Orientador: Carmen Sílvia Fernandes Boaro / Banca: João Domingos Rodrigues / Banca: Conceição Aparecida Cossa / Resumo: A Lippia alba (Mill.) N.E.Br. ex Britt & Wilson é uma importante espécie medicinal de uso popular conhecida como erva cidreira brasileira. Trata-se de um arbusto, cujas folhas frescas ou secas e inflorescências são utilizadas na forma de chás, macerados, compressas, pomadas, banhos e extratos alcoólicos. Suas folhas apresentam ação antiespasmódica, moluscicida, fungicida, calmante e digestiva. Considerando, a) a inexistência de estudos sobre a L. alba em hidroponia b) a utilização de solução nutritiva para atender as necessidades da espécie, fornecendo nutrientes de maneira balanceada e possibilitando a produção de plantas com adequada qualidade e em menor espaço de tempo, c) a necessidade de produção de matéria prima para uso medicinal popular e farmacêutico, o presente estudo objetivou avaliar o desenvolvimento e as trocas gasosas de L. alba submetida à variação das concentrações dos nutrientes a partir da diluição da solução nutritiva de Hoagland e Arnon (1950). Assim, as plantas foram cultivadas em quatro tratamentos, constituídos pela variação de nutrientes na solução nutritiva n°2 de Hoagland e Arnon (1950), ou seja, em solução completa (100%) e diluída à 80%, 60% e 40% em relação à completa. As variáveis avaliadas foram área foliar, massas secas dos diferentes órgãos, razão de área foliar (RAF), área foliar específica (AFE), razão de massa foliar (RMF), taxa de crescimento absoluto (TCA), taxa assimilatória líquida (TAL), taxa de crescimento relativo (TCR), taxa de assimilação de CO2 (A, mmolCO2 m-2 s-1), condutância estomática (gs, mol m-2s-1), transpiração (E, mmol H2O m-2 s-1), concentração intercelular de CO2 na folha (Ci, mmolCO2 mol-1ar) e eficiência de uso da água (EUA). Os resultados obtidos permitem concluir que: 1. As concentrações dos nutrientes na solução nutritiva, de maneira geral, foram excessivas para... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Lippia alba (Mill.) N.E.Br. ex Britt & Wilson is a native species popular known as "erva-cidreira brasileira". It is a shrub who's fresh or dried leaves and flowers are used as teas, macerated, bandages, ointments, baths and alcoholic extracts. Its leaves have an antispasmodic, molluscicidal, fungicidal, sedative and digestive. Considering a) the lack of studies about L. alba in hydroponic cultivation b) the use of nutrient solution to meet the needs of the species, providing nutrients in a balanced manner and enabling the production of plants with adequate quality and in shortest time, c) the need for production of raw materials for folk medical and pharmacist, the present study evaluate the development and gas exchange of L. alba subjected to varying concentrations of nutrients from the dilution of Hoagland and Arnon (1950). Thus, plants were grown in four treatments, consisting by variation of nutrients in the nutrient solution No 2 of Hoagland and Arnon (1950), full solution (100%), diluted to 80%, 60% and 40% compared to the full. Variables evaluated were leaf area, dry masses of different organs, leaf area ratio (LAR), specific leaf area (SLA), leaf mass ratio (LMR), absolute growth rate (AGR), net assimilation rate (NAR), rate relative growth (RGR), rate of CO2 assimilation (A, molCO2 m m-2 s-1), stomatal conductance (gs, mol m-2s-1), transpiration (E, mmol H2O m-2 s -1), intercellular CO2 concentration in the leaf (Ci, molCO2 m mol-1AR) and efficiency of water use (USA). The results showed that: 1. The concentrations of nutrients in the nutrient solution, in general, were excessive for the development and gas exchange of Lippia alba, 2. The cultivation of the species with a dilute solution of 80% resulted in higher total dry matter in the shortest time possible, which, however, was highest among the various treatments, 3. Diluted solutions at 60 and 40% ...(Complete abstract click electronic access below) / Mestre

A simple HPLC procedure for the quantitative determination of citral, the major fragrant component in the lemon grass, has been developed. The procedure involves a C-8 stationary phase using a 90:10 methanol: water pH 5 mobile phase containing 0.25% 1-octanesulfonic acid and an UV detector (set at 233 nm). The lemon grass leaves were harvested fresh at different times of the year and were soaked in methanol for 48 hours without any mechanical assistance to extract the citral and other methanol soluble components. The method showed good reproducibility with relative standard deviation of 2.8% and 10.8% for two different sets of samples. The method showed linearity in the range of 0.89 - 35.52 μg/mL. The average recovery was 104.8%. The amount of citral found as a percentage of the dried leaves are, 0.093, 0.27, 0.10, 0.13, 0.16, and 0.066 for fall, winter, three summer, and 1 commercial store samples, respectively.

