A high-resolution solid-state NMR study on nano-structured HZSM-5 zeolite

Variations in the structure and acidity properties of HZSM-5 zeolites with reduction in crystal sizes down to nanoscale (less than 100 nm) have been investigated by XRD, TEM and solid-state NMR with a system capable of in situ sample pretreatment. As evidenced by a combination of Al-27 MAS NMR, Si-29 MAS, CP/MAS NMR and H-1 MAS NMR techniques, the downsize of the zeolite crystal leads to an obvious line broadening of the Al-27, Si-29 MAS NMR spectrum, an increasing of the silanol concentration on the external surface, and a pronounced alteration of the acidity distribution between the external and internal surfaces of the zeolite. In a HZSM-5 zeolite with an average size at about 70 nm, the nonacidic hydroxyl groups (silanols) are about 14% with respect to the total amount of Si, while only 4% of such hydroxyl groups exist in the same kind of zeolite at 1000 nm crystal size. The result of H-1 MAS NMR obtained using Fluorinert(R) FC-43 (perfluorotributyl amine) as a probe molecule demonstrates that most of the silanols are located on the external surface of the zeolite. Moreover, the concentration of Bronsted acid sites on the external surface of the nano-structured zeolite appears to be distinctly higher than that of the microsized zeolite.

Synthesis of titanium silicalites in different template systems and their catalytic performance

Titanium silicalites have been synthesized in the TPABr+ammonia, TPABr+hexanediamine, TPABr+ethylenediamine, TPABr+diethylamine, TPABr+TEAOH, TPABr+n-butylamine, TPABr+TBAOH and TBAOH+n-butylamine systems. As-synthesized titanium silicalites were characterized by XRD, IR and C-13 CP MAS NMR. Catalytic performance in epoxidation of propylene and template effect was investigated. It has been shown that both TPABr and TBAOH serve as templating agent in TPABr+TBAOH system. But in other systems, when there is enough TPABr, organic amines or ammoniums only act as the bases. TEAOH or n-butylamine can take the role of template when less TPABr is added. It indicates that the ability of organic amines or ammoniums to direct the Pentasil structure decreases as follows: TPA(+)>TBA(+)>TEA(+)>n-butylamine. Catalysts exhibiting good performance in epoxidation of propylene can be attained using TPABr as the template and ammonia, n-butylamine, diethylamine, hexanediamine or TBAOH as bases. (C) 1999 Elsevier Science B.V. All rights reserved.

The active sites in different TS-1 zeolites for propylene epoxidation studied by ultraviolet resonance Raman and ultraviolet visible absorption spectroscopies

The titanium species in four kinds of titanium-containing MFI zeolites have been studied by ultraviolet (UV)-Raman and ultraviolet visible (UV-Vis) absorption spectroscopies and by the epoxidation of propylene with diluted H2O2 solution (30%). UV-Raman spectroscopy is proved to be a suitable means to estimate qualitatively the framework titanium in TS-l zeolites. Based on the comparison of the relative intensity ratio I-1125/I-380 of UV-Raman spectra, the TS-1(conv.) sample synthesized hydrothermally by the conventional procedure shows the highest amount of framework titanium. UV-Vis spectroscopy reveals that besides minor anatase. titanium species are mainly tetrahydrally coordinated into the framework for TS-l(conv.) or the Ti-ZSM-5 sample prepared by gas-solid reaction between deboronated B-ZSM-5 and TiCl4 vapor at elevated temperatures. For the TS-1(org.) and TS-1(inorg.) samples synthesized hydrothermally using tetrapropylammonium bromide (TPABr) as template and tetrabutylorthotitanite (TBOT) and TiCl3 as titanium source, respectively, the presence of mononuclear and isolated TiOx species which are proposed to bond to the zeolite extraframework is observed. In addition to the framework titanium species, these isolated TiOx species are assumed to be also active for propylene epoxidation.

Titanium species in titanium silicalite TS-1 prepared by hydrothermal method

The titanium species existing in titanium silicalite TS-1, which is prepared by hydrothermal method, were investigated using chemical analysis, XRD, FT-IR, Si-29 MAS NMR, UV-VIS, ESR. It has been observed that several kinds of titanium species may exist in titanium silicalite. The form that titanium atoms incorporate into the framework of titanium silicalite synthesized using tetrapropylammonium bromide (TPABr) as template differs from that using the classical method. But, the symmetry of titanium silicalite, changes from monoclinic to orthorhombic with the increase of titanium content in both methods. The Ti-O-2(-) originated from framework titanium and H2O2 has the moderate stability and may be active site in oxidation reaction. TS-1 synthesized using TPABr as template does not contain anatase, but contains a kind of partly condensed titanium species with six-fold coordination. The titanium species may correspond to 270-280 mn band in UV-VIS spectra and also can form Ti-O-2(-). But, this kind of Ti-O-2(-) is very stable and cannot be catalytic active site. So, the six-fold coordination titanium species may be inactive in both the oxidation reaction and the decomposition of H2O2. The hypothesis has been further proved by the phenomena that the titanium species is easily washed off using acid, and acid treating will not influence the catalytic performance of TS-1. (C) 2001 Elsevier Science B.V. All rights reserved.

