Evidence of Intracrystalline Mesostructured Porosity in Zeolites by Advanced Gas Sorption, Electron Tomography and Rotation Electron Diffraction

The small size of micropores (typically <1 nm) in zeolites causes slow diffusion of reactant and product molecules in and out of the pores and negatively impacts the product selectivity of zeolite based catalysts, for example, fluid catalytic cracking (FCC) catalysts. Size-tailored mesoporosity was introduced into commercial zeolite Y crystals by a simple surfactant-templating post-synthetic mesostructuring process. The resulting mesoporous zeolite Y showed significantly improved product selectivity in both laboratory testing and refinery trials. Advanced characterization techniques such as electron tomography, three-dimensional rotation electron diffraction, and high resolution gas adsorption coupled with hysteresis scanning and density functional theory, unambiguously revealed the intracystalline nature and connectivity of the introduced mesopores. They can be considered as molecular highways that help reactant and product molecules diffuse quickly to and away from the catalytically active sites within the zeolite crystals and, thus, shift the selectivity to favor the production of more of the valuable liquid fuels at reduced yields of coke and unconverted feed.

Synthesis of palladium nanoparticles over graphite oxide and carbon nanotubes by reduction in ethylene glycol and their catalytic performance on the chemoselective hydrogenation of para-chloronitrobenzene

Pd nanoparticles have been synthesized over carbon nanotubes (CNT) and graphite oxide (GO) by reduction with ethylene glycol and by conventional impregnation method. The catalysts were tested on the chemoselective hydrogenation of p-chloronitrobenzene and the effect of the synthesis method and surface chemistry on their catalytic performance was evaluated. The catalysts were characterized by N2 adsorption/desorption isotherms at 77 K, TEM, powder X-ray diffraction, thermogravimetry, infrared and X-ray photoelectron spectroscopy and ICP-OES. It was observed that the synthesis of Pd nanoparticles employing ethylene glycol resulted in metallic palladium particles of smaller size compared to those prepared by the impregnation method and similar for both supports. The presence of oxygen groups on the support surface favored the activity and diminished the selectivity. It seems that ethylene glycol reacted with the surface groups of GO, this favoring the selectivity. The activity was higher over the CNT-based catalysts and both catalysts prepared by reduction in ethylene glycol were quite stable upon recycling.

Catalytic wet peroxide oxidation: a route towards the application of hybrid magnetic carbon nanocomposites for the degradation of organic pollutants. A review

Several motivations have prompted the scientific community towards the application of hybrid magnetic carbon nanocomposites in catalytic wet peroxide oxidation (CWPO) processes. The most relevant literature on this topic is reviewed, with a special focus on the synergies that can arise from the combination of highly active and magnetically separable iron species with the easily tuned properties of carbon-based materials. These are mainly ascribed to increased adsorptive interactions, to good structural stability and low leaching levels of the metal species, and to increased regeneration and dispersion of the active sites, which are promoted by the presence of the carbon-based materials in the composites. The most significant features of carbon materials that may be further explored in the design of improved hybrid magnetic catalysts are also addressed, taking into consideration the experimental knowledge gathered by the authors in their studies and development of carbon-based catalysts for CWPO. The presence of stable metal impurities, basic active sites and sulphur-containing functionalities, as well as high specific surface area, adequate porous texture, adsorptive interactions and structural defects, are shown to increase the activity of carbon materials when applied in CWPO, while the presence of acidic oxygen-containing functionalities has the opposite effect.

