Your browser doesn't support javascript.
Mostrar: 20 | 50 | 100
Resultados 1 - 10 de 10
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
ChemSusChem ; 10(14): 2891-2896, 2017 07 21.
Artigo em Inglês | MEDLINE | ID: mdl-28603841

RESUMO

The presence of biogenic or process-derived impurities poses a major problem on the efficient catalytic hydrogenation of biomass-derived levulinic acid to γ-valerolactone; hence, studies on their influence on catalyst stability are now required. Herein, the influence of sulfuric acid as feed impurity on the performance of Ru-based heterogeneous catalysts, including Ru/ZrO2 and mono- and bimetallic Ru-on-carbon catalysts in dioxane as solvent, was investigated. The carbon-supported Ru catalysts proved to be very sensitive to minor amounts of sulfuric acid. In stark contrast, Ru/ZrO2 showed a remarkable stability in the presence of the same impurity, which is attributed to the sulfate-ion adsorption capacity of the support. Preferential sulfate adsorption onto the surface of ZrO2 effectively protects the Ru active phase from deactivation by sulfur poisoning. A simple catalyst regeneration strategy was effective in removing adsorbed impurities, allowing efficient catalyst recycling.


Assuntos
Lactonas/química , Ácidos Levulínicos/química , Rutênio/química , Ácidos Sulfúricos/química , Catálise , Hidrogenação , Zircônio/química
2.
ChemSusChem ; 10(1): 277-286, 2017 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-27557889

RESUMO

Bio-based furanics can be aromatized efficiently by sequential Diels-Alder (DA) addition and hydrogenation steps followed by tandem catalytic aromatization. With a combination of zeolite H-Y and Pd/C, the hydrogenated DA adduct of 2-methylfuran and maleic anhydride can thus be aromatized in the liquid phase and, to a certain extent, decarboxylated to give high yields of the aromatic products 3-methylphthalic anhydride and o- and m-toluic acid. Here, it is shown that a variation in the acidity and textural properties of the solid acid as well as bifunctionality offers a handle on selectivity toward aromatic products. The zeolite component was found to dominate selectivity. Indeed, a linear correlation is found between 3-methylphthalic anhydride yield and the product of (strong acid/total acidity) and mesopore volume of H-Y, highlighting the need for balanced catalyst acidity and porosity. The efficient coupling of the dehydration and dehydrogenation steps by varying the zeolite-to-Pd/C ratio allowed the competitive decarboxylation reaction to be effectively suppressed, which led to an improved 3-methylphthalic anhydride/total aromatics selectivity ratio of 80 % (89 % total aromatics yield). The incorporation of Pd nanoparticles in close proximity to the acid sites in bifunctional Pd/H-Y catalysts also afforded a flexible means to control aromatic products selectivity, as further demonstrated in the aromatization of hydrogenated DA adducts from other diene/dienophile combinations.


Assuntos
Furanos/química , Paládio/química , Carbono/química , Catálise , Concentração de Íons de Hidrogênio , Vapor , Zeolitas/química
3.
Angew Chem Int Ed Engl ; 55(4): 1368-71, 2016 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-26684008

RESUMO

Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels-Alder (DA) aromatization route, to effectively block retro-DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal-based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80% selectivity in a solid-phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H-Y was found to perform the best and can be easily reused after calcination.

4.
ChemSusChem ; 8(18): 3052-6, 2015 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-26235971

RESUMO

A novel route for the production of renewable aromatic chemicals, particularly substituted phthalic acid anhydrides, is presented. The classical two-step approach to furanics-derived aromatics via Diels-Alder (DA) aromatization has been modified into a three-step procedure to address the general issue of the reversible nature of the intermediate DA addition step. The new sequence involves DA addition, followed by a mild hydrogenation step to obtain a stable oxanorbornane intermediate in high yield and purity. Subsequent one-pot, liquid-phase dehydration and dehydrogenation of the hydrogenated adduct using a physical mixture of acidic zeolites or resins in combination with metal on a carbon support then allows aromatization with yields as high as 84 % of total aromatics under relatively mild conditions. The mechanism of the final aromatization reaction step unexpectedly involves a lactone as primary intermediate.


