Ga and In Modified Ceria as a Support for Cobalt Fischer-Tropsch Synthesis

Ceria modified by the addition of gallium or indium (20 mol%) was used as a support for cobalt Fischer-Tropsch synthesis. The addition of gallium to ceria improved the CO conversion for cobalt, whereas indium tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts that were doped with Ga or In. For Ag promoted catalysts, doping with Ga or In decreased methane and increased the product selectivities of olefins and alcohols. The sum of olefins and alcohols in terms of product selectivity for the Ag-promoted catalysts decreased in the following order: Ag-Co/Ce-Ga \u3e Ag-Co/Ce-In \u3e Ag-Co/Ce. The H2-TPR-XANES data shown that addition of gallium or indium to ceria increased the fraction of surface Ce3+ for both unpromoted and Ag promoted catalysts. This partially reduced ceria plays an important role in the product selectivity of cobalt for FT synthesis

Accelerated deployment of nanostructured hydrotreating catalysts. Final CRADA Report.

Nanomanufacturing offers an opportunity to create domestic jobs and facilitate economic growth. In response to this need, U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy issued a Research Call to develop nanomanufacturing capabilities at the National Laboratories. High performance catalysts represent a unique opportunity to deploy nanomanufacturing technologies. Re-refining of used lube oil offers an opportunity to create manufacturing jobs and decrease dependence on imported petroleum. Improved catalysts are required to produce a better quality product, decrease environmental impact, extend catalyst life, and improve overall economics of lube oil re-refining. Argonne National Laboratory (Argonne) in cooperation with Universal Lubricants, Inc. (ULI) and Chemical Engineering Partners (CEP) have carried out a Cooperative Research and Development Agreement (CRADA) to prepare nanostructured hydrotreating catalysts using atomic layer deposition (ALD) to exhibit superior performance for the re-refining of used lube oil. We investigated the upgrading of recycled lube oil by hydrogenation using commercial, synthetically-modified commercial catalysts, and synthesized catalysts. A down-flow (trickle bed) catalytic unit was used for the hydrogenation experiments. In addition to carrying out elemental analyses of the various feed and product fractions, characterization was undertaken using H{sup 1} and C{sup 13} NMR. Initially commercial were evaluated. Second these commercial catalysts were promoted with precious metals using atomic layer deposition (ALD). Performance improvements were observed that declined with catalyst aging. An alternate approach was undertaken to deeply upgrade ULI product oils. Using a synthesized catalyst, much lower hydrogenation temperatures were required than commercial catalysts. Other performance improvements were also observed. The resulting lube oil fractions were of high purity even at low reaction severity. The products recovered from both the ALD and other processes were water-white (even those from the low temperature, low residence time (high space velocity), low conversion runs). These results indicate that highly upgraded recycle lube oils can be produced using ALD-deposited active metal catalysts. The use of H{sup 1} and C{sup 13} NMR for the characterization of the treated lube oils has been shown to be effective

Secreted Frizzled-related protein-1 is a negative regulator of androgen receptor activity in prostate cancer

Secreted Frizzled-related protein-1 (sFRP1) associates with Wnt proteins and its loss can lead to activation of Wnt/β-catenin signalling. It is frequently downregulated in cancer, including prostate cancer, but its function in prostate cancer is unclear because it can increase proliferation of prostate epithelial cells. We investigated the function of sFRP1 in androgen-dependent prostate cancer and found that sFRP1 inhibited androgen receptor (AR) transcriptional activity. In addition, sFRP1 inhibited the proliferation of androgen-dependent LNCaP cells but not of an androgen-independent subline LNCaP-r, suggesting a role in androgen-dependent growth. The inhibition of AR by sFRP1 was unaffected by co-expression of Wnt3a, stabilised β-catenin or β-catenin shRNA, suggesting it does not involve Wnt/β-catenin signalling. Wnt5a also inhibited AR and expression of Wnt5a and sFRP1 together did not further inhibit AR, suggesting that Wnt5a and sFRP1 activate the same signal(s) to inhibit AR. However, sFRP1 inhibition of AR was unaffected by inhibitors of kinases involved in Wnt/Ca2+ and Wnt/planar cell polarity non-canonical Wnt signalling. Interestingly, the cysteine-rich domain of sFRP1 interacted with Frizzled receptors expressed in prostate cancer cells, suggesting that sFRP1/Frizzled complexes activate a signal that leads to repression of AR. Taken together, these observations highlight the function of β-catenin-independent Wnt signalling in the control of AR activity and provide one explanation for sFRP1 downregulation in prostate cancer

