MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst

A bifunctional MOF catalyst containing coordinatively unsaturated Cr3+ sites and palladium nanoparticles (Pd@MIL-101) has been used for the cyclization of citronellal to isopulegol and for the one-pot tandem isomerization/hydrogenation of citronellal to menthol. The MOF was found to be stable under the reaction conditions used, and the results obtained indicate that the performance of this bifunctional solid catalyst is comparable with other state-of-the-art materials for the tandem reaction: Full citronellal conversion was attained over Pd@MIL-101 in 18 h, with 86% selectivity to menthols and a diastereoselectivity of 81% to the desired (-)-menthol, while up to 30 h were necessary for attaining similar values over Ir/H-beta under analogous reaction conditions.Financial support by Ministerio de Educacion y Ciencia e Innovacion (Project MIYCIN, CSD2009-00050; PROGRAMA CONSOLIDER. INGENIO 2009), Generalidad Valenciana (GV PROMETEO/2008/130) and the CSIC (Proyectos Intramurales Especiales 201080I020) is gratefully acknowledged.García Cirujano, F.; Llabrés I Xamena, FX.; Corma Canós, A. (2012). MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst. Dalton Transactions. 41:4249-4254. https://doi.org/10.1039/c2dt12480gS4249425441Corma, A., García, H., & Llabrés i Xamena, F. X. (2010). Engineering Metal Organic Frameworks for Heterogeneous Catalysis. Chemical Reviews, 110(8), 4606-4655. doi:10.1021/cr9003924Farrusseng, D., Aguado, S., & Pinel, C. (2009). Metal-Organic Frameworks: Opportunities for Catalysis. Angewandte Chemie International Edition, 48(41), 7502-7513. doi:10.1002/anie.200806063Lee, J., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. T., & Hupp, J. T. (2009). Metal–organic framework materials as catalysts. 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Effects of Anacetrapib in Patients with Atherosclerotic Vascular Disease

BACKGROUND: Patients with atherosclerotic vascular disease remain at high risk for cardiovascular events despite effective statin-based treatment of low-density lipoprotein (LDL) cholesterol levels. The inhibition of cholesteryl ester transfer protein (CETP) by anacetrapib reduces LDL cholesterol levels and increases high-density lipoprotein (HDL) cholesterol levels. However, trials of other CETP inhibitors have shown neutral or adverse effects on cardiovascular outcomes. METHODS: We conducted a randomized, double-blind, placebo-controlled trial involving 30,449 adults with atherosclerotic vascular disease who were receiving intensive atorvastatin therapy and who had a mean LDL cholesterol level of 61 mg per deciliter (1.58 mmol per liter), a mean non-HDL cholesterol level of 92 mg per deciliter (2.38 mmol per liter), and a mean HDL cholesterol level of 40 mg per deciliter (1.03 mmol per liter). The patients were assigned to receive either 100 mg of anacetrapib once daily (15,225 patients) or matching placebo (15,224 patients). The primary outcome was the first major coronary event, a composite of coronary death, myocardial infarction, or coronary revascularization. RESULTS: During the median follow-up period of 4.1 years, the primary outcome occurred in significantly fewer patients in the anacetrapib group than in the placebo group (1640 of 15,225 patients [10.8%] vs. 1803 of 15,224 patients [11.8%]; rate ratio, 0.91; 95% confidence interval, 0.85 to 0.97; P=0.004). The relative difference in risk was similar across multiple prespecified subgroups. At the trial midpoint, the mean level of HDL cholesterol was higher by 43 mg per deciliter (1.12 mmol per liter) in the anacetrapib group than in the placebo group (a relative difference of 104%), and the mean level of non-HDL cholesterol was lower by 17 mg per deciliter (0.44 mmol per liter), a relative difference of -18%. There were no significant between-group differences in the risk of death, cancer, or other serious adverse events. CONCLUSIONS: Among patients with atherosclerotic vascular disease who were receiving intensive statin therapy, the use of anacetrapib resulted in a lower incidence of major coronary events than the use of placebo. (Funded by Merck and others; Current Controlled Trials number, ISRCTN48678192 ; ClinicalTrials.gov number, NCT01252953 ; and EudraCT number, 2010-023467-18 .)

The Role of Acidity in Terephthalic Acid Synthesis from Renewable Carbon Source

In this study, manganese-cobalt (MnCo) mixed oxide catalysts were prepared by two different routes: co-precipitation and citrate method. The structures and properties of the mixed oxide catalysts were investigated by several techniques: nitrogen adsorption-desorption isotherms, X-ray diffraction, X-ray photoelectron spectroscopy, SEM, FTIR and UV-Vis spectroscopies, temperature-programmed reduction with H2 (H2-TPR) and temperature-programmed desorption of NH3 (NH3-TPD). Their catalytic performance was investigated in the liquid-phase selective oxidation of naturally occurred p-cymene to terephthalic acid, as an alternative to p-xylene, a fossil derivative fuel component. Within this study, we demonstrate that the materials prepared by the co-precipitation method present strong acid sites that boost the oxidation rate and allow oxidation of p-cymene up to terephthalic acid. The co-existence of a significant number of strong acid and centers in higher oxidation state (Co3+) are required for these materials to be selective

La0.75Sr0.25XO3 (X = Fe, Mn or Cr) with coking tolerance for CH4/H2O reaction: effect of H2S on catalytic performance

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Photocatalytic decomposition of acetone over dc-magnetron sputtering supported vanadia/TiO2 catalysts

Two series of titania-based photocatalysts were prepared by the sputtering method, in pure Ar atmosphere at a pressure of 0.5 Pa using a vanadium target source in a direct dc mode with a discharge of 300 V. The time of deposition was varied between 1 and 10 min in order to obtain different thickness of vanadium films. The first catalysts series (samples V/TiO2(A)-n) was prepared deposing vanadium Oil pure TiO2 anatase, while for the second series (samples V/TiO2(AR)-n) the deposition was made onto TiO2 Degussa P25. The samples have been investigated by means of vibrational (DRIFT and Raman) and optical (UV-vis in the DRS mode). Chemical analysis of the samples was made using the ICP-AES technique, while the crystalline structure of the deposed films onto the TiO2 supports was checked by X-ray diffraction (XRD). The samples morphology was analyzed using the AFM microscopy. The photocatalytic decomposition of acetone was considered as a reaction test. The activity of the investigated catalysts was found to be influenced by both the amount of vanadium and the Support nature. Among the investigated catalysts V/TiO2(AR)-32 nm exhibited the higher activity. The activity of this catalyst was also superior to that of TiO2 Degussa P25. (C) 2008 Elsevier B.V. All rights reserved

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Ceria synthesis by modified precipitation route

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Gold imidazolium-based ionic liquids, efficient catalysts for cycloisomerization of gamma-acetylenic carboxylic acids

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Influence of Gd and Pr doping on the properties of ceria: texture, structure, redox behaviour and reactivity in CH4/H2O reactions in the presence of H2S

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Doped ceria prepared by precipitation route for steam reforming of methane

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