Peter Wasserscheid

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

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Publications (355)1516.82 Total impact

  • Journal of Chemical & Engineering Data 11/2015; DOI:10.1021/acs.jced.5b00671 · 2.04 Impact Factor

  • The Journal of Physical Chemistry C 11/2015; DOI:10.1021/acs.jpcc.5b10392 · 4.77 Impact Factor
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    ABSTRACT: Liquid Organic Hydrogen Carrier (LOHC) systems offer a very attractive way for storing and distributing hydrogen from electrolysis using excess energies from solar or wind power plants. In this contribution, an alternative, high-value utilization of such hydrogen is proposed namely its use in steady-state chemical hydrogenation processes. We here demonstrate that the hydrogen-rich form of the LOHC system dibenzyltoluene/perhydro-dibenzyltoluene can be directly applied as sole source of hydrogen in the hydrogenation of toluene, a model reaction for large-scale technical hydrogenations. Equilibrium experiments using perhydro-dibenzyltoluene and toluene in a ratio of 1:3 (thus in a stoichiometric ratio with respect to H2) yield conversions above 60%, corresponding to an equilibrium constant significantly higher than 1 under the applied conditions (270 °C).
    International Journal of Hydrogen Energy 11/2015; DOI:10.1016/j.ijhydene.2015.10.013 · 3.31 Impact Factor

  • Applied Surface Science 11/2015; DOI:10.1016/j.apsusc.2015.11.045 · 2.71 Impact Factor
  • S. Bajus · F. Agel · M. Kusche · N.Ní Bhriain · P. Wasserscheid ·

