Desenvolvimento de materiais nanoestruturados à base de SiO2-Nb2O5 preparados por uma nova rota sol-gel com aplicações em fotônica

Este trabalho concentra-se na preparação e caracterizações estrutural e espectroscópica de materiais nanoestruturados à base de SiO2-Nb2O5 dopados e codopados com íons Er3+, Yb3+ e Eu3+ na forma de pós e guias de onda planares. Os nanocompósitos foram preparados através de uma nova rota sol-gel utilizando óxido de nióbio como precursor em substituição ao alcóxido de nióbio. A correlação estrutura propriedades luminescentes foi estudada por difração de raios X, microscopia eletrônica de transmissão, espectroscopia vibracional de absorção no infravermelho, espectroscopia vibracional de espalhamento Raman, análise térmica, reflectância difusa e especular, espectroscopia de fotoluminescência e acoplamento M-line. Inicialmente foi avaliado a influência da concentração de nióbio nas propriedades estruturais e luminescentes de nanocompósitos (100-x)Si-xNb dopados e codopados com íons Er3+, Yb3+ e Eu3+ tratados termicamente a 900 °C por 3h. A cristalização do Nb2O5 foi dependente da concentração de Nb na matriz, com a distribuição dos íons lantanídeos preferencialmente no Nb2O5, afetando as propriedades luminescentes. Para os nanocompósitos codopados com íons Er3+ e Yb3+ foram obtidos valores de largura de banda a meia altura (FWHM) da ordem de 70 nm na região de 1550 nm e tempos de vida de até 5,2 ms. A emissão na região do visível, decorrente de processos de conversão ascendente, revelou-se dependente da concentração de nióbio. Foi verificada emissão preferencial na região do verde para menores concentrações de Nb. Enquanto que, para as maiores concentrações, processos de relaxação cruzada levaram a um aumento relativo na intensidade de emissão na região do vermelho. A eficiência quântica de emissão dos nanocompósitos (100-x)Si-xNb dopados com Eu3+ variou com o comprimento de onda de excitação, refletindo os diferentes sítios de simetria ocupados por este íons nesta estrutura complexa. A influência da temperatura de tratamento térmico no processo de cristalização do Nb2O5 em nanocompósitos 70Si:30Nb codopados com íons Er3+ e Yb3+ foi avaliada. Material amorfo foi obtido a 700 °C enquanto que a 900 e 1100 °C foram identificas as fases ortorrômbica (fase T) e monoclínica (fase M) do Nb2O5. Intensa emissão na região de 1550 nm com valores de FWHM de 52 e 67 nm e tempos de vida de 5,6 e 5,4 ms foram verificados a 700 e 900 °C sob excitação em 977 nm, respectivamente. Por fim, foram obtidos guias de onda planares com excelentes propriedades ópticas e com grande potencial de aplicação em dispositivos de amplificação óptica. Especificamente, materiais fotônicos com banda larga de emissão na região do infravermelho foram preparados, indicando fortemente a potencialidade para a aplicação em telecomunicações envolvendo não somente a banda C como também as bandas L e S em materiais contendo somente íons Er3+ como centros emissores.

Catalisadores Ni/MgO-SiO2 aplicados na reação de reforma a vapor de glicerol

Catalisadores de Ni (10% em massa) suportado em matrizes mistas MgO-SiO2 foram aplicados na reação de reforma a vapor de glicerol. Os efeitos do teor de MgO como aditivo e do método de preparação foram avaliados frente às propriedades físico-químicas e texturais dos materiais; assim como à atividade, seletividade, estabilidade e formação de carbono na reforma a vapor do glicerol. Os catalisadores foram preparados com diferentes teores mássicos de MgO (10%, 30% e 50%) sobre SiO2 comercial, utilizando processo via seca (mistura física) e via úmida (impregnação sequencial com diferentes solventes: água, etanol e acetona). Foram utilizadas as técnicas de caracterização de espectroscopia de energia dispersiva de raios X, fisissorção de nitrogênio, difratometria de raios X, termogravimetria, difratometria de raios X in situ com O2, redução a temperatura programada com H2, difratometria de raios X in situ com H2, dessorção a temperatura programada com H2 e microscopia eletrônica de varredura. Foi observado que o Ni(II) interage de forma variada com os suportes com diferentes teores de MgO, e que a polaridade do solvente de impregnação utilizado no processo de preparação influencia as propriedades dos catalisadores. A fim de verificar a atividade, seletividade e deposição de carbono; os catalisadores foram testados na reação de reforma a vapor de glicerol a 600oC, por um período de 5h e razão molar água:glicerol de 12:1. Após as reações, os catalisadores foram novamente submetidos às análises de termogravimetria, difratometria de raios X e microscopia eletrônica de varredura, visando a caracterização dos depósitos de carbono obtidos durante o processo catalítico. Os catalisadores de matrizes mistas se mostraram ativos e apresentaram seletividades similares para os produtos gasosos CH4, CO e CO2, além de um alto rendimento em H2. Observou-se que a adição de MgO no suporte, aumentou a dispersão do Ni(II) no material, que por sua vez, influenciou na quantidade de carbono depositado ao longo da reação. A polaridade do solvente de impregnação também teve influência na dispersão metálica, sendo que, quanto menor a polaridade do solvente, maior foi a dispersão obtida no catalisador, e menor a deposição de carbono na reação. O material que apresentou o melhor desempenho catalítico frente ao rendimento de H2 e à deposição de carbono, foi o catalisador preparado com 30% de MgO com etanol como solvente de impregnação.