Hauptaufgabe dieser Promotionsarbeit war es, eine neue Sol-Gel basierte Syntheseroute zur Darstellung edelmetallbeladener (Pd, Pt, Ag und Au) Aluminiumhydroxidfluoride zu entwickeln. Derartige Katalysatoren besitzen sowohl Lewis- als auch Brønsted-saure, sowie hydrogenierungsaktive Zentren. Solche multifunktionellen Katalysatoren können für mehrstufige Umsetzungen von Substraten in Eintopfverfahren eingesetzt werden. Das Potential der dargestellten Katalysatoren wurde in der zweistufigen Umsetzung von Citronellal zu Mentholen und der dreistufigen Reaktion von Citral zu Mentholen gezeigt. / The main aim of this thesis was to develop a new sol gel based synthesis route to noble metal loaded (Pd, Pt, Ag and Au) aluminium hydroxide fluorides. These catalysts provide Lewis as well as Brønsted acidity and hydrogenation ability. Those multifunctional catalysts can be used for multi step conversions of substrates performed in a one pot process. The potential of the synthesized catalysts was shown in the two step conversion of citronellal to menthols and in the three step conversion of citral to menthols.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-06-20T14:50:48Z No. of bitstreams: 1 2015 - Uir? do Amaral.pdf: 1011379 bytes, checksum: cf85bc1dcca1c891320f8683e0b406b1 (MD5) / Made available in DSpace on 2017-06-20T14:50:48Z (GMT). No. of bitstreams: 1 2015 - Uir? do Amaral.pdf: 1011379 bytes, checksum: cf85bc1dcca1c891320f8683e0b406b1 (MD5) Previous issue date: 2015-12-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Biodiversity, one of the fundamental properties of nature, is a source of immense economic potential. Brazil holds a rich biodiversity, and is considered one of the most important mega-diverse countries on the planet. Among the various links that make up this biodiversity Brazilian native flora noteworthy. Despite this, there have been few studies that promote intelligent and rational use of this genetic resource. Domestication and breeding of native plants, including those already known and used by local or regional populations, but without penetration at the national or international market is the great opportunity offered to the countries rich in genetic resources. Medicinal and aromatic plants represent a significant part of this potential market, and the lemongrass-Brazilian species (Lippia alba) is an important example of medicinal and aromatic plant, long used in folk medicine for his duties as soothing, antispasmodic, sedative, and produce various kinds of essential oils can be used by the perfume industry, food and cleaning products, beyond the control of pests and diseases in agriculture. Thus, the objective of this study was to evaluate the genetic variability, genetic parameters and the agronomic behavior of different accesses of L. alba, coming from the metropolitan region of the State of Rio de Janeiro. The experiment was conducted in November 2011 on Medicinal Plants Sector of Agronomy Institute of Rural Federal University of Rio de Janeiro, and crops were obtained in the spring of 2013 and summer of 2014. This study was divided into three chapters: Polymorphism in clones of L. alba coming from the metropolitan area of Rio de Janeiro (Chapter I); Genetic variation for morphological characters in clones of A. alba (Chapter II) and seasonality effect in producing chemotypes of L. alba (Chapter III). In Chapter I the accessions were grouped into dendrogram, five groups being formed and the group I met two similar access (UFRRJLA 17 and UFRRJLA 18). In Chapter II it was shown that the characters analyzed showed variability according to the season (spring or summer) confirming the strong influence of the environment on quantitative variables. The total dry matter and yield were higher in access UFRRJLA05 with citral chemotype, which showed the highest average values in the two seasons in which the data were evaluated. As for the essential oil yield and productivity stood out access UFRRJLA03 with limonene-carvone chemotype, both in spring and in summer. / A biodiversidade, uma das propriedades fundamentais da natureza, ? fonte de imenso potencial de uso econ?mico. O Brasil ? detentor de uma rica biodiversidade, e ? considerado um dos pa?ses megadiversos mais importantes do planeta. Dentre os v?rios elos que comp?e esta biodiversidade a flora nativa brasileira merece destaque. Apesar disto, poucos t?m sido os estudos que promovem a utiliza??o inteligente e racional destes recursos gen?ticos. A domestica??o e o melhoramento de plantas nativas, incluindo aquelas j? conhecidas e utilizadas por popula??es locais ou regionais, por?m sem penetra??o no mercado nacional ou internacional, ? a