Tailoring and visualizing the pore architecture of hierarchical zeolites

Recently the concept of hierarchical zeolites invoked more explicit attention to enhanced accessibility of zeolites. By realizing additional meso-/macroporosity with the intrinsic microporosity of zeolites, a hierarchical pore system arises which facilitates mass transport while maintaining the zeolite shape selectivity. A great number of synthesis strategies have been developed for tailoring the pore architecture of hierarchical zeolites. In this review, we give a general overview of different synthesis methods for introduction of additional porosity. Advantages and limitations of these different synthesis approaches are addressed. The assessment of pore structure is essential to build the link between the zeolite pore structure and its functionality. A variety of 2D and 3D microscopy techniques are crucial to visualize the hierarchical pore structure, providing unique and comprehensive information that, however, should be linked to the results of bulk characterization techniques as much as possible. The microscopy techniques are classified and discussed according to the different probes used, such as optical light, X-rays and electrons. Representative work is reviewed to elucidate the capability of each technique and their drawbacks

Facile synthesis of precious-metal single-site catalysts using organic solvents

Single-site catalysts can demonstrate high activity and selectivity in many catalytic reactions. The synthesis of these materials by impregnation from strongly oxidizing aqueous solutions or pH-controlled deposition often leads to low metal loadings or a range of metal species. Here, we demonstrate that simple impregnation of the metal precursors onto activated carbon from a low-boiling-point, low-polarity solvent, such as acetone, results in catalysts with an atomic dispersion of cationic metal species. We show the generality of this method by producing single-site Au, Pd, Ru and Pt catalysts supported on carbon in a facile manner. Single-site Au/C catalysts have previously been validated commercially to produce vinyl chloride, and here we show that this facile synthesis method can produce effective catalysts for acetylene hydrochlorination in the absence of the highly oxidizing acidic solvents previously used

Robust estimation of bacterial cell count from optical density

Optical density (OD) is widely used to estimate the density of cells in liquid culture, but cannot be compared between instruments without a standardized calibration protocol and is challenging to relate to actual cell count. We address this with an interlaboratory study comparing three simple, low-cost, and highly accessible OD calibration protocols across 244 laboratories, applied to eight strains of constitutive GFP-expressing E. coli. Based on our results, we recommend calibrating OD to estimated cell count using serial dilution of silica microspheres, which produces highly precise calibration (95.5% of residuals <1.2-fold), is easily assessed for quality control, also assesses instrument effective linear range, and can be combined with fluorescence calibration to obtain units of Molecules of Equivalent Fluorescein (MEFL) per cell, allowing direct comparison and data fusion with flow cytometry measurements: in our study, fluorescence per cell measurements showed only a 1.07-fold mean difference between plate reader and flow cytometry data

Tailoring and visualizing the pore architecture of hierarchical zeolites

Recently the concept of hierarchical zeolites invoked more explicit attention to enhanced accessibility of zeolites. By realizing additional meso-/macroporosity with the intrinsic microporosity of zeolites, a hierarchical pore system arises which facilitates mass transport while maintaining the zeolite shape selectivity. A great number of synthesis strategies have been developed for tailoring the pore architecture of hierarchical zeolites. In this review, we give a general overview of different synthesis methods for introduction of additional porosity. Advantages and limitations of these different synthesis approaches are addressed. The assessment of pore structure is essential to build the link between the zeolite pore structure and its functionality. A variety of 2D and 3D microscopy techniques are crucial to visualize the hierarchical pore structure, providing unique and comprehensive information that, however, should be linked to the results of bulk characterization techniques as much as possible. The microscopy techniques are classified and discussed according to the different probes used, such as optical light, X-rays and electrons. Representative work is reviewed to elucidate the capability of each technique and their drawbacks

Effect of support surface treatment on the synthesis, structure, and performance of Co/CNT Fischer-Tropsch catalysts

We report the preparation of supported cobalt catalysts (9 wt% Co) on untreated (CNT) and surface-oxidized (CNT-ox) carbon nanotube materials by incipient wetness impregnation with solutions of cobalt nitrate in water, ethanol, or 1-propanol. The results show that by a judicious selection of solvent and drying method, similar cobalt oxide particle sizes in the range of 4-5 nm on CNT and CNT-ox materials were obtained for the fresh catalysts. Cobalt particles supported on unfunctionalized CNT showed higher initial activities and C5+-selectivities than catalysts on functionalized CNT; however, the former catalysts were more prone to cobalt particle growth due to the lack of anchoring sites. The activities and cobalt particle sizes of catalysts after 60 h on stream revealed for particles larger than 6 nm a turnover frequencies (TOF) of 0.07 s(-1) for Co/CNT and 0.03 s(-1) for Co/CNT-ox. In situ XAS/XRPD studies showed a similar degree of reduction for the catalysts on untreated and oxidized CNT and the formation of hcp cobalt metal on untreated CNT which rationalizes the higher activity and TOF of the Co/CNT catalysts. (C) 2014 Elsevier Inc. All rights reserved

Support Functionalization To Retard Ostwald Ripening in Copper Methanol Synthesis Catalysts

A main reason for catalyst deactivation in supported catalysts for methanol synthesis is copper particle growth. We have functionalized the support surface in order to suppress the formation and/or transport of mobile copper species and thereby catalyst deactivation. A Stober silica support was functionalized by treatment with aminopropyltriethoxysilane, which introduces aminopropyl groups on the surface. Copper was deposited on both unfunctionalized and functionalized Stober silica via incipient wetness impregnation with aqueous copper nitrate solutions followed by drying and calcination. Similar particle size distributions (1-5 nm) were obtained for both supports by changing the flow of N-2 to a flow of 2% NO/N-2 during calcination of the unfunctionalized and amine-functionalized silica, respectively. The effect of support functionalization with aminopropyl groups was an increased stability in the methanol synthesis reaction (40 bar, 260 degrees C, 23% CO/7% CO2/60% H-2/10% Ar, 3% COx conversion) due to more limited copper particle growth as determined by transmission electron microscopy (TEM). Changing the interparticle distance did not have an influence on the deactivation rate, while the addition of few very large copper particles did, indicating that Ostwald ripening was most probably the dominant particle growth mechanism for these samples. In situ TEM images showed the contact angle between the reduced copper particles and the support. As shape and size was similar on silica as on amine-functionalized silica, the thermodynamic stability of the copper particles was unaltered. The driving force for copper particle growth was thus unchanged upon functionalization. We therefore suggest that Ostwald ripening in methanol synthesis catalysts was retarded by inhibiting the transport of copper species over the support surface. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed a decrease in the number of surface groups (hydroxyl, methoxy, and aminopropyl) upon functionalization because aminopropyltriethoxysilane reacted with multiple hydroxyl groups. Because of that, the distance between neighboring functional groups was increased, suppressing the mobility of Ostwald ripening species from one copper particle to another