Preparation of supported PtRu/C electrocatalyst for direct methanol fuel cells

In this work, high-surface supported PtRu/C were prepared with Ru(NO)(NO3)(3) and [Pt(H2NCH2CH2NH2)(2)]Cl-2 as the precursors and hydrogen as a reducing agent. XRD and TEM analyses showed that the PtRu/C catalysts with different loadings possessed small and homogeneous metal particles. Even at high metal loading (40 wt.% Pt, 20 wt.% Ru) the mean metal particle size is less than 4 nm. Meanwhile, the calculated Pt crystalline lattice parameter and Pt (220) peak position indicated that the geometric structure of Pt was modified by Ru atoms. Among the prepared catalysts, the lattice parameter of 40-20 wt.% PtRu/C contract most. Cyclic voltammetry (CV), chronoamperometry (CA), CO stripping and single direct methanol fuel cell tests jointly suggested that the 40-20 wt.% PtRu/C catalyst has the highest electrochemical activity for methanol oxidation. (c) 2004 Elsevier Ltd. All rights reserved.

Improvement of direct methanol fuel cell performance by modifying catalyst coated membrane structure

A five-layer catalyst coated membrane (CCM) based upon Nation 115 membrane for direct methanol fuel cell (DMFC) was designed and fabricated by introducing a modified Nafion layer between the membrane and the catalyst layer. The properties of the CCM were determined by SEM, cyclic voltammetry, impedance spectroscopy, ruinous test and I-V curves. The characterizations show that the modified Nation layers provide increased interface contact area and enhanced interaction between the membrane and the catalyst layer. As a result, higher Pt utilization, lower contact resistance and superior durability of membrane electrode assembly was achieved. A 75% Pt utilization efficiency was obtained by using the novel CCM structure, whereas the conventional structure gave 60% efficiency. All these features greatly contribute to the increase in DMFC performance. The DMFC with new CCM structure presented a maximum power density of 260 MW cm(-2), but the DMFC with conventional structure gave only 200 mW cm(-2) under the same operation condition. (c) 2005 Elsevier B.V. All rights reserved.

Determination of ionic resistance and optimal composition in the anodic catalyst layers of DMFC using AC impedance

In the present study, a method based on transmission-line mode for a porous electrode was used to measure the ionic resistance of the anode catalyst layer under in situ fuel cell operation condition. The influence of Nafion content and catalyst loading in the anode catalyst layer on the methanol electro-oxidation and direct methanol fuel cell (DMFC) performance based on unsupported Pt-Ru black was investigated by using the AC impedance method. The optimal Nafion content was found to be 15 wt% at 75 degrees C. The optimal Pt-Ru loading is related to the operating temperature, for example, about 2.0 mg/cm(2) for 75-90 degrees C, 3.0 mg/cm2 for 50 degrees C. Over these values, the cell performance decreased due to the increases in ohmic and mass transfer resistances. It was found that the peak power density obtained was 217 mW/cm(2) with optimal catalyst and Nafion loading at 75 degrees C using oxygen. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

'Mining money': science, legal technologies & working the borderlands of global finance

This paper explores the roles of science and market devices in the commodification of ‘nature’ and the configuration of flows of speculative capital. It focuses on mineral prospecting and the market for shares in ‘junior’ mining companies. In recent years these companies have expanded the reach of their exploration activities overseas, taking advantage of innovations in exploration methodologies and the liberalisation of fiscal and property regimes in ‘emerging’ mineral rich developing countries. Recent literature has explored how the reconfiguration of notions of ‘risk’ has structured the uneven distribution of rents. It is increasingly evident that neoliberal framing of environmental, political, social and economic risks has set in motion overflows that multinational mining capital had not bargained for (e.g. nationalisation, violence and political resistance). However, the role of ‘geological risk’ in animating flows of mining finance is often assumed as a ‘technical’ given. Yet geological knowledge claims, translated locally, designed to travel globally, assemble heterogeneous elements within distanciated regimes of metrology, valuation and commodity production. This paper explores how knowledge of nature is enrolled within systems of property relations, focusing on the genealogy of the knowledge practices that animate contemporary circuits of speculative mining finance. It argues that the financing of mineral prospecting mobilises pragmatic and situated forms of knowledge rather than actuarially driven calculations that promise predictability. A Canadian public enquiry struck in the wake of scandal associated with Bre-X’s prospecting activities in Indonesia is used to glean insights into the ways in which the construction of a system of public warrant to underpin financial speculation is predicated upon particular subjectivities and the outworking of everyday practices and struggles over ‘value’. Reflection on practical investments in processes of standardisation, rituals of verification and systems of accreditation reveal much about how the materiality of things shape the ways in which regional and global financial circuits are integrated, selectively transforming existing social relations and forms of knowledge production.

