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- ItemA Highly Active Cobalt Catalyst for the General and Selective Hydrogenation of Aromatic Heterocycles(Weinheim : Wiley-VCH, 2023) Bauer, Christof; Müller, Felix; Keskin, Sercan; Zobel, Mirijam; Kempe, RhettNanostructured earth abundant metal catalysts that mediate important chemical reactions with high efficiency and selectivity are of great interest. This study introduces a synthesis protocol for nanostructured earth abundant metal catalysts. Three components, an inexpensive metal precursor, an easy to synthesize N/C precursor, and a porous support material undergo pyrolysis to give the catalyst material in a simple, single synthesis step. By applying this catalyst synthesis, a highly active cobalt catalyst for the general and selective hydrogenation of aromatic heterocycles could be generated. The reaction is important with regard to organic synthesis and hydrogen storage. The mild reaction conditions observed for quinolines permit the selective hydrogenation of numerous classes of N-, O- and S-heterocyclic compounds such as: quinoxalines, pyridines, pyrroles, indoles, isoquinoline, aciridine amine, phenanthroline, benzofuranes, and benzothiophenes.
- ItemOptical, electrical and chemical properties of PEO:I2 complex composite films(Heidelberg [u.a.] : Springer, 2022) Telfah, Ahmad; Al-Bataineh, Qais M.; Tolstik, Elen; Ahmad, Ahmad A.; Alsaad, Ahmad M.; Ababneh, Riad; Tavares, Carlos J.; Hergenröder, RolandSynthesized PEO:I2 complex composite films with different I2 concentrations were deposited onto fused silica substrates using a dip-coating method. Incorporation of PEO films with I2 increases the electrical conductivity of the composite, reaching a maximum of 46 mS/cm for 7 wt% I2. The optical and optoelectronic properties of the complex composite films were studied using the transmittance and reflectance spectra in the UV-Vis region. The transmittance of PEO decreases with increasing I2 content. From this study, the optical bandgap energy decreases from 4.42 to 3.28 eV as I2 content increases from 0 to 7 wt%. In addition, the refractive index for PEO films are in the range of 1.66 and 2.00.1H NMR spectra of pure PEO film shows two major peaks at 3.224 ppm and 1.038 ppm, with different widths assigned to the mobile polymer chains in the amorphous phase, whereas the broad component is assigned to the more rigid molecules in the crystalline phase, respectively. By adding I2 to the PEO, both peaks (amorphous and crystal) are shifted to lower NMR frequencies indicating that I2 is acting as a Lewis acid, and PEO is acting as Lewis base. Hence, molecular iodine reacts favorably with PEO molecules through a charge transfer mechanism, and the formation of triiodide (I3-), the iodite (IO2-) anion, I 2· · · PEO and I2+···PEO complexes. PEO:I2 complex composite films are expected to be suitable for optical, electrical, and optoelectronic applications.
- ItemCobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid(Weinheim : Wiley-VCH, 2019) Zhou, Wei; Wei, Zhihong; Spannenberg, Anke; Jiao, Haijun; Junge, Kathrin; Junge, Henrik; Beller, MatthiasAmong the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3. Compared to related ruthenium and manganese complexes 7 and 8, this optimal cobalt complex showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on the triplet state potential energy surface. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemSignatures of Sixfold Degenerate Exotic Fermions in a Superconducting Metal PdSb2(Weinheim : Wiley-VCH, 2020) Kumar, Nitesh; Yao, Mengyu; Nayak, Jayita; Vergniory, Maia G.; Bannies, Jörn; Wang, Zhijun; Schröter, Niels B.M.; Strocov, Vladimir N.; Müchler, Lukas; Shi, Wujun; Rienks, Emile D.L.; Mañes, J.L.; Shekhar, Chandra; Parkin, Stuart S.P.; Fink, Jörg; Fecher, Gerhard H.; Sun, Yan; Bernevig, B. Andrei; Felser, ClaudiaMultifold degenerate points in the electronic structure of metals lead to exotic behaviors. These range from twofold and fourfold degenerate Weyl and Dirac points, respectively, to sixfold and eightfold degenerate points that are predicted to give rise, under modest magnetic fields or strain, to topological semimetallic behaviors. The present study shows that the nonsymmorphic compound PdSb2 hosts six-component fermions or sextuplets. Using angle-resolved photoemission spectroscopy, crossing points formed by three twofold degenerate parabolic bands are directly observed at the corner of the Brillouin zone. The group theory analysis proves that under weak spin–orbit interaction, a band inversion occurs. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemRevealing all states of dewetting of a thin gold layer on a silicon surface by nanosecond laser conditioning(Amsterdam : Elsevier, 2021) Ernst, Owen C.; Uebel, David; Kayser, Stefan; Lange, Felix; Teubner, Thomas; Boeck, TorstenDewetting is a ubiquitous phenomenon which can be applied to the laser synthesis of nanoparticles. A classical spinodal dewetting process takes place in four successive states, which differ from each other in their morphology. In this study all states are revealed by interaction of pulsed nanosecond UV laser light with thin gold layers with thicknesses between 1 nm and 10 nm on (100) silicon wafers. The specific morphologies of the dewetting states are discussed with particular emphasis on the state boundaries. The main parameter determining which state is formed is not the duration for which the gold remains liquid, but rather the input energy provided by the laser. This shows that each state transition has a separate measurable activation energy. The temperature during the nanosecond pulses and the duration during which the gold remains liquid was determined by simulation using the COMSOL Multiphysics® software package. Using these calculations, an accurate local temperature profile and its development over time was simulated. An analytical study of the morphologies and formed structures was performed using Minkowski measures. With aid of this tool, the laser induced structures were compared with thermally annealed samples, with perfectly ordered structures and with perfectly random structures. The results show that both, structures of the laser induced and the annealed samples, strongly resemble the perfectly ordered structures. This reveals a close relationship between these structures and suggests that the phenomenon under investigation is indeed a spinodal dewetting generated by an internal material wave function. The purposeful generation of these structures and the elucidation of the underlying mechanism of dewetting by short pulse lasers may assist the realisation of various technical elements such as nanowires in science and industry. © 2020
- ItemShape-Memory Metallopolymers Based on Two Orthogonal Metal–Ligand Interactions(Weinheim : Wiley-VCH, 2021) Meurer, Josefine; Hniopek, Julian; Bätz, Thomas; Zechel, Stefan; Enke, Marcel; Vitz, Jürgen; Schmitt, Michael; Popp, Jürgen; Hager, Martin D.; Schubert, Ulrich S.A new shape-memory polymer is presented, in which both the stable phase as well as the switching unit consist of two different metal complexes. Suitable metal ions, which simultaneously form labile complexes with histidine and stable ones with terpyridine ligands, are identified via isothermal titration calorimetry (ITC) measurements. Different copolymers are synthesized, which contain butyl methacrylate as the main monomer and the metal-binding ligands in the side chains. Zn(TFMS)2 and NiCl2 are utilized for the dual crosslinking, resulting in the formation of metallopolymer networks. The switching temperature can simply be tuned by changing the composition as well as by the choice of the metal ion. Strain fixity rates (about 99%) and very high strain recovery rates (up to 95%) are achieved and the mechanism is revealed using different techniques such as Raman spectroscopy. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
- ItemDoes the Processing Method Resulting in Different States of an Interconnected Network of Multiwalled Carbon Nanotubes in Polymeric Blend Nanocomposites Affect EMI Shielding Properties?(Washington, DC : ACS Publications, 2018) Pawar, Shital Patangrao; Rzeczkowski, Piotr; Pötschke, Petra; Krause, Beate; Bose, SuryasarathiElectromagnetic interference (EMI), an unwanted phenomenon, often affects the reliability of precise electronic circuitry. To prevent this, an effective shielding is prerequisite to protect the electronic devices. In this study, an attempt was made to understand how processing of polymeric blend nanocomposites involving multiwalled carbon nanotubes (MWCNTs) affects the evolving interconnected network structure of MWCNTs and eventually their EMI shielding properties. Thereby, the overall blend morphology and especially the connectivity of the polycarbonate (PC) component, in which the MWCNTs tend to migrate, as well as the perfectness of their migration, and the state of nanotube dispersion are considered. For this purpose, blends of varying composition of PC and poly(methyl methacrylate) were chosen as a model system as they show a phase diagram with lower critical solution temperature type of characteristic. Such blends were processed in two different ways: solution mixing (from the homogeneous state) and melt mixing (in the biphasic state). In both the processes, MWCNTs (3 wt %) were mixed into the blends, and the evolved structures (after phase separation induced by annealing in solution-mixed blends) and the quenched structures (as the blends exit the extruder) were systematically studied using transmission electron microscopy (TEM). Both the set of blends were subjected to the same thermal history, however, under different conditions such as under quiescent conditions (in the case of solution mixing) and under shear (in the case of melt mixing). The electrical volume conductivity and the evolved morphologies of these blend nanocomposites were evaluated and correlated with the measured EMI shielding behavior. The results indicated that irrespective of the type of processing, the MWCNTs localized in the PC component; driven by thermodynamic factors and depending on the blend composition, sea-island, cocontinuous, and phase-inverted structures evolved. Interestingly, the better interconnected network structures of MWCNTs observed using TEM in the solution-mixed samples together with larger nanotube lengths resulted in higher EMI shielding properties (-27 dB at 18 GHz) even if slightly higher electrical volume conductivities were observed in melt-mixed samples. Moreover, the shielding was absorption-driven, facilitated by the dense network of MWCNTs in the PC component of the blends, at any given concentration of nanotubes. Taken together, this study highlights the effects of different blend nanocomposite preparation methods (solution and melt) and the developed morphology and nanotube network structure in MWCNT filled blend nanocomposites on the EMI shielding behavior.
