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- ItemSynthesis of flow‐compatible Ru-Me/Al2O3 catalysts and their application in hydrogenation of 1-iodo-4-nitrobenzene([Cham] : Springer International Publishing, 2021) Sebek, Michael; Atia, Hanan; Steinfeldt, NorbertThe development of an active, selective, and long-term stable heterogeneous catalyst for the reductive hydrogenation of substituted nitrorarenes in continuous operation mode is still challenging. In this work, Ru based nanoparticles catalysts promoted with different transition metals (Zn, Co, Cu, Sn, or Fe) were supported on alumina spheres using spray wet impregnation method. The freshly prepared catalysts were characterized using complementary methods including scanning transmission electron microscopy (STEM) and temperature programmed reduction (TPR). The hydrogenation of 1-iodo-4-nitrobenzene served as model reaction to assess the catalytic performance of the prepared catalysts. The addition of the promotor affected the reducibility of Ru nanoparticles as well as the performance of the catalyst in the hydrogenation reaction. The highest yield of 4-iodoaniline (89 %) was obtained in a continuous flow process using Ru-Sn/Al2O3. The performance of this catalyst was also followed in a long-term experiment. With increasing operation time, a catalyst deactivation occurred which could only briefly compensate by an increase of the reaction temperature.
- ItemDissipation losses limiting first-order phase transition materials in cryogenic caloric cooling: A case study on all-d-metal Ni(-Co)-Mn-Ti Heusler alloys(Amsterdam [u.a.] : Elsevier Science, 2023) Beckmann, Benedikt; Koch, David; Pfeuffer, Lukas; Gottschall, Tino; Taubel, Andreas; Adabifiroozjaei, Esmaeil; Miroshkina, Olga N.; Riegg, Stefan; Niehoff, Timo; Kani, Nagaarjhuna A.; Gruner, Markus E.; Molina-Luna, Leopoldo; Skokov, Konstantin P.; Gutfleisch, OliverNi-Mn-based Heusler alloys, in particular all-d-metal Ni(-Co)-Mn-Ti, are highly promising materials for energy-efficient solid-state refrigeration as large multicaloric effects can be achieved across their magnetostructural martensitic transformation. However, no comprehensive study on the crucially important transition entropy change Δst exists so far for Ni(-Co)-Mn-Ti. Here, we present a systematic study analyzing the composition and temperature dependence of Δst. Our results reveal a substantial structural entropy change contribution of approximately 65 J(kgK)-1, which is compensated at lower temperatures by an increasingly negative entropy change associated with the magnetic subsystem. This leads to compensation temperatures Tcomp of 75 K and 300 K in Ni35Co15Mn50-yTiy and Ni33Co17Mn50-yTiy, respectively, below which the martensitic transformations are arrested. In addition, we simultaneously measured the responses of the magnetic, structural and electronic subsystems to the temperature- and field-induced martensitic transformation near Tcomp, showing an abnormal increase of hysteresis and consequently dissipation energy at cryogenic temperatures. Simultaneous measurements of magnetization and adiabatic temperature change ΔTad in pulsed magnetic fields reveal a change in sign of ΔTad and a substantial positive and irreversible ΔTad up to 15 K at 15 K as a consequence of increased dissipation losses and decreased heat capacity. Most importantly, this phenomenon is universal, it applies to any first-order material with non-negligible hysteresis and any stimulus, effectively limiting the utilization of their caloric effects for gas liquefaction at cryogenic temperatures.
- ItemEmerging, hydrogen-driven electrochemical water purification(Amsterdam [u.a.] : Elsevier Science, 2022) Suss, M.E.; Zhang, Y.; Atlas, I.; Gendel, Y.; Ruck, E.B.; Presser, V.Energy-efficient technologies for the remediation of water and generation of drinking water is a key towards sustainable technologies. Electrochemical desalination technologies are promising alternatives towards established methods, such as reverse osmosis or nanofiltration. In the last few years, hydrogen-driven electrochemical water purification has emerged. This review article explores the concept of desalination fuel cells and capacitive-Faradaic fuel cells for ion separation.
