Scientific Highlights ENE
Radiation grafted membranes developed at PSI outlast state-of-the art commercial membranes in the fuel cell
Components for the polymer electrolyte fuel cell (PEFC) are required to show high performance and durability under application relevant conditions. Furthermore, for commercial viability the materials and processes for component fabrication need to be of los cost. The polymer electrolyte membrane developed at PSI on the basis of the radiation grafting technique has the potential of being produced in cost-effective manner. In recent years, we have collaborated with the Belenos Clean Power to further develop the membrane to commercial competitiveness. We managed, by careful analysis and optimization of the synthesis conditions, to close the performance gap to commercial membranes (Nafion). The durability of the PSI membranes was evaluated in a dynamic (accelerated) test to simulate an automotive cycle. Our membrane showed a durability much superior to that of the unreinforced commercial Nafion 212 membrane. It even outlasted the reinforced and chemically stabilized Nafion XL-100 membrane, a state-of-the-art material for challenging automotive applications. Beyond fuel cells, the radiation grafting technology can be adapted to design polymer electrolyte materials for other electrochemical applications of current and future interest, such as water electrolyzers, redox flow batteries and next-generation lithium batteries.
DFT Modelling of Ru Nanoparticles Supported on Graphene and Graphite Surface: A Study of the B5 Active Sites Localisation
Carbon-supported Ruthenium catalysts exhibit very good catalytic properties, and are applied in the ammonia synthesis as well as for methanation processes e.g. in the gasification of wet biomass in super-critical water. Both reactions are known to be structure sensitive and require specific active sites at the catalyst. It has been found experimentally that mainly B5 sites are present and actively taking part in the catalytic reactions. Epitaxial growth of Ru on the carbon support can be considered following two orientations, one with the same orientation as the hexagonal carbon lattice, the other being rotated by 30° around the surface normal. We describe a DFT study on the self-organizing of Ru nanoparticles deposited on carbon cluster models. The carbon support has been modelled using a single carbon layer (graphene-type) and double carbon layer (graphite-type). Our DFT results indicate that only one of them results in a stable epitaxial adsorption configuration. Basing on that result we were able to build and stabilize three-dimensional Ru nanoparticles containing up to 17 atoms. The smallest three-dimensional Ru cluster exhibiting B5-type active sites (three sites) contains eleven Ru atoms and has a particle diameter of 0.55 nm. The calculations provide insights into the nature and structure of Ru B5-type sites supported on carbon. Further molecule adsorption and reaction mechanism studies will follow.
Supported gold as catalyst for the decomposition of ammonia precursors in the selective catalytic reduction of NOx
Titaniumdioxide supported gold was found to catalyze the hydrolysis of formate-based ammonia precursor compounds which are proposed for the selective catalytic reduction of nitrogen oxides (NOx) in combustion exhaust gas. In contrast to other noble metals, the supported gold does not oxidize the released NH3, while it maintains decomposition of intermediate formic acid. Efficient formic acid decomposition is essential as it avoids the formation of side products which previously restricted the use of formate-based ammonia precursors.
The stability of the catalyst under operating conditions was investigated by an accelerated hydrothermal aging treatment and sulfur poisoning. Both procedures affected the catalytic decomposition performance only to a small extent, which is unprecedented for supported gold catalysts.
The novel catalyst was implemented into an up-scaled prototype system of an ammonia generator for automotive applications and successfully tested in an exhaust gas aftertreatment system of a 3.0 L Diesel engine on an engine test bench at the Technical University of Munich. The system was then transferred to an industrial company and is currently tested for commercial utilization.
Influence of Methyl Halide Treatment on Gold Nanoparticles Supported on Activated Carbon
Gold particles supported on carbon when subjected to a flow of methyl iodide or bromide redisperse from large ensembles to single atoms and/or dimers of gold. Methyl halide oxidizes gold leading to gradual particle dissolution. The process could be carried out at temperatures as low as 50 °C. The excess of halide could be removed by a post-treatment of the material with 1%H2O/H2, which does not influence the metal dispersion. This remarkable transformation opens the possibility of re-activating gold catalysts that lost their performance due to metal particles sintering.
The finding was proposed based on a combination of in situ (XAS), ex situ characterization (aberration corrected HAADF-TEM, XRD and XPS) and kinetic measurements. The work was a combined effort from Queen’s University Belfast (UK), Paul Scherrer Institute (Switzerland), Lehigh University (USA) and Cardiff University (UK)
Flow modeling in gas diffusion layers of PEFCs at the micro- and mesoscale.
The optimization of thermochemical and electrochemical conversion systems is of high mportance for a sustainable energy future society. Of particular interest regarding the performance of polymer electrolyte fuel cells (PEFCs) is the study of the gas flow in the gas diffusion layers (GDL). More specifically, permeability and diffusivity measurements in a model PEFC under normal operating conditions are highly desirable. As laboratory-measurements of these quantities under such conditions are very demanding, an alternative is the use of computer-based simulations. For this, two key elements are needed: a) an advanced numerical tool capable of modeling key microscale processes, and b) in-situ X-ray tomographic microscopy (XTM) scans of the GDL material. Physical modeling of 3D gas flows is accomplished through novel mesoscale computational algorithms based on the lattice Boltzmann method (LBM).
The provided figure illustrates computed flow streamlines through the GDL porous structure (carbon fiber paper Toray TGPH 060, domain size: 444x222x160 microns). The GDL microstructures, wherein the produced liquid water can be distinguished from the solid material, are obtained at the TOMCAT beamline of the Swiss Light Source (SLS). The results show that permeability and relative effective diffusivities of dry and partially liquid saturated GDL samples follow a relation proportional to (1-s)x, where (s) is the saturation level and the exponent x is approximately 3.
 N. I. Prasianakis, T. Rosen, J. Kang, J. Eller, J. Mantzaras, F. N. Büchi, Simulation of 3D porous media flows with application to polymer electrolyte fuel cells
, Comm. in Comp. Phys. (in press) (2012).
 T. Rosén, J. Eller, J. Kang, N. I. Prasianakis, J. Mantzaras, F. N. Büchi, Saturation dependent effective transport properties of PEFC gas diffusion layers
, (submitted) (2012)
Further publications: Electrochemistry Laboratory
X-Ray Tomography of Water in Operating Fuel Cell
Polymer electrolyte fuel cells (PEFC) convert the chemical energy of hydrogen with a high efficiency (40-70 %) directly into electricity. The product of the overall reaction is water, produced at the cathode of the cell.
The interaction of liquid water with the porous structures of the cell is one of the mechanisms in the PEFC that are commonly believed to be key for further optimization with regard to performance, durability and cost.
Synchrotron based X-ray tomographic microscopy (XTM) allows for the simultaneous in situ visualization of the water and carbonaceous structures in the gas diffusion layer (GDL) on the pore scale level [1, 2]. In-situ XTM scans of operating PEFC are performed within a few seconds per scan and pixel sizes of 2 - 3 µm. Experiments are made at the TOMCAT beamline of the Swiss Light Source (SLS).
The figure shows XTM surface renderings of the cathode channel with flow field plate, GDL, liquid water and catalyst layer.
 R. Flueckiger, F. Marone, M. Stampanoni, A. Wokaun, F.N. Buechi, Electrochim. Acta, 56, 2254 (2011)  J. Eller, T. Rosen, F. Marone, M. Stampanoni, A. Wokaun, and F.N. Buechi J. Electrochem. Soc., 158, B963 (2011)
Further publications: Electrochemistry Laboratory
Shedding light on a dark state: The energetically lowest high-spin state of C2
The Swan band emission between 400 and 700 nm is a prominent feature in all carbon-containing flames. The intense d 3∏g - a 3∏u electronic transition is widely used to detect the molecule in combustion and astronomy studies to characterize and test chemical mechanisms.
The quantitative interpretation of spectra requires precise molecular constants for the computation of the complex molecular spectra of C2
In this work we report on the deperturbation of the d 3∏g , v=6 state by double-resonant four-wave mixing. The high sensitivity and dynamic range of the method allows observation of 'extra lines'. These weak spectral features originate from nearby-lying, optically dark states that gain transition strength through the perturbation process. The study unveils the presence of the energetically lowest high-spin state of C2
in the vicinity of the d 3∏g , v=6 state. This quintet state (5∏g) unravels major issues of the so-called high-pressure bands of C2
. The anomalous nonthermal emission initially observed in 1910 and later in numerous experimental environments is rationalized by taking into account 'gateway' states, i.e. rotational levels of the d 3∏g , v=6 state that exhibit significant quintet character through which all population flows from one electronic state to the other.
A two-step solar thermochemical CO2-splitting cycle using Zn/ZnO redox reactions
A two-step thermochemical cycle for reducing CO2
into CO has been experimentally demonstrated using concentrated solar radiation as the energy source of high-temperature process heat. The first, endothermic, solar step is the thermal dissociation of zinc oxide into zinc. The second, exothermic, non-solar step is the reaction of zinc with CO2
, yielding CO and the initial zinc oxide, which is recycled to the first step. A Second-Law thermodynamic analysis for the net reaction CO2
indicates the potential of reaching solar-to-chemical energy conversion efficiencies of up to 39%. CO can be used as combustion fuel for power generation or further processed to synthetic liquid fuels for transportation.
The adjacent scheme depicts the solar chemical reactor configuration for the production of Zn by ZnO-reduction at 2000 K. It features a cavity-receiver lined with AUTHOR_WWW/ENE.ZnO particles that are directly exposed to high-flux solar irradiation, providing a very efficient heat transfer mechanism to the reaction site.
Hydrocarbon-fueled catalytic microcombustors
The design of portable power generation units using small-scale thermal engines requires a deep understanding of combustion and heat transfer processes at the microscale. Sophisticated CFD models accounting for flow-field description, combined heterogeneous and homogeneous chemical reactions and heat transfer mechanisms, have been used to delineate the stable combustion regimes of methane- and propane-fueled catalytic honeycomb microcombustors. Stability diagrams of hydrocarbon-fueled catalytic microreactors, in terms of maximum allowable heat losses to the environment versus channel inlet velocity, have identified favorable reactor wall materials for steady-state microreactor operation. Metallic materials (such as AUTHOR_WWW/ENE.FeCr alloy) display wider combustion stability envelopes compared to ceramic materials (e.g. cordierite), owing to the higher upstream heat transfer through the microreactor walls, which in turn enhances the preheating of the incoming fuel/air mixture. Comparison between different hydrocarbon fuels, namely methane and propane, revealed a significant impact of fuel transport properties on microreactor stability, particularly on the high-velocity (blow-out) branch of the stability envelope. While methane is less reactive than propane, both catalytically and in the gas phase, it compensates more efficiently for heat losses towards the environment than propane, owing to its higher diffusive transport towards the catalytic surface.
Identification of the SCR active sites in Fe-ZSM-5
The identification of the SCR active sites in Fe-ZSM-5 is of utmost importance for the understanding and optimization of the catalyst performance. No method (e.g. UV/VIS, IR, EPR, EXAFS, XPS, XRD) can definitively distinguish between isolated iron species and iron oxide clusters of different nuclearity in the same sample. A statistical approach was used to solve this problem. From the correlation of the measured SCR activity with the calculated concentration of different species the temperature dependent activities of isolated, dimeric and oligomeric iron species and iron particles could be determined.
S. Brandenberger, O. Kröcher, A. Tissler, R. Althoff, Estimation of the fractions of different nuclear iron species in uniformly metal-exchanged Fe-ZSM-5 samples based on a Poisson distribution, Appl. Catal. A 2009, accepted manuscript.
Further publications: Exhaust Gas Aftertreatment Group
Local current measurement in PEFCs
Major barriers for a successful commercialization of Polymer Electrolyte Fuel Cells (PEFCs) are insufficient lifetime and high cost of platinum catalyst. A comprehensive understanding of aging and transport phenomena on all relevant length scales is a key to improve durability and to reduce precious metal loading.
Flow fields as used in PEFCs for the distribution of the reactant gases over the electrode area cause inhomogeneities. The importance of down the channel inhomogeneities has been realized. Inhomogeneities in the perpendicular to the flow channel direction, however, have not received adequate attention to date, possibly due to the lack of direct experimental evidence. A novel approach allows for the first time the direct measurement of the local cell current in channel and land areas of PEFCs with sub-millimeter resolution. The high potential of our method is demonstrated here in the evaluation of in-plane current transients during start-up of a PEFC and in transient flooding experiments in combination with neutron radiography for liquid water detection. The method provides key information that is badly needed for the understanding of transport and degradation phenomena and for the assessment of mitigation strategies.
I.A. Schneider, G.G. Scherer, Handbook of Fuel Cells – Fundamentals, Technology and Applications. Edited by Wolf Vielstich, Hubert A. Gasteige, Harumi Yokokawa.Volumes 5&6, Part 4, Chapter 45, 2009: Advances in Electrocatalysis, Materials, Diagnostics and Durability.
Further publications: Electrochemistry Laboratory
Evolution of Organic Aerosols in the Atmosphere
Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.
J. L. Jimenez, M. R. Canagaratna, N. M. Donahue, A. S. H. Prevot, Q. Zhang, J. H. Kroll, P. F. DeCarlo, J. D. Allan, H. Coe, N. L. Ng, A. C. Aiken, K. S. Docherty, I. M. Ulbrich, A. P. Grieshop, A. L. Robinson, J. Duplissy, J. D. Smith, K. R. Wilson, V. A. Lanz, C. Hueglin, Y. L. Sun, J. Tian, A. Laaksonen, T. Raatikainen, J. Rautiainen, P. Vaattovaara, M. Ehn, M. Kulmala, J. M. Tomlinson, D. R. Collins, M. J. Cubison, E., J. Dunlea, J. A. Huffman, T. B. Onasch, M. R. Alfarra, P. I. Williams, K. Bower, Y. Kondo, J. Schneider, F. Drewnick, S. Borrmann, S. Weimer, K. Demerjian, D. Salcedo, L. Cottrell, R. Griffin, A. Takami, T. Miyoshi, S. Hatakeyama, A. Shimono, J. Y Sun, Y. M. Zhang, K. Dzepina, J. R. Kimmel, D. Sueper, J. T. Jayne, S. C. Herndon, A. M. Trimborn, L. R. Williams, E. C. Wood, A. M. Middlebrook, C. E. Kolb, U. Baltensperger, and D. R. Worsnop, Science 326
(5959) 2009 1525
Further publications: LAC Publications
Vibrational Spectra of Adsorbates from DFT
The hydrolysis of isocyanic acid was studied experimentally and theoretically and a reaction mechanism on different catalysts was established. The decreasing NOx emission limits for diesel vehicles impel the further development of the existing NOx deactivation technologies, particularly the selective catalytic reduction (SCR) of nitrogen oxides with urea. In the urea-SCR process, urea is injected into the hot exhaust gas, where it thermally decomposes into isocyanic acid (HNCO) and ammonia. HNCO quickly hydrolyses on the surface of SCR catalysts and even faster on the surface of specialized hydrolysis catalysts. The theoretical Density Functional Theory (DFT) method with cluster model was used. The reaction path was studied by adsorption of water and isocyanic acid, followed by optimization of the adsorbates structure. Additionally, vibrational analyses of the adsorbates were made. In the experimental part activity tests and surface sensitive techniques (XRD, XPS and DRIFTS) were applied. Measured DRIFT spectra could be reproduced by theoretical calculations. Based on the computational screening of different catalysts we can confirm the experimental results, which show that TiO2 is the best catalyst for isocyanic acid hydrolysis. Presented methodology of DFT modeling and "virtual" catalyst screening can be used for successful combination with different experimental methods available at PSI and for variety of questions and complex catalytic systems.