grande oportunidade que se oferece aos pa?ses ricos em recursos gen?ticos. As plantas medicinais e arom?ticas representam uma parte expressiva deste mercado em potencial, sendo que a esp?cie erva-cidreira-brasileira (Lippia alba) ? um exemplo importante de planta medicinal e arom?tica, h? muito tempo utilizada pela medicina popular por suas fun??es como calmante, antiespasm?dica, sedativo, al?m de produzir v?rios tipos de ?leos essenciais podendo ser utilizada pela ind?stria de perfumes, alimentos e produtos de limpeza, al?m do controle de pragas e doen?as na agricultura. Diante do exposto, o objetivo deste trabalho foi avaliar a variabilidade gen?tica e par?metros gen?ticos de acessos de L. alba e o comportamento agron?mico de diferentes clones oriundos da regi?o Metropolitana do Estado do Rio de Janeiro. O experimento foi instalado em novembro de 2011 no Setor de Plantas Medicinais do Instituto de Agronomia da Universidade Federal Rural do Rio de Janeiro, e as colheitas foram obtidas na primavera de 2013 e no ver?o de 2014. Este estudo foi dividido em tr?s cap?tulos: Polimorfismo em clones de L. alba oriundos da regi?o Metropolitana do Rio de Janeiro (Cap?tulo I) e Par?metros gen?ticos e avalia??o agron?mica em clones de L. alba (Mill) N.E.Brown em duas esta??es no ano (Cap?tulo II). No cap?tulo I os acessos foram agrupados em dendrograma, sendo formados cinco grupos e o grupo I reuniu os dois acessos similares (UFRRJLA 17 e UFRRJLA 18). No cap?tulo II foi demonstrado que os caracteres analisadas apresentaram comportamento vari?vel conforme a esta??o do ano (primavera ou ver?o) confirmando a forte influ?ncia do ambiente sobre as vari?veis quantitativas. A mat?ria seca total e a produtividade foram maiores no clone com quimiotipo citral (UFRRJLA05), com os maiores valores m?dios nas duas esta??es do ano em que os dados foram avaliados. J? para o rendimento e produtividade de ?leo essencial destacou-se o acesso com quimiotipo limoneno-carvona (UFRRJLA03), tanto na primavera quanto no ver?o

Abstract Degradation of the support and sintering of catalyst nanoparticles inherently leads to a loss of functionality of catalyst materials in converters and sensors. Malfunction in such devices may lead to serious economic and environmental damage. The quest for novel and sustainable catalyst materials with better durability is thus ongoing. In this thesis, one-dimensional nanomaterials such as carbon nanotubes and titanium dioxide nanowires are studied and compared to their conventional zero-dimensional counterparts in regard to their structural and functional stability. With the combination of several catalyst nanomaterials and supporting surfaces, aging properties of more than 70 different materials are assessed by the means of X-ray diffraction, transmission electron microscopy and energy-dispersive X-ray analyses. Although CNTs were shown to be thermally the most stable carbonaceous supports for metal nanoparticles, they are, similar to other carbon supports, more sensitive to high temperatures than metal oxide supports and can suffer deactivation by catalytic oxidation and gasification even at moderate temperatures. In addition, the irradiation of the samples with e-beams caused the most dramatic changes in CNT based materials, where nanosized deformities (voids, channels) were formed when either nanoparticles or defects were present. The prepared nanocompositions have been utilized successfully in three different applications including (i) synthesis of hydrogen from ethanol via a steam reforming reaction, (ii) hydrogenation of citral to form value added chemicals and (iii) the application of advanced electrode materials in electric double-layer capacitors. Both CNT and TiO₂ nanowire based nanomaterials were shown to outperform their conventional nano- and microparticle based counterparts in the studied catalytic reactions, i.e. in citral hydrogenation and steam reforming of ethanol, respectively. Furthermore, nanostructured CNTs obtained by catalytic partial oxidation of the material showed an increased specific surface area, which could be exploited in supercapacitor electrodes with enhanced specific capacitance. / Tiivistelmä Katalyyttitukimateriaalin pilaantuminen ja katalyyttinanopartikkelien sintrautuminen johtavat siihen, että muuntajissa ja sensoreissa käytettävät katalyyttiset materiaalit eivät enää toimi, mikä voi aiheuttaa sekä vakavia taloudellisia haittoja että ympäristöhaittoja. Tämän vuoksi kehitetään uusia kestävämpiä katalyyttimateriaaleja. Tässä väitöskirjassa tutkittiin yksiulotteisia nanomateriaaleja, kuten hiilinanoputkia sekä titaanidioksidinanojohtimia ja verrattiin niiden rakenteellista ja