Assuntos
Biomassa , Furanos/química , Química Verde/métodos , Anidridos Ftálicos/química , Hidrogenação
5.
J Am Chem Soc ; 135(23): 8594-605, 2013 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-23679582

RESUMO

Manganese-containing MFI-type Mn-ZSM-5 zeolite was synthesized by a facile one-step hydrothermal method using tetrapropylammonium hydroxide (TPAOH) and manganese(III)-acetylacetonate as organic template and manganese salts, respectively. A highly crystalline MFI zeolite structure was formed under pH = 11 in 2 days, without the need for additional alkali metal cations. Direct evidence of the incorporation of Mn in the zeolite framework sites was observed by performing structure parameter refinements, supported by data collected from other characterization techniques such as IR, Raman, UV-vis, TGA, N2-adsorption, SEM, TEM, EDAX, and XPS. UV-vis spectra from the unique optical properties of Mn-ZSM-5 show two absorption peaks at 250 and 500 nm. The absorption varies in different atmospheres accompanied by a color change of the materials due to oxygen evolution. Raman spectra show a significant and gradual red shift from 383 cm(-1) to 372 cm(-1) when the doping amount of Mn is increased from 0 to 2 wt %. This suggests a weakened zeolite structural unit induced by the Mn substitution. The catalytic activity was studied in both gas-phase benzyl alcohol oxidation and toluene oxidation reactions with remarkable oxidative activity presented for the first time. These reactions result in a 55% yield of benzaldehyde, and 65% total conversion of toluene to carbon dioxide for the 2% Mn-ZSM-5. Temperature programmed reduction (TPR) using CO in He demonstrates two reduction peaks: one between 300 and 500 °C and the other between 500 and 800 °C. The first reduction peak, due to manganese-activated oxidation sites shifted from higher temperature to lower temperature, and the peak intensity of CO2 rises when the dopant amount increases. For the first time, calculated photophysical properties of a model Mn(O-SiH3)4(-) compound, an Mn-embedded zeolite cluster, and model Mn oxides help to explain and interpret the diffuse reflectance spectroscopy of Mn-ZSM-5 zeolites.


Assuntos
Hidrocarbonetos/química , Manganês/química , Temperatura , Zeolitas/química , Catálise , Estrutura Molecular , Oxirredução , Tamanho da Partícula , Propriedades de Superfície
6.
Photochem Photobiol Sci ; 11(4): 692-702, 2012 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-22297791

RESUMO

The effects of visible and UV light on the characteristics and properties of Prudhoe Bay (PB) and South Louisiana (SL) emulsions were investigated to better understand the role of sunlight on the fate of spilled crude oils that form emulsions with a dispersant in the aquatic environment. Before irradiation, crude oil emulsions showed the presence of dispersed crude oil micelles in a continuous water phase and crude oil components floating on the surface. The crude oil micelles decreased in size with irradiation, but emulsions retained their high degree of polydispersity. UV irradiation reduced the stability of emulsions more effectively than visible light. The reduction of micelles size caused the viscosity of emulsions to increase and melting point to decrease. Further, irradiation increased acid concentrations and induced ion formation which lowered the pH and increased the conductivity of emulsions, respectively. Ni and Fe in PB emulsions were extracted from crude oil with UV irradiation, which may provide an efficient process for metal removal. The emulsions were stable toward freeze/thaw cycles and their melting temperatures generally decreased with irradiation. Evidence of ˙OH production existed when emulsions were exposed to UV but not to visible light. The presence of H(2)O(2) enhanced the photodegradation of crude oil. Overall, the changes in emulsion properties were attributed to direct photodegradation and photooxidation of crude oil components.

7.
Arch Environ Contam Toxicol ; 62(3): 369-79, 2012 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-21892761

RESUMO

Significant levels of potentially carcinogenic bromate were measured in chlorinated tap drinking water in Metropolitan Manila, Philippines, using an optimized ion-chromatographic method. This method can quantify bromate in water down to 4.5 µg l⁻¹ by employing a postcolumn reaction with acidic fuchsin and subsequent spectrophotometric detection. The concentration of bromate in tap drinking water samples collected from 21 locations in cities and municipalities within the 9-month study period ranged from 7 to 138 µg l⁻¹. The average bromate concentration of all tap drinking water samples was 66 µg l⁻¹ (n = 567), almost seven times greater than the current regulatory limit in the country. The levels of bromate in other water types were also determined to identify the sources of bromate found in the distribution lines and to further uncover contaminated sites. The concentration of bromate in water sourced from two rivers and two water treatment plants ranged from 15 to 80 and 12 to 101 µg l⁻¹, respectively. Rainwater did not contribute bromate in rivers but decreased bromate level by dilution. Groundwater and wastewater samples showed bromate concentrations as high as 246 and 342 µg l⁻¹, respectively. Bromate presence in tap drinking water can be linked to pollution in natural water bodies and the practice of using hypochlorite chemicals in addition to gaseous chlorine for water disinfection. This study established the levels, occurrence, and possible sources of bromate in local drinking water supplies.


Assuntos
Bromatos/análise , Água Potável/química , Poluentes Químicos da Água/análise , Cidades , Monitoramento Ambiental , Água Doce/química , Filipinas , Eliminação de Resíduos Líquidos , Poluição Química da Água/estatística & dados numéricos , Purificação da Água
8.
J Am Chem Soc ; 133(12): 4186-9, 2011 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-21332136

RESUMO

Short reaction times and morphology control in the synthesis of inorganic materials under nonthermal conditions remain a challenge. Herein we report a rapid, self-templating, and nonthermal method based on ultraviolet light to prepare metal oxide hierarchical structures. With this method, the morphology of the metal oxides was controlled readily without using templates.


Assuntos
Metais/química , Óxidos/síntese química , Raios Ultravioleta , Catálise , Estrutura Molecular , Nanoestruturas/química , Óxidos/química , Tamanho da Partícula , Propriedades de Superfície
9.
Langmuir ; 27(1): 264-71, 2011 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-21133391

RESUMO

Iron and silver nanoparticles were synthesized using a rapid, single step, and completely green biosynthetic method employing aqueous sorghum extracts as both the reducing and capping agent. Silver ions were rapidly reduced by the aqueous sorghum bran extracts, leading to the formation of highly crystalline silver nanoparticles with an average diameter of 10 nm. The diffraction peaks were indexed to the face-centered cubic (fcc) phase of silver. The absorption spectra of colloidal silver nanoparticles showed a surface plasmon resonance (SPR) peak centered at a wavelength of 390 nm. Amorphous iron nanoparticles with an average diameter of 50 nm were formed instantaneously under ambient conditions. The reactivity of iron nanoparticles was tested by the H(2)O(2)-catalyzed degradation of bromothymol blue as a model organic contaminant.


Assuntos
Ferro/metabolismo , Nanopartículas Metálicas/química , Extratos Vegetais/metabolismo , Prata/metabolismo , Sorghum/química , Temperatura , Água/química , Catálise , Cristalografia por Raios X , Ferro/química , Cinética , Oxirredução , Prata/química , Sorghum/anatomia & histologia , Espectrofotometria Ultravioleta
10.
Chem Commun (Camb) ; 46(32): 5945-7, 2010 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-20596572

RESUMO

A facile single-step method was developed for synthesizing todorokite-type manganese oxide octahedral molecular seieves (OMS-1) and 2 x 4 tunnel structured manganese oxide (OMS-5) materials. Selection of starting materials and initial pH conditions in the syntheses are crucial.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA