Grafting luminescent metal-organic species into mesoporous MCM-41 silica from europium(III)tetramethylheptanedionate, Eu(thd)3

Mixed systems with Eu(III) β-diketonates as optically active guest species, and mesoporous silicas MCM-41 as a host matrix have been investigated. The grafting of europium(III) onto the inner walls of unmodified MCM-41 has been achieved starting from Eu(thd)3 (thd = 2,2,6,6- tetramethyl-3,5-heptanedionate), using two routes: wet impregnation (WI) at room temperature,and chemical vapour infiltration (CVI) at 185 °C. In received hybrids, denoted Eu(thd)x@MCM- 41, the same maximum yield [Eu]/[Si] = 8.2 at% on average has been achieved with either methods. The molar ratio x = [thd]/[Eu] is 0.6 on average for WI samples, and 1.5 for CVI samples. In the latter, higher contents in thd compensate lower contents in silanols with respect to the former. Rationalizing the possible bonds exchanged at the silica surface leads to a great diversity of possible co-ordination schemes according to the expression Σ[Si(OH)nx (O)xEu(thd)3-x] (where Σ means that surface species are considered). Chromophore neutral ligands phenanthroline (phen) or bipyridine (bipy) have been added to induce efficient Eu3+ luminescence under 270–280 nm excitation, via the antenna effect. For the most favourable case, (phen)yEu(thd)x@MCM-41, the emission intensity at 612 nm under excitation at 270 nm is 2/3 that for the genuine heteroleptic complex Eu(thd)3(phen). Moreover the hybrid material is stable up to 440 °C

Hydrocracking of surgical face masks over Y zeolites : catalyst development, process design and life cycle assessment

Acknowledgement This study was funded by The LEVERHULME TRUST (Grant DS-2017-073). Muhammad Usman Azam, a Leverhulme Trust Doctoral Scholar, is part of the 15 PhD scholarships of the “Leverhulme Centre for Doctoral Training in Sustainable Production of Chemicals and Materials” at the University of Aberdeen (Scotland, United Kingdom). Auguste Fernandes thanks Portuguese FCT for funding (CQE - UIDB/00100/2020 and UIDP/00100/2020; IMS-LA/P/0056/2020; contract hiring under DL57/2016 law).Peer reviewedPublisher PD

Bio-oils/FCC co-processing : Insights into the adsorption of guaiacol on Y zeolites with distinct acidity and textural properties

Acknowledgments The authors thank Fundação para a Ciência e a Tecnologia (FCT, Portugal) for financial funding (UIDB/00100/2020 and UIDP/00100/2020). Fernandes also thanks FCT for researcher contract hiring (DL No. 57/2016 regulation).Peer reviewedPostprin

Gas-phase conversion of glycerol to allyl alcohol over vanadium-supported zeolite beta

Vanadium oxide supported beta zeolite (Si/Al=25, 4% V) was used as catalyst for the one-pass gas-phase conversion of glycerol to allyl alcohol without any external reductant. The catalytic data strongly suggest a consecutive reactions path involving the dehydration to acrolein over the zeolite acid sites followed by a selective reduction through a hydrogen-transfer reaction. Acidity is expected to play a major role in what concerns the selectivity, as demonstrated by the catalytic results obtained by the impregnation of vanadium on a previously Cs-exchanged sample that achieved ca. 30% selectivity to allyl alcohol at ca. 20% glycerol conversion.info:eu-repo/semantics/publishedVersio

Modification of MOR by desilication treatments: structural, textural and acidic characterization

The effect of several desilication experimental parameters (base concentration, temperature and time) on the characteristics of MOR zeolite was studied. The samples were characterized by X-ray diffraction, Al-27 and Si-29 MAS-NMR, chemical analysis, and FTIR (framework vibration region). The textural characterization was made by N-2 adsorption and the acidity was evaluated by pyridine adsorption followed by FTIR and by the catalytic model reaction of n-heptane cracking. The alkaline treatments promoted the Si extraction from the zeolite framework, without considerable loss of crystallinity and, as it was envisaged, an important increase of the mesoporous structure was attained. A linear correlation between the number of framework Si per unit cell. N-Si and the asymmetric stretching wavenumber, nu(i), was observed. The acidity characterization shows that the desilicated samples exhibit practically the same acid properties than the parent HMOR zeolite. The optimum desilication conditions were those used to obtain sample M/0.2/85/2, i.e., sample treated with 0.2 M NaOH solution at 85 degrees C for 2 h