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    ABSTRACT: Ionic liquid (ILs) are flexible reaction media and solvents for the synthesis of metal nanoparticles (NPs). Here, we describe a new preparation method for metallic NPs in nanometer thick films of ultraclean ILs in an ultrahigh vacuum (UHV) environment. CO-covered Pd NPs are formed by simultaneous and by sequential physical vapor deposition (PVD) of the IL and the metal in the presence of a low partial pressure of CO. The film thickness and the particle size can be controlled by the deposition parameters. We have followed the formation of the NPs and their thermal behavior by time-resolved IR reflection absorption spectroscopy (TR-IRAS) and by temperature-programmed IRAS (TR-IRAS). Codeposition of Pd and [C1C2Im][OTf] in CO at 100 K leads to the growth of homogeneous multilayer films of CO-covered Pd aggregates in an IL matrix. The size of these NPs can be controlled by the metal fraction in the co-deposit. With increasing metal fraction the size of the Pd NP also increases. At very low metal content, small Pd carbonyl-like species are formed, which bind CO in on-top geometry only. Upon annealing, the [OTf]- anion coadsorbs at the NP surface and partially displaces CO. Coadsorption of CO and IL is indicated by a strong red-shift of the CO stretching bands. While the weakly bound on-top CO is mainly replaced below the melting transition of the IL, coadsorbate shells with bridge-bonded CO and IL are stable well above the melting point. Larger three-dimensional Pd NPs can be prepared by PVD of Pd onto a solid [C1C2Im][OTf] film at 100 K. Upon annealing, on-top CO desorbs from these NPs below 200 K. Upon melting of the IL film, the CO-covered Pd NPs immerse into the IL and again form a stable coadsorbate shell that consists of bridge-bonded CO and the IL.
    Langmuir 10/2015; DOI:10.1021/acs.langmuir.5b03386 · 4.46 Impact Factor
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    ABSTRACT: This contribution deals with pore diffusion influences on the dehydrogenation kinetics of perhydro-N-ethylcarbazole (H12-NEC). The reaction is of high interest in the context of hydrogen storage in the N-ethylcarbazole (NEC)/perhydro-N-ethylcarbazole (H12-NEC) Liquid Organic Hydrogen Carrier (LOHC) system. The hydrogen content of H12-NEC is 5.8 wt% and total dehydrogenation releases for each mL of H12-NEC more than 600 mL of H2. Further optimization of H12-NEC dehydrogenation catalysis requires a better understanding of the role of mass transfer effects. Pore diffusion effects have been studied by preparing egg-shell catalysts (Pt/γ-alumina layer on α-alumina core) of different active layer thicknesses (24 -88 μm). It has been found that even at very thin catalyst layers (24 μm) the kinetic regime is limited to 235 °C, thus pore diffusion effects the dehydrogenation in almost all commercial catalysts strongly. This journal is
    Energy & Environmental Science 10/2015; 8(10). DOI:10.1039/C5EE02024G · 20.52 Impact Factor
  • Jenny Reichert · Birgit Brunner · Andreas Jess · Peter Wasserscheid · Jakob Albert ·
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    ABSTRACT: Herein, we report a remarkable finding that biomass oxidation to formic acid (FA) in water-organic biphasic reaction systems is far more selective than the same reaction in a monophasic aqueous media. While literature claims that the yield of FA from carbohydrates and biomass is limited to less than 68%, even for simple substrates such as glucose or glycerol, we demonstrate in this study that FA yields of up to 85% can be obtained from glucose. Using our biphasic reaction protocol, even raw lignocellulosic biomass, such as beech wood, leads to FA yields of 61%. This is realized by applying polyoxometalate H8PV5Mo7O40 as a homogeneous catalyst, oxygen as the oxidant and water as the solvent in the presence of a long-chain primary alcohol as an in-situ extracting agent. The new, liquid-liquid biphasic operation opens a highly effective way to produce pure FA, a liquid syngas equivalent, from wood in a robust, integrated, and low-temperature process. This journal is
    Energy & Environmental Science 10/2015; 8(10). DOI:10.1039/C5EE01706H · 20.52 Impact Factor
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    ABSTRACT: We investigated the surface reaction of the liquid organic hydrogen carrier dicyclohexylmethane (DCHM) on Pt(111) in ultrahigh vacuum by high-resolution X-ray photoelectron spectroscopy, temperature-programmed desorption, near-edge X-ray absorption fine structure, and infrared reflection-absorption spectroscopy. Additionally, the hydrogen-lean molecule diphenylmethane and the relevant molecular fragments of DCHM, methylcyclohexane, and toluene were studied to elucidate the reaction steps of DCHM. We find dehydrogenation of DCHM in the range of 200-260 K, to form a double-sided π-allylic species coadsorbed with hydrogen. Subsequently, ∼30% of the molecules desorb, and for ∼70%, one of the π-allyls reacts to a phenyl group between 260 and 330 K, accompanied by associative hydrogen desorption. Above 360 K, the second π-allylic species is dehydrogenated to a phenyl ring. This is accompanied by C-H bond scission at the methylene group, which is an unwanted decomposition step in the hydrogen storage cycle, as it alters the original hydrogen carrier DCHM. Above 450 K, we find further decomposition steps which we assign to C-H abstraction at the phenyl rings.
    The Journal of Physical Chemistry C 08/2015; 119(35):150819142701001. DOI:10.1021/acs.jpcc.5b06178 · 4.77 Impact Factor
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    ABSTRACT: The surface tension of nine tricyanomethanide ([C(CN)3]−)- and tetracyanoborate ([B(CN)4]−)-based ionic liquids (ILs) carrying a homologous series of the 1-alkyl-3-methylimidazolium ([alkyl-MIM]+) cations [EMIM]+ (ethyl), [BMIM]+ (butyl), [HMIM]+ (hexyl), [OMIM]+ (octyl), and [DMIM]+ (decyl) was measured with the pendant drop method in the temperature range between (283 and 353) K at atmospheric pressure with an estimated uncertainty of 2 % (k = 2). For the probed ILs, the surface tension decreases with increasing temperature and increasing alkyl chain length of the cation. Smaller values for the [B(CN)4]−-based ILs compared to the [C(CN)3]−-based ILs having the same cation were observed. The measured surface tensions agree with the limited number of experimental data found in the literature for the two IL families. A simple prediction based on the surface tension measured at 293 K and the temperature dependence of density showed good agreement with the measured temperature-dependent data. In comparison to other [alkyl-MIM]+-based ILs with anions of varying molecular size, the fairly large surface tensions of the ILs investigated in this study could be attributed to the strong charge delocalization in their relatively small anions.