Identification of Clinically Relevant Protein Targets in Prostate Cancer with 2D-DIGE Coupled Mass Spectrometry and Systems Biology Network Platform

Prostate cancer (PCa) is the most common type of cancer found in men and among the leading causes of cancer death in the western world. In the present study, we compared the individual protein expression patterns from histologically characterized PCa and the surrounding benign tissue obtained by manual micro dissection using highly sensitive two-dimensional differential gel electrophoresis (2D-DIGE) coupled with mass spectrometry. Proteomic data revealed 118 protein spots to be differentially expressed in cancer (n = 24) compared to benign (n = 21) prostate tissue. These spots were analysed by MALDI-TOF-MS/MS and 79 different proteins were identified. Using principal component analysis we could clearly separate tumor and normal tissue and two distinct tumor groups based on the protein expression pattern. By using a systems biology approach, we could map many of these proteins both into major pathways involved in PCa progression as well as into a group of potential diagnostic and/or prognostic markers. Due to complexity of the highly interconnected shortest pathway network, the functional sub networks revealed some of the potential candidate biomarker proteins for further validation. By using a systems biology approach, our study revealed novel proteins and molecular networks with altered expression in PCa. Further functional validation of individual proteins is ongoing and might provide new insights in PCa progression potentially leading to the design of novel diagnostic and therapeutic strategies

Shape selective catalysts for F-T chemistry. Interim report : January 2001 - December 2002.

Argonne National Laboratory (ANL) is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (F-T) chemistry, specifically the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to F-T catalysts needing high activity, it is desirable that they have high selectivity and stability with respect to both mechanical strength and aging properties. In this project, selectivity is directed toward the production of diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Shape-selective catalysts have the potential to both limit the formation of long-chain products and yet retain the active metal sites in a protected ''cage.'' This cage also restricts their loss by attrition during use in slurry-bed reactors. Experimentation has included evaluation of samples of (1) iron-based F-T catalysts prepared at Argonne National Laboratory, (2) iron-based F-T catalysts prepared by B.H. Davis of the Center of Applied Energy Research (CAER), (3) the Davis catalyst that were sized by differential gravity separation, and (4) the Davis catalyst onto which inorganic or catalytic ''shells'' were deposited. The ANL-prepared samples had a wide range of particle size and were irregular in shape. A sizeable portion of the samples provided by Davis were spherical, because they had been prepared by spray-drying. To compare the catalytic activities of the samples, we used a micro-scale fixed-bed reactor system for F-T runs of low conversion to avoid thermal and mass transfer effects. In summary, the highest activity was that of the original Davis catalyst; additional research must be carried out to generate more permeable surface cages. A number of approaches that have been published for other applications will be tested

Shape-selective catalysts for Fischer-Tropsch chemistry. Final report : January 1, 2001 - December 31, 2008.

