Nitrogen-assisted electroless assembling of 3D nanodendrites consisting of Pd and N-doped carbon nanoparticles as bifunctional catalysts

We report a facile synthesis of three-dimensional (3D) nanodendrites of Pd nanoparticles (NPs) and nitrogen-doped carbon NPs (N-CNPs) by electroless deposition of Pd2+ ions. N-CNPs being an electron-enriched material act as a reducing agent. Moreover, the availability of a variety of nitrogen species in N-CNPs promotes the open arm structure as well as stabilizes the oriented 3D assembly of primary Pd NPs. The dendrites exhibit superior catalytic activity for methanol (0.5 M) oxidation in alkaline media (1 M NaOH) which is ascribed to the large electrochemical active surface area and the enhanced mass activity with repeated use. Further mass activity improvement has been realized after acid-treatment of dendrites which is attributed to the increment in the -OH group. The dendrites show higher mass activity (J(f) similar to 653 A g(-1)) in comparison with a commercial Pt-carbon/Pd-carbon (Pt-C/Pd-C) catalyst (J(f) similar to 46 and 163 A g(-1), respectively), better operational stability, superior CO tolerance with I-f/I-b (similar to 3.7) over a commercial Pt-C/Pd-C catalyst (I-f/I-b similar to 1.6 and 1.75, respectively) and may serve as a promising alternative to commercial Pt-C catalysts for anode application in alkaline fuel cells. To ensure the adaptability of our 3D-nanodendrites for other catalytic activities, we studied 4-nitrophenol reduction at room temperature. The 3D-nanodendrites show excellent catalytic activity toward 4-nitrophenol reduction, as well.

Bifunctional organorhodium solid acid catalysts for methanol carbonylation

Robust, bifunctional catalysts comprising Rh(CO)(Xantphos) exchanged phosphotungstic acids of general formulas [Rh(CO)(Xantphos)]+n[H3–nPW12O40]n− have been synthesized over silica supports which exhibit tunable activity and selectivity toward direct vapor phase methanol carbonylation. The optimal Rh:acid ratio = 0.5, with higher rhodium concentrations increasing the selectivity to methyl acetate over dimethyl ether at the expense of lower acidity and poor activity. On-stream deactivation above 200 °C reflects Rh decomplexation and reduction to Rh metal, in conjunction with catalyst dehydration and loss of solid acidity because of undesired methyl acetate hydrolysis, but can be alleviated by water addition and lower temperature operation.

Structure and acidity of Mo/H-MCM-22 catalysts studied by NMR spectroscopy

A comprehensive study on physical and chemical properties of Mo/MCM-22 bifunctional catalysts has been made by using combined analytic and spectroscopic techniques, such as adsorption, elemental analysis, and Xe-129 and P-31 NMR of adsorbed trialkylphosphine oxide probe molecules. Samples prepared by the impregnation method with Mo loadings ranging from 2-10 wt.% have been examined and the results are compared with that obtained from samples prepared by mechanical mixing using MoO3 or Mo2C as agents. Sample calcination treatment is essential in achieving a well-dispersed metal species in Mo/MCM-22. It was found that, upon initial incorporation, the Mo species tend to inactivate both Bronsted and Lewis sites locate predominantly in the supercages rather than the 10-membered ring channels of MCM-22. However, as the Mo loading exceeds 6 wt.%, the excessive Mo species tend to migrate toward extracrystalline surfaces of the catalyst. A consistent decrease in concentrations of acid sites with increasing Mo loading < 6 wt.% was found, especially for those with higher acid strengths. Upon loading of Mo > 6 wt.%, further decreases in both Bronsted and Lewis acidities were observed. These results provide crucial supports for interpreting the peculiar behaviors previously observed during the conversion of methane to benzene over Mo/MCM-22 catalyst under non-oxidative conditions, in which an optimal performance was achieved with a Mo loading of 6 wt.%. The effects of Mo incorporation on porosity and acidity features of the catalyst are discussed. (C) 2004 Published by Elsevier B.V.

One-step glycerol oxidehydration to acrylic acid on multifunctional zeolite catalysts

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estimation of catalyst activity profiles and deactivation parameters from reactor operating data with applications to naphtha reforming

Techniques are developed for estimating activity profiles in fixed bed reactors and catalyst deactivation parameters from operating reactor data. These techniques are applicable, in general, to most industrial catalytic processes. The catalytic reforming of naphthas is taken as a broad example to illustrate the estimation schemes and to signify the physical meaning of the kinetic parameters of the estimation equations. The work is described in two parts. Part I deals with the modeling of kinetic rate expressions and the derivation of the working equations for estimation. Part II concentrates on developing various estimation techniques.

