Synthesis and electron emission properties of aligned carbon nanotube arrays

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

Estudo da polimerização térmica de óleos e gorduras

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2011.

Catalytic activity evaluation of industrial Pd/C catalyst via gray-box dynamic modeling and simulation of hydropurification reactor

In this paper, dynamic modeling and simulation of the hydropurification reactor in a purified terephthalic acid production plant has been investigated by gray-box technique to evaluate the catalytic activity of palladium supported on carbon (0.5 wt.% Pd/C) catalyst. The reaction kinetics and catalyst deactivation trend have been modeled by employing artificial neural network (ANN). The network output has been incorporated with the reactor first principle model (FPM). The simulation results reveal that the gray-box model (FPM and ANN) is about 32 percent more accurate than FPM. The model demonstrates that the catalyst is deactivated after eleven months. Moreover, the catalyst lifetime decreases about two and half months in case of 7 percent increase of reactor feed flowrate. It is predicted that 10 percent enhancement of hydrogen flowrate promotes catalyst lifetime at the amount of one month. Additionally, the enhancement of 4-carboxybenzaldehyde concentration in the reactor feed improves CO and benzoic acid synthesis. CO is a poison to the catalyst, and benzoic acid might affect the product quality. The model can be applied into actual working plants to analyze the Pd/C catalyst efficient functioning and the catalytic reactor performance.

MoNi/gamma-Al2O3 Catalyst: Preparation and Catalytic Activity for Acetic Acid Hydrotreating

MoNi/gamma-Al2O3 catalysts were prepared by the impregnation method. The catalyst samples were characterized by XRD and TPR. The effects of Mo promoter content and the catalyst reducing temperature Oil hydrotreatment activity of the catalyst were studied under 200 degrees C and 3 MPa hydrogen pressure using acetic acid as the model compound. The XRD results indicate that the addition of Mo promoter is beneficial to the uniformity of nickel species on the catalyst and decreases the Interaction between nickel species and the support Which results in the decrease the of NiAl2O4 spinel formation. The addition of Mo promoter also decreases the reducing temperature of the catalyst. After the catalyst of 0.06 MoNi/gamma-Al2O3 being reduced Under the atmosphere of H-2/N-2(5/95, V/V), nickel oxide was reduced to Ni-0. The reaction was promoted obviously upon the addition of the MoNi/gamma-Al2O3 catalyst reduced at 600 degrees C. The Mo-modified Ni/gamma-Al2O3 catalyst reduced at 600 degrees C displayed the highest activity during the reaction, the conversion of acetic acid reached the highest point of 33.2%. The products included ethyl acetate and water.

Promotional effect of colloidal alumina on the activity of the In/HZSM-5 catalyst for the selective reduction of NO with methane

Colloidal alumina was used to improve the activity of an In/HZSM-5 catalyst for the selective reduction of NO with CH4 in the excess of oxygen. Compared with In/HZSM-5, the In/HZSM-5/Al2O3 catalyst showed higher activity in a wide range of reaction temperatures. It is visualized that a synergetic effect between In/HZSM-5 and Al2O3 enhances the conversion of NOx. The addition of Al2O3 improved the conversion of NO to NO2 and facilitated the activation of methane. An In/HZSM-5/Al2O3 pre-treated with steam for 15 h at 700 degreesC still showed a high activity for the removal of NOx with methane, while an In/HZSM-5 similarly pre-treated with steam showed a lower activity than the fresh sample. The activity of the In/HZSM-5/Al2O3 catalyst could be restored completely after water vapor was removed from the feed gas. Furthermore, it was found that the In/HZSM-5/Al2O3 remained fairly active under high GHSV and O-2 concentration conditions. It was also interesting to find that an increase in NO content could enhance the conversion of methane, and this illustrates that the existence of NO is beneficial for the activation of methane. (C) 2002 Elsevier Science B.V. All rights reserved.

Effect of addition of Zn on the catalytic activity of a Co/HZSM-5 catalyst for the SCR of NOx with CH4

The selective catalytic reduction (SCR) of NOx by methane in the presence of excess oxygen was studied on a Zn-Co/HZSM-5 catalyst. It was found that the addition of Zn could improve effectively the selectivity of methane towards NOx reduction. When prepared by a coimpregnation method, the Zn-Co/HZSM-5 catalyst showed much higher catalytic activity than the two catalysts of a Zn/Co/HZSM-5 and Co/Zn/HZSM-5 prepared by the successive impregnation method. It is considered that there exists a cooperative effect among the Zn, Co and zeolite, which enhances the reduction of NO to NO2 reaction and the activation of methane. (C) 2002 Elsevier Science B.V. All rights reserved.

Electrochemical designing of Au/Pt core shell nanoparticles as nanostructured catalyst with tunable activity for oxygen reduction

Au/Pt core shell nanoparticles (NPs) have been prepared via a layer-by-layer growth of Pt layers on An NPs using underpotential deposition (UPD) redox replacement technique. A single UPD Cu monolayer replacement with Pt(11) yielded a uniform Pt film on Au NPs, and the shell thickness can be tuned by controlling the number of UPD redox replacement cycles. Oxygen reduction reaction (ORR) in air-saturated 0.1 M H2SO4 was used to investigate the electrocatalytic behavior of the as-prepared core shell NPs. Cyclic voltammograms of ORR show that the peak potentials shift positively from 0.32 V to 0.48 V with the number of Pt layers increasing from one to five, suggesting the electrocatalytic activity increases with increasing the thickness of Pt shell. The increase in electrocatalytic activity may originate mostly from the large decrease of electronic influence of Au cores on surface Pt atoms. Rotating ring-disk electrode voltammetry and rotating disk electrode voltammetry demonstrate that ORR is mainly a four-electron reduction on the as-prepared modified electrode with 5 Pt layers and first charge transfer is the rate-determining step.

Effect of pretreatment of black carbon on electrocatalytic activity of Pt/C catalyst for methanol oxidation

Direct methanol fuel cell (DMFC) has attracted wide attention due to its many advantages. However, its practical application is limited by the low electrocatalytic activity of the anodic Pt/C catalyst usually used for the methanol oxidation. In this paper, in order to increase the electrocatalytic performance of the Pt/C catalyst for the methanol oxidation, the black carbon, usually used as the supporter, was pretreated with CO2, air, HNO3 or H2O2. The cyclic voltarnmetric results indicated that the current densities of the anodic peak of methanol oxidation at the Pt/C catalysts with the black carbon pretreated with CO2,air, HN03, H202 and untreated black carbon were 39, 33, 32, 20 and 18 mA center dot cm(-2), respectively, illustrating that among the above five kinds of the Pt/C catalysts, the Pt/C catalyst with the black carbon pretreated with CO2 shows the best electrocatalytic activity and stability for the methanol oxidation. Its main reason is that the CO2 pretreatment could reduce the content of the oxygen-containing groups on the surface of the black carbon and increase the content of graphite in the black carbon, leading to the low resistance of the black carbon and the increase in the dispersion extent of the Pt particles in the Pt/C catalyst.