(Bio)funcionalização de superfícies nanoestruturadas para eletrocatálise e desenvolvimento de biossensores eletroquímicos e óticos

Tese de doutoramento, Química (Química Física), Universidade de Lisboa, Faculdade de Ciências, 2016

Degradation of azo-dye Orange II by a photoassisted Fenton reaction using a novel composite of iron oxide and silicate nanoparticles as a catalyst

A novel nanocomposite of iron oxide and silicate, prepared through a reaction between a solution of iron salt and a dispersion of Laponite clay, was used as a catalyst for the photoassisted Fenton degradation of azo-dye Orange II. This catalyst is much cheaper than the Nafion-based catalysts, and our results illustrate that it can significantly accelerate the degradation of Orange II under the irradiation of UV light (lambda = 254 nm). An advantage of the catalyst is its long-term stability that was confirmed through using the catalyst for multiple runs in the degradation of Orange II. The effects of the H2O2 molar concentration, solution pH, wavelength and power of the LTV light, catalyst loading, and initial Orange II concentration on the degradation of Orange 11 were studied in detail. In addition, it was also found that discoloration of Orange 11 undergoes a faster kinetics than mineralization of Orange II and 75% total organic carbons of 0.1 mM Orange II can be eliminated after 90 min in the presence of 1.0 g of Fe-nanocomposite/L, 4.8 mM H2O2, and 1 x 8W UVC.

Rearrangement of α-pinene oxide using a surface catalysed spinning disc reactor (SDR)

Isomerisation of α-pinene oxide to campholenic aldehyde was performed by immobilising zinc triflate based catalysts on the surface of a spinning disc reactor (SDR). Two types of catalyst have been studied and the influence of operating parameters such as rotational speed, feed flow rate and reaction temperature on conversion and selectivity towards campholenic aldehyde has been investigated in considerable detail. The findings of the study suggest that immobilising the catalyst on the reactor surface and performing the reaction in continuous mode has potential for achieving benefits of Green Chemical Technology (GCT).

Asymmetric oxidation of sulfides

This review discusses synthesis of enantiopure sulfoxides through the asymmetric oxidation of prochiral sulfides. The use of metal complexes to promote asymmetric sulfoxidation is described in detail, with a particular emphasis on the synthesis of biologically active sulfoxides. The use of non-metal-based systems, such as oxaziridines, chiral hydroperoxides and peracids, as well as enzyme-catalyzed sulfoxidations is also examined.

Produzione di alcol furfurilico da furfurale in fase gas con catalizzatori a base di CaO

The hydrogenation of biomass-derived molecules is a key reaction in upgrading these compounds into chemicals and fuels. The use of catalytic transfer hydrogenation, employing alcohols as hydrogen sources, offers an alternative approach to this process, avoiding the use of H2 under high pressure and precious metal catalysts. In this work, the gas-phase conversion of biomass-derived furfural into furfuryl alcohol and 2-methylfuran was studied, using methanol as the H-transfer agent and CaO-based catalysts. The results obtained with this catalyst were compared with those obtained by using MgO, which due to its basic properties and to its high surface area, at present appears to be among the best basic catalysts used for the conversion of biomass-derived molecules. Pure CaO, despite having a very low surface area, compared to MgO catalyst (5 m2/g vs. 172 m2/g), was shown to reduce furfural into its corresponding unsaturated alcohol at 350°C, thus allowing selective H-transfer from methanol to the substrate. These results highlight the potential application of the H-transfer reaction over CaO based catalysts as an efficient process for the selective reduction of biomass-derived molecules.

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Enhanced oxidation activity from modified ceria: MnOx-ceria, CrOx-ceria and Mg doped VOx-ceria

Ceria is an important component of catalysts for oxidation reactions that proceed through the Mars-van Krevelen mechanism, promoting activity. A paradigm example of this is the VOx–CeO2 system for oxidative dehydrogenation reactions, where vanadium oxide species are supported on ceria and a special synergy between them is behind the enhanced activity: reduction of the catalyst is promoted by ceria undergoing reduction. This leads to favourable oxygen vacancy formation and hydrogen adsorption energies—useful descriptors for the oxidation activity of VOx–CeO2 catalysts. In this paper, we examine if this promoting effect on ceria-based catalysts holds for other metal oxide modifiers and we investigate MnOn– and CrOn–CeO2(111) (n = 0 − 4) as examples. We show, combining density functional theory calculations and statistical thermodynamics that similarly to the vanadia modifier, the stable species in each case is MnO2– and CrO2–CeO2. Both show favourable energetics for oxygen vacancy formation and hydrogen adsorption, indicating that VO2–CeO2 is not the only system of this type that can have an enhanced activity for oxidation reactions. However, the mechanism involved in each case is different: CrO2–CeO2 shows similar properties to VO2–CeO2 with ceria reduction upon oxygen removal stabilising the 5+ oxidation state of Cr. In contrast, with MnO2–CeO2, Mn is preferentially reduced. Finally, a model system of VO2–Mg:CeO2 is explored that shows a synergy between VO2 modification and Mg doping. These results shed light on the factors involved in active oxidation catalysts based on supported metal oxides on ceria that should be taken into consideration in a rational design of such catalysts.

Tailored norbornene-based copolymer with systematic variation of norbornadiene as a crosslinker obtained via ROMP with alternative amine Ru catalysts

Copolymers of norbornene (NBE) with norbomadiene (NBD) were obtained via ROMP with [RuCl2(PPh3)(2)(L)] type complexes as initiators (1 for L = piperidine and 2 for L = 3,5-Me(2)piperidine). The reactions were performed using a fixed quantity of NBE (5000 equivalents/[Ru]) for different concentrations of NBD (500, 1000, 1500 and 2000 equivalents/ [Ru]) in CHCl3, initiated with ethyl diazoacetate at room temperature. The presence of NBD in the NBE chains was characterized by H-1 and C-13 NMR. Whereas the copolymer microstructure was influenced neither by the NBD quantity nor by the initiator type, the N-n and PDI values were improved when increasing the NBD quantity in the medium. When raising the NBD amount, DMA results indicated increased cross-linking with increasing T-g and E ' storage modulus, as well as the fact that SEM micrographs indicated decreased pore sizes in the porous isolated copolymers. (C) 2011 Elsevier Ltd. All rights reserved.

Pt based anode catalysts for direct ethanol fuel cells

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt1Sn1/C > Pt1Ru1/C > Pt1W1/C > Pt1Pd1/C > Pt/C. Moreover, Pt1Ru1/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt1Sn1/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt1Sn1/C or Pt3Sn2/C or Pt2Sn1/C as anode catalyst showed better performances than those with Pt3Sn1/C or Pt4Sn1/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt1Ru1/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OHads, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low current density regions where the electro-oxidation of ethanol is considered not so fast and its chemisorption is not the rate-determining step, the Pt3Sn2/C seems to be more suitable for the direct ethanol fuel cell. At 75 degreesC, the single ethanol fuel cell with Pt3Sn2/C as anode catalyst showed a comparable performance to that with Pt2Sn1/C, but at higher temperature of 90 degreesC, the latter presented much better performance. It is thought from a practical point of view that Pt2Sn1/C, supplying sufficient -OHads and having adequate active Pt sites and acceptable ohmic effect, could be the appropriate anode catalyst for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

The influence of different co-catalysts in Pt-based ternary and quaternary electro-catalysts on the electro-oxidation of methanol and ethanol in acid media

One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.

Nb2O5 Schottky based ethanol vapour sensors : effect of metallic catalysts

The aim of this paper is to compare the performances of the highly porous Nb2O5 Schottky based sensors formed using different catalytic metals for ethanol vapour sensing. The fabricated sensors consist of a fairly ordered nano-vein like porous Nb2O5 prepared via an elevated temperature anodization method. Subsequently, Pt, Pd and Au were sputtered as both Schottky contacts and catalysts for the comparative studies. These metals are chosen as they have large work functions in comparison to the electron affinity of the anodized Nb2O5. It is demonstrated that the device based on Pd/Nb2O5 Schottky contact has the highest sensitivity amongst the developed sensors. The sensing behaviors were studied in terms of the Schottky barrier height variations and properties of the metal catalysts.