| 1. |
- Bounechada, Djamela, 1984, et al.
(författare)
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Mechanisms behind sulfur promoted oxidation of methane
- 2013
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 15:22, s. 8648-8661
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Tidskriftsartikel (refereegranskat)abstract
- The promoting effect of SO2 on the activity for methane oxidation over platinum supported on silica, alumina and ceria has been studied by flow-reactor, in situ infrared spectroscopy and in situ high-energy x-ray diffraction experiments under transient reaction conditions. The catalytic activity is clearly dependent on the support material and its interaction with the noble metal both in absence and presence of sulfur. On platinum, the competitive reactant adsorption favors oxygen dissociation such that oxygen self-poisoning is observed for Pt/silica and Pt/alumina. Contrarily for Pt/ceria, no oxygen self-poisoning is observed, which seems to be due to additional reaction channels via sites on the platinum-ceria boundary and/or ceria surface considerably far from the Pt crystallites. Addition of sulfur dioxide generally leads to the formation of ad-SOx species on the supports with a concomitant removal and/or blockage/rearrangement of surface hydroxyl groups. Thereby, the methane oxidation is inhibited for Pt/silica, enhanced for Pt/alumina and temporary enhanced followed by inhibition after long-term exposure to sulfur for Pt/ceria. The observations can be explained by competitive oxidation of SO2 and CH4 on Pt/silica, formation of new active sites at the noble metal-support interface promoting dissociative adsorption of methane on Pt/alumina, and in the case of Pt/ceria, formation of promoting interfacial surface sulfates followed by formation of deactivating bulk-like sulfate species. Furthermore, it can be excluded that reduction of detrimental high oxygen coverage and/or oxide formation on the platinum particles through SO2 oxidation is the main cause for the promotional effects observed.
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| 2. |
- Fouladvand, Sheedeh, 1984, et al.
(författare)
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Methane oxidation over Pd supported on ceria–alumina under rich/lean cycling conditions
- 2013
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Ingår i: Topics in Catalysis. - : Springer Science and Business Media LLC. - 1572-9028 .- 1022-5528. ; 56:1-8, s. 410-415
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Tidskriftsartikel (refereegranskat)abstract
- Catalysts with highly dispersed palladium on alumina, alumina doped with 20 wt% ceria and ceria have been prepared, characterized and examined for net-lean methane oxidation. In particular, the activity and selectivity were investigated during rich/lean cycling of the feed. The ceria content is found to influence both the general and the instantaneous activity responses. The results indicate that the active phase of palladium changes between reduced and oxidised Pd during the rich/lean cycling, and that the process is influenced by the presence of ceria.
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| 3. |
- Pingel, Torben, 1984, et al.
(författare)
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Three-dimensional probing of catalyst ageing on different length scales: A case study of changes in microstructure and activity for CO oxidation of a Pt-Pd/Al2O3 catalyst
- 2017
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Ingår i: ChemCatChem. - : Wiley. - 1867-3899 .- 1867-3880. ; 9:18, s. 3544-3553
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Tidskriftsartikel (refereegranskat)abstract
- In the present study the effects of thermal treatment on the microstructure of a Pt-Pd/Al2O3 oxidation catalyst and its activity for CO oxidation have been studied. The microstructural analysis was performed using several high-resolution electron microscopy techniques like STEM, FIB/SEM slice & view, SEM and EDX. A combination of these analysis techniques and advanced TEM specimen preparation allowed for three-dimensional probing at different length scales avoiding the random character of conventionally crushed powder specimens due to site specificity. A core-shell distribution of Pt-Pd nanoparticles within the alumina support particles, with enlarged nanoparticles (≈ 1.5 to 40 nm) being present in the shell and small nanoparticles (
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| 4. |
- Shishkin, Alexander, 1988, et al.
(författare)
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Functionalization of SSZ-13 and Fe-Beta with copper by NH3 and NO facilitated solid-state ion-exchange
- 2017
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Ingår i: Catalysts. - : MDPI AG. - 2073-4344. ; 7:8, s. 1-10
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Tidskriftsartikel (refereegranskat)abstract
- We show that functionalization of SSZ-13 (CHA) and Fe-beta (*BEA) with copper using a recently reported solid-state ion-exchange method, facilitated by NH3 and nitrogen oxides (NO), is a viable route to prepare Cu-SSZ-13 and (Cu + Fe)-beta catalysts, starting from H-SSZ-13 and Fe-beta, respectively. The physicochemical properties of the prepared catalysts are characterized by XRD, UV-Vis-spectroscopy and STEM-EDS, confirming that copper originally present in the physical mixture of CuO and H-SSZ-13, and CuO and Fe-beta, is inserted into the micropores of SSZ-13 and Fe-beta, respectively. Activity measurements in gas-flow reactor show that the samples are active for NO reduction by NH3-SCR over a broad temperature range, i.e., 150–500 C. For the Cu-SSZ-13 catalysts, which have a copper loading range of 0.5–4 wt. %, the sample prepared from the physical mixture with a CuO/SSZ-13 ratio corresponding to 2 wt.% Cu is the most active catalyst for NH3-SCR under the present reaction conditions. Furthermore, the (Cu + Fe)-beta catalyst shows higher NH3-SCR activity over a broader temperature range and especially at low temperature as compared to the Fe-beta and Cu-beta counterparts. The results encourage further elaboration on sequential ion-exchange procedures for bimetallic functionalization of zeolites.
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| 5. |
- Townsend, Philip, 1991, et al.
(författare)
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Tessellation-based stochastic modelling of 3D coating structures imaged with FIB-SEM tomography
- 2021
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Ingår i: Computational Materials Science. - : Elsevier BV. - 0927-0256 .- 1879-0801. ; 197
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Tidskriftsartikel (refereegranskat)abstract
- To facilitate printing, coatings are typically applied to paperboard used for packaging to provide a good surface for application. To optimise the performance of the coating, it is important to understand the relationship between the microstructure of the material and its mass transport properties. In this work, three samples of paperboard coating are imaged using combined focused ion beam and scanning electron microscope (FIB-SEM) tomography data appropriately segmented to characterise the internal microstructure. These images are used to inform a parametric, tessellation-based stochastic three-dimensional model intended to mimic the irregular geometry of the particles that can be seen in the coating. Parameters for the model are estimated from the FIBSEM image data, and we demonstrate good agreement between the real and virtual structures both in terms of geometrical measures and mass transport properties. The development of this model facilitates exploration of the relationship between the structure and its properties.
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| 6. |
- Auvray, Xavier, 1986, et al.
(författare)
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The effect gas composition during thermal aging on the dispersion and NO oxidation activity over Pt/Al2O3 catalysts
- 2013
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Ingår i: Applied Catalysis B: Environmental. - : Elsevier BV. - 0926-3373 .- 1873-3883. ; 129, s. 517-527
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Tidskriftsartikel (refereegranskat)abstract
- The aging of a model 1 wt.% Pt/Al2O3 catalyst was performed stepwise under different reactive atmosphere to study the evolution of metal dispersion and NO oxidation activity. After each aging step the dispersion was evaluated by CO chemisorptions and the activity of the catalyst for NO oxidation was measured using 500 ppm NO and 8%O-2 diluted in Ar. After a degreening step at 500 degrees C, aging was performed at 600, 700,800 and 900 degrees C. Five wash-coated cordierite monoliths were aged in Ar, 10% O-2, 1% H-2 30 ppm SO2 and 30 ppm SO2 + 10% O-2, respectively. The general trend showed a linear decrease in dispersion when increasing the aging temperature for the lower aging temperatures and for the highest ones the dispersion levels off. When the platinum dispersion decreased the NO oxidation activity increased, due to that the reaction is structure sensitive. H-2 seemed to hinder sintering at low aging temperature. Interestingly, after aging in 10% oxygen at 600 degrees C the NO oxidation activity was significantly higher compared to the Ar aged sample, although the dispersions were similar. Aging in oxygen at higher temperatures resulted in a decrease of dispersion and a slightly decreasing NO oxidation activity. Moreover lower dispersion limit was reached with oxygen aging. Aging in SO2 provoked a severe dispersion drop at low aging temperature meanwhile the activity increased only moderately. However, activity kept increasing with further treatments at higher temperature. The combination of O-2 and SO2 enabled to decrease rapidly the dispersion and to greatly enhance the catalytic NO oxidation activity after the first aging step at only 600 degrees C. The best overall conversion was obtained for the catalyst treated with this mixture after aging at 800 degrees C. A 22-h aging at 250 degrees C in a mixture containing 500 ppm NO, 10% O-2 and 30 ppm SO2 led to a significant decrease of Pt dispersion, which shows the ability of SO2 to promote platinum sintering already 250 degrees C. The low temperature sintering was confirmed with STEM measurements. Several larger particles were observed, but also many small particles remained. Thus the SO2 + O-2 induced low temperature sintering results in a large variation of particle sizes. This treatment resulted in an increase of the maximum NO conversion (after reduction of the sample) from 45% to 76%. The different aging experiments show that it is beneficial to add SO2 during aging and the reason is the increased particle size, but also a clear chemical effect was observed.
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| 7. |
- Carmona, Pierre, 1995, et al.
(författare)
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Controlling the structure of spin-coated multilayer ethylcellulose/ hydroxypropylcellulose films for drug release
- 2023
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Ingår i: International Journal of Pharmaceutics. - 0378-5173 .- 1873-3476. ; 644
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Tidskriftsartikel (refereegranskat)abstract
- Porous phase-separated ethylcellulose/hydroxypropylcellulose (EC/HPC) films are used to control drug transport out of pharmaceutical pellets. Water-soluble HPC leaches out and forms a porous structure that controls the drug transport. Industrially, the pellets are coated using a fluidized bed spraying device, and a layered film exhibiting varying porosity and structure after leaching is obtained. A detailed understanding of the formation of the multilayered, phase-separated structure during production is lacking. Here, we have investigated multilayered EC/HPC films produced by sequential spin-coating, which was used to mimic the industrial process. The effects of EC/HPC ratio and spin speed on the multilayer film formation and structure were investigated using advanced microscopy techniques and image analysis. Cahn-Hilliard simulations were performed to analyze the mixing behavior. A gradient with larger structures close to the substrate surface and smaller structures close to the air surface was formed due to coarsening of the layers already coated during successive deposition cycles. The porosity of the multilayer film was found to vary with both EC/HPC ratio and spin speed. Simulation of the mixing behavior and in situ characterization of the structure evolution showed that the origin of the discontinuities and multilayer structure can be explained by the non-mixing of the layers.
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| 8. |
- Jonsson, Rasmus, 1989, et al.
(författare)
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Chemical poisoning by zinc and phosphorous of Pt/Ba/Al2O3 NOx storage catalysts
- 2019
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Ingår i: Applied Catalysis A: General. - : Elsevier BV. - 1873-3875 .- 0926-860X. ; 571, s. 158-169
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Tidskriftsartikel (refereegranskat)abstract
- The effects of phosphorous and zinc on the performance of Pt/Ba/Al2O3 catalysts were investigated through wet impregnation of ammonium phosphate and zinc acetate aqueous solutions. Six different sample combinations were studied; 1 wt-% P, 1 wt-% Zn, 1 wt-% P with 1 wt-% Zn, 2 wt-% P, 2 wt-% Zn, 2 wt-% P with 2 wt-% Zn. NOx storage and reduction (NSR) activity and NO2 temperature programmed desorption (TPD) profiles were measured before and after impregnation of P and Zn. Samples containing P performed significantly worse than samples only containing Zn in both NSR activity and TPD measurements. The increased NOx slip during lean phase in activity measurements for P-poisoned samples is mainly related to an increased slip of NO2. This was found for both NO and NO2 in the gas feed during lean phase and suggests that it is mainly the storage component that is poisoned and not the noble metal. Furthermore, the combination (1 wt-% P and 1 wt-% Zn) proved to result in slightly worse performance than only 1 wt-% P, however this was not the case for samples containing 2 wt-%, where the addition of zinc reduced the negative effect of phosphorous. Measurements from NO2-TPD experiments showed that NOx release at low temperature was not affected by the addition of P, while desorption in the temperature range 425–475 °C was significantly reduced. It can therefore be concluded that the poisoning mainly is related to barium NOx storage sites and not to alumina sites. Moreover, X-ray diffraction measurements indicate that some of the barium species are affected by phosphorous. Images from scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDX) mapping were in line with the results seen in both the activity tests and NO2-TPD experiments. Phosphorous was concentrated at the same position as barium in the observed images, whereas zinc was more evenly distributed over the surface. For the sample with both 2 wt-% P and 2 wt-% Zn, X-ray photoelectron spectroscopy measurements indicate that Zn and P have a low interaction and this suggests that most of the zinc and phosphorous are separated. However, STEM-EDX showed agglomerates of some zinc and phosphorous, which could be zinc phosphates. This is a plausible explanation of the decreased deactivation observed after introducing 2 wt-% Zn compared to the sample only containing 2 wt-% P.
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| 9. |
- Kannisto, Hannes, 1979, et al.
(författare)
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On the performance of Ag/Al2O3 as a HC-SCR catalyst – influence of silver loading, morphology and nature of the reductant
- 2013
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Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 3:3, s. 644-653
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Tidskriftsartikel (refereegranskat)abstract
- This study focuses on the performance of Ag/Al2O3 catalysts for hydrocarbon selective catalytic reduction (HC-SCR) of NOx under lean conditions, using complex hydrocarbons as reductants. The aim is to elucidate the correlation towards the silver loading and morphology, with respect to the nature of the reductant. Ag/Al2O3 samples with either 2 or 6 wt% silver loading were prepared, using a sol–gel method including freeze-drying. The catalytic performance of the samples was evaluated by flow reactor experiments, with paraffins, olefins and aromatics of different nature as reductants. The physiochemical properties of the samples were characterized by scanning electron microscopy/energy dispersive X-ray spectroscopy, scanning transmission electron microscopy/high angle annular dark field imaging, X-ray photoelectron spectroscopy and N2-physisorption. The 2 wt% Ag/Al2O3 sample was found to be the most active catalyst in terms of NOx reduction. However, the results from the activity studies revealed that the decisive factorfor high activity at low temperatures is not only connected to the silver loading per se. There is also a strong correlation between the silver loading and morphology (i.e. the ratio between low- and high- coordinated silver atoms) and the nature of the hydrocarbon, on the activity for NOx reduction. Calculated reaction rates over the low-coordinated step and high- coordinated terrace sites showed that the morphology of silver has a significant role in the HC-SCR reaction.For applications which include complex hydrocarbons as reductants (e.g. diesel), these issues need to be considered when designing highly active catalysts.
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| 10. |
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