Electrooxidation methods to produce pseudocapacitance-containing porous carbons

Surface oxygen groups play a key role on the performance of porous carbon electrodes for electrochemical capacitors in aqueous media. The electrooxidation method in NaCl electrolyte using a filter press cell and dimensionally stable anodes is proposed as a viable process for the generation of oxygen groups on porous carbon materials. The experimental set-up is so flexible that allows the easy modification of carbon materials with different configurations, i.e. cloths and granular, obtaining different degrees of oxidation for both conformations without the requirement of binders and conductivity promoters. After the electrooxidation method, the attained porosity is maintained between 90 and 75% of the initial values. The surface oxygen groups generated can increase the capacitance up to a 30% when compared to the pristine material. However, a severe oxidation is detrimental since it may decrease the conductivity and increase the resistance for ion mobility.

Ordered porous nanomaterials: the merit of small

This paper will introduce the reader to some of the “classical” and “new” families of ordered porous materials which have arisen throughout the past decades and/or years. From what is perhaps the best-known family of zeolites, which even now to this day is under constant research, to the exciting new family of hierarchical porous materials, the number of strategies, structures, porous textures, and potential applications grows with every passing day. We will attempt to put these new families into perspective from a synthetic and applied point of view in order to give the reader as broad a perspective as possible into these exciting materials.

Effect of the porous structure in carbon materials for CO2 capture at atmospheric and high-pressure

Activated carbons prepared from petroleum pitch and using KOH as activating agent exhibit an excellent behavior in CO2 capture both at atmospheric (∼168 mg CO2/g at 298 K) and high pressure (∼1500 mg CO2/g at 298 K and 4.5 MPa). However, an exhaustive evaluation of the adsorption process shows that the optimum carbon structure, in terms of adsorption capacity, depends on the final application. Whereas narrow micropores (pores below 0.6 nm) govern the sorption behavior at 0.1 MPa, large micropores/small mesopores (pores below 2.0–3.0 nm) govern the sorption behavior at high pressure (4.5 MPa). Consequently, an optimum sorbent exhibiting a high working capacity for high pressure applications, e.g., pressure-swing adsorption units, will require a poorly-developed narrow microporous structure together with a highly-developed wide microporous and small mesoporous network. The appropriate design of the preparation conditions gives rise to carbon materials with an extremely high delivery capacity ∼1388 mg CO2/g between 4.5 MPa and 0.1 MPa. Consequently, this study provides guidelines for the design of carbon materials with an improved ability to remove carbon dioxide from the environment at atmospheric and high pressure.

Non-porous reference carbon for N2 (77.4 K) and Ar (87.3 K) adsorption

A new non-porous carbon material from granular olive stones has been prepared to be used as a reference material for the characterization of the pore structure of activated carbons. The high precision adsorption isotherms of nitrogen at 77.4 K and argon at 87.3 K on the newly developed sample have been measured, providing the standard data for a more accurate comparative analysis to characterize disordered porous carbons using comparative methods such as t- and αS-methods.

