A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

A comparative study of two different conductive carbon-black pigments, Vulcan XC-72 R and Printex L6, for the electrogeneration of hydrogen peroxide (H(2)O(2)) by reducing dissolved oxygen in an alkaline solution was performed. The materials were physically characterized by X-ray diffraction (XRD), Fourier transform infrared attenuated total reflection (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). XRD shows the presence of SO(2) and ATR-FTIR technique indicates a difference in NO and SO(2) functional groups between the two carbon pigments. XPS indicated presence of SO and NO and more oxygenated acid species on Printex L6. A rotating ring-disk electrode was used for electrochemical analysis of the oxygen reduction reaction (ORR). The results showed that the Printex L6 was better than Vulcan XC-72 R for H(2)O(2) production. Results also indicate that the number of electrons transferred in the ORR for Printex L6 and Vulcan XC-72 R were 2.2 and 2.9, respectively, while the percentages of H(2)O(2) formed were 88% and 51%. Scanning electrochemistry microscopy images confirmed the higher amount of H(2)O(2) formed in the Printex L6 pigment. Printex L6 was shown to be a more promising for H(2)O(2) production than Vulcan XC-72 R, while the latter was shown to have more potential for fuel cells. (C) 2011 Elsevier Ltd. All rights reserved.

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.

Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

B3LYP/6-31 + G(d) calculations were employed to investigate the mechanism of the transesterification reaction between a model monoglyceride and the methoxide and ethoxide anions. The gas-phase results reveal that both reactions have essentially the same activation energy (5.9 kcal mol(-1)) for decomposition of the key tetrahedral intermediate. Solvent effects were included by means of both microsolvation and the polarizable continuum solvation model CPCM. Both solvent approaches reduce the activation energy, however, only the microsolvation model is able to introduce some differentiation between methanol and ethanol, yielding a lower activation energy for decomposition of the tetrahedral intermediate in the reaction with methanol (1.1 kcal mol(-1)) than for the corresponding reaction with ethanol (2.8 kcal mol(-1)), in line with experimental evidences. Analysis of the individual energy components within the CPCM approach reveals that electrostatic interactions are the main contribution to stabilization of the transition state. (C) 2009 Elsevier Ltd. All rights reserved.

Provning av tappvattenautomater kopplade till ackumulatortank

Dagens vanliga ackumulatortanksystem har för dålig skiktning i ackumulatortanken, vilket leder till försämrad effektivitet hos systemen. För att förbättra den krävs komponenter, som kan ladda och framförallt urladda med bättre skiktningsegenskaper. Ackumulatorvärmesystem som t ex vedpanna med tank och solvärmesystem kan öka sin effektivitet, om tankens skiktning främjas. En ny typ av varmvattenberedare, sk tappvattenautomater har tagits fram bl a för att ersätta trasiga eller igenkalkade varmvattenberedare i villapannor. Dessa tappvattenautomater har visat sig kunna vara intressanta även för anslutning till ackumulatortankar. Konsumentverket gav SERC uppdraget att testa dessa nya automater för att se hur väl de fungerar i ackumulatorsystem. Vi har testat tre olika fabrikat: Alfajet, Cetetherm och Solvis. Cetetherm provades förutom i grundversionen med trevägsventil, även med en tvåvägsventil. Totalt testades således fyra olika konstruktioner, som skiljer sig i värmeväxlarstorlek och reglerstrategi. I rapporten visas driftsegenskaper och termiska prestanda för tappvattenautomaterna med hjälp av diagram, som upprättades efter omfattande mätningar. Tappvattenautomaterna, som i grundutförande var avsedda för värmepannor, är inte lämpliga för användning tillsammans med ackumulatortank. Tappvattenautomater med god termisk prestanda och till ackumulatorsystem anpassad reglerstrategi ger däremot gott resultat. Alfajet och Cetetherm med trevägsventil är mindre lämpade för ackumulatorvärme-system. En onödigt hög returtemperatur till ackumulatortanken leder till dålig skiktning vid urladdning och därigenom kan en mindre del av energiinnehållet i tanken tillgodogöras. Genom att ersätta trevägsventilen hos Cetetherm med en tvåvägsventil, förbättras den termiska funktionen vid användning med ackumulatortank. Solvis tappvattenautomat var från början konstruerad för solvärmesystem med ackumulatortank och visade sig ha god prestanda. Tappvattenautomaterna testades även med avseende på varmvattenkomforten vid flödesändringar. Ingen av tappvattenautomaterna visade sig kunna reglera varmvattentemperaturen lika bra som ett traditionellt system med väl fungerande blandningsventil. Tappvattenautomatens inverkan på ett solvärmesystems täckningsgrad under sommarhalvårets väderförhållanden testades i SERCs sexdagarstest. I jämförelse till de hittills bästa konventionella system med inbyggda värmeväxlare av typ kamflänsrör kunde täckningsgraden för ett i övrigt likvärdigt system höjas med upp till 15 procentenheter. Marknadspriset för tappvattenautomater på omkring 10 000 kr är fortfarande för högt, för att den skall kunna konkurrera med konventionella system. Vidareutvecklade förenklade system, som produceras i större serier kommer enligt vår bedömning att kunna erbjudas till lägre pris i framtiden.

Villasystem för solvärme

Del 1:Innehållsförteckning och korta sammanfattningarDEL 2:Verksamhetsberättelsen för perioden maj 1992 till april 1993 beskriver de arbeten som har gjorts av villasolvärmegruppen på SERC efter den inledande studie (SERC/UCFB-91/0039), där villasolvärmesystem kartlades. Följande arbeten beskrivs:- Utveckling av lågflödessystem och internationella kontakter- Uppbyggnad av värmelaboratorium på SERC- Praktiska test av värmelagringsenheten- Praktiska test av nya systemkomponenter i solvärmekretsen- Datasimulering inkluderande nyutvecklade systemkomponenterI verksamhetsplanen beskrivs huvudmålet för de arbeten som ska utföras under trårsperioden 93 - 96. Mera detaljerat beskrivs de arbeten som ska utföras under budgetåret 1993/94:- Beräkningsprogram för nogrannare dimensionering av finrörsvärmeväxlare- Konstruktion av maskiner för värmeväxlartillverkning- Utveckling av värmeväxlare för tappvarmvatten- Simuleringsberäkningar för hela systemet med PRESIM/TRNSYS.DEL 3:Del 3 innehåller en redovisning av mätresultat för den undersökta kombitanken. Temperaturförloppen på olika höjd i tankens har studerats vid uppvärmning genom solvärmeväxlaren och nedkylning genom tappning av varmvatten. Resultaten diskuteras kvalitativt och redovisas kvantitativt i form av diagram. Mätresultaten på två prototyper av den på SERC utvecklade finrörsvärmeväxlaren redovisas och diskuteras i jämförelse till traditionell värmeväxlare. De erhållna mätresultaten används som ingångsvärden för simuleringsberäkningar med PRESIM/TRNSYS. Problemen med de i PRESIM/TRNSYS befintliga modellerna diskuteras. De utförda modellberäkningarna tillåter en uppskattning av möjliga förbättringar i form av höjd årsverkningsgrad för ett svenskt villasolvärmesystem med kombitank. I del 3 redovisas dessutom de mätningar som har utförts på otika pumpar vilka skulle kunna användas i solfångarkretsen. Sex olika pumpar analyseras och diskuteras. Del 3 har följande rubriker:- Beskrivning av den undersökta lagringstanken- Mätningar på tappvarmvattenväxlare- Mätningar på solvärmeväxlare (kamflänsrör och finrörsvärmeväxlare)- Simuleringsberäkningar- PumpmätningarDEL 4:Del 4 innehåller publicerade rapporter under 1992 och 93 samt patentansökan för SERC?s finrörsvärmeväxlare: - NORTH SUN 1992, Solar Energy at High Latitudes, June 24-26 1992 Trondheim, Norway. Domestic solar heating system - a systematic study i progress Patentansökan på finrorsvärmeväxlare till Patent- och Registreringsverket från 93 01 23. ISES SOLAR WORLD CONGRESS, 23-27 augusti 1993, Budapest, HUNGARY Criteria for cost efficient small scale solar hot water installations.DEL 5:Del 5 hänvisar till rapporterna från IEA Task-1 4 mötena om solfångarsystem i- Hameln, Tyskland, augusti 1992 och- Rom, Italien, januari 1993.I rapporterna beskrivs aktiviteten inom den internationella arbetsgruppen speciellt med hänsyn på utveckling av villasolvärmesystem. I Rom presenterades principlösningen för den på SERC utvecklade finrörsvärmeväxlare. De har publicerats separat som nr 42 och 46 i SERCs rapportserie.

