Síntese, caracterização e modificação de superfícies de sílicas mesoporosas ordenadas para captura de CO2

Processos como a purificação do metano (CH4) e a produção de hidrogênio gasoso (H2) envolvem etapas de separação de CO2. Atualmente, etanolaminas como monoetanolamina (MEA), dietanolamina (DEA), metildietanolamina (MDEA) e trietanolamina (TEA) são as substâncias mais utilizadas no processo de separação/captura de CO2 em processos industriais. Entretanto, o uso destas substâncias apresenta alguns inconvenientes devido à alta volatilidade, dificuldade de se trabalhar com material líquido, também ao alto gasto energético envolvido das etapas de regeneração e à baixa estabilidade térmica e química. Com base nessa problemática, esse trabalho teve por objetivo a síntese de um tipo de sílica mesoporosa altamente ordenada (SBA-15) de modo a utilizá-la no processo de captura de CO2. O trabalho foi dividido em quatro etapas experimentais que envolveram a síntese da SBA-15, o estudo do comportamento térmico de algumas etanolaminas livres, síntese e caracterização de materiais adsorventes preparados a partir de incorporação de etanolaminas à SBA-15 e estudo da eficiência de captura de CO2 por esses materiais. Novas alternativas de síntese da SBA-15 foram estudadas neste trabalho, visando aperfeiçoar as propriedades texturais do material produzido. Tais alternativas são baseadas na remoção do surfatante, utilizado como molde na síntese da sílica mesoporosa, por meio da extração por Soxhlet, utilizando diferentes solventes. O processo contribuiu para melhorar as propriedades do material obtido, evitando o encolhimento da estrutura que pode ser ocasionado durante a etapa de calcinação. Por meio de técnicas como TG/DTG, DSC, FTIR e Análise Elementar de C, H e N foi realizada a caracterização físico-química e termoanalítica da MEA, DEA, MDEA e TEA, visando melhor conhecer as características destas substâncias. Estudos cinéticos baseados nos métodos termogravimétricos isotérmicos e não isotérmicos (Método de Ozawa) foram realizados, permitindo a determinação de parâmetros cinéticos envolvidos nas etapas de volatilização/decomposição térmica das etanolaminas. Além das técnicas acima mencionadas, MEV, MET, SAXS e Medidas de Adsorção de N2 foram utilizadas na caraterização da SBA-15 antes e após a incorporação das etanolaminas. Dentre as etanolaminas estudadas, a TEA apresentou maior estabilidade térmica, entretanto, devido ao seu maior impedimento estérico, é a etanolamina que apresenta menor afinidade com o CO2. Diferentemente das demais etanolaminas estudadas, a decomposição térmica da DEA envolve uma reação intramolecular, levando a formação de MEA e óxido de etileno. A incorporação destes materiais à SBA-15 aumentou a estabilidade térmica das etanolaminas, uma vez que parte do material permanece dentro dos poros da sílica. Os ensaios de adsorção de CO2 mostraram que a incorporação da MEA à SBA-15 catalisou o processo de decomposição térmica da mesma. A MDEA foi a etanolamina que apresentou maior poder de captura de CO2 e sua estabilidade térmica foi consideravelmente aumentada quando a mesma foi incorporada à SBA-15, aumentando também seu potencial de captura de CO2.

Estudo das propriedades inibidoras de corrosão das imidazolinas oleica e quaternária e seu encapsulamento em partículas inertes.

Entre os inibidores de corrosão clássicos que já são utilizados na indústria do petróleo, foram estudadas a imidazolina oleica e a quaternária através de técnicas eletroquímicas, gravimétrica e analíticas, para avaliar a eficiência de inibição e como esses inibidores atuam em meio ácido. O meio agressivo foi uma solução de NaCl 3,5% em massa acidificada com ácido clorídrico até atingir um pH=2 com o objetivo de simular o ambiente de extração petrolífera. O substrato empregado foi o aço carbono 1020. As técnicas eletroquímicas utilizadas foram: monitoramento do potencial de circuito aberto, medidas de resistência de polarização linear, espectroscopia de impedância eletroquímica (EIE ) e curvas de polarização. Os valores das componentes real e imaginária de impedância indicam uma resistência maior aos processos de transferência de carga com o aumento da concentração dos inibidores e os Diagramas de Bode de ângulo de fase, revelaram a presença de uma camada de inibidor adsorvida sobre o metal com uma constante de tempo em altas frequências observada para a imidazolina oleica e quaternária. Para a imidazolina quaternária, verificou-se que só para tempos maiores de imersão é que o filme se adsorve de forma eficiente demonstrando uma cinética mais lenta de adsorção. Nos ensaios gravimétricos, os resultados de taxa de corrosão em m/ano foram decrescentes com o tempo após período de imersão de 30 dias, para ambas as imidazolinas. O uso das técnicas analíticas foi necessário a fim de se compreender melhor o comportamento das imidazolinas sobre o aço no meio estudado. Os resultados da análise de íons férricos em solução, por emissão atômica, foram obtidos durante várias amostragens durante o período do ensaio de perda de massa, e foi possível verificar um processo de inibição da corrosão até doze dias de imersão do metal, depois disto ocorre um disparo na quantidade de ferro liberado em solução, sugerindo que pode estar ocorrendo uma degradação do inibidor após 12 dias de imersão. Para esclarecer esse ponto, análises por espectroscopia Raman dos produtos de fundo formados durante os ensaios de perda de massa indicaramm que a degradação pode realmente estar ocorrendo. Foi confirmado, também por espectroscopia Raman sobre a superfície do aço após imersão prévia em solução contendo a imidazolina oleica, que há uma película adsorvida que protege o metal do meio agressivo. Técnica de microscopia eletrônica de varredura foi utilizada para caracterizar os corpos de prova na ausência e presença do inibidor, depois dos ensaios eletroquímicos e foi possível caracterizar, através dessa técnica a maior eficiência inibidora do filme de imidazolina quaternária. Dois tipos de nanoconatiners foram avaliados para o encapsulamento das duas imidazolinas estudadas: nanocontainers a base do argilomineral haloiista e sílica mesoporosa tipo SBA 15. Resultados de impedância eletroquímica mostraram a liberação dos inibidores de corrosão encapsulados com o tempo de imersão. Análise na região do infravermelho por sonda de fibra ótica foi utilizada para comprovar química e qualitativamente a liberação do inibidor a partir dos nanorreservatórios, no meio agressivo.

Síntesis y caracterización de Materiales Nanoscópicos y Nano-especies activas y sus aplicaciones en Energía y Medio Ambiente

Se estudiara la síntesis, caracterización y aplicación de Materiales Nanoscópicos (Nanoestructurados, MN y Nanocomposites, NC), con propiedades definidas en el campo de la Energía, Medio Ambiente y Bioingeniería, especialmente las MCM y SBA ( MCM-41 y MCM-48, SBA-1, SBA-3, SBA-15 y SBA-16, Silíceas o Al/Ga/Ti como Heteroátomo, y la Al-SBA-3, recientemente desarrollada por nosotros, primera publicación a nivel mundial). Se pondrá énfasis en el diseño, preparación y caracterización de sus réplicas con C (CMK-1 y CMK-3). Determinación y optimización de las estrategias de síntesis de MN y NC y Nano especies Activas en nuevos catalizadores (Ir/ TiO2, Pt/Pd etc.), cuyas propiedades fundamentales (estructurales, electrónicas, conductividad, actividad catalítica, etc.) sean aplicables en los Campos Citados. Comprensión de los parámetros que definen dichas propiedades, relación estructura/actividad, rediseño y aplicaciones de MN y NC en dos procesos específicos (de los cuales ya hemos publicado resultados): Energía y Medioambiente: 1) Almacenamiento de H2, Adsorción/Absorción de H2 en los MN Silíceos y Carbonosos y NC y Desarrollo de NC híbridos formados por reservorios en base a los MN por oclusión de nano-alambres moleculares de polímeros orgánicos, modificando las propiedades de conductividad / semiconductividad y adsorción de H2; 2) Estudio de las reacciones de hidrotratamiento catalítico (HDT), que comprende la hidrogenación, la hidrodesulfurizacion (HDS) y la hidrodenitrogenacion (HDN) de compuestos refractarios presentes en los cortes de combustibles. La determinación del mecanismo de las reacciones de HDS y HDN.

Pore size characterization of mesoporous materials by a thermodynamic approach: A curvature-dependent solid-fluid potential

A thermodynamic analysis of nitrogen adsorption in cylindrical pores of MCM-41 and SBA-15 samples at 77 K is presented within the framework of the Broekhoff and de Boer (BdB) theory. We accounted for the effect of the solid surface curvature on the potential exerted by the pore walls. The developed model is in quantitative agreement with the non-local density functional theory (NLDFT) for pores larger than 2 tun. This modified BdB theory accounting for the Curvature Dependent Potential (CDP-BdB) was applied to determine the pore size distribution (PSD) of a number of MCM-41 and SBA-15 samples on the basis of matching the equilibrium theoretical isotherm against the adsorption branch of the experimental isotherm. In all cases investigated the PSDs determined with the new approach are very similar to those determined with the non-local density functional theory also using the same basis of matching of theoretical isotherm against the experimental adsorption branch. The developed continuum theory is very simple in its utilization, suggesting that CDP-BdB could be used as an alternative tool to obtain PSD for mesoporous solids from the analysis of adsorption branch of adsorption isotherms of any sub-critical fluids.

Comparative Analysis of Structural and Morphological Properties of Large-Pore Periodic Mesoporous Organosilicas and Pure Silicas

A systematic study on the structural properties and external morphologies of large-pore mesoporous organosilicas synthesized using triblock copolymer EO20PO70EO20 as a template under low-acid conditions was carried out. By employing the characterization techniques of SAXS, FE-SEM, and physical adsorption of N-2 in combination with alpha(s)-plot method, the structural properties and external morphologies of large-pore mesoporous organosilicas were critically examined and compared with that of their pure-silica counterparts synthesized under similar conditions. It has been observed that unlike mesoporous pure silicas, the structural and morphological properties of mesoporous organosilicas are highly acid-sensitive. High-quality mesoporous organosilicas can only be obtained from synthesis gels with the molar ratios of HCl/H2O between 7.08 x 10(-4) and 6.33 x 10(-3), whereas mesoporous pure silicas with well-ordered structure can be obtained in a wider range of acid concentration. Simply by adjusting the HCl/H2O molar ratios, the micro-, meso-, and macroporosities of the organosilica materials can be finely tuned without obvious effect on their structural order. Such a behavior is closely related to their acid-controlled morphological evolution: from necklacelike fibers to cobweb-supported pearl-like particles and to nanosized particulates.

Facile route to conformal hydrotalcite coatings over complex architectures:a hierarchically ordered nanoporous base catalyst for FAME production

An alkali- and nitrate-free hydrotalcite coating has been grafted onto the surface of a hierarchically ordered macroporous-mesoporous SBA-15 template via stepwise growth of conformal alumina adlayers and their subsequent reaction with magnesium methoxide. The resulting low dimensional hydrotalcite crystallites exhibit excellent per site activity for the base catalysed transesterification of glyceryl triolein with methanol for FAME production.

Can surface energy measurements predict the impact of catalyst hydrophobicity upon fatty acid esterification over sulfonic acid functionalised periodic mesoporous organosilicas?

Sulfonic acid functionalised periodic mesoporous organosilicas (PrSO3 H-PMOs) with tunable hydrophobicity were synthesised via a surfactant-templating route, and characterised by porosimetry, TEM, XRD, XPS, inverse gas chromatography (IGC) and ammonia pulse chemisorption. IGC reveals that incorporation of ethyl or benzyl moieties into a mesoporous SBA-15 silica framework significantly increases the non-specific dispersive surface energy of adsorption for alkane adsorption, while decreasing the free energy of adsorption of methanol, reflecting increased surface hydrophobicity. The non-specific dispersive surface energy of adsorption of PMO-SO3H materials is strongly correlated with their activity towards palmitic acid esterification with methanol, demonstrating the power of IGC as an analytical tool for identifying promising solid acid catalysts for the esterification of free fatty acids. A new parameter [-ΔGCNP-P], defined as the per carbon difference in Gibbs free energy of adsorption between alkane and polar probe molecules, provides a simple predictor of surface hydrophobicity and corresponding catalyst activity in fatty acid esterification. © 2014 Elsevier B.V.

