Bäumer, Marcus
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Item type:Publication, The origin of a large apparent tortuosity factor for the Knudsen diffusion inside monoliths of a samaria-alumina aerogel catalyst: a diffusion NMR study(RSC, Royal Society of Chemistry, 2015-09-23); ; ; ; Pulsed field gradient (PFG) NMR was applied to measure tortuosity factors for carbon dioxide diffusion in the Knudsen and gas regimes inside monoliths of a samaria-alumina aerogel catalyst, a high porosity material containing micropores in addition to meso- and macropores. The apparent tortuosity factor obtained from PFG NMR measurements for the Knudsen diffusion in the meso- and macropores of the catalyst has an unexpectedly large value of approximately 6 if carbon dioxide adsorption in the micropores and other types of surface adsorption sites of the catalyst is ignored. At the same time, the corresponding apparent tortuosity factor in the gas regime was found to be around 2. Application of a proposed model which describes fast molecular exchange between the surface adsorption sites and the main pore volume of the catalyst yields corrected tortuosity factors which depend only on the pore system geometry. Using this model, the corrected tortuosity factors were found to be around 2 for both diffusion regimes, in agreement with the expectations based on a high porosity of the studied catalyst.journal article83 118 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, The Influence of the Pyrolysis Temperature on the Material Properties of Cobalt and Nickel Containing Precursor Derived Ceramics and their Catalytic Use for CO2 Methanation and Fischer–Tropsch Synthesis(2016-11-25); ; ; ; Ni and Co containing precursor derived ceramics (ceramers) were prepared from a polysiloxane based preparation route. All catalysts were characterised by BET, XRD and TEM as well as by water and heptane adsorption and tested for CO2 methanation and Fischer–Tropsch synthesis. Different pyrolysis temperatures between 400 and 600 °C were used to get catalysts with different surface hydrophilicities. With increasing synthesis temperature less organic groups remain on the surface, resulting in a more hydrophilic catalyst. For all Ni containing ceramers, well dispersed particles in the range of 3 nm were formed and comparable surface areas were found. The catalysts with the lowest tendency towards water adsorption showed the highest activity for CO2 methanation. In contrast to the Ni catalysts, for the Co containing ceramers particle formation was dependent on the pyrolysis temperature. While no metallic particles were formed at 400 °C, small particles in the range of ~5 nm were obtained, using a pyrolysis temperature of 500 °C. Increasing the pyrolysis temperature to 600 °C, the particle size increased to ~10 nm. First tests for CO2 methanation and Fischer–Tropsch reaction were successfully carried out and the catalysts with the less hydrophilic surface showed higher activity and a higher selectivity towards C5+-products.journal article312 552 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Doped samarium oxide xerogels for oxidative coupling of methane - Effects of high-valence dopants at very low concentrations(Elsevier, 2021-04-01); ; Hagelin Weaver HelenaThe effects of high-valance dopants on the catalytic properties of samarium oxide xerogels were investigated at concentrations of 0.1 and 1.0 % (by mol) in the oxidative coupling of methane (OCM). Gd, Y, Zr, and V dopants were selected to examine the influence of oxidation states between +3 and +5 on the OCM performance. Even at these low loadings, the high-valance dopants were observed to have a significant impact on the OCM reaction. At the lowest loading, 0.1 mol %, and below 700 °C, all dopants improved the activity over that of the pure Sm2O3 xerogel, and most also improved the selectivity. In particular, the ethylene yield was significantly improved over these catalysts between 500 and 700 °C. However, the stability of the doped catalysts compared to the undoped Sm2O3 xerogel were inferior above 700 °C, and the higher concentration (1.0 mol %) resulted in catalysts with a lower stability. Time-on-stream experiments revealed that the 0.1 mol % high valence dopants improved the stability of the Sm2O3 xerogel at 700 °C. As a result of the higher stability, the doped catalysts retain more of the original specific surface area and appear to stabilize the more active cubic Sm2O3 phase compared with the undoped catalyst. Therefore, the doped catalysts have a higher number of available basic sites during reaction. This study reveals that high-valence dopants have potential to improve the low temperature (500–700 °C) activity of OCM catalysts. However, the concentrations must be kept very low, as dopants that increase the activity and selectivity at concentrations of 0.1 mol % can result in inferior catalysts at 1.0 mol %, and temperatures above 700 °C must be avoided or rapid deactivation can occur.journal articleBand:36533 41 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, CO2 methanation and reverse water gas shift reaction. Kinetic study based on in situ spatially-resolved measurements(Elsevier, 2020-07-15); ; Kopyscinski, JanThe reaction kinetics for the CO2 methanation and reverse water gas shift reaction over an ordered-mesoporous Ni/Al2O3 catalyst were determined. For the parameter estimation and model discrimination, the kinetic data were obtained by means of spatially-resolved measurement in a catalytic plate reactor. In detail, ~21,000 high-resolution gas composition data were gathered along the reactor axis using a movable sampling capillary connected to a mass spectrometer. Additionally, the catalyst surface temperature was determined via infrared thermography. The influence of reaction temperature (320–420 °C), total pressure (1.2–7.3 barabs), and GHSV, as well as possible inhibition of products such as CH4 and H2O, were investigated. A one-dimensional model of the reactor was developed describing the conservation of mass in the bulk gas and catalyst phase. The Bayesian approach was used to estimate the kinetic parameters of 20 proposed Langmuir-Hinshelwood rate expressions for the CO2 methanation that were derived based on three different mechanisms (i.e., direct dissociation, hydrogen assisted dissociation, and hybrid mechanism). Two kinetic models reflected the measured data very well. The most probable models suggest that the rate determining step includes the reaction of an oxygenated complex (COH* or HCOO*) with an active site (*) or an adsorbed hydrogen (H*). Furthermore, water was assumed to be adsorbed as a hydroxyl species (OH*), while methane did not influence the reaction. Temperature- and time-resolved Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) measurements confirmed the presence of both adsorbed surface intermediates.journal articleBand:39049 63 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, On thermal stability and decomposition mechanisms of aromatic diamines employed as links in novel Pt nanoparticle network catalysts(Elsevier, 2023-01-05); ; ; The thermal stability of microporous networks of Pt nanoparticles interlinked by p-Phenylenediamine (PDA) was investigated by temperature-programmed desorption spectroscopy (TPD) and transmission electron microscopy (TEM). The detection of aniline, benzene, and NH3 as major desorbing fragments in TPD revealed cleavage of the C-N bonds in PDA as a major route of thermally induced decomposition, probably via hydrogenolysis assisted by dehydrogenation reactions of PDA running alongside. Varying the Pt:PDA ratio in the networks demonstrated that the Pt nanoparticles catalytically promote the decomposition of their PDA links. A quantitative analysis of the TPD spectra indicated that the thermal stability of PDA strongly correlates with the number of bonds (0, 1 or 2) formed by the amino groups of an individual PDA molecule with Pt. Only the most stable PDA species appears to be of relevance for the structural stability of the nanoparticle network, as heating experiments with in situ TEM showed. The results have strong implications for the application of PDA-linked Pt nanoparticles as heterogeneous catalysts in hydrogen gas microsensors where the choice of operating temperature has to balance maximization of signal-to-noise ratio and maintenance of structural stability. An anealing step up to 450–500 K after synthesis of the catalyst is suggested in order to optimize its catalytic activity by removing PDA species that are not essential for structural stabilty.journal articleBand:656, Part A57 54 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Effects of low molar concentrations of low-valence dopants on samarium oxide xerogels in the oxidative coupling of methane(Elsevier, 2021-04-01); ; The effects of low-valence dopants on the catalytic properties of samarium oxide xerogel catalysts were investigated in the oxidative coupling of methane (OCM). More specifically, very low concentrations (0.1 and 1.0 % by mol) of transition metal (Ag, Ni, and Cu) and traditional alkali metal (Li and K) dopants were investigated. At these low loadings, it was shown that transition metal dopants have potential to improve the activity and selectivity over an undoped Sm2O3 xerogel, but these dopants can only outperform alkali metal dopants under certain conditions. Even at a concentration of 0.1 mol %, the dopants significantly increased the number of basic sites compared with the pure Sm2O3 xerogel. However, no trend is evident between the number or strength of the basic sites and the activity or selectivity in the methane coupling reaction. The XRD data reveal a lattice expansion upon addition of the low valence dopants, which is consistent with substitutional doping and the formation of oxygen vacancies due to charge compensation. In most cases the majority of the dopant stayed in the lattice during reaction. The dopants were also shown to influence the Sm2O3 structure, and the dopants that were more effective in suppressing the transformation from cubic to monoclinic Sm2O3 in general resulted in the more active and selective catalysts. While the Ag- and Ni-dopants could outperform the alkali metal doped catalysts in narrow temperature ranges, the best performing catalysts were still the K-doped Sm2O3 catalysts, as the 1.0 % K catalyst exhibited the highest activity at the lowest temperature (500 °C) and the 0.1 % K-doped catalyst was the most stable during extended operation. These results indicate that transition metal dopants, at low concentrations, can positively affect the activity and selectivity of a methane coupling catalyst, such as Sm2O3, and suggests that there may be benefits to other OCM catalyst systems from traditionally non-selective dopants, as long as the concentrations are kept very low and stability issues are addressed.journal articleHeft:36532 40 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Characterization of a highly sensitive and selective hydrogen gas sensor employing Pt nanoparticle network catalysts based on different bifunctional ligands(Elsevier, 2020-11-01); ; ; ; A catalytic hydrogen gas sensor of superior sensitivity, selectivity, resolution and dynamic response was developed with catalysts composed of ligand-stabilized Pt nanoparticles. We have characterized different catalysts utilizing the bi-functional ligands trans-1,4-diaminocyclohexane (DACH), 1,5-diaminonaphthalene (DAN), 4,4´´-diamino-p-terphenyl (DATER), benzidine (BEN) and p-phenylene diamine (PDA) for hydrogen gas sensing. A comprehensive evaluation by comparison, with respect to both, structural aspects (TEM and SEM) and gas sensing performance of the 5 types of ligand-linked Pt nanoparticles and non-stabilized Pt nanoparticles was conducted to select the optimized catalysts. From this investigation, DATER-linked Pt nanoparticles appear immensely promising: the sensor is selective to hydrogen and shows extremely high sensitivity, around 400 mV/1% vol., but exhibits no crosssensitivity to methane and ethane. Likewise, sensors with DATER- and DAN-linked Pt nanoparticles can detect down to 0.001 % (10 ppm) alongside 650 ms average response time (t90).journal articleBand:32245 40 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Coatings of active and heat-resistant cobalt-aluminium xerogel catalysts(Elsevier, 2016-05-28); ; ; ; The application of catalytically coated metallic foams in catalytic processes has a high potential for exothermic catalytic reactions such as CO2 methanation or Fischer-Tropsch synthesis due to good heat conductivity, improved turbulent flow properties and high catalyst efficiencies. But the preparation of homogenous catalyst coats without pore blocking is challenging with conventional wash coating techniques. Here, we report on a stable and additive free colloidal CoAlOOH suspension (sol) for the preparation of catalytically active Co/Al2O3 xerogel catalysts and coatings. Powders with 18wt% Co3O4 prepared from this additive free synthesis route show a catalytic activity in Fischer-Tropsch synthesis and CO2 methanation which is similar to a catalyst prepared by incipient wetness impregnation (IWI) after activating the material under flowing hydrogen at 430°C. Yet, the xerogel catalyst exhibits a much higher thermal stability as compared to the IWI catalyst, as demonstrated in catalytic tests after different heat agings between 430°C and 580°C. It was also found that the addition of polyethylene glycol (PEG) to the sol influences the catalytic properties of the formed xerogels negatively. Only non-reducible cobalt spinels were formed from a CoAlOOH sol with 20wt% PEG. Metallic foams with pores sizes between 450 and 1200μm were coated with the additive free CoAlOOH sol, which resulted in homogenous xerogel layers. First catalytic tests of the coated metal foams (1200μm) showed good performance in CO2 methanation.journal articleBand:47783 116 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, On the suppression of background signals originating from NMR hardware components. Application to zero echo time imaging and relaxation time analysisModern NMR imaging systems used for biomedical research are equipped with B0 gradient systems with strong maximum gradient strength and short switching time enabling (1)H NMR measurements of samples with very short transverse relaxation times. However, background signal originating from non-optimized RF coils may hamper experiments with ultrashort delays between RF excitation and signal reception. We demonstrate that two simple means, outer volume suppression and the use of shaped B0 fields produced by higher-order shim coils, allow a considerable suppression of disturbing background signals. Thus, the quality of NMR images acquired at ultrashort or zero echo time is improved and systematic errors in quantitative data evaluation are avoided. Fields of application comprise MRI with ultrashort echo time or relaxation time analysis, for both biomedical research and characterizing porous media filled with liquids or gases.journal article114 101 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Assessment of PBE+U and HSE06 methods and determination of optimal parameter U for the structural and energetic properties of rare earth oxides(American Institute of Physics, 2020-10-27); ; ; Rare earth oxides are attracting increasing interest as a relatively unexplored group of materials with potential applications in heterogeneous catalysis and electrocatalysis; therefore, a credible and universal computational approach is needed for modeling their reactivity. In this work, we systematically assessed the performance of the PBE+U method against the results of the hybrid HSE06 method with respect to the description of structural parameters and energetic properties of the selected hexagonal lanthanide sesquioxides and the cubic fluorite-type cerium dioxide. In addition, we evaluated the performance of PBE+U in describing the electronic structure and adsorption properties of the CeO2(111) and Nd2O3(0001) surfaces. The HSE06 method reproduces rather well the lattice parameters and selected energetic properties with respect to the experimental values. The PBE+U method is able to reproduce the results of HSE06 or the experimental values only if the U parameter is selected from an appropriate range of values. The U value around 3 eV gives the best description of the lattice parameters of most bulk oxides. 2 eV–3 eV is also found to be the optimal range of U for the reaction energies of bulk La2O3, Ce2O3, Nd2O3, Er2O3, and Ho2O3. U = 1 eV gives the best results for Pr2O3, Pm2O3, Eu2O3, Tm2O3, and Lu2O3, whereas Gd2O3 could not be accurately described by the PBE+U method. The U values (∼3 eV) found optimal for most bulk oxides also work well in the calculations of adsorption of small molecules on Nd2O3(0001) and CeO2(111), although larger U values are required to obtain sufficient localization of 4f electrons.journal articleBand:153Heft:1647 33