The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Brönsted and Lewis acidity, with the Brönsted:Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Brönsted:Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO 2 /SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a threefold enhancement in 5-HMF productivity over non-porous SZ counterparts. The co-existence of accessible solid basic/Lewis acid and Brönsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively-formed fructose to the desired 5-HMF platform chemical.

Here we describe a simple route to creating conformal sulphated zirconia monolayers throughout an SBA-15 architecture that confers efficient acid-catalysed one-pot conversion of glucose to ethyl levulinate.

Liquid-phase trimerization of 2-methyl-1-butene and 2-methyl-2-butene mixtures over solid acid catalysts was carried out in a batch-stirred tank reactor in the temperature range 333−373 K. Diisoamylenes and triisoamylenes were the main products. Cracking products among C6−C9 and C11−C14 were also obtained under the assayed conditions. The catalityc performance of five different acidic ion exchange resins (Amberlyst 15, Amberlyst 35, Amberlyst 70, Purolite CT-252, Purolite CT-276) and four zeolites (H-BEA-25, H-FAU-30, H-FAU-6 and H-MOR-20) was assessed. Experimental results showed that Amberlyst 15 and H-FAU-30 were the best catalysts for isoamylene trimerization, with selectivities above 40% at 373 K. The most influencing physical properties of the catalysts on the selectivity toward dimers and trimers were acid capacity, acid strength, and specific surface area for resins, and microporous surface area for zeolites. Isoamylene trimerization extent was larger at higher temperature. The most probable mechanism of formation of these compounds involves the reaction between one molecule of dimer with one molecule of isoamylenes, although trimers could also be formed directly from three molecules of isoamylenes.

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Catalytic acetoxylation of lactic acid to 2-acetoxypropionic acid, en route to acrylic acid Beerthuis, R.; Granollers, M.; Brown, D.R.; Salavagione, H.J.; Rothenberg, G.; Shiju, N.R. Published in: RSC Advances DOI:10.1039/c4ra12695eLink to publication Citation for published version (APA):Beerthuis, R., Granollers, M., Brown, D. R., Salavagione, H. J., Rothenberg, G., & Shiju, N. R. (2015). Catalytic acetoxylation of lactic acid to 2-acetoxypropionic acid, en route to acrylic acid. RSC Advances, 5(6), 4103-4108. DOI: 10.1039/c4ra12695e General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We present an alternative synthetic route to acrylic acid, starting from the platform chemical lactic acid and using heterogeneous catalysis. To improve selectivity, we designed an indirect dehydration reaction that proceeds via acetoxylation of lactic acid to 2-acetoxypropionic acid. This intermediate can then be pyrolized to acrylic acid. Acetic acid is used both as a reagent and a solvent in the first step, and may be recovered in the subsequent pyrolysis step. We tested a range of solid acid catalysts for the acetoxylation step (Y zeolites, sulfated zirconia, ion-exchange resins, sulfonated graphene, and various sulfonated silica gels and mixed oxides). Recycling studies were carried out for the most active catalysts. To enable quantitative analysis using gas chromatography we also developed a reliable silylation derivatization method, which is also reported. These results open opportunities for improving the biorenewable production of acrylic acid.

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Tribo-electrification is a common occurrence within the pharmaceutical industry where solid dosage forms constitute majority of pharmaceutical formulations. Tribo-electrification of powders leads to a range of complications such as adhesion of particulate material to the processing equipment resulting in segregation, affecting the content uniformity. Flurbiprofen, a highly charging material, was used as a model drug to investigate the tribo-electrification and adhesion characteristics by impregnating the model drug inside a mesoporous silica matrix. The model drug was impregnated using i) solvent loading, and ii) physical mixing methods, at varying degree of silica to drug ratio (5-20% w/w). The resulting mixtures were tribo-charged using a custom built device based on a shaking concept inside a stainless steel capsule, consisting of a Faraday cup and connected to electrometer. The electrostatic charge and the percentage adhesion of Flurbiprofen were reduced in both drug loading methods. The solvent impregnation method using acetone was more successful at reducing the electrostatic charge build up on flurbiprofen than physical powder mixing. The percentage adhesion to the shaking capsule was reduced notably as a result of loading the drug in the SBA-15 porous network. The results illustrate that the incorporation of highly charged model drug inside a low-charging pharmaceutical carrier system to be an effective approach in control the induction of tribo-electrification phenomena during powder processing.