMS e SBA-15 preparados pelos métodos de deposição estrutural e impregnação ao ponto úmido. Os fotocatalisadores foram testados na reação de separação da água para a produção de hidrogênio usando
radiação UV. Estudou-se também a influência da razão molar Si/Ti de 20 e 40, e o uso de diferentes fontes de titânio como: isopropóxido de titânio, oxalato de titânio, butóxido de titânio, incluindo o óxido de titânio comercial P25. Também foi estudado o uso da platina e do cério como cocatalisadores. Os suportes e os
fotocatalisadores foram caracterizados pelas técnicas de ICP-OES, FRX, DRX, isotermas de adsorção e dessorção de N2, ATG, MET, MEV, DRS UV-Vis e espectroscopia de IV. Os resultados mostraram que a substituição parcial do Ti na rede da sílica mesoporosa modificou a estrutura sem destruir os canais cilíndricos dos suportes. Os fotocatalisadores preparados por deposição estrutural em HMS usando diferentes fontes de Ti apresentaram produções de H2 diferentes, seguindo a ordem isopropóxido maior do que oxalato maior do que butóxido, devido à formação de diferentes espécies de Ti isoladas tetraedricamente e octaedricamente coordenadas. Foi comprovado também que com o aumento do teor de Ti a atividade fotocatalítica diminui. A comparação entre os suportes mostraram que a produção de H2 para os fotocatalisadores baseados em HMS foram superiores aos preparados em SBA-15. Quanto aos métodos de preparo, a atividade fotocatalítica para as amostras preparadas por impregnação foi maior após 3 h de reação que nos fotocatalisadores preparados por deposição estrutural. O TiO2-P25 incorporado na HMS também criou espécies octaédricas isoladas possibilitando uma produção de H2 mais eficiente que o TiO2-P25 puro. / [en] Photocatalysts were synthesized based on Ti and supported on mesoporous silica SBA-15 and HMS. They were prepared by structural deposition and wet impregnation methods. The photocatalysts were tested in the reaction of water splitting to produce hydrogen using UV radiation. It was also studied the influence of the Si/Ti molar ratio of 20 and 40 and the use of different titanium sources: titanium isopropoxide, titanium oxalate, titanium butoxide and titanium oxide P25. Platinum and cerium were also studied as cocatalysts. The supports and photocatalysts were characterized by the techniques of ICP-OES, XRF, XRD, N2 adsorption–desorption isotherms, TGA, TEM, SEM, FT-IR and UV-Vis DRS. The results showed that when Ti was partly substituted into the silica framework the structure was modified without destroying the supports cylindrical channels. The photocatalysts prepared by structural deposition into HMS using different
sources of Ti showed different production of H2, following the order: isopropoxide more than oxalate more than butoxide due to the formation of different isolated Ti species tetrahedrally and octahedrally coordinated. It was also demonstrated that increasing Ti content the photocatalytic activity decreases. The comparison between the supports showed that H2 production for photocatalysts based on HMS were superior to those prepared with SBA-15. Regarding methods of preparation, the photocatalytic activity for the samples prepared by impregnation method was higher after 3 h of reaction than photocatalysts prepared by deposition structure. The TiO2-P25 incorporated into HMS also create the octahedral isolated species enabling a H2 production more efficient than pure TiO2-P25.
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