Part I: The reactions used to describe naphtha reforming are dehydrogenation and dehydroisomerization of cycloparaffins; isomerization, dehydrocyclization and hydrocracking of paraffins; and the catalyst deactivation reactions, namely coking on alumina sites and sintering of platinum crystallites. The rate expressions for the above reactions are formulated, and the effects of transport limitations on the overall reaction rates are discussed in the appendices. Moreover, various types of interaction between the metallic and acidic active centers of reforming catalysts are discussed as characterizing the different types of reforming reactions.

Part II: In catalytic reactor operation, the activity distribution along the reactor determines the kinetics of the main reaction and is needed for predicting the effect of changes in the feed state and the operating conditions on the reactor output. In the case of a monofunctional catalyst and of bifunctional catalysts in limiting conditions, the cumulative activity is sufficient for predicting steady reactor output. The estimation of this cumulative activity can be carried out easily from measurements at the reactor exit. For a general bifunctional catalytic system, the detailed activity distribution is needed for describing the reactor operation, and some approximation must be made to obtain practicable estimation schemes. This is accomplished by parametrization techniques using measurements at a few points along the reactor. Such parametrization techniques are illustrated numerically with a simplified model of naphtha reforming.

To determine long term catalyst utilization and regeneration policies, it is necessary to estimate catalyst deactivation parameters from the the current operating data. For a first order deactivation model with a monofunctional catalyst or with a bifunctional catalyst in special limiting circumstances, analytical techniques are presented to transform the partial differential equations to ordinary differential equations which admit more feasible estimation schemes. Numerical examples include the catalytic oxidation of butene to butadiene and a simplified model of naphtha reforming. For a general bifunctional system or in the case of a monofunctional catalyst subject to general power law deactivation, the estimation can only be accomplished approximately. The basic feature of an appropriate estimation scheme involves approximating the activity profile by certain polynomials and then estimating the deactivation parameters from the integrated form of the deactivation equation by regression techniques. Different bifunctional systems must be treated by different estimation algorithms, which are illustrated by several cases of naphtha reforming with different feed or catalyst composition.

Catalisadores para hidroisomerização de n-hexadecano

No processo de hidrocraqueamento para a produção de lubrificantes ocorre a formação de uma corrente rica em compostos parafínicos que possuem alto ponto de fluidez, apesar dos mesmos apresentarem excelentes desempenhos em termos de estabilidade térmica e oxidativa. A transformação das n-parafinas obtidas nestas correntes em isoparafinas e compostos naftênicos, os quais possuem menores pontos de fluidez, se faz necessária a fim de enquadrar esta propriedade. Uma das rotas catalíticas mais importantes neste sentido é a hidroisodesparafinação ou HIDW (hydroisodewaxing) que consiste na conversão de n-parafinas nas respectivas isoparafinas, onde são empregados catalisadores bifuncionais zeolíticos com a ocorrência de seletividade de forma. No caso dos catalisadores industriais, se faz necessária a dispersão da fase metálica e da zeólita em uma matriz amorfa para viabilizar sua conformação e melhorar a resistência mecânica do catalisador final. Neste cenário, o objetivo deste trabalho foi preparar e analisar o desempenho de uma série de catalisadores à base de zeólita beta inseridos numa matriz de alumina, variando-se o teor de zeólita e o tipo de precursor de Pt utilizado. Os catalisadores foram avaliados na reação de hidroisomerização de um composto modelo, no caso, n-hexadecano. Os testes realizados para avaliação da atividade e seletividade foram conduzidos em um reator de fluxo contínuo em alta pressão e fase líquida em unidade de laboratório. Os catalisadores foram testados em condições operacionais que proporcionassem uma ampla faixa de conversões do n-C16. Verificou-se que as atividades dos catalisadores foram proporcionais ao teor de zeólita no catalisador, indicando que a função ácida, neste catalisador bifuncional, é a etapa limitante do processo. Quanto à natureza do precursor de Pt, o catalisador preparado com ácido cloroplatínico foi sensivelmente mais ativo que os preparados com o complexo aminplatina. No entanto, para todos os catalisadores, a distribuição de produtos em função da conversão foi similar, independente do teor de zeólita e da natureza do precursor de platina. Foi também determinado o ponto de fluidez de uma série de produtos de reação, obtendo-se valores entre 17,5 C (n-hexadecano) e - 41 C (produto com 98% de conversão). Obteve-se uma boa correlação entre o ponto de fluidez e a composição dos produtos, considerando-se a presença de isômeros mono, di e tri-substituídos e compostos de menor peso molecular que C16

A influência da acidez do suporte de catalisadores Ni-Mo sobre a atividade da reação de hidrogenação de aromáticos e abertura de ciclo naftênico

Três catalisadores contendo o mesmo teor de fase ativa (20% de óxido de molibdênio e 4% de óxido de níquel), mas constituídos por diferentes suportes (alumina, sílica-alumina e alumina zeólita) foram preparados com o objetivo de se obter catalisadores bifuncionais com acidez distinta e boa dispersão da fase metálica visando analisar o papel da acidez do suporte na conversão da tetralina. Os catalisadores e seus respectivos suportes foram caracterizados na formas óxido e sulfeto e avaliados na reação de hidrogenação da tetralina, que representa bem os monoaromáticos presentes nas correntes de petróleo. A caracterização textural mostrou que tanto a área específica quanto o volume de poros foram pouco alterados após a incorporação dos óxidos metálicos aos suportes. Os catalisadores apresentaram uma dispersão relativamente boa da fase ativa, conforme indicado pelos resultados de MET, DRX e DRS. Os resultados obtidos por TPD de n-propilamina e por espectroscopia de IV de piridina mostraram que a incorporação de óxidos de molibdênio e níquel levou a um aumento da acidez de Brönsted, o que foi atribuído à criação de novos sítios ácidos associados ao óxido de molibdênio ou a sítios de interface deste com o suporte. Obteve-se uma boa correlação entre a atividade de conversão da tetralina e o rendimento em produtos aromáticos e abertura de ciclo naftênico com a acidez de Brönsted do suporte, com a seguinte ordem de atividade para a conversão da tetralina: NiMo/alumina < NiMo/sílica-alumina < NiMo/alumina zeólita. O aumento do rendimento de produtos de hidrogenação foi relacionado à existência de um efeito eletrônico entre os sítios de Brönsted do suporte e as partículas de sulfeto suportado. No entanto, para o catalisador suportado em alumina-zeólita, onde em princípio a fase hidrogenante estaria distante dos sítios ácidos, sugeriu-se a possibilidade de uma rota alternativa de hidrogenação a partir do metil-indano formado nos centros ácidos da zeólita.

Desenvolvimento de catalisadores bifuncionais de óxido de zircônio modificado por óxidos de tungstênio e molibdênio contendo platina para a reação de isomerização de n-parafinas

Bifunctional catalysts based on zircon oxide modified by tungsten (W = 10, 15 and 20 %) and by molybdenum oxide (Mo= 10, 15 e 20 %) containg platinum (Pt = 1%) were prepared by the polymeric precursor method. For comparison, catalysts the tungsten base was also prepared by the impregnation method. After calcinations at 600, 700 and 800 ºC, the catalysts were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, thermogravimetric and differential thermal analysis, nitrogen adsorption and scanning electron microscopy. The profile of metals reduction was determined by temperature programmed reduction. The synthesized catalysts were tested in n-heptane isomerization. X-ray diffractogram of the Pt/WOx-ZrO2 and Pt/MoOx-ZrO2 catalysts revealed the presence of tetragonal ZrO2 and platinum metallic phases in all calcined samples. Diffraction peaks due WO3 and ZrO2 monoclinic also were observed in some samples of the Pt/WOx-ZrO2 catalysts. In the Pt/MoOx-ZrO2 catalysts also were observed diffraction peaks due ZrO2 monoclinic and Zr(MoO4)2 oxide. These phases contained on Pt/WOx-ZrO2 and Pt/MoOx-ZrO2 catalysts varied in accordance with the W or Mo loading and in accordance with the calcination temperature. The infrared spectra showed absorption bands due O-W-O and W=O bonds in the Pt/WOx-ZrO2 catalysts and due O-Mo-O, Mo=O and Mo-O bonds in the Pt/MoOx-ZrO2 catalysts. Specific surface area for Pt/WOx-ZrO2 catalysts varied from 30-160 m2 g-1 and for the Pt/MoOx-ZrO2 catalysts varied from 10-120 m2 g-1. The metals loading (W or Mo) and the calcination temperature influence directly in the specific surface area of the samples. The reduction profile of Pt/WOx-ZrO2 catalysts showed two peaks at lower temperatures, which are attributed to platinum reduction. The reduction of WOx species was evidenced by two reduction peak at high temperatures. In the case of Pt/MoOx-ZrO2 catalysts, the reduction profile showed three reduction events, which are attributed to reduction of MoOx species deposited on the support and in some samples one of the peak is related to the reduction of Zr(MoO4)2 oxide. Pt/WOx-ZrO2 catalysts were active in the n-heptane isomerization with high selectivity to 3-methyl-hexane, 2,3- dimethyl-pentane, 2-methyl-hexane among other branched hydrocarbons. The Pt/MoOx-ZrO2 catalysts practically didn't present activity for the n-heptane isomerization, generating mainly products originating from the catalytic cracking

Addizione di Michael organocatalitica asimmetrica di composti 1,3-dicarbonilici ad orto-chinoni metidi: un nuovo e semplice approccio alla preparazione di 4H-cromeni e croman-2-oni otticamente attivi

The work described in this thesis deals with the development of the asymmetric organocatalytic conjugate addition reaction of 1,3-dicarbonyl compounds to ortho-quinone methides. Due to their instability, these synthetically appealing intermediates have not been fully exploited in catalytic asymmetric settings. In this work, the instability of ortho-quinone methides is overcome by their generation in situ under mild basic conditions, starting from the corresponding sulfonyl derivatives. The bifunctional catalysts used are able to activate both substrates for the reaction, by means of a synergic action of the two catalytic sites, inducing at the same time high enantioselection in the addition step. The reaction leads to the generation of a 2-alkylphenolic framework, featuring a chiral centre at the benzylic position. In particular, the employment of acetylacetone and Meldrum acid as nucleophiles has allowed the obtainment of 4H-chromenes and chroman-2-ones in good yields and generally excellent enantioselectivities. These compounds are synthetic precursors of several natural products, some of which showing interesting biological activity, and of some active pharmaceutical ingredients used in commercial drugs.

Complessi carbenici N-eterociclici di rutenio: catalizzatori omogenei in reazioni di idrogenazione e deidrogenazione

Il presente lavoro di tesi si inserisce in un progetto di ricerca volto alla sintesi di nuovi complessi di metalli di transizione per lo sviluppo di catalizzatori bifunzionali metallo-legante da impiegare in reazioni di catalisi omogenea, in particolare in reazioni redox quali idrogenazione e deidrogenazione attraverso il trasferimento di idrogeno. Il mio progetto ha riguardato la messa a punto della sintesi di complessi di Ru(0) che combinano leganti ciclopentadienonici e carbeni N-eterociclici e la sintesi dei corrispondenti complessi cationici per protonazione. Inoltre, è stato sintetizzato e caratterizzato un nuovo complesso cationico attraverso la metilazione del corrispettivo complesso neutro. I complessi sintetizzati sono stati utilizzati come precursori di catalizzatori nella riduzione tramite trasferimento di idrogeno del 4-fluoroacetofenone, valutandone l’attività catalitica in relazione a leganti, additivi e controioni. Allo scopo di delineare qualche ipotesi sul meccanismo di reazione sono stati effettuati diversi studi sulla reattività dei complessi impiegati in catalisi, in particolare usando la piridina come agente di “trapping”. Infine, è stato condotto uno studio preliminare dell’attività catalitica dei complessi sintetizzati nell’ossidazione di benzilalcol a benzaldeide. The present work is part of a research project that involves the study of new ruthenium-based transition metal complexes in order to develop new metal-ligand bifunctional catalysts to employ in homogeneous catalytic systems, in particular in redox reactions such as hydrogenation and dehydrogenation through hydrogen transfer. My project is focused on the optimization of the synthesis of Ru(0) complexes that combines different ligands as tetraphenylcyclopentadienone and N-heterocyclic carbenes and the synthesis of the corresponding cationic complexes by protonation. Furthermore, it is reported the synthesis and characterization of a new cationic complex obtained by methylation of the corresponding neutral complex. All the prepared complexes were employed as catalyst precursors in the transfer hydrogenation of 4-fluoroacetophenone and their performances were investigated in relation to the type of ligands, additives and counterions. The reactivity of these ruthenium complexes was also investigated with the aim of delineate some hypothesis on the reaction mechanism, in particular employing pyridine as a trapping agent. Finally, preliminary studies on the oxidation of benzyl alcohol have been carried out.

Proceedings of the Fifth Biochemical Engineering Symposium

This report presents the proceedings of the Biochemical Engineering Symposium held at Kansas State University, April 26, 1975. Since a number of the contributions will be published in detail elsewhere, only brief summaries of each contribution are included here. Requests for additional information on projects conducted at Iowa State University should be directed to Dr. Peter J. Reilly, and those at Kansas State University to the editors. Contents"Enzymatic Breakdown of Hemicellulose," Alfred R. Fratzke, Iowa State University "Biochemical Aspects of Hydrocarbon Uptake in Hydrocarbon Fermentations," Tadaatsu Nakahara, Kansas State University "Optimal Concentration Profiles for Bifunctional Catalysts with Langmuir-Hinshelwood Kinetics and Varying Effectiveness Factors," Ho Nam Chang, Iowa State University "Single Cell Protein Production from Hydrocarbons in Tower Systems," J. R. Gutierrez, Kansas State University "Effect of Temperature and pH on the Stability and Activity of Immobilized Glucoamylase and Glucose Isomerase," Gene K. Lee, Iowa State University "Oxygen Transfer in a Tower System with Two Liquid Phases," G. T. MacLean, Kansas State University "Continuous Production of Glucose from Dextrin by Glucoamylase Immlobilized on Porous Silica," Douglas D. Lee, Iowa State University

Bifunctional SO4/ZrO2 catalysts for 5-hydroxymethylfufural (5-HMF) production from glucose

The telescopic conversion of glucose to fructose and then 5-hydroxymethylfurfural (5-HMF), the latter a potential, bio-derived platform chemical feedstock, has been explored over a family of bifunctional sulfated zirconia catalysts possessing tuneable acid-base properties. Characterisation by acid-base titration, XPS, XRD and Raman reveal that submonolayer SO4 coverages offer the ideal balance of basic and Lewis-Brønsted acid sites required to respectively isomerise glucose to fructose, and subsequently dehydrate fructose to 5-HMF. A constant acid site normalised turnover frequency is observed for fructose dehydration to 5-HMF, confirming a common Brønsted acid site is responsible for this transformation. This journal is © The Royal Society of Chemistry.

Bifunctional SO4/ZrO2 catalysts for 5-hydroxymethylfufural (5-HMF) production from glucose

The telescopic conversion of glucose to fructose and then 5-hydroxymethylfurfural (5-HMF), the latter a potential, bio-derived platform chemical feedstock, has been explored over a family of bifunctional sulfated zirconia catalysts possessing tuneable acid-base properties. Characterisation by acid-base titration, XPS, XRD and Raman reveal that submonolayer SO4 coverages offer the ideal balance of basic and Lewis-Brønsted acid sites required to respectively isomerise glucose to fructose, and subsequently dehydrate fructose to 5-HMF. A constant acid site normalised turnover frequency is observed for fructose dehydration to 5-HMF, confirming a common Brønsted acid site is responsible for this transformation. This journal is © The Royal Society of Chemistry.

Kinetics of carbon monoxide oxidation with Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts

Base metal substituted Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts were synthesized by the solution combustion method and characterized by XRD, XPS, TEM and BET surface area analysis. The catalytic activities of these materials were investigated by performing CO oxidation. The rates and the apparent activation energies of the reaction for CO oxidation were determined for each catalyst. All the substituted catalysts showed high rates and lower activation energies for the oxidation of CO as compared to unsubstituted SnO(2). The rate was found to be much higher over copper substituted SnO(2) as compared to other studied catalysts. 100% CO conversion was obtained below 225 degrees C over this catalyst. A bifunctional reaction mechanism was developed that accounts for CO adsorption on base metal and support ions and O(2) dissociation on the oxide ion vacancy. The kinetic parameters were determined by fitting the model to the experimental data. The high rates of the CO oxidation reactions at low temperatures were rationalized by the high dissociative chemisorption of adsorbed O(2) over these catalysts.