Russian Arctic Ports : Problems with the development and management of tourist flows

The potential changes to the territory of the Russian Arctic open up unique possibilities for the development of tourism. More favourable transport opportunities along the Northern Sea Route (NSR) create opportunities for tourism development based on the utilisation of the extensive areas of sea shores and river basins. A major challenge for the Russian Arctic sea and river ports is their strong cargo transport orientation originated by natural resource extraction industries. A careful assessment of the prospects of current and future tourism development is presented here based on the development of regions located along the shores of the Arctic ocean (including Murmansk and Arkhangelsk oblast, Nenets Autonomous okrug (AO), Yamal-Nenets AO, Taymyr AO, Republic of Sakha, Chykotsky AO). An evaluation of the present development of tourism in maritime cities suggests that a considerable qualitative and quantitative increase of tourism activities organised by domestic tourism firms is made virtually impossible. There are several factors contributing to this. The previously established Soviet system of state support for the investments into the port facilities as well as the sea fleet were not effectively replaced by creation of new structures. The necessary investments for reconstruction could be contributed by the federal government but the priorities are not set towards the increased passenger transportation. Having in mind, increased environmental pressures in this highly sensitive area it is especially vital to establish a well-functioning monitoring and rescue system in the situation of ever increasing risks which come not only from the increased transports along the NSR, but also from the exploitation of the offshore oil and gas reserves in the Arctic seas. The capacity and knowledge established in Nordic countries (Norway, Finland) concerning cruise tourism should not be underestimated and the already functioning cooperation in Barents Region should expand towards this particular segment of the tourism industry. The current stage of economic development in Russia makes it clear that tourism development is not able to compete with the well-needed increase in the cargo transportation, which means that Russia’s fleet is going to be utilised by other industries. However, opening up this area to both local and international visitors could contribute to the economic prosperity of these remote areas and if carefully managed could sustain already existing maritime cities along the shores of the Arctic Ocean.

Copolimeros de propileno-etileno com baixos teores de etileno : estrutura, morfologia e propriedades

A estrutura básica predomínante encontrada em todos os copolímeros foi a de longos blocos de polipropileno cristalizáveis, separados por unidades isoladas de etileno, que atuaram como defeitos cristalínos, reduzindo o grau de cristalínidade, além da perfeição e da espessura dos cristais. O gradual aumento do teor de etileno nas amostras origínais, até aproximadamente5 moI % provocou redução progressiva no comprimento dos blocos de propileno em ambas as frações cristalizável e elastomérica. Acima daquela concentração, o etileno mostrou por principal efeito a elevação do teor de borracha de etileno-propileno(EPR), refletíndo-seem pronunciado aumento da resistência ao impacto dos copolímeros, com pouca alteração do comprimento das seqüências propiJênicas nas frações cristaJizáveJe elastomérica. A estrutura e a morfologia da borracha EPR gerada foram analisadas, observando-se sua excepcional dispersão na fase contínua cristalína. Análise das curvas de fusão por DSC, utilizando-se conceitos cínéticos, demonstrou a existência de uma energia de ativação aparente de fusão, associada à introdução de unidades etilênicas nas cadeias, e relacionada ao processo de fusão dos cristais poliméricos. A redução de cristalínidade das amostras e o aumento de mobilidade de cadeia da fase amorfa para teores crescentes de etileno resultaram em redução da rigidez dos copolímeros. Propriedades ópticas, como "haze" e brilho mostraram-se dependentesdo balanço entre o teor de cristais e o teor de borracha. Um balanço global das propriedades analisadas sugere uma composição ótima para aplicações típicas de copolímeros de propileno-etileno aquela com teores de etileno entre 4 e 6 moI % (aproximadamente 3 -4 % em massa).

