Auguste Fernandes

Acid-Catalysed Conversion of Saccharides into Furanic Aldehydes in the Presence of Three-Dimensional Mesoporous Al-TUD-1

The one-pot acid-catalysed conversion of mono/di/polysaccharides (inulin, xylan, cellobiose, sucrose, glucose, fructose, xylose) into 2-furfuraldehyde (FUR) or 5-hydroxymethylfurfural (HMF) in the presence of aluminium-containing mesoporous TUD-1 (denoted as Al-TUD-1, Si/Al = 21), at 170 ºC was investigated. Xylose gave 60% FUR yield after 6 h reaction; hexose-based mono/disaccharides gave less than 20% HMF yield; polysaccharides gave less than 20 wt % FUR or HMF yields after 6 h. For four consecutive 6 h batches of the xylose reaction in the presence of Al-TUD-1, the FUR yields achieved were similar, without significant changes in Si/Al ratio.

Production of biomass-derived furanic ethers and levulinate esters using heterogeneous acid catalysts

Mesoporous aluminosilicates of the type Al-TUD-1, prepared via “green”, low-cost, non-surfactant templating routes, are effective and versatile heterogeneous acid catalysts for the production of useful bio-based furanic ethers and levulinate esters, via the reactions of the biorenewable substrates 5-hydroxymethyl-2-furfural (Hmf) or furfuryl alcohol (FA) with aliphatic alcohols. The identification of reaction intermediates and products by comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry was carried out, giving mechanistic insights. Ethyl levulinate (EL) was formed from FA or Hmf as substrates, with higher EL yields being reached in the former case. Different types of alkyl levulinates may be synthesized from FA using Al-TUD-1 catalysts. On the other hand, 5-(ethoxymethyl)furan-2-carbaldehyde may be formed as the main product from Hmf. Modifications of the properties of Al-TUD-1 involved varying the Si/Al ratio and applying a post-synthesis acid treatment. The influence of these factors and of the reaction conditions on the catalytic reactions was investigated. The efficient regeneration and recyclability of Al-TUD-1 was assessed.

Zinc(II) phthalocyanines immobilized in mesoporous silica Al-MCM-41 and their applications in photocatalytic degradation of pesticides

In the present study the authors investigated a set of three new zinc(II) phthalocyanines (zinc(II) tetranitrophthalocyanine (ZnTNPc), zinc(II) tetra(phenyloxy)phthalocyanine (ZnTPhOPc) and the tetraiodide salt of zinc(II)tetra(N,N,N-trimethylaminoethyloxy) phthalocyaninate (ZnTTMAEOPcI)) immobilized into Al-MCM-41 prepared via ship-in-a-bottle methodology. The samples were fully characterized by diffuse reflectance-UV-vis spectroscopy (DRS-UV-vis), luminescence, thermogravimetric analysis (TG/DSC), N(2) adsorption techniques and elemental analysis. A comparative study was made on the photocatalytic performance upon irradiation within the wavelength range 320-460nm of these three systems in the degradation of pesticides fenamiphos and pentachlorophenol. ZnTNPc@Al-MCM-41 and ZnTTMAEOPcI@Al-MCM-41 were found to be the most active systems, with the best performance observed with the immobilized cationic phthalocyanine, ZnTTMAEOPcI@Al-MCM-41. This system showed high activity even after three photocatalytic cycles. LC-MS product characterization and mechanistic studies indicate that singlet oxygen ((1)O(2)), produced by excitation of these immobilized photosensitizers, is a key intermediate in the photocatalytic degradation of both pesticides.

An information system architectural framework for enterprise application integration

Information system (IS) architectures have not paid enough attention to integration in the past because integration was not important to build ISs from scratch. However, with the variety and number of ISs in medium/large organizations increasing, including ERP systems, the need for integration is bigger than ever. Furthermore, most organizations now want to integrate their ISs with those belonging to other organizations. In this paper we propose an extension to our previous proposals for representing IS architectures in order to properly support a large variety of integration scenarios between IS, including intra and inter organizations. In particular we support manual and automatic, synchronous and asynchronous integration. We also present an example to illustrate the proposal with real world IS integration needs.

Immobilization of 5,10,15,20-tetrakis-(2-fluorophenyl)porphyrin into MCM-41 and NaY: Routes toward photodegradation of pesticides

NaY zeolite and MCM-41 mesoporous molecular sieve were used as supports for immobilization of 5,10,15,20-tetrakis-(2-fluorophenyl)porphyrin (TFPP) using adsorption and ship-in-the-bottle routes involving the nitrobenzene method. The materials obtained were characterized by thermogravimetry/differential thermal analysis (TG/DTA), nitrogen adsorption, UV–vis absorption, diffuse reflectance (DRS), and luminescence spectroscopy. Although the porphyrin could easily be synthesized inside MCM-41 pores using the ship-in-the-bottle route, no significant porphyrin was formed in the smaller supercages of NaY zeolite, since the reaction stops at the dipyrrolylmethene intermediate (FDPM). Promising preliminary studies were made in the photodegradation of the pesticides, 2,3,5-trimethylphenol (TMP) and mecoprop (MCPP), using as catalyst TFPP encapsulated in mesoporous MCM-41 material. The 2-hydroxy-methyl-hydroquinone and 4-chloro-2-methylphenol were identified as the main degradation products of MCPP. The encapsulated system resulting from the TFPP template synthesis shows significantly enhanced performance when compared with adsorbed porphyrin in both supports.