Temperature influence on the physical and mechanical properties of a porous rock: San Julian's calcarenite

This work discusses the results from tests which were performed in order to study the effect of high temperatures in the physical and mechanical properties of a calcarenite (San Julian's stone). Samples, previously heated at different temperatures (from 105 °C to 600 °C), were tested. Non-destructive tests (porosity and ultrasonic wave propagation) and destructive tests (uniaxial compressive strength and slake durability test) were performed over available samples. Furthermore, the tests were carried out under different conditions (i.e. air-cooled and water-cooled) in order to study the effect of the fire off method. The results show that uniaxial compressive strength and elastic parameters (i.e. elastic modulus and Poisson's ratio), decrease as the temperature increases for the tested range of temperatures. A reduction of the uniaxial compressive strength up to 35% and 50% is observed in air-cooled and water-cooled samples respectively when the samples are heated to 600 °C. Regarding the Young's modulus, a fall over 75% and 78% in air-cooled and water-cooled samples respectively is observed. Poisson's ratio also declines up to 44% and 68% with the temperature in air-cooled and water-cooled samples respectively. Slake durability index also exhibits a reduction with temperature. Other physical properties, closely related with the mechanical properties of the stone, are porosity, attenuation and propagation velocity of ultrasonic waves in the material. All exhibit considerable changes with temperature.

Structural and photoelectrochemical properties of porous TiO2 nanofibers decorated with Fe2O3 by sol-flame

The hybrid structure of Fe2O3 nanoparticles/TiO2 nanofibers (NFs), combines the merits of large surface areas of TiO2 NFs and absorption in ultraviolet light–visible light range. This structure can be used for many applications such as photoelectrochemical water splitting and photo-catalysis. Here, a sol-flame method is used for depositing Fe2O3 on TiO2 NFs that were prepared by hydrothermal on Ti sheets. The obtained materials were characterized by XRD, SEM, UV/Vis diffuse reflectance, Raman, and XPS. The results revealed the formation of rutile and anatase crystalline phases together with Fe2O3. This process moves the absorption threshold of TiO2 NFs support into visible spectrum range and enhances the photocurrent in comparison to bare TiO2 NFs, although no hole scavenger was used. The impedance measurement at low and high frequencies revealed an increase in series resistance and a decrease in resistance of charge transfer with sol-flame treatment time. A mechanism for explaining the charge transfer in these TiO2 NFs decorated with Fe2O3 nanoparticles was proposed.

Insight into the immobilization of ionic liquids on porous carbons

Very different carbon materials have been used as support in the preparation of supported ionic liquid phase samples (SILP). Some of them have been oxidized, either strongly (with ammonium persulfate solution) or weakly (with air at 300 °C, 2 h). The purpose is to establish which properties of the supports (e.g., porosity -volume and type-, surface area, oxygen surface chemistry and morphology) determine the IL adsorption capacity and the stability (immobilization) of the supported IL phase. The ionic liquid used in this work is 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6]). For each support, samples with different amounts of ionic liquid have been prepared. The maximum IL that can be loaded depends mainly on the total pore volume of the supports. For comparable pore volumes, the porosity type and the oxygen surface content have no influence on the IL loading. The supported IL fills most of the pores, leaving some blocked porosity. The stability of the supported IL phase (especially important for its subsequent use in catalysis) has been tested in water under general hydrogenation conditions (60 °C and 10 bar H2). In general, leaching is low but it increases with the amount of IL loaded and with the oxidation treatments of the supports.

High-Pressure Methane Storage in Porous Materials: Are Carbon Materials in the Pole Position?

Natural gas storage on porous materials (ANG) is a promising alternative to conventional on-board compressed (CNG) or liquefied natural gas (LNG). To date, Metal–organic framework (MOF) materials have apparently been the only system published in the literature that is able to reach the new Department of Energy (DOE) value of 263 cm3 (STP: 273.15 K, 1 atm)/cm3; however, this value was obtained by using the ideal single-crystal density to calculate the volumetric capacity. Here, we prove experimentally, and for the first time, that properly designed activated carbon materials can really achieve the new DOE value while avoiding the additional drawback usually associated with MOF materials (i.e., the low mechanical stability under pressure (conforming), which is required for any practical application).