toiminnallista stabiiliutta perinteisiin nollaulotteisiin vastineisiin. Erilaisten katalyyttinanomateriaalien ja tukimateriaalien yhdistelmien ikääntymistä arvioitiin röntgendiffraktion, läpäisyelektronimikroskopian ja energiadispersiivisen röntgenanalyysin avulla yli 70 erilaisesta näytteestä. Vaikka hiilinanoputket osoittautuivat termisesti stabiileimmaksi hiilipohjaiseksi tukimateriaaliksi metallinanopartikkeleille, ne ovat kuten kaikki hiilimateriaalit, metallioksiditukimateriaaleja herkempiä korkeille lämpötiloille. Hiilinanoputkipohjaiset katalyytit voivat deaktivoitua katalyyttisen hapettumisen tai kaasuuntumisen vuoksi jo kohtalaisissa lämpötiloissa. Lisäksi elektronisäteellä säteilytetyt nanopartikkelit tai pintavirheitä sisältävät hiilinanoputkipohjaiset katalyytit olivat tutkituista nanomateriaaleista herkimpiä muodostamaan nanorakenteita (koloja, kanavia). Valmistettuja nanokomposiitteja käytettiin onnistuneesti kolmessa eri sovelluksessa: i) vedyn valmistuksessa etanolista höyryreformointireaktiolla, ii) hienokemikaalien valmistuksessa sitraalin hydrauksella sekä iii) elektrodimateriaalina EDLC-kondensaattorissa. Sekä hiilinanoputki- sekä TiO₂-nanojohdinpohjaiset nanomateriaalit toimivat testatuissa katalyyttisissa reaktioissa (etanolin reformointi sekä sitraalin hydraus) paremmin kuin niiden perinteiset vastineet. Lisäksi superkondensaattorin ominaiskapasitanssia onnistuttiin nostamaan lisäämällä hiilinanoputkipohjaisen elektrodin ominaispinta-alaa katalyyttisella hapetusreaktiolla.

Tesis por compendio / [EN] In the present Doctoral Thesis, antimicrobial active packaging materials, at lab and at semi-industrial scale, have been developed with the aim to reduce the natural flora of peeled and cut fruit and extend its shelf life. Packaging prototypes have been developed for their further application. Prior to developing the active materials, the most suitable active agents were selected. To that end, the antimicrobial properties of the volatile active agents citral, hexanal and linalool and mixtures thereof were evaluated against typical microorganisms related to fruit spoilage, molds and yeast, concluding that the effectiveness of the mixture is higher than the sum of the effectiveness of the individual agents. Likewise, non-volatile antimicrobial agents such as potassium sorbate and sodium benzoate were selected, which are widely used in the food industry due to their antifungal properties. With the selected active agents, monolayer polypropylene (PP) films with different concentration of the active mixture citral, hexanal and linalool, at lab scale by means of extrusion, and bilayer films at semi-industrial scale with different active layer thickness by means of coextrusion were prepared. Besides, active packaging trays were developed at semi-industrial scale by thermoforming active sheets obtained by coextrusion of PP and ethyl vinyl acetate (EVA) compounds containing potassium sorbate and sodium benzoate as active agents. Mechanical, barrier and thermal properties of the developed active packaging materials, as well as their sealability and transparency were evaluated. In general, the materials' properties were not affected in a significant manner. However, active trays decreased in transparency due to the incorporation of non-volatile active agents. The release kinetics of the volatile and non-volatile active agents were studied at different temperatures, defining their diffusion coefficients by the adjustment to mathematic models based on Second's Law Fick. Among the volatile active agents, hexanal showed a higher diffusion coefficient, followed by citral and linalool. On the other hand, very small differences were observed between potassium sorbate and sodium benzoate diffusion coefficients, being of the same order of magnitude. In vitro tests were also performed at different temperatures to evaluate the antimicrobial properties of the developed materials. In general, the active packaging materials showed high antimicrobial properties which were enhanced with the increment of temperature. Once the properties of the developed materials were evaluated, in vivo tests with peeled and cut orange and pineapple were performed by packing these fruits with the active film, active tray and their combination (active packaging system). In general, the active packaging system improved the microbiological preservation of the fruit for longer times, between 2 and 7 days for orange and pineapple, respectively, and maintained quality parameters of the fruit at stable levels for longer times. Lastly, the safety of the active packaging materials was evaluated according to the European food contact materials