Early and post transition metal complexes as a single of combined components in the ethylene and isoprene polynerization

In this work is reported, in a first step, the effect of different experimental parameters and their relation with polymer properties using the homogeneous binary catalyst system composed by Ni(α-diimine)Cl2 (α-diimine = 1,4-bis(2,6-diisopropylphenyl)- acenaphthenediimine) and {TpMs*}V(Ntbu)Cl2 (TpMs* = hydridobis(3-mesitylpyrazol-1- yl)(5-mesitylpyrazol-1-yl)) activated with MAO. This complexes combination produces, in a single reactor, polyethylene blends with different and controlled properties dependent on the polymerization temperature, solvent and Nickel molar fraction (xNi). In second, the control of linear low density polyethylene (LLDPE) production was possible, using a combination of catalyst precursors {TpMs}NiCl (TpMs = hydridotris(3- mesitylpyrazol-1-yl)) and Cp2ZrCl2, activated with MAO/TMA, as Tandem catalytic system. The catalytic activities as well as the polymer properties are dependent on xNi. Polyethylene with different Mw and controlled branches is produced only with ethylene monomer. Last, the application group 3 metals catalysts based, M(allyl)2Cl(MgCl2)2.4THF (M = Nd, La and Y), in isoprene polymerization with different cocatalysts systems and experimental parameters is reported. High yields and polyisoprene with good and controlled properties were produced. The metal center, cocatalysts and the experimental parameters are determinant for the polymers properties and their control. High conversions in cis-1,4- or trans-1,4-polyisoprene were obtained and the polymer microstructure depending of cocatalyst and metal type. Combinations of Y and La precursors were effective systems for the cis/transpolyisoprene blends production, and the control of cis-trans-1,4-microstructures by Yttrium molar fraction (xY) variation was possible.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.

Polimerização de propeno com catalisadores metalocênicos via suportação in-situ utilizando SMAO como suporte

Os catalisadores metalocênicos Me2Si(Ind)2ZrCl2 e Me2Si(2-Me-Ind)2ZrCl2 foram suportados in-situ sobre SMAO e empregados na polimerização de propeno na presença de alquilalumínios tais como TEA, IPRA ou TIBA. Os resultados obtidos demonstraram que o tipo e a concentração de alquilalumínio presente no meio reacional influenciaram tanto a atividade catalítica quanto as propriedades dos polímeros gerados. Os polímeros obtidos com o catalisador suportado in-situ apresentaram propriedades distintas das obtidas no polímero gerado através da polimerização homogênea, além de morfologia controlada, confirmando que de fato a polimerização ocorreu sobre a superfície do SMAO. Através da deconvolução das curvas de GPC foi constatado o aumento do número de tipos de sítios ativos no sistema catalítico suportado in-situ, resultado que também confirmou a heterogeneização do catalisador sobre o suporte. Com o auxílio de cálculos teóricos e da deconvolução das curvas de GPC foi possível propor estruturas para os sítios ativos dos sistemas homogêneo metaloceno/MAO e heterogêneo (suportado in-situ) metaloceno/SMAO/alquilalumínio. Quando eteno foi utilizado como monômero, o comportamento do sistema catalítico metaloceno/SMAO/alquilalumínio suportado in-situ foi distinto do obtido com propeno. O catalisador Me2Si(Ind)2ZrCl2 suportado ex-situ sobre SMAO através de técnicas convencionais de suportação foi avaliado por EXAFS e foi constatado que a vizinhança eletrônica do zircônio é influenciada pela razão Zr/SMAO. Os resultados obtidos por EXAFS foram correlacionados com a variação na atividade catalítica na polimerização de eteno em função da alteração na razão Zr/SMAO.

