Rosana Balzer

Synthesis and structure-activity relationship of a WO3 catalyst for the total oxidation of BTX

In this study we prepared a WO3-based catalyst to investigate its catalytic activity in the total oxidation of the volatile organic compounds known as benzene, toluene and xylene (BTX). For a range of low temperatures (50-450oC) the only reaction products were CO2 and H2O. The results for the catalyst characterization suggested that the high catalytic activity could be attributed to the effects of a strong metal interaction, which is possibly originated from the small lattice parameter difference between the (111), (020) and (002) lattice planes and the presence of W4+, W5+ and W6+ species on the surface of the catalyst which react with active oxygen species.

Catalytic Properties of AgPt Nanoshells as a Function of Size: Larger Outer Diameters Lead to Improved Performances

We report herein a systematic investigation on the effect of the size of silver (Ag) nanoparticles employed as starting materials over the morphological features and catalytic performances of AgPt nanoshells produced by a combination of galvanic replacement between Ag and PtCl6(2-) and PtCl6(2-) reduction by hydroquinone. More specifically, we focused on Ag nanoparticles of four different sizes as starting materials, and found that the outer diameter, shell thickness, and the number of Pt surface atoms of the produced nanoshells increased with the size of the starting Ag nanoparticles. The produced AgPt nanoshells were supported into SiO2, and the catalytic performances of the AgPt/SiO2 nanocatalysts toward the gas-phase oxidation of benzene, toluene, and o-xylene (BTX oxidation) followed the order: AgPt 163 nm/SiO2 > AgPt 133 nm/SiO2 > AgPt 105 nm/SiO2 > AgPt 95 nm/SiO2. Interestingly, bigger AgPt nanoshell sizes lead to better catalytic performances in contrast to the intuitive prediction that particles having larger outer diameters tend to present poorer catalytic activities due to their lower surface to volume ratios as compared to smaller particles. This is in agreement with the H2 chemisorption results, and can be assigned to the increase in the Pt surface area with size due to the presence of smaller NPs islands at the surface of the nanoshells having larger outer diameters. This result indicates that, in addition to the overall diameters, the optimization of the surface morphology may play an important role over the optimization of catalytic activities in metal-based nanocatalysts, which can be even more pronounced that the size effect. Our data demonstrate that the control over surface morphology play a very important role relative to the effect of size to the optimization of catalytic performances in catalysts based on noble-metal nanostructures.

Combining active phase and support optimization in MnO2-Au nanoflowers: Enabling high activities towards green oxidations

Among the several classes of chemical reactions, the green oxidation of organic compounds has emerged as an important topic in nanocatalysis. Nonetheless, examples of truly green oxidations remain scarce due to the low activity and selectivity of reported catalysts. In this paper, we present an approach based on the optimization of both the support material and the active phase to achieve superior catalytic performances towards green oxidations. Specifically, our catalysts consisted of ultrasmall Au NPs deposited onto MnO2 nanoflowers. They displayed hierarchical morphology, large specific surface areas, ultrasmall and uniform Au NPs sizes, no agglomeration, strong metal-support interactions, oxygen vacancies, and Auδ+ species at their surface. These features led to improved performances towards the green oxidations of CO, benzene, toluene, o-xylene, glucose, and fructose relative to the pristine MnO2 nanoflowers, commercial MnO2 decorated with Au NPs, and other reported catalysts. We believe that the catalytic activities, stabilities, and mild/green reaction conditions described herein for both gas and liquid phase oxidations due to the optimization of both the support and active phase may inspire the development of novel catalytic systems for a wealth of sustainable transformations.

SBA-15 as a Support for Nickel-Based Catalysts for Polymerization Reactions

Two mesoporous SBA-15 materials with different morphologies (spherical and fiber-shaped) were synthesized and evaluated as supports for nickel-based catalysts for polymerization reactions. The supports were pretreated with trimethylaluminum (TMA), and the catalyst dibromo-bis(4-amino-2,3,5,6-tetramethylimino)acenaphthene nickel(II) was attached to the supports and activated with TMA or MAO (methylaluminoxane). Characterization showed that the insertion of cetyltrimethylammonium bromide (CTABr) as a cosurfactant led to spherical SBA-15 with a decrease in particle and pore sizes to 4.8 nm compared to 6.5 nm in traditional fiber-shaped SBA-15. The spherical SBA-15 showed thicker walls than the fiber-shaped SBA-15, attributed to the increase in functional groups of the cosurfactant. The different spherical and fiber-shaped morphologies did not show any significant difference in the productivity of polyethylene. The catalyst supported on spherical SBA-15 materials showed 58% productivity compared to its homogeneous analogue using TMA as a cocatalyst.

Removal of BTX Compounds in air by total catalytic oxidation promoted by catalysts based on SiO2(1-x)Cu x

The aim of this study was to reduce the emissions of organic compounds, such as BTX (benzene, toluene and xylenes), due to their toxicity and adverse effects on the environment. In this regard, catalysts (SiO2(1-x)Cux) were developed which exhibit high catalytic activity for converting BTX compounds to CO2 and H2O, and which do not require the use of solvents and materials detrimental to the environment, with low production cost and good reproducibility. Cu (from copper(II) nitrate) was loaded (2.99; 5.01; 10.01 and 19.97 wt.%) onto supports (SiO2) by wet impregnation. The study was carried out within the temperature range of 50-350 oC. The catalysts described in this paper have high catalytic activity in the total oxidation of BTX. The conversion of benzene in this study exceeded 85% at 150 oC.