Gas-phase dehydration of glycerol over thermally-stable SAPO-40 catalyst

SAPO-40 was used as a catalyst for the gas-phase dehydration of glycerol towards acrolein. At 350 °C the catalyst attained full conversion of glycerol with a negligible deactivation in the first 48 h, a glycerol conversion above 50% after 120 h on stream and a nearly constant selectivity to acrolein above 70%. This catalyst proved to be highly resistant under the experimental conditions used and can be regenerated without loss of activity or significant structural damage. The comparison of SAPO-40 with SAPO-34 and SAPO-11 illustrates the importance of the porous structure and emphasizes the good catalytic performance of this material.

An insight into dapsone co-crystals: sulfones as participants in supramolecular interactions

Herein we disclose a new pathway for the design of dapsone co-crystals exploring the formation of N–H⋯O/N interactions using amide and pyridinic derivatives as potential co-formers. Two new co-crystals of dapsone, a sulfonamide antibiotic, with e-caprolactam and 4,4′-bipyridine have been synthesized preferentially by traditional solution techniques, but mechanochemistry has also been addressed. The full structural characterization of these forms is discussed and shows that: (a) in the co-crystal with e-caprolactam the typical NNH2⋯OSO2 interactions of dapsone molecules and the cages formed between them are disrupted by a new NNH2⋯OCONH interaction, in which e-caprolactam molecules further form amide⋯amide R22(8) synthons and (b) in the co-crystal with 4,4′-bipyridine, the NNH2⋯OSO2 interactions between dapsone molecules are maintained and additional NNH2⋯Npyridine interactions are responsible for the formation of 4,4′-bipyridine channels between dapsone cages. Moreover, the thermal stability of these co-crystals is also discussed, showing that the co-formers leave the structure and hence the reported melting corresponds to the melting of pure dapsone.

Bulk and composite catalysts combining BEA topology and mesoporosity for the valorisation of furfural

The sustainable conversion of biomass and biomass-derived platform chemicals demands efficient catalytic processes for which modified versions of zeolites can be strategically important. The catalytic potential of bulk and composite catalysts which simultaneously feature zeolite crystallinity, mesoporosity and Zr and Al sites were explored for the valorisation of furfural (Fur; industrially produced from hemicelluloses) via integrated reduction and acid reactions in alcohol media, to give useful bio-products (bioP), namely, furanic ethers, levulinate esters and angelica lactones. Different synthetic strategies were used starting from zeolite microcrystals or nanocrystals. A composite consisting of nanocrystals of Zr,Al-Beta embedded in a mesoporous matrix is reported for the first time. In a different synthesis approach, a bulk mesoporous zeotype material was prepared by post-synthesis alkaline/acid/impregnation treatments, and explored for the first time as a catalyst for a one-pot reduction/acid reaction system. Characterisation studies of the morphology, structure, texture and nature of the Al and Zr sites (27Al MAS NMR spectroscopy, FT-IR spectroscopy of adsorbed pyridine or deuterated acetonitrile) helped understand the influence of material properties on catalytic performance. These types of materials are active and stable catalysts for the integrated conversion of Fur to bioP.

An elegant way to increase acidity in SAPOs: use of methylamine as co-template during synthesis

SAPO-34 and SAPO-11 with an increased number of acid sites were synthesized by adding methylamine (MA) as co-template to tetraethylammonium hydroxide (TEAOH) or dipropylamine (DPA) respectively currently used as true templates. Along with minor changes of the final chemical and morphological properties of the as-synthesized materials, the major role of methylamine was shown to prevent a rapid silica polymerization (or to slow down its depolymerization) in the early synthesis steps, thereby favoring the progressive framework insertion of small Si oligomers that further generate an increased number of SAPO domains, with respect to Si islands.

Functionalization of Mesoporous MCM‐41 (Nano)particles: Preparation Methodologies, Role on Catalytic Features, and Dispersion Within Polyethylene Nanocomposites

MCM‐41 micro‐ and nanoparticles are prepared and functionalized with silane coupling agents. These pristine and silane‐decorated mesoporous MCM‐41s are further used in the synthesis of MCM‐41/ethylene nanocomposites by in situ polymerization, utilizing either supported or non‐supported catalytic systems. The catalytic behavior of those systems is discussed, taking into consideration the effects of the particle size, surface characteristics, and functionalization. The results have shown that the initial surface state of MCM‐41 is of paramount importance to achieve high catalytic activity if a polymerization catalyst is to be supported. Functionalization changes the surface chemistry, thus, a positive or negative effect may be observed, depending on the previous features of the surface. The particle size of MCM‐41 and its functionalization affect its final dispersion within the polymeric matrix, this distribution is evaluated by SEM, TEM, and microhardness measurements.