High-growth SMEs and the availability of private equity and venture capital in Brazil

This chapter discusses private equity and venture capital (PE/VC) in Brazil. Firstly, it is shown that PE/VC has a strong impact in the Brazilian capital markets, with PE/VC-backed companies representing close to half the amount raised by initial public offerings (IPOs) in the stock exchanges. By examining two of these deals, which involved small and mediumsized enterprises (SMEs), it is argued that PE/VC managers have acted as catalysts of the impressive growth rates experienced before these companies entered the stock markets. Indeed, PE/VC firms represent an important segment of the capital market, with specialization to invest in high-growth innovative SMEs. PE/VC managers exercise superior selection, monitoring and governance that mitigate the uncertainty and risks of investing in such companies. Despite its successes in Brazil, PE/VC is still very much restrained by the challenging local economic and institutional environment. Thus, changes in the legal and fiscal system, simplification in bureaucratic procedures, and other such improvements will most likely result in a sensible growth in the Brazilian PE/VC industry, with positive impact in the SME access to finance in Brazil. Since most countries in Latin America share similar economic and institutional traits with Brazil, the path followed by the local PE/VC industry can serve as an example for other countries to learn with its successes and failures.

Consórcios públicos intermunicipais no Brasil: panorama após os 10 anos da Lei 11.107/2005

Com a promulgação da Lei 11.107/2005 que regulamentou o artigo 241 da Constituição Federal, também conhecida como a Lei dos Consórcios, os mesmos passaram a ter um marco regulatório que proporcionou maior segurança jurídica e permitiu a expansão deste tipo de arranjo para diversas áreas além daquelas já utilizadas, bem como foi estruturada uma arquitetura de gestão para os mesmos. Com isso, a expectativa era de que a cooperação e a ação coordenada entre os entes federados seriam ampliadas. Assim, este estudo apresenta um panorama deste período de dez anos para os Consórcios, iniciando com a histórico da Lei desde sua fase de projeto até a sua promulgação. Nesta análise foi identificado que a Lei promulgada é resultado da mescla de dois projetos apresentados sobre o tema, um de origem do Poder Legislativo e outro do Poder Executivo, sendo que este último teve forte influência sobre o primeiro. Ainda, a promulgação da Lei foi fruto de um acordo entre estes dois poderes. Para que se identificasse a realidade dos Consórcios, o presente trabalho buscou no Federalismo e na Municipalização o pano de fundo como referencial teórico para a discussão do tema de associativismo entre entes públicos. Também se verificou a produção acadêmica existente no Brasil sobre os Consórcios Públicos que, a despeito de ainda ser pequena, relata diversas soluções já implementadas pelo país afora bem como os desafios que os Consórcios enfrentam para o efetivo atingimentos dos seus objetivos. Ainda, foi realizado um levantamento da tipologia dos Consórcios existentes no Brasil, cuja base de dados foi a pesquisa realizada pela organização não governamental Observatório dos Consórcios Públicos e do Federalismo em 2012, para se identificar a distribuição dos mesmos pelo país, dada a inexistência de levantamentos por entes oficiais sobre a existências de Consórcios no Brasil. Por fim, é apresentada uma perspectiva para os consórcios sobre quatro diferentes contextos, todos com vistas a estimular este tipo de arranjo para que eles se tornem fortes ferramentas catalizadoras do associativismo e da cooperação entre entes públicos e promovam efetivamente a geração de valor público.