    Journal of Chemical & Engineering Data 08/2015; 60(9):150806093707009. DOI:10.1021/acs.jced.5b00303 · 2.04 Impact Factor
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    ABSTRACT: The telomerization of butadiene with methanol was investigated in the presence of different palladium catalysts modified either with triphenylphosphine (TPP) or 1,3-dimesityl-imidazol-2-ylidene (IMes) ligand. When pure butadiene was used as substrate, a moderate selectivity for the Pd-TPP catalyst toward the desired product 1-methoxy-2,7-octadiene (1-Mode) of around 87% was obtained, while the IMes carbene ligand almost exclusively formed 1-Mode with 97.5% selectivity. The selectivity remained unchanged when the pure butadiene feed was replaced by synthetic crack-C4 (sCC4), a technical feed of 45 mol% butadiene and 55 mol% inerts (butenes and butanes). The TPP-modified catalyst showed a lower reaction rate, which was attributed to the expected dilution effect caused by the inerts. Surprisingly, the IMes-modified catalyst showed a higher rate with sCC4 compared to the pure feed. By means of a model-based experimental analysis, kinetic rate equations could be derived. The kinetic modeling supports the assumption that the two catalyst systems follow different kinetic rate equations. For the Pd-TPP catalyst, the reaction kinetics were related to the Jolly mechanism. In contrast, the Jolly mechanism had to be adapted for the Pd-IMes catalyst as the impact of the base seems to differ strongly from that for the Pd-TPP catalyst. The Pd-IMes system was found to be zero order in butadiene at moderate to high butadiene concentrations and first order in base while the nucleophilicity of the base is influenced by the methanol amount resulting in a negative reaction order for methanol.
    Journal of Catalysis 08/2015; 329:547 - 559. DOI:10.1016/j.jcat.2015.06.004 · 6.92 Impact Factor
  • Jakob Albert · Peter Wasserscheid ·
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    ABSTRACT: The selective oxidation of complex, water-insoluble and wet biomasses from second and third generation to formic acid including effective catalyst recycling is reported. Additionally, the relevance and limits of potential contaminants are illustrated by different experimental approaches. By using a very robust homogeneous polyoxometalate catalyst in aqueous solution, molecular oxygen as oxidant and an acid as solubilizer, it is possible to convert different lignocellulosic and algae feedstock into formic acid and pure carbon dioxide. The applied green oxidation system benefits from its low reaction temperature (below 100 °C) and its very selective nature. Furthermore, catalyst recycling over three batches has been successfully carried out.
    Green Chemistry 07/2015; DOI:10.1039/C5GC01474C · 8.02 Impact Factor
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    ABSTRACT: Ionic liquids (ILs) are possible working fluids for the separation of carbon dioxide (CO2) from flue gases. For evaluating their performance in such processes, reliable mutual-diffusivity data are required for mixtures of ILs with relevant flue gas components. In the present study, dynamic light scattering (DLS) and Molecular Dynamics (MD) simulations were used for the investigation of the molecular diffusion in binary mixtures of the IL 1-ethyl-3-methylimidazolium tetracyanoborate ([EMIM][B(CN)4]) with the dissolved gases carbon dioxide, nitrogen, carbon monoxide, hydrogen, methane, oxygen, and hydrogen sulfide at temperatures from 298.15 to 363.15 K and pressures up to 63 bar. At conditions approaching infinite dilution of a gas, the Fick mutual diffusivity of the mixture measured by DLS and the self-diffusivity of the corresponding gas calculated by MD simulations match, which could be generally found within combined uncertainties. The obtained diffusivities are in agreement with literature data for the same or comparable systems as well as with the general trend of increasing diffusivities for decreasing IL viscosities. The DLS and MD results reveal distinctly larger molecular diffusivities for [EMIM][B(CN)4]-hydrogen mixtures compared to mixtures with all other gases. This behavior results in the failure of an empirical correlation with the molar volumes of the gases at their normal boiling points. The DLS experiments also showed that there is no noticeable influence of the dissolved gas and temperature on the thermal diffusivity of the studied systems.
    The Journal of Physical Chemistry B 06/2015; 119(27). DOI:10.1021/acs.jpcb.5b02659 · 3.30 Impact Factor
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    ABSTRACT: A high viscosity-index (VI) is crucial for lubricants in industrial gearboxes exposed to changing load or weather conditions. Especially in the field of wind turbine oil, viscosity indices of 150 or higher are demanded to reduce power losses and ensure reliability at the same time. In this context the use of dissolved CO2 to improve viscosity-temperature behavior has been investigated for task-specific, halogen-free ionic liquids and benchmarked against polyalpha olefins. Measuring viscosity and density of the lubricants with dissolved CO2, it was proven that the VI can be increased significantly even at moderate pressures. In addition, measurements and simulation on CO2 solubility and studies on corrosion and tribology under CO2 pressure are presented.
    Industrial & Engineering Chemistry Research 04/2015; 54(21):150422132437002. DOI:10.1021/acs.iecr.5b00494 · 2.59 Impact Factor