- ItemNon-instantaneous third-order optical response of gases in low-frequency fields(Washington, DC : Soc., 2022) Morales, Felipe; Richter, Maria; Ivanov, Misha; Husakou, AntonIt is commonly assumed that for low-intensity short optical pulses far from resonance, the third-order optical nonlinear response is instantaneous. We solve the three-dimensional time-dependent Schrödinger equation for the hydrogen atom and show that this is not the case: the polarization is not simply proportional to the cube of the electric field even at low intensities. We analyze the fundamental-frequency and third-harmonic nonlinear susceptibilities of hydrogen, investigate their dependence on intensity, and find that the delays in the Kerr response rapidly approach the femtosecond time-scale at higher intensities, while the delays in the third harmonic generation remain much lower. We also propose an experimental scheme to detect and characterize the above effects.
- ItemKinetic investigation of para-nitrophenol reduction with photodeposited platinum nanoparticles onto tunicate cellulose(London : RSC Publishing, 2022) Thiel, T.A.; Zhang, X.; Radhakrishnan, B.; van de Krol, R.; Abdi, F.F.; Schroeter, M.; Schomäcker, R.; Schwarze, M.Photodeposition is a specific method for depositing metallic co-catalysts onto photocatalysts and was applied for immobilizing platinum nanoparticles onto cellulose, a photocatalytically inactive biopolymer. The obtained Pt@cellulose catalysts show narrow and well-dispersed nanoparticles with average sizes between 2 and 5 nm, whereby loading, size and distribution depend on the preparation conditions. The catalysts were investigated for the hydrogenation of para-nitrophenol via transfer hydrogenation using sodium borohydride as the hydrogen source, and the reaction rate constant was determined using the pseudo-first-order reaction rate law. The Pt@cellulose catalysts are catalytically active with rate constant values k from 0.09 × 10−3 to 0.43 × 10−3 min−1, which were higher than the rate constant of a commercial Pt@Al2O3 catalyst (k = 0.09 × 10−3 min−1). Additionally, the Pt@cellulose catalyst can be used for electrochemical hydrogenation of para-nitrophenol where the hydrogen is electrocatalytically formed. The electrochemical hydrogenation is faster compared to the transfer hydrogenation (k = 0.11 min−1).
- ItemB12X11(H2)−: exploring the limits of isotopologue selectivity of hydrogen adsorption(London : RSC Publishing, 2021) Wulf, Toshiki; Warneke, Jonas; Heine, ThomasWe study the isotopologue-selective binding of dihydrogen at the undercoordinated boron site of B12X11− (X = H, F, Cl, Br, I, CN) using ab initio quantum chemistry. With a Gibbs free energy of H2 attachment reaching up to 80 kJ mol−1 (ΔG at 300 K for X = CN), these sites are even more attractive than most undercoordinated metal centers studied so far. We thus believe that they can serve as an edge case close to the upper limit of isotopologue-selective H2 adsorption sites. Differences of the zero-point energy of attachment average 5.0 kJ mol−1 between D2 and H2 and 2.7 kJ mol−1 between HD and H2, resulting in hypothetical isotopologue selectivities as high as 2.0 and 1.5, respectively, even at 300 K. Interestingly, even though attachment energies vary substantially according to the chemical nature of X, isotopologue selectivities remain very similar. We find that the H–H activation is so strong that it likely results in the instantaneous heterolytic dissociation of H2 in all cases (except, possibly, for X = H), highlighting the extremely electrophilic nature of B12X11− despite its negative charge. Unfortunately, this high reactivity also makes B12X11− unsuitable for practical application in the field of dihydrogen isotopologue separation. Thus, this example stresses the two-edged nature of strong H2 affinity, yielding a higher isotopologue selectivity on the one hand but risking dissociation on the other, and helps define a window of adsorption energies into which a material for selective adsorption near room temperature should ideally fall.