Electrochemical Performance of Hierarchical Porous Carbon Materials Obtained from the Infiltration of Lignin into Zeolite Templates

Hierarchical porous carbon materials prepared by the direct carbonization of lignin/zeolite mixtures and the subsequent basic etching of the inorganic template have been electrochemically characterized in acidic media. These lignin-based templated carbons have interesting surface chemistry features, such as a variety of surface oxygen groups and also pyridone and pyridinic groups, which results in a high capacitance enhancement compared to petroleum-pitch-based carbons obtained by the same procedure. Furthermore, they are easily electro-oxidized in a sulfuric acid electrolyte under positive polarization to produce a large amount of surface oxygen groups that boosts the pseudocapacitance. The lignin-based templated carbons showed a specific capacitance as high as 250 F g−1 at 50 mA g−1, with a capacitance retention of 50 % and volumetric capacitance of 75 F cm−3 at current densities higher than 20 A g−1 thanks to their suitable porous texture. These results indicate the potential use of inexpensive biomass byproducts, such as lignin, as carbon precursors in the production of hierarchical carbon materials for electrodes in electrochemical capacitors.

Capillary microreactors based on hierarchical SiO2 monoliths incorporating noble metal nanoparticles for the Preferential Oxidation of CO

Novel hierarchical SiO2 monolithic microreactors loaded with either Pd or Pt nanoparticles have been prepared in fused silica capillaries and tested in the Preferential Oxidation of CO (PrOx) reaction. Pd and Pt nanoparticles were prepared by the reduction by solvent method and the support used was a mesoporous SiO2 monolith prepared by a well-established sol–gel methodology. Comparison of the activity with an equivalent powder catalyst indicated that the microreactors show an enhanced catalytic behavior (both in terms of CO conversion and selectivity) due to the superior mass and heat transfer processes that take place inside the microchannel. TOF values at low CO conversions have been found to be ∼2.5 times higher in the microreactors than in the powder catalyst and the residence time seems to have a noticeable influence over the selectivity of the catalysts designed for this reaction. The Pd and Pt flexible microreactors developed in this work have proven to be effective for the CO oxidation reaction both in the presence and absence of H2, standing out as a very interesting and suitable option for the development of CO purification systems of small dimensions for portable and on-board applications.

Acoustic properties of porous concrete made from arlite and vermiculite lightweight aggregates

The use of sustainable materials is becoming a common practice for noise abatement in building and civil engineering industries. In this context, many applications have been found for porous concrete made from lightweight aggregates. This work investigates the acoustic properties of porous concrete made from arlite and vermiculite lightweight aggregates. These natural resources can still be regarded as sustainable since they can be recycled and do not generate environmentally hazardous waste. The experimental basis used consists of different type specimens whose acoustic performance is assessed in an impedance tube. Additionally, a simple theoretical model for granular porous media, based on parameters measurable with basic experimental procedures, is adopted to predict the acoustic properties of the prepared mixes. The theoretical predictions compare well with the absorption measurements. Preliminary results show the good absorption capability of these materials, making them a promising alternative to traditional porous concrete solutions.

Electrocatalytic oxidation of ascorbic acid on mesostructured SiO2-conducting polymer composites

The conducting self-doping copolymer poly(aniline-co-ABA) preserves its redox activity at pH values as high as 7. This observation was the starting point to synthesize an organic–inorganic hybrid composite able to electrochemically oxidize ascorbic acid molecules at that pH. The inorganic part of the catalytic element was an ordered mesoporous electrodeposit of SiO2, which has been used as the template for the electrochemical insertion of the self-doping copolymer. The oxidation of ascorbate ions at a fixed potential on this composite was studied by means of the kinetic model proposed by Bartlett and Wallace (2001). It was observed that the effective kinetic constant KME increased significantly but, simultaneously, k′ME remained almost constant when the composite was employed as the electrocatalytic substrate. These results were interpreted in the light of two combinations of kinetic constants, which strongly suggested that the increase in KME should be ascribed to the improvement in electronic conductivity of the copolymer induced by the highly ordered silica template.

Electrochemical Behaviour of PSS-Functionalized Silica Films Prepared by Electroassisted Deposition of Sol–Gel Precursors

Porous, electrically insulating SiO2 layers containing polystyrene sulfonate (PSS) were deposited on glassy carbon electrodes by an electrochemically assisted deposition method. The obtained material was characterized by microscopic, spectroscopic and thermal techniques. Silica-PSS films modify the electrochemical response of the glassy carbon electrodes against selected redox probes. Positively charged species show reduced diffusivities across the SiO2-PSS pores, which resulted in a concentration ratio higher than 1 for these species. The opposite behaviour was found for negatively charged redox probes. These observations can be interpreted in terms of the different affinity of the GC/SiO2-PSS-modified electrode for the electroactive species, as a consequence of the negatively charged porous silica.