and food legislation, and it was concluded that these materials were not of any safety concern for the consumers. / [ES] En la presente Tesis Doctoral se han desarrollado materiales de envase activo antimicrobiano, a escala laboratorio y a escala semi-industrial, con el objetivo de reducir la proliferación de la flora natural de la fruta pelada y cortada y extender su vida útil. Se han desarrollo distintos prototipos para su posterior aplicación industrial Previo al desarrollo de los materiales de envase, se ha realizado una selección de agentes activos más idóneos. Para ello se han estudiado mediante ensayos in vitro las propiedades antimicrobianas de agentes activos volátiles, citral, hexanal y linalool y diferentes mezclas de los mismos, frente a distintos microorganismos típicos del deterioro de las frutas, mohos y levaduras, concluyendo que la efectividad de la mezcla de los tres es superior a la suma de la efectividad de los activos de forma individual. Así mismo, también se han seleccionado antimicrobianos no volátiles como el sorbato potásico y benzoato sódico, los cuáles son ampliamente empleados en la industria alimentaria debido principalmente a sus propiedades antifúngicas. Con los agentes activos seleccionados, se han desarrollado películas monocapa de polipropileno (PP) con distintas concentraciones de la mezcla activa, citral, hexanal y linalool, a escala laboratorio, mediante técnicas de extrusión, y películas bicapa a escala semi-industrial con distintos espesores de capa activa mediante coextrusión. Por otra parte, se desarrollaron bandejas activas a escala semi-industrial mediante termoconformado de láminas obtenidas por coextrusión de compuestos de PP y etilvinilaceteto (EVA) con sorbato potásico o benzoato sódico como agentes antimicrobianos. Se han evaluado las propiedades mecánicas, barrera y térmicas de los materiales activos desarrollados, así como su sellabilidad y transparencia. En general, las propiedades de los polímeros no se vieron afectadas de manera relevante. Sin embargo, las bandejas activas perdieron su carácter transparente debido a la incorporación de los agentes activos no volátiles. Se ha estudiado la cinética de liberación de los compuestos activos volátiles y no volátiles a distintas temperaturas, determinando los coeficientes de difusión de los agentes activos mediante el ajuste a modelos matemáticos de difusión basados en la Segunda Ley de Fick. Entre los agentes volátiles, el hexanal mostró un mayor coeficiente de difusión seguido de citral y linalool. Por otra parte, no hubo apenas diferencia en los coeficientes de difusión del sorbato potásico y benzoato sódico, siendo éstos del mismo orden de magnitud. Igualmente, se han realizado diferentes experimentos in vitro a distintas temperaturas para determinar las propiedades antimicrobianas de los materiales desarrollados. En general, los materiales activos presentan una elevada capacidad antimicrobiana que se ve potenciada al aumentar la temperatura de exposición. Una vez evaluadas las características de los materiales desarrollados, se han efectuado ensayos de envasado de naranja y piña pelada y cortada con las películas y las bandejas activas y con la combinación del sistema de envase bandeja activa termosellada con la película activa. En general, el sistema de envase activo mejoró la conservación de la fruta por un mayor tiempo, entre 2 y 7 días para la naranja y piña, respectivamente, presentando una gran capacidad antimicrobiana y manteniendo los parámetros de calidad de la fruta en niveles estables por un mayor tiempo. Por último, se ha estudiado la seguridad de estos materiales de acuerdo a la legislación de materiales en contacto con alimentos y la legislación alimentaria europea, concluyendo que los materiales activos desarrollados no presentan preocupación para la seguridad de los consumidores. / [CA] En la present Tesi Doctoral s'han desenvolupat materials d'envasament actiu antimicrobià, a escala de laboratori i a escala semi-industrial amb l'objectiu de reduir la proliferació de la flora natural de la fruita pelada i tallada i estendre la seua vida útil. S'han desenvolupament diferents prototips per a la seua posterior aplicació industrial. Previ al desenvolupament dels materials actius, s'han seleccionat els agents actius mes idonis estudiant mitjançant assajos in vitro les propietats antimicrobianes d'agents actius volàtils, citral, hexanal i linalool i diferents mescles dels mateixos, enfront de diferents microorganismes típics de la deterioració de les fruites -floridures i llevats- concloent que l'efectivitat de la mescla dels tres és superior a la suma de l'efectivitat dels actius de forma