Argilas modificadas como catalisadores ácidos sólidos

Important bentonitic deposits are present in Porto Santo Island, part of the Madeira Archipelago. Several locations were selected and samples were collected and characterised. The bentonite obtained at Serra de Dentro (SD) was selected for further laboratorial work. The fine fraction of SD bentonite was purified using several methods and the sodium homoionic form was prepared. This was the starting material used in the three generic types of modifications: metal exchange, acid activation and pillaring. These modifications produce materials with markedly different acidic (e.g. Brönsted and/or Lewis acidity), textural (e.g. increase of the surface area and active site accessibility) or structural (e.g. creation of permanent porous structures) properties. The wide range of materials obtained (including reference clays counterparts) was characterised in terms of chemical, structural, textural and catalytic properties. Limonene is an important raw material produced in Portugal, and its aromatisation reaction was chosen for the catalytic characterisation of the clay catalysts prepared.

Nanocatalysts for sustainable industrial processses

In Chapter 1, rhodium nanoparticles were supported on multiwalled carbon nanotubes (MWCNTs) and bound to the magnetic core-shell system Fe3O4@TiO2. The composite Fe3O4@TiO2-Rh-MWCNT and the intermediates were characterized by SEM, EDS and TEM. Their catalytic activity was studied using i) the hydrogenation transfer of nitroarenes and cyclohexene in the presence of hydrazine hydrate; ii) the reduction of 2-nitrophenol with NaBH4; and iii) the decoloration of pigments in the presence of hydrogen peroxide. The results were monitored by gas chromatography (i) and UV Visible (ii and iii). In the second chapter, the catalytic activity of six oxidovanadium(V) aroylhydrazone complexes, viz. [VOL1(OEt)][VOL1(OEt)(EtOH)] (1), [VOL2(OEt)] (2), [Et3NH][VO2L1] (3), [VO2(H2L2)]2·EtOH (4), [VOL1(µ -O)VOL1] (5) and [VOL2(µ -O)VOL2] (6) (H2L1 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2hydroxybenzohydrazide and H2L2 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2 aminobenzohydrazide), anchored on nanodiamonds with different treatments, was studied towards the microwave-assisted partial oxidation of 1-phenylethanol to acetophenone in the presence of tert-butyl hydroperoxide (TBHP) as oxidant. A high selectivity for acetophenone was achieved for the optimized conditions. The possibility of recycling and reuse the heterogeneous catalysts was also investigated. In chapter 3, the catalytic activity of gold nanoparticles supported at different metal oxides, such as Fe2O3, Al2O3 ZnO or TiO2, was studied for the above reaction. The effect of the support, quantity of the catalyst and temperature was investigated. The recyclability of the gold catalysts was also studied. In the last chapter, a new copper nanocomposite with functionalized mutiwalled carbon nanotubes (Cu-MWCNT) was synthesized using a microwave assisted polyol method. The characterization was performed using XRD and SEM. The catalytic activity of Cu-MWCNT was studied through the degradation of pigments, such as amaranth, brilliant blue, indigo, tartrazine and methylene blue.

Síntese, caracterização e estudo da regeneração do silicoaluminofosfato-11 (SAPO-11)

heterogeneous catalyst such as a silicoaluminophosphate, molecular sieve with AEL (Aluminophosphate eleven) structure such as SAPO-11, was synthesized through the hydrothermal method starting from silica, pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. For the preparation of SAPO-11 in a dry basis it was used as reactants: DIPA; H3PO4; SiO4; Pseudoboehmite and distilled water. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 200ºC for a period of 72 hours under autogeneous pressure. The obtained material was washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), nitrogen adsorption (BET) and thermal analysis (TG/DTG). The acidic properties were determined using adsorption of nbutylamine followed by programmed thermodessorption. This method revealed that SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by artificial coking followed by the cracking of the n-hexane in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the regeneration and removal of the coke