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    ABSTRACT: Ultrahigh vacuum (UHV) surface science techniques are used to study the heterogeneous catalytic dehydrogenation of a liquid organic hydrogen carrier in its liquid state close to the conditions of real catalysis. For this purpose, perhydrocarbazole (PH), otherwise volatile under UHV, is covalently linked as functional group to an imidazolium cation, forming a non-volatile ionic liquid (IL). The catalysed dehydrogenation of the PH unit as a function of temperature is investigated for a Pt foil covered by a macroscopically thick PH-IL film and for Pd particles suspended in the PH-IL film, and for PH-IL on Au as inert support. X-ray photoelectron spectroscopy and thermal desorption spectroscopy allows us to follow in situ the catalysed transition of perhydrocarbazole to carbazole at technical reaction temperatures. The data demonstrate the crucial role of the Pt and Pd catalysts in order to shift the dehydrogenation temperature below the critical temperature of thermal decomposition. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    ChemPhysChem 04/2015; 16(9). DOI:10.1002/cphc.201500236 · 3.42 Impact Factor
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    ABSTRACT: Due to their low vapour pressures, non-flammability, high thermal stabilities and excellent tribological properties Ionic Liquids (ILs) are highly attractive lubricant base oils and additives. However, for practical applications of ILs in lubrication, two requirements are often limiting, the required miscibility with standard mineral oils (≥ 5 wt%) and the complete absence of corrosive halide ions in the ionic liquid. Moreover, the need for full compatibility with standard oil additives reduces the number of potential IL-based lubricant additives even further. In this contribution, an economic halide-free synthesis route to oil-miscible ionic liquids is presented and very promising tribological properties of such ILs as base oil or additive are demonstrated. Therefore sliding tests on bearing steel and XPS analysis of the formed surface films are shown. Corrosion test results of different bearing metals in contact with our halide-free ILs and (salt) water prove their applicability as real life lubricants. In the Sustainable Chemistry and Engineering context, we present a halide-free design approach for ionic performance chemicals that may contribute to significant energy savings due to their enhanced lubrication properties.
    ACS Sustainable Chemistry & Engineering 04/2015; 3(5):150413124513007. DOI:10.1021/sc500517n · 4.64 Impact Factor
  • Sabine Popp · Andreas Bösmann · René Wölfel · Peter Wasserscheid ·
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    ABSTRACT: Due to the known corrosion and crystallization issues of LiBr/H2O, the state-of-the-art working pair in sorption heat pump (SHP) systems, research into alternative working pairs is of high practical relevance. We have studied a wide range of ionic liquids (ILs) for this application in order to find potential new systems with enhanced performance. The screening was conducted with a focus on vapor pressure measurements of, in total, 74 examined working pairs. As common vapor-liquid-equilibrium measurements are very precise but rather time-consuming, we developed a new setup allowing a fast relative determination of humidities with very small sample volumes for screening purposes. By this method we identified seventeen IL/H2O working pairs fulfilling the technical relevant criterion of a water vapor pressure pH2O ≤ 10 mbar at T = 308 K with an IL content of less than 80 wt % (wIL < 0.8). Further evaluation of these candidates with respect to their thermal stability and viscosity allowed us to identify [MMIM][HCOO]/H2O, [MMIM][OAc]/H2O, [MMIM][C2H5COO]/H2O, [Me4N][HCOO]/H2O, [Me4N][OAc]/H2O and [Me4N] [C2H5COO]/H2O as the most promising IL/H2O systems for a possible application in SHP systems.Keywords: Ionic liquid; Sorption heat pump; Vapor pressure; Thermal stability
    ACS Sustainable Chemistry & Engineering 04/2015; 3(4):750-757. DOI:10.1021/acssuschemeng.5b00062 · 4.64 Impact Factor
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    ABSTRACT: Low-viscosity ionic liquids (ILs) based on the anions [B(CN)4]- (tetracyanoborate) and [C(CN)3]- (tricyanomethanide) are currently discussed as alternative working fluids for various applications. The dynamic viscosity of such ILs carrying [1-alkyl-MIM]+ (1-alkyl-3-methylimidazolium) cations was investigated via determining the translational particle diffusion coefficient by dynamic light scattering (DLS). The long-term stability of suspensions of different particles in the ILs, their particle diameters, and the influence of laser power on the measured particle diffusion coefficient for semi-transparent ILs were studied. For temperatures from 283 to 353 K at atmospheric pressure, the dynamic viscosity of the four pure ILs forming stable suspensions was obtained with an uncertainty of less than 5% (k = 2) and agrees with literature. Absorption of CO2 at pressures up to 0.87 MPa induced a distinct decrease in the dynamic viscosity. Differences between the viscosities of the different systems can be explained by varying strength of molecular interactions.
    Industrial & Engineering Chemistry Research 03/2015; 54(11):150309114145005. DOI:10.1021/acs.iecr.5b00086 · 2.59 Impact Factor
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    ABSTRACT: Liquid Organic Hydrogen Carrier (LOHC) systems offer a very attractive way to store and transport hydrogen, a technical feature that is highly desirable to link unsteady energy production from renewables with the vision of a sustainable, CO2-free, hydrogen-based energy system. LOHCs can be charged and discharged with considerable amounts of hydrogen in cyclic, catalytic hydrogenation and dehydrogenation processes. As their physico-chemical properties are very similar to diesel, today’s infrastructure for liquid fuels can be used for their handling thus greatly facilitating the step-wise transition from today’s fossil system to a CO2 emission free energy supply for both, stationary and mobile applications. However, for a broader application of these liquids it is mandatory to study in addition to their technical performance also their potential impact on environment and human health. This paper presents the first account on the toxicological profile of some potential LOHC structures. Moreover, it documents the importance of an early integration of hazard assessment into technology development and reveals for the specific case of LOHC structures the need for additional research in order to overcome some challenges in the hazard assessment for these liquids.
    Energy & Environmental Science 03/2015; 8(3). DOI:10.1039/C4EE03528C · 20.52 Impact Factor
  • Hans‐Peter Steinrueck · Peter Wasserscheid ·

    ChemInform 03/2015; 46(13). DOI:10.1002/chin.201513315

Publication Stats

11k Citations
1,516.82 Total Impact Points


  • 1970-2015
    • Friedrich-Alexander Universität Erlangen-Nürnberg
      • • Department of Chemical and Bioengineering
      • • Institute of Law and Technology
      • • Lehrstuhl für Technische Elektronik
      Erlangen, Bavaria, Germany
  • 2005-2014
    • Universitätsklinikum Erlangen
      Erlangen, Bavaria, Germany
  • 2010
    • University of Rostock
      Rostock, Mecklenburg-Vorpommern, Germany
  • 2009
    • BASF SE
      Ludwigshafen, Rheinland-Pfalz, Germany
  • 2004
    • French National Centre for Scientific Research
      Lutetia Parisorum, Île-de-France, France
  • 2003
    • University of Mobile
      Mobile, Alabama, United States
    • Queen's University Belfast
      Béal Feirste, Northern Ireland, United Kingdom
  • 2000-2003
    • RWTH Aachen University
      • • Institute of Physical Chemistry
      • • Institute for Technical und Macromolecular Chemistry
      Aachen, North Rhine-Westphalia, Germany
    • Fachhochschule Aachen
      Aachen, North Rhine-Westphalia, Germany