Heterogeneous catalysis in an oscillatory baffled flow reactor

The first demonstration of heterogeneous catalysis within an oscillatory baffled flow reactor (OBR) is reported, exemplified by the solid acid catalysed esterification of organic acids, an important prototypical reaction for fine chemicals and biofuel synthesis. Suspension of a PrSOH-SBA-15 catalyst powder is readily achieved within the OBR under an oscillatory flow, facilitating the continuous esterification of hexanoic acid. Excellent semi-quantitative agreement is obtained between OBR and conventional stirred batch reaction kinetics, demonstrating efficient mixing, and highlighting the potential of OBRs for continuous, heterogeneously catalysed liquid phase transformations. Kinetic analysis highlights acid chain length (i.e. steric factors) as a key predictor of activity. Continuous esterification offers improved ester yields compared with batch operation, due to the removal of water by-product from the catalyst, evidencing the versatility of the OBR for heterogeneous flow chemistry and potential role as a new clean catalytic technology. © The Royal Society of Chemistry 2013.

Mesoporous silicas as versatile supports to tune the palladium-catalyzed selective aerobic oxidation of allylic alcohols

Surfactant templating offers a simple route to synthesize high-surface area silicas with ordered, tunable mesopore architectures. The use of these materials as versatile catalyst supports for palladium nanoparticles has been explored in the aerobic selective oxidation (selox) of allylic alcohols under mild conditions. Families of Pd/mesoporous silicas, synthesized through incipient wetness impregnation of SBA-15, SBA-16, and KIT-6, have been characterized by using nitrogen porosimetry, CO chemisorption, diffuse reflection infrared Fourier transform spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and high-resolution TEM and benchmarked in liquid phase allylic alcohol selox against a Pd/amorphous SiO2 standard. The transition from amorphous to two-dimensional parallel and three-dimensional interpenetrating porous silica networks conferred significant selox rate enhancements associated with higher surface densities of active palladium oxide sites. Dissolved oxygen was essential for insitu stabilization of palladium oxide, and thus maintenance of high activity on-stream, whereas selectivity to the desired aldehyde selox product over competing hydrogenolysis pathways was directed by using palladium metal. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced selective aerobic alcohol oxidation through nanoengineered catalyst supports

The selective conversion of alcohols to their carbonyl derivatives is a critical step towards a sustainable chemical industry. Heterogeneous Pd catalysts represent some of the most active systems known, even so further studies into the active species and role of support are required. Through controlling support mesostructure, using non-interconnected SBA-15 and interlinked SBA-16 and KIT-6, we have evaluated the role of pore architecture on supported Pd nanoparticles and their subsequent activity for liquid phase aerobic allylic alcohol selective oxidation.[1,2] These synthesised silica supports exhibit high surface areas (>800 m2g-1), and similar mesopore diameters (3.5 to 5 nm), but differ in their pore connectivity and arrangement; p6mm (SBA-15), I3mm (SBA-16) and I3ad (KIT-6). When evaluated alongside commercial non-mesoporous silica (200 m2 g-1) they promote enhanced Pd dispersion with interpenetrating assemblies providing further elevation. Macropore introduction into SBA-15, producing a hierarchical macro-mesoporous silica (MM-SBA-15), allows control over mesopore length and accessibility which escalates Pd distribution to levels akin to KIT-6 and SBA-16. Controlling dispersion, and likewise nanoparticle size, is thus facilitated through the choice of support and additionally Pd loading, with cluster sizes spanning 3.2 to 0.8 nm. X-ray spectroscopies indicate nanoparticles are PdO terminated with the oxide content a function of dispersion. Kinetic studies allude to surface PdO being the active site responsible, with a constant TOF observed, independent of loading and support. This confirms activity is governed by PdO density, whilst also overruling internal mass diffusion constraints. MM-SBA-15 facilitates superior activity and TOFs for long chain acyclic terpene alcohols due to reduced internal mass transport constraints.