individual. Així mateix, s'han seleccionat antimicrobians no volàtils, sorbat potàssic i benzoat sòdic, els quals son àmpliament empleats a l'industria alimentaria per les seues propietats antifúngiques. Amb els agents actius seleccionats, s'han desenvolupat pel·lícules monocapa de polipropilè (PP) amb diferents concentracions de la mescla activa, citral, hexanal i linalool, a escala laboratori, mitjançant tècniques d'extrusió, i pel·lícules bicapa a escala semi-industrial amb diferents espessors de capa activa mitjançant coextrusió. D'altra banda, s'han desenvolupat safates actives a escala semi-industrial mitjançant termoconformació de làmines obtingudes per coextrusió de compostos de PP i etil vinil acetat (EVA) amb sorbat potàssic o benzoat sòdic com a agents antimicrobians. S'han avaluat les propietats mecàniques, barrera i tèrmiques dels materials actius desenvolupats, així com la seua sellabilidad i transparència. En general, les propietats dels polímers no es van veure afectades de manera rellevant. No obstant això, les safates actives van perdre el seu caràcter transparent a causa de la incorporació dels agents actius no volàtils. S'ha estudiat la cinètica d'alliberament dels compostos actius volàtils i no volàtils a diferents temperatures, determinant els coeficients de difusió dels agents actius mitjançant l'ajust a models matemàtics de difusió basats en la Segona Llei de Fick. Entre els agents volàtils, l' hexanal va mostrar un major coeficient de difusió seguit de citral i linalool. D'altra banda, no va haver-hi a penes diferències en els coeficients de difusió del sorbat potàssic i benzoat sòdic, sent aquests del mateix ordre de magnitud. Igualment, s'han realitzat diferents experiments in vitro a diferents temperatures per determinar les propietats antimicrobianes dels materials desenvolupats. En general, els materials actius presenten una elevada capacitat antimicrobiana que es veu potenciada en augmentar la temperatura d'exposició. Una vegada avaluades les característiques dels materials desenvolupats s'han efectuat assajos d'envasament de taronja i pinya pelada i tallada amb la safata, la pel·lícula activa i la seva combinació (sistema d'envàs actiu). En general, el sistema d'envàs actiu va millorar la conservació de la fruita per un major temps, entre 2 i 7 dies per a la taronja i pinya respectivament, presentant una gran capacitat antimicrobiana i mantenint els paràmetres de qualitat de la fruita en nivells estables per un major temps. Finalment, s'ha estudiat la seguretat d'aquests materials d'acord a la legislació de materials en contacte amb aliments i la legislació alimentària europea, concloent que els materials actius desenvolupats no presenten preocupació per a la seguretat dels consumidors. / Lara Lledó, MI. (2016). Antimicrobial packaging system for minimally processed fruit [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/61388 / TESIS / Premios Extraordinarios de tesis doctorales / Compendio

The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, γ- and θ-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on θ-Al2O3. Desorption energies obtained from TPD ranged 85 – 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD, TEOM and NMR relaxometry. Interaction of adsorbates with hydrocarbon occurred predominantly on weak adsorption sites. 13C NMR T1 relaxometry provided in addition atom-specific adsorbate-adsorbent interaction strengths, showing the molecular geometry of adsorption, and applied in co adsorption measurements. The selective hydrogenation of citral as a model α,β-unsaturated aldehyde and the effect of different solvents on the activity and product distribution was studied at 298 and 373 K. A series of polar protic, polar aprotic and non polar solvents was investigated. Results showed higher initial reaction rates in non polar solvents but higher selectivities towards desired products on polar protic solvents. Solvent used also affected by product formation. The strong variations in reaction rates and selectivities reported were related with adsorbate catalyst interactions, as well as solvent reactant interactions. For example, adsorption isotherms showed that ethanol notably reduced the adsorption capacity of citral as compared with hexane, related with the rate differences observed. ATR-IR measurements indicated solvent citral interactions were solely present in polar protic solvents in line with higher yields of geraniol and nerol. Finally, 13C T1 NMR and 1H 2D T1-T2 correlation experiments determined that the geometry of adsorption of citral, influenced by solvent, affected product selectivity, and that product adsorption affected selectivity and deactivation.