- ItemCurvature in Biological Systems: Its Quantification, Emergence, and Implications across the Scales(Weinheim : VCH Verl.-Ges., 2022) Schamberger, Barbara; Ziege, Ricardo; Anselme, Karine; Ben Amar, Martine; Bykowski, Michał; Castro, André P. G.; Cipitria, Amaia; Coles, Rhoslyn A.; Dimova, Rumiana; Eder, Michaela; Ehrig, Sebastian; Escudero, Luis M.; Evans, Myfanwy E.; Fernandes, Paulo R.; Fratzl, Peter; Geris, Liesbet; Gierlinger, Notburga; Hannezo, Edouard; Iglič, Aleš; Kirkensgaard, Jacob J. K.; Kollmannsberger, Philip; Kowalewska, Łucja; Kurniawan, Nicholas A.; Papantoniou, Ioannis; Pieuchot, Laurent; Pires, Tiago H. V.; Renner, Lars D.; Sageman‐Furnas, Andrew O.; Schröder‐Turk, Gerd E.; Sengupta, Anupam; Sharma, Vikas R.; Tagua, Antonio; Tomba, Caterina; Trepat, Xavier; Waters, Sarah L.; Yeo, Edwina F.; Roschger, Andreas; Bidan, Cécile M.; Dunlop, John W. C.Surface curvature both emerges from, and influences the behavior of, living objects at length scales ranging from cell membranes to single cells to tissues and organs. The relevance of surface curvature in biology is supported by numerous experimental and theoretical investigations in recent years. In this review, first, a brief introduction to the key ideas of surface curvature in the context of biological systems is given and the challenges that arise when measuring surface curvature are discussed. Giving an overview of the emergence of curvature in biological systems, its significance at different length scales becomes apparent. On the other hand, summarizing current findings also shows that both single cells and entire cell sheets, tissues or organisms respond to curvature by modulating their shape and their migration behavior. Finally, the interplay between the distribution of morphogens or micro-organisms and the emergence of curvature across length scales is addressed with examples demonstrating these key mechanistic principles of morphogenesis. Overall, this review highlights that curved interfaces are not merely a passive by-product of the chemical, biological, and mechanical processes but that curvature acts also as a signal that co-determines these processes.
- ItemThiophene-Bridged Donor–Acceptor sp2-Carbon-Linked 2D Conjugated Polymers as Photocathodes for Water Reduction(Weinheim : Wiley-VCH, 2021) Xu, Shunqi; Sun, Hanjun; Addicoat, Matthew; Biswal, Bishnu P.; He, Fan; Park, SangWook; Paasch, Silvia; Zhang, Tao; Sheng, Wenbo; Brunner, Eike; Hou, Yang; Richter, Marcus; Feng, XinliangPhotoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene-bridged donor–acceptor-based 2D sp2-carbon-linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron-accepting building block 2,3,8,9,14,15-hexa(4-formylphenyl) diquinoxalino[2,3-a:2′,3′-c]phenazine (HATN-6CHO) and the first electron-donating linker 2,2′-([2,2′-bithiophene]-5,5′-diyl)diacetonitrile (ThDAN) provides the 2D CCP-HATNThDAN (2D CCP-Th). Compared with the corresponding biphenyl-bridged 2D CCP-HATN-BDAN (2D CCP-BD), the bithiophene-based 2D CCP-Th exhibits a wide light-harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital–lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP-Th a promising candidate for PEC water reduction. As a result, 2D CCP-Th presents a superb H2-evolution photocurrent density up to ≈7.9 µA cm−2 at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09–6.0 µA cm−2). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H2. © 2020 The Authors. Advanced Materials published by Wiley-VCH GmbH
- ItemLarge-Area Single-Crystal Graphene via Self-Organization at the Macroscale(Weinheim : Wiley-VCH, 2020) Ta, Huy Quang; Bachmatiuk, Alicja; Mendes, Rafael Gregorio; Perello, David J.; Zhao, Liang; Trzebicka, Barbara; Gemming, Thomas; Rotkin, Slava V.; Rümmeli, Mark H.In 1665 Christiaan Huygens first noticed how two pendulums, regardless of their initial state, would synchronize. It is now known that the universe is full of complex self-organizing systems, from neural networks to correlated materials. Here, graphene flakes, nucleated over a polycrystalline graphene film, synchronize during growth so as to ultimately yield a common crystal orientation at the macroscale. Strain and diffusion gradients are argued as the probable causes for the long-range cross-talk between flakes and the formation of a single-grain graphene layer. The work demonstrates that graphene synthesis can be advanced to control the nucleated crystal shape, registry, and relative alignment between graphene crystals for large area, that is, a single-crystal bilayer, and (AB-stacked) few-layer graphene can been grown at the wafer scale. © 2020 The Authors. Published by Wiley-VCH GmbH