Bifurcations in the wake of a thick circular disk

Using DNS, we investigate the dynamics in the wake of a circular disk of aspect ratio χ = d/w = 3(where d is the diameter and w the thickness) embedded in a uniform flow of magnitude U0 perpendicular to its symmetry axis. As the Reynolds number Re = U0d/ν is increased, the flow is shown to experience an original series of bifurcations leading to chaos. The range Re ∈ [150, 218] is analysed in detail. In this range, five different non-axisymmetric regimes are successively encountered, including states similar to those previously identified in the flow past a sphere or an infinitely thin disk, as well as a new regime characterised by the presence of two distinct frequencies. A theoretical model based on the theory of mode interaction with symmetries, previously introduced to explain the bifurcations in the flow past a sphere or an infinitely thin disk (Fabre et al. in Phys Fluids 20:051702, 2008), is shown to explain correctly all these results. Higher values of the Reynolds number, up to 270, are also considered. Results indicate that the flow encounters at least four additional bifurcations before reaching a chaotic state

Aluminum containing dendrimeric silica nanoparticles as promising metallocene catalyst supports for ethylene polymerization

Several aluminum containing dendrimeric silica nanospheres, DSAl materials, were prepared using different synthesis and post-synthetic procedures. These materials were used for the immobilization of Cp2ZrCl2 via direct impregnation. The support materials were rigorously characterized by TEM, N2 adsorption, FTIR (using pyridine as probe molecule) and SS-NMR to assess their morphological, textural and surface acidic properties. Supported catalysts were tested in ethylene homopolymerization using methylaluminoxane (MAO) as co-catalyst and scavenger. The relationships between the types and strength of acid sites, as well as the textural and morphological parameters of DSAl materials with the behavior of catalytic systems are explored in this work. The results analyzed in this paper confirm the importance that support surface acidity plays in the formation of the active species for ethylene polymerization and in its activity without neglecting the contribution of support textural properties as well.info:eu-repo/semantics/publishedVersio

Hydroisomerization of n-decane over SAPO-11 catalysts synthesized with methylamine as co-template

The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed

Incorporation of niobium in SAPO-11 materials: Synthesis and characterization

The present work concerns a new synthesis approach to prepare niobium based SAPO materials with AEL structure and the characterization ofNb species incorporated within the inorganic matrixes. The SAPO-11 materials were synthesized with or without the help of a small amine, methylamine (MA) as co-template, while Nb was added directly during the preparation of the initial gel. Structural, textural and acidic properties of the different supports were evaluated by XRD, TPR, UV-Vis spectroscopy, pyridine adsorption followed by IR spectroscopy and thermal analyses. Pure and well crystalline Nb based SAPO-11 materials were obtained, either with or without MA, using in the initial gel a low Si content of about 0.6. Increasing the Si content of the gel up to 0.9 led to an important decrease of the samples crystallinity. Niobium was found to incorporate the AEL pores support as small Nb2O5 oxide particles and also as extra framework cationic species (Nb5+), compensating the negative charges from the matrix and generating new Lewis acid sites. (C) 2011 Elsevier Inc. All rights reserved

Exploring the Effect of Hierarchical Porosity in BEA Zeolite in Friedel-Crafts Acylation of Furan and Benzofuran

Hierarchical BEA zeolite was prepared through desilication or desilication followed by acid treatment. The catalytic performance of BEA zeolite samples was evaluated using Friedel-Crafts acylations with two substrates of different molecular sizes, furan (5.7 Å) and benzofuran (6.9 Å), in the presence of acetic anhydride as acylating agent. The application of the simplified Langmuir-Hinshelwood kinetic model showed that the size of the substrate leads to different catalytic activities, with improved rate constant and turnover frequency (TOF) solely in the presence of benzofuran for both desilicated and further acid treated samples. The mesopores developed during the zeolite treatments have an important role as transportation channels by reducing diffusion limitations. The application of Quantitative Structure–Property Relationships (QSPR) allowed the finding of the most relevant properties of the zeolite and substrate with impact on the catalytic parameters.publishe