Near real-time flood detection in urban and rural areas using high resolution Synthetic Aperture Radar images

A near real-time flood detection algorithm giving a synoptic overview of the extent of flooding in both urban and rural areas, and capable of working during night-time and day-time even if cloud was present, could be a useful tool for operational flood relief management. The paper describes an automatic algorithm using high resolution Synthetic Aperture Radar (SAR) satellite data that builds on existing approaches, including the use of image segmentation techniques prior to object classification to cope with the very large number of pixels in these scenes. Flood detection in urban areas is guided by the flood extent derived in adjacent rural areas. The algorithm assumes that high resolution topographic height data are available for at least the urban areas of the scene, in order that a SAR simulator may be used to estimate areas of radar shadow and layover. The algorithm proved capable of detecting flooding in rural areas using TerraSAR-X with good accuracy, and in urban areas with reasonable accuracy. The accuracy was reduced in urban areas partly because of TerraSAR-X’s restricted visibility of the ground surface due to radar shadow and layover.

Ω-results for Beurling's zeta function and lower bounds for the generalised Dirichlet divisor problem

In this paper we study generalised prime systems for which the integer counting function NP(x) is asymptotically well behaved, in the sense that NP(x)=ρx+O(xβ), where ρ is a positive constant and . For such systems, the associated zeta function ζP(s) is holomorphic for . We prove that for , for any ε>0, and also for ε=0 for all such σ except possibly one value. The Dirichlet divisor problem for generalised integers concerns the size of the error term in NkP(x)−Ress=1(ζPk(s)xs/s), which is O(xθ) for some θ<1. Letting αk denote the infimum of such θ, we show that .

Se In é um ideal finitamente gerado então I é um ideal finitamente gerado?

Suponhamos que M seja um ideal maximal de um domínio R e que alguma potência de M seja finitamente gerada. Vamos mostrar que M será finitamente gerado em cada um dos seguintes casos: i M tem altura um, ii R é inteiramente fechado e altura de M é 2, iii R K X,S é um domínio monóide sobre um corpo K, onde S S 0 é um monóide cancelativo e livre de torção, tal que i 1 iS e M é o ideal maximal gerado por Xs/s S . Estendemos os resultados anteriores aos ideais I de um anel reduzido R tal que RI é anel Noetheriano. Provamos que um anel reduzido R é Noetheriano se cada ideal primo de R possui uma potência que é finitamente gerada. Para cada d tal que 3 d , estabelecemos a existência de um domínio de integridade d-dimensional que possui um ideal maximal M não finitamente gerado, de altura d tal que M2 é 3-gerado.

Processos de gerenciamento de projetos de gestão: uma análise comparativa com o guia PMBOK

O objetivo deste trabalho é identificar e descrever os processos de gerenciamento dos projetos de ajuste na estrutura organizacional, processos e governança de uma grande empresa brasileira. Os processos de gerenciamento de projetos são o encadeamento das ações e atividades que permitem atingir os objetivos do projeto, constituindo o objeto de estudo do Guia PMBOK e outras bases de conhecimento em gestão de projetos. A pesquisa identificou e descreveu o fluxo de gerenciamento dos projetos de gestão de uma das gerências da Empresa “X” a partir de análise documental, entrevistas e observação participativa. Os resultados foram analisados à luz do referencial teórico sobre processos de gerenciamento de projetos, processos de gerenciamento “front-end” e governança de projetos. A pesquisa concluiu que, comparado ao processo de gerenciamento previsto no Guia PMBOK, o gerenciamento dos projetos de gestão analisados coloca ênfase relativamente maior nos processos que antecedem o início formal do projeto (processos front-end), responsáveis por garantir seu alinhamento aos direcionadores e variáveis organizacionais.

Receptores GPS de três precisões e estação total na caracterização de cotas básicas para projetos rurais

O objetivo deste estudo foi comparar cotas de vértices de uma poligonal, considerando dados coletados por três diferentes receptores GPS, usando como testemunha uma estação total. Os dados foram obtidos em uma poligonal fechada, sendo posteriormente tratados pelo software Topograph. As cotas obtidas pelos três receptores foram confrontadas com aquelas calculadas a partir do levantamento com a estação total, mediante a aplicação do teste t, constatando-se que as mesmas foram satisfatórias para o equipamento GPS Trimble® 4600 LS. Para o equipamento GPS Trimble® modelo PRO XR, as cotas não foram totalmente satisfatórias, mas possíveis de serem consideradas em anteprojetos. Para o equipamento GPS Garmin® de navegação 12 XS, as cotas mostraram-se inaceitáveis para a finalidade estudada.

Non-newtonian flow and pressure drop of pineapple juice in a plate heat exchanger

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Supersymmetry flows, semi-symmetric space sine-Gordon models and the Pohlmeyer reduction

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)