Argonne National Laboratory carried out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry-specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it was desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It was desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The original goal was to produce shape-selective catalysts that had the potential to limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' This cage would also restrict their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. Such catalysts were prepared with silica-containing fractal cages. The activity and strength was essentially the same as that of catalysts without the cages. Since there was no improvement, the program plan was modified as discussed below. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide surfaces. The first series of experiments using coated membranes demonstrated that the technology needed further improvement. Specifically, observed catalytic FT activity was low. This low activity appeared to be due to: (1) low available surface area, (2) atomic deposition techniques that needed improvements, and (3) insufficient preconditioning of the catalyst surface prior to FT testing. Therefore, experimentation was expanded to the use of particulate silica supports having defined channels and reasonably high surface area. An effective FT catalyst consisting of ALD-deposited Co and Pt on a silica support has been prepared and demonstrated. This catalyst was more effective than a similar catalyst deposited upon a support of ALD-deposited Al{sub 2}O{sub 3} on silica. This result implies that the deposition of Al{sub 2}O{sub 3} to form a support is not as effective as desired. The addition of Pt as a Co-containing catalyst promoter has been demonstrated; it appears to primarily affect the catalyst pre-conditioning step. Co on Al{sub 2}O{sub 3} catalyst prepared by the Center for Applied Energy Research (CAER) is more effective than Argonne-prepared ALD-deposited Co on ALD-deposited Al{sub 2}O{sub 3} catalyst. The FT activity of ALD-coated Co catalyst on Al{sub 2}O{sub 3} is about linear with Co level from about 9 to 25%. A cooperative research effort was undertaken to test the deposition of platinum on Co FT catalysts; this Pt influences the effectiveness of catalyst conditioning and its continuing activity. In summary, the ALD Pt at a low concentration (0.1 wt %) was as effective as that of the wet chemical deposition technique of CAER (specifically incipient deposition on a Co catalyst that had been prepared and calcined before the Pt deposition.) The ALD technique appeared to be nominally better than the incipient wetness technique that involved co-deposition of Pt and Co prior to calcination. The activation energy of the rate of CO conversion was tightly grouped about an average of 29.2 Kcal/mol when all of the Co-containing catalysts other than those with high Pt promoter levels were taken into account; this implies a uniform reaction mechanism. Catalysts containing Pt and Ru that were ALD-deposited on an ALD-Al{sub 2}O{sub 3} coated catalyst support were found to be relatively inactive. Additional tests were made with a low concentration (0.1 wt %) of Ru or Ir deposited on the reference Co catalyst. The Ir coated catalysts were particularly effective. In support of the above, there was an opportunity to undertake a study of cobalt/promoter/support interaction using the Advanced Photon Source (APS) of Argonne. A number of catalysts (including reference cobalt oxide and iron oxides) were tested using temperature programmed EXAFS/XANES experiments

Shape-selective catalysts for Fischer-Tropsch chemistry : atomic layer deposition of active catalytic metals. Activity report : January 1, 2005 - September 30, 2005.

Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry - specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. The broad goal is to produce diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Originally the goal was to prepare shape-selective catalysts that would limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' Such catalysts were prepared with silica-containing fractal cages. The activity was essentially the same as that of catalysts without the cages. We are currently awaiting follow-up experiments to determine the attrition strength of these catalysts. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide surfaces. The first series of experiments using coated membranes demonstrated that the technology needed further improvement. Specifically, observed catalytic FT activity was low. This low activity appeared to be due to: (1) low available surface area, (2) atomic deposition techniques that needed improvements, and (3) insufficient preconditioning of the catalyst surface prior to FT testing. Therefore, experimentation was expanded to the use of particulate silica supports having defined channels and reasonably high surface area. This later experimentation will be discussed in the next progress report. Subsequently, we plan to evaluate membranes after the ALD techniques are improved with a careful study to control and quantify the Fe and Ru loadings. The preconditioning of these surfaces will also be further developed. (A number of improvements have been made with particulate supports; they will be discussed in the subsequent report.) In support of the above, there was an opportunity to undertake a short study of cobalt/promoter/support interaction using the Advanced Photon Source (APS) of Argonne. Five catalysts and a reference cobalt oxide were characterized during a temperature programmed EXAFS/XANES experimental study with the combined effort of Argonne and the Center for Applied Energy Research (CAER) of the University of Kentucky. This project was completed, and it resulted in an extensive understanding of the preconditioning step of reducing Co-containing FT catalysts. A copy of the resulting manuscript has been submitted and accepted for publication. A similar project was undertaken with iron-containing FT catalysts; the data is currently being studied

Na Promotion of Pt/m-ZrO₂ Catalysts for the Steam Reforming of Formaldehyde

The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H2O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO2 temperature programmed desorption results, as well as a greater splitting observed between the formate νasym(OCO) and νsym(OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer

Na Promotion of Pt/m-ZrO2 Catalysts for the Steam Reforming of Formaldehyde

The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H2O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO2 temperature programmed desorption results, as well as a greater splitting observed between the formate νasym(OCO) and νsym(OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer