Peter Wasserscheid

Friedrich-Alexander Universität Erlangen-Nürnberg, Erlangen, Bavaria, Germany

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Publications (282)1010.35 Total impact

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    ABSTRACT: The isomerisation reaction of 1,4-dichlorobenzene leading to the thermodynamically favoured and technically desired 1,3-dichlorobenzene has been studied comparing highly acidic chloroaluminate melts with organic imidazolium and alkali metal ions. Interestingly, the inorganic melts show much higher reactivity and full recyclability if small AlCl3 losses are compensated and the reaction is carried out under slight HCl pressure.
    Chemical communications (Cambridge, England). 08/2014;
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    ABSTRACT: We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %.
    ChemSusChem 08/2014; · 7.48 Impact Factor
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    ABSTRACT: We review recent results towards a molecular understanding of the adsorption and dehydrogenation of carbazole-derived liquid organic hydrogen carriers on platinum and palladium single crystals and on Al2O3-supported Pt and Pd nanoparticles. By combining synchrotron-based high-resolution X-ray photoelectron spectroscopy, infrared reflection-absorption spectroscopy, advanced molecular beam methods and temperature-programmed desorption spectroscopy, detailed insights into the reaction mechanism are obtained. On Pt(111), dehydrogenation of perhydro-N-ethylcarbazole, H12-NEC, starts with activation of the hydrogen atoms at the pyrrole unit, yielding H8-NEC as the first stable reaction intermediate at ∼340 K, followed by further dehydrogenation to NEC at ∼380 K. Above 390 K, dealkylation starts, yielding carbazole as an undesired byproduct. On small supported Pt particles, the dealkylation sets in at lower temperatures, due to the higher reactivity of low-coordinated sites, while on larger particles with (111) facets a reactivity as on the flat surface is observed. Carbazole derivatives with ethyl, propyl and butyl chains show an overall very similar reactivity, both on Pt(111) and on Pt nanoparticles. When comparing the dealkylation behavior of H12-NEC on Pt(111) and Pt nanoparticles to that on Pd(111) and Pd nanoparticles, we find a higher reactivity for the Pd systems.
    The Chemical Record 08/2014; · 4.38 Impact Factor
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    ABSTRACT: Novel supported ionic liquid phase (SILP) gas purification materials have been developed to remove ammonia irreversibly from an ambient gas flow of nitrogen (1000 ppm NH3 in N2, wet and dry). In the applied SILP materials, thin films of imidazolium based ionic liquids and ionic solutions of metal complexes, namely [C8C1Im][NTf2], [C8C1Im][NTf2]/Cu(NTf2)2, [C8C1Im][NTf2]/Co(NTf2)2 and [CnC1Im]Cl/CuCl2 (n = 2, 4, 8), were dispersed onto the large surface area of polymer-based spherical activated carbon supports. For the [CnC1Im]Cl/CuCl2 (n = 2, 4, 8) based SILP materials the use of a humid gas flow significantly enhances NH3 absorption as demonstrated by a clear increase of breakthrough times. The irreversibility of the ammonia sorption and the broadband capability (e.g. Cl2, H2S and cyclohexane) of the prepared SILP absorber materials are reported and compared to typical standards for gas purification adsorber materials (ABEK regulations).
    Green Chemistry 06/2014; 16(7). · 6.83 Impact Factor
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    ABSTRACT: Hollow-core photonic crystal fibre (HC-PCF) offers strong light confinement and long interaction lengths in an optofluidic channel. These unique advantages have motivated its recent use as a highly efficient and versatile microreactor for liquid-phase photochemistry and catalysis. In this work, we use a soft-glass HC-PCF to carry out photochemical experiments in a high-index solvent such as toluene. The high-intensity and strong confinement in the fibre is demonstrated to enhance the performance of a proof-of-principle photolysis reaction.
    23rd International Conference on Optical Fibre Sensors; 06/2014
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    ABSTRACT: The concept of liquid organic hydrogen carriers (LOHC) holds the potential for large scale chemical storage of hydrogen at ambient conditions. Herein, we compare the dehydrogenation and decomposition of three alkylated carbazole-based LOHCs, dodecahydro-N-ethylcarbazole (H12-NEC), dodecahydro-N-propylcarbazole (H12-NPC), and dodecahydro-N-butylcarbazole (H12-NBC), on Pt(111) and on Al2O3-supported Pt nanoparticles. We follow the thermal evolution of these systems quantitatively by in situ high-resolution X-ray photoelectron spectroscopy. We show that on Pt(111) the relevant reaction steps are not affected by the different alkyl substituents: for all LOHCs, stepwise dehydrogenation to NEC, NPC, and NBC is followed by cleavage of the C-N bond of the alkyl chain starting at 380-390 K. On Pt/Al2O3, we discern dealkylation on defect sites already at 350 K, and on ordered, (111)-like facets at 390 K. The dealkylation process at the defects is most pronounced for NEC and least pronounced for NBC.
    The Journal of chemical physics. 05/2014; 140(20):204711.
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    ABSTRACT: Five to thirty monolayer thick films of the ionic liquid [C2C1Im][OTf] were vaporized in vacuo onto an atomically clean Pd(111) single crystal surface at 220 K. Time- and temperature-resolved infrared reflection-absorption spectroscopy reveals growth, interactions with the metallic support, and the macroscopic phase behavior of the layer. At 220 K, the IL layer first grows in form of a glassy phase. Crystallization of the IL was witnessed above a critical thickness of about ten monolayers. Based on the known bulk crystal structure of the IL, we suggest the formation of well-oriented checkerboard-like crystalline film structures on the surface. The preferential orientation manifested by the crystal phase with regard to the macroscopic metallic surface is attributed to strong interactions between anionic headgroups and the metal.
    Langmuir : the ACS journal of surfaces and colloids. 05/2014;
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    ABSTRACT: Hydrogen can be stored conveniently using so-called liquid organic hydrogen carriers (LOHCs), for example, N-ethylcarbazole (NEC), which can be reversibly hydrogenated to dodecahydro-N-ethylcarbazole (H12-NEC). In this study, we focus on the dealkylation of H12-NEC, an undesired side reaction, which competes with dehydrogenation. The structural sensivity of dealkylation was studied by high-resolution X-ray photoelectron spectroscopy (HR-XPS) on Al2O3-supported Pt model catalysts and Pt(111) single crystals. We show that the morphology of the Pt deposit strongly influences LOHC degradation via C–N bond breakage. On smaller, defect-rich Pt particles, the onset of dealkylation is shifted by 90 K to lower temperatures as compared to large, well-shaped particles and well-ordered Pt(111). We attribute these effects to a reduced activation barrier for C–N bond breakage at low-coordinated Pt sites, which are abundant on small Pt aggregates but are rare on large particles and single crystal surfaces.
    Journal of Physical Chemistry Letters 04/2014; 5(8):1498–1504. · 6.59 Impact Factor
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    ABSTRACT: Ionic liquids (ILs) are promising solvents for gas separation processes such as carbon dioxide (CO2) capture from flue gases. For the design of corresponding processes and apparatus, thermophysical properties of ILs containing dissolved gases are required. In the present study, it is demonstrated that with a single optical setup, mutual and thermal diffusivities as well as refractive indices can be measured quasi-simultaneously for such mixtures. Dynamic light scattering (DLS) from bulk fluids was applied to determine mutual and thermal diffusivities for mixtures of 1 butyl-3-methylimidazolium tricyanomethanide ([BMIM][C(CN)3]) or 1 butyl-3-methylimidazolium tetracyanoborate ([BMIM][B(CN)4]) with dissolved CO2 at temperatures from 303.15 to 333.15 K and pressures between 2 and 26 bar in macroscopic thermodynamic equilibrium. Good agreement with literature data and only slight differences between the diffusivities measured for the two systems at the same temperature and comparable mole fractions of CO2 were found. Increasing mutual diffusivities with increasing mole fractions of CO2 are consistent with decreasing viscosities reported for other IL-CO2 mixtures in the literature and can be attributed to weakening of molecular interactions by the dissolved gas. For the conditions studied, no dependence of the thermal diffusivity on the temperature or the mole fraction of CO2 could be found.
    The Journal of Physical Chemistry B 04/2014; · 3.61 Impact Factor
  • Advanced Materials Interfaces 04/2014;
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    ABSTRACT: We have performed a systematic study addressing the surface behavior of a variety of functionalized and non-functionalized ionic liquids (ILs). From angle-resolved X-ray photoelectron spectroscopy, detailed conclusions on the surface enrichment of the functional groups and the molecular orientation of the cations and anions is derived. The systems include imidazolium-based ILs methylated at the C2 position, a phenyl-functionalized IL, an alkoxysilane-functionalized IL, halo-functionalized ILs, thioether-functionalized ILs, and amine-functionalized ILs. The results are compared with the results for corresponding non-functionalized ILs where available. Generally, enrichment of the functional group at the surface is only observed for systems that have very weak interaction between the functional group and the ionic head groups.
    Chemistry 03/2014; · 5.93 Impact Factor
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    ABSTRACT: We introduce a new type of silane-based ionogels that are produced by gelation of the ionic liquid 3-methyl-1-(3-(triethoxysilyl)propyl)-imidazolium bis(trifluoromethylsulfonyl)imide ([(EtO)3SiPMIM][TFSI]) with tetramethylorthosilane and formic acid. In the obtained ionogels the cations are involved in the network formation while the anions can move freely. The ionogels show advantageous properties for application in flexible electronics, such as low modulus, solution processability and high specific capacitance. Spray-coated ionogels were used as high capacitance gate dielectrics for organic (poly[3-hexylthiophene], P3HT) electrolyte-gated transistors (EGTs) that operated at very low voltages (<2 V) with high on/off ratios in air over weeks. Devices fabricated on polymer foil remained functional during repeated bending cycles with strains up to 2.3%.
    J. Mater. Chem. C. 03/2014; 2(13).
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    ABSTRACT: Liquid organic hydrogen carriers (LOHC) are compounds that enable chemical energy storage through reversible hydrogenation. They are considered a promising technology to decouple energy production and consumption by combining high-energy densities with easy handling. A prominent LOHC is N-ethylcarbazole (NEC), which is reversibly hydrogenated to dodecahydro-N-ethylcarbazole (H12-NEC). We studied the reaction of H12-NEC on Pt(111) under ultrahigh vacuum (UHV) conditions by applying infrared reflection-absorption spectroscopy, synchrotron radiation-based high resolution X-ray photoelectron spectroscopy, and temperature-programmed molecular beam methods. We show that molecular adsorption of H12-NEC on Pt(111) occurs at temperatures between 173 and 223 K, followed by initial C-H bond activation in direct proximity to the N atom. As the first stable dehydrogenation product, we identify octahydro-N-ethylcarbazole (H8-NEC). Dehydrogenation to H8-NEC occurs slowly between 223 and 273 K and much faster above 273 K. Stepwise dehydrogenation to NEC proceeds while heating to 380 K. An undesired side reaction, C-N bond scission, was observed above 390 K. H8-NEC and H8-carbazole are the dominant products desorbing from the surface. Desorption occurs at higher temperatures than H8-NEC formation. We show that desorption and dehydrogenation activity are directly linked to the number of adsorption sites being blocked by reaction intermediates.
    ACS Catalysis 02/2014; 4(2):657-665. · 5.27 Impact Factor
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    ABSTRACT: The interactions between ionic liquids and their supports determine many of their applications. The adsorption of the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [C2C1Im][OTf] on Pd(111), ordered Al2O3/NiAl(110), and Pd nanoparticles supported on Al2O3/NiAl(110) was investigated under ultrahigh vacuum (UHV) conditions using time-resolved infrared reflection absorption spectroscopy (TR-IRAS). On Pd, the [OTf]− anion stands up with its CF3 group directed toward the vacuum, whereas the anion is less clearly oriented on the oxide. We also find that strong interactions of the IL with the Pd result in migration of the IL from the oxide to the metal nanoparticles.
    The Journal of Physical Chemistry C. 02/2014; 118(6):3188–3193.
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    ABSTRACT: A new class of biofriendly ionogels produced by gelation of microcellulose thin films with tailored 1‐ethyl‐3‐methylimidazolium methylphosphonate ionic liquids are demonstrated. The cellulose ionogels show promising properties for application in flexible electronics, such as transparency, flexibility, transferability, and high specific capacitances of 5 to 15 μF cm−2. They can be laminated onto any substrate such as multilayer‐coated paper and act as high capacitance dielectrics for inorganic (spray‐coated ZnO and colloidal ZnO nanorods) and organic (poly[3‐hexylthiophene], P3HT) electrolyte‐gated field‐effect transistors (FETs), that operate at very low voltages (2 V−1 s−1 and a typical increase of mobility with decreasing specific capacitance of the ionogel is observed. Solution‐processed, colloidal ZnO nanorods and laminated cellulose ionogels enable the fabrication of the first electrolyte‐gated, flexible circuits on paper, which operate at bending radii down to 1.1 mm. Highly flexible and biofriendly ionogels are produced by gelation of microcellulose thin films with 1‐ethyl‐3‐methylimidazolium methylphosphonate ionic liquids. The obtained ionogels can be laminated onto any substrate such as paper and act as high capacitance dielectrics for electrolyte‐gated inorganic (ZnO) and organic (P3HT) field‐effect transistors. They operate at very low voltages ( Keywords: cellulose; electrolyte gating; field‐effect transistors; flexible electronics; ionogels; zinc oxide Document Type: Research Article DOI: http://dx.doi.org/10.1002/adfm.201302026 Publication date: February 1, 2014 $(document).ready(function() { var shortdescription = $(".originaldescription").text().replace(/\\&/g, '&').replace(/\\, '<').replace(/\\>/g, '>').replace(/\\t/g, ' ').replace(/\\n/g, ''); if (shortdescription.length > 350){ shortdescription = "" + shortdescription.substring(0,250) + "... more"; } $(".descriptionitem").prepend(shortdescription); $(".shortdescription a").click(function() { $(".shortdescription").hide(); $(".originaldescription").slideDown(); return false; }); }); Related content In this: publication By this: publisher By this author: Thiemann, Stefan ; Sachnov, Swetlana J. ; Pettersson, Fredrik ; Bollström, Roger ; Österbacka, Ronald ; Wasserscheid, Peter ; Zaumseil, Jana GA_googleFillSlot("Horizontal_banner_bottom");
    Advanced Functional Materials. 02/2014; 24(5):625-634.
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    ABSTRACT: Catalyst systems for the gas-phase oxycarbonylation of methanol often suffer from low catalyst activities and strong catalyst deactivation. In this work, the continuous gas-phase oxycarbonylation of methanol was realized by using Supported Ionic Liquid-Phase (SILP) catalysts. Copper(I) bromide dissolved in various ionic liquids and dispersed on Polymer-Based Spherical Activated Carbon (PBSAC) as supporting material was found to be an active catalyst. The poor activity and stability of copper halide catalysts reported in literature was substantially increased by the presence of ionic liquids. In particular, trioctylmethylammonium bromide in combination with a basic salt additive increased the activity of the CuBr catalyst and led to comparatively stable SILP catalyst operation reaching a total turnover number of 600 over 50 h time-on-stream.
    Journal of Catalysis. 01/2014; 309:71–78.
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    ABSTRACT: Owing to shifting market demands, it is important to convert ethylene to propylene. One attractive way to achieve this conversion is the dimerization of ethylene to 1-butene, followed by isomerization to 2-butene and subsequent metathesis of 2-butene/ethylene olefin. Our contribution focuses on combining the first two steps. Herein, we report a highly selective tandem dimerization/isomerization of ethylene to 2-butene catalyzed by homogeneously dissolved cationic nickel complexes. These catalysts can be efficiently immobilized by using the supported ionic liquid phase technology. Such supported ionic liquid phase materials have been tested under continuous gas phase conditions and demonstrated attractive catalytic performance with respect to both catalyst stability and productivity after the optimization of support, ionic liquid, ligand, and process parameters. The limited thermal stability of the nickel complexes and olefin condensation at too low temperatures require a careful thermal management of the fixed-bed reactor.
    ChemCatChem 01/2014; 6(1). · 5.18 Impact Factor
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    ABSTRACT: The complexes [(mall)Ni(dppanis)][SbF6] (mall = methallyl, dppanis = (2-methoxyphenyl)diphenylphosphine) 1, [(mall)Ni(PPh3OC10)][SbF6] (PPh3OC10 = (2-decyloxyphenyl)diphenylphosphine) 2, and [(mall)Ni(PPh3OdiMePh)][SbF6] (PPh3OdiMePh = (2-(2,6-dimethylphenoxy)phenyl)diphenylphosphine) 3 were immobilized as Supported Ionic Liquid Phase (SILP) catalysts and applied for the tandem dimerization/isomerization of ethylene to 2-butene in a fluidized bed reactor. The better heat removal in the fluidized bed improves the catalyst stability and allows for a more detailed investigation of the deactivation mechanism. Based on kinetic studies, a second order deactivation mechanism is proposed, in which two nickel complexes dimerize if the supply of ethene is insufficient.
    Catalysis Science & Technology 01/2014; 4(4):936-947. · 4.76 Impact Factor
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    ABSTRACT: Different Keggin-type polyoxometalates have been synthesized and characterized in order to identify optimized homogeneous catalysts for the selective oxidation of biomass to formic acid (FA) using oxygen as an oxidant and p-toluenesulfonic acid as an additive. Applying the optimized polyoxometalate catalyst system H8[PV5Mo7O40] (HPA-5), a total FA-yield (with respect to carbon in the biogenic feedstock) of 60% for glucose within 8 h reaction time and 28% for cellulose within 24 h reaction time could be achieved. The transformation is characterized by its mild reaction temperature, its excellent selectivity to FA in the liquid product phase and its applicability to a very wide range of biogenic raw materials including non-edible biopolymers and complex biogenic mixtures.
    Green Chemistry 12/2013; 16(1). · 6.83 Impact Factor
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    ABSTRACT: Carbon dioxide (CO2) absorption by the amine-functionalized ionic liquid (IL) dihydroxyethyl dimethylammonium taurinate at 310 K was studied using surface- and bulk-sensitive experimental techniques. From near-ambient pressure X-ray photoelectron spectroscopy at 0.9 mbar CO2, the amount of captured CO2 per mol IL in the near-surface region is quantified to ~0.58 mol, with ~0.15 mol in form of carbamate dianions and ~0.43 mol in form of carbamic acid. From isothermal uptake experiments combined with infrared spectroscopy, CO2 is found to be bound in the bulk as carbamate (with nominally 0.5 mol CO2 bound per 1 mol IL) up to ~2.5 bar CO2, and as carbamic acid (with nominally 1 mol CO2 bound per 1 mol IL) at higher pressures. We attribute the fact that at low pressures carbamic acid is the dominating species in the near-surface region, while only carbamate is formed in the bulk, to differences in solvation in the outermost IL layers as compared to the bulk situation.
    Journal of the American Chemical Society 12/2013; · 10.68 Impact Factor

Publication Stats

2k Citations
1,010.35 Total Impact Points

Institutions

  • 2004–2014
    • Friedrich-Alexander Universität Erlangen-Nürnberg
      • Department of Chemical and Bioengineering
      Erlangen, Bavaria, Germany
    • French National Centre for Scientific Research
      Lutetia Parisorum, Île-de-France, France
  • 2012
    • University of Aberdeen
      • School of Engineering
      Aberdeen, SCT, United Kingdom
  • 2006–2012
    • Universitätsklinikum Erlangen
      Erlangen, Bavaria, Germany
  • 2010
    • Fachhochschule Aachen
      Aachen, North Rhine-Westphalia, Germany
  • 2002–2010
    • University of Rostock
      • Institut für Chemie
      Rostock, Mecklenburg-Vorpommern, Germany
  • 2009
    • Wichita State University
      • Department of Chemistry
      Wichita, KS, United States
  • 2008
    • University of Amsterdam
      Amsterdamo, North Holland, Netherlands
  • 2003–2006
    • Technical University of Denmark
      • Department of Chemistry
      Copenhagen, Capital Region, Denmark
    • University of Mobile
      Mobile, Alabama, United States
  • 2002–2004
    • RWTH Aachen University
      • Institute for Technical und Macromolecular Chemistry
      Aachen, North Rhine-Westphalia, Germany