Size-controlled TiO2 nanoparticles on porous hosts for enhanced photocatalytic hydrogen production

Nanocystalline TiO2 particles were successfully synthesized on porous hosts (SBA-15 and ZSM-15) via a sol-gel impregnation method. Resulting nanocomposites were characterized by XRD, TEM, BET surface analysis, Raman and UV-vis diffuse reflectance spectroscopy, and their photocatalytic activity for H2 production evaluated. XRD evidences the formation of anatase nanoparticles over both ZSM-5 and SBA-15 porous supports, with TEM highlighting a strong particle size dependence on titania precursor concentration. Photocatalytic activities of TiO2/ZSM-5 and TiO2/SBA-15 composites were significantly enhanced compared to pure TiO2, owing to the smaller TiO2 particle size and higher surface area of the former. TiO2 loadings over the porous supports and concomitant photocatalytic hydrogen production were optimized with respect to light absorption, available surface reaction sites and particle size. 10%TiO2/ZSM-5 and 20%TiO2/SBA-15 proved the most active photocatalysts, exhibiting extraordinary hydrogen evolution rates of 10,000 and 8800μmolgTiO2 -1 h-1 under full arc, associated with high external quantum efficiencies of 12.6% and 5.4% respectively under 365nm irradiation.

Zr-containing hybrid organic-inorganic mesoporous materials:hydrophobic acid catalysts for biodiesel production

Zirconium-containing periodic mesoporous organosilicas (Zr-PMOs) with varying framework organic content have been synthesized through a direct synthesis method. These materials display the excellent textural properties of the analogous inorganic solid acid Zr-SBA-15 material. However, the substitution of silica by organosilicon species provides a strong hydrophobic character. This substitution leads to meaningful differences in the environment surrounding the zirconium metal sites, leading the modification of the catalytic properties of these materials. Although lower metal incorporation is accomplished in the final materials, leading to a lower population of metal sites, hydrophobisation leads to an impressive beneficial effect on the intrinsic catalytic activity of the zirconium sites in biodiesel production by esterification/transesterification of free fatty acid -containing feedstock. Moreover, the catalytic activity of the highly hybridised materials is hardly affected in presence of large amounts of water, confirming their very good water-tolerance. This makes Zr-PMO materials interesting catalysts for biodiesel production from highly acidic water-containing feedstock. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Pt nanocatalysts for the aerobic selox of cinnamyl alcohol

The selective aerobic oxidation of cinnamyl alcohol over Pt nanoparticles has been tuned via the use of mesoporous silica supports to control their dispersion and oxidation state. High area two-dimensional SBA-15, and three-dimensional, interconnected KIT-6 silica significantly enhance Pt dispersion, and thus surface PtO2 concentration, over that achievable via commercial low surface area silica. Selective oxidation activity scales with Pt dispersion in the order KIT-6 ≥ SBA-15 > SiO2, evidencing surface PtO2 as the active site for cinnamyl alcohol selox to cinnamaldehyde. Kinetic mapping has quantified key reaction pathways, and the importance of high O2 partial pressures for cinnamaldehyde production. © 2013 The Royal Society of Chemistry.

Tunable KIT-6 mesoporous sulfonic acid catalysts for fatty acid esterification

We report the first catalytic application of pore-expanded KIT-6 propylsulfonic acid (PrSO H) silicas, in fatty acid esterification with methanol under mild conditions. As-synthesized PrSO H-KIT-6 exhibits a 40 and 70% enhancement in turnover frequency (TOF) toward propanoic and hexanoic acid esterification, respectively, over a PrSO H-SBA-15 analogue of similar 5 nm pore diameter, reflecting the improved mesopore interconnectivity of KIT-6 over SBA-15. However, pore accessibility becomes rate-limiting in the esterification of longer chain lauric and palmitic acids over both solid acid catalysts. This problem can be overcome via hydrothermal aging protocols which permit expansion of the KIT-6 mesopore to 7 nm, thereby doubling the TOF for lauric and palmitic acid esterification over that achievable with PrSO H-SBA-15. © 2012 American Chemical Society.

Support-enhanced selective aerobic alcohol oxidation over Pd/mesoporous silicas

The influence of silica mesostructure upon the Pd-catalyzed selective oxidation of allylic alcohols has been investigated for amorphous and surfactant-templated SBA-15, SBA-16, and KIT-6 silicas. Significant rate enhancements can be achieved via mesopore introduction, most notably through the use of interconnected porous silica frameworks, reflecting both improved mass transport and increased palladium dispersion; catalytic activity decreases in the order Pd/KIT-6 ≈ Pd/SBA-16 > Pd/SBA-15 > Pd/SiO2. Evidence is presented that highly dispersed palladium oxide nanoparticles, not zerovalent palladium, are the catalytically active species. © 2011 American Chemical Society.