Developing efficient catalysts for electrolysis, in particular for the oxygen evolution in the anodic half cell reaction, is an important challenge in energy conversion technologies. By taking ...inspiration from the catalytic properties of single-atom catalysts and metallo-proteins, we exploit the potential of metal–organic networks as electrocatalysts in the oxygen evolution reaction (OER). A dramatic enhancement of the catalytic activity toward the production of oxygen by nearly 2 orders of magnitude is demonstrated for novel heterobimetallic organic catalysts compared to metallo-porphyrins. Using a supramolecular approach we deliberately place single iron and cobalt atoms in either of two different coordination environments and observe a highly nonlinear increase in the catalytic activity depending on the coordination spheres of Fe and Co. Catalysis sets in at about 300 mV overpotential with high turnover frequencies that outperform other metal–organic catalysts like the prototypical hangman porphyrins.
The elastic modulus of freely suspended graphene monolayers, obtained via chemical reduction of graphene oxide, was determined through tip-induced deformation experiments. Despite their defect ...content, the single sheets exhibit an extraordinary stiffness (E = 0.25 TPa) approaching that of pristine graphene, as well as a high flexibility which enables them to bend easily in their elastic regime. Built-in tensions are found to be significantly lower compared to mechanically exfoliated graphene. The high resilience of the sheets is demonstrated by their unaltered electrical conductivity after multiple deformations. The electrical conductivity of the sheets scales inversely with the elastic modulus, pointing toward a 2-fold role of the oxygen bridges, that is, to impart a bond reinforcement while at the same time impeding the charge transport.
Further development of the field of all-electric spintronics requires the successful integration of spin transport channels with spin injector/generator elements. While with the advent of graphene ...and related 2D materials high performance spin channel materials are available, the use of nanostructured spin generators remains a major challenge. Especially promising for the latter purpose are 3D topological insulators, whose 2D surface states host massless Dirac Fermions with spin-momentum locking. Here, we demonstrate injection of spin-polarized current from a topological insulator into graphene, enabled by its intimate coupling to an ultrathin Bi2Te2Se nanoplatelet within a van der Waals epitaxial heterostructure. The spin switching signal, whose magnitude scales inversely with temperature, is detectable up to ∼15 K. Our findings establish topological insulators as prospective future components of spintronic devices wherein spin manipulation is achieved by purely electrical means.
In this review, the suitability of the major types of carbon nanostructures as conducting channels of field‐effect transistors (FETs) is compared on the basis of the dimensionality and size of their ...π‐conjugated system. For each of these materials, recent progress in its synthesis, electrical and structural characterization, as well as its implementation into various gate configurations is surveyed, with emphasis laid onto nanoscale aspects of the FET design and the attainable device performance. Finally, promising future research directions, such as the integration of different carbon nanostructures into novel device architectures, are outlined.
The carbon nanostructures graphene, carbon nanotubes, and π‐conjugated organic molecules currently attract immense interest as conducting channels in field‐effect transistors. In this review, we highlight recent strategies to enhance the carrier mobility in these devices. Moreover, advances in their implementation into logic circuits on flexible substrates are presented.
Electrochemical conversions at fuel cell electrodes are complex processes. In particular, the oxygen reduction reaction has substantial overpotential limiting the electrical power output efficiency. ...Effective and inexpensive catalytic interfaces are therefore essential for increased performance. Taking inspiration from enzymes, earth-abundant metal centres embedded in organic environments present remarkable catalytic active sites. Here we show that these enzyme-inspired centres can be effectively mimicked in two-dimensional metal-organic coordination networks self-assembled on electrode surfaces. Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine coordinating to single iron and manganese atoms on Au(111) effectively catalyse the oxygen reduction and reveal distinctive catalytic activity in alkaline media. These results demonstrate the potential of surface-engineered metal-organic networks for electrocatalytic conversions. Specifically designed coordination complexes at surfaces inspired by enzyme cofactors represent a new class of nanocatalysts with promising applications in electrocatalysis.
Unification of the techniques of ultrafast science and scanning tunneling microscopy (STM) has the potential of tracking electronic motion in molecules simultaneously in real space and real time. ...Laser pulses can couple to an STM junction either in the weak-field or in the strong-field interaction regime. The strong-field regime entails significant modification (dressing) of the tunneling barrier of the STM junction, whereas the weak-field or the photon-driven regime entails perturbative interaction. Here, we describe how photons carried in an ultrashort pulse interact with an STM junction, defining the basic fundamental framework of ultrafast photon-induced tunneling microscopy. Selective dipole coupling of electronic states by photons is shown to be controllable by adjusting the DC bias at the STM junction. An ultrafast tunneling microscopy involving photons is established. Consolidation of the technique calls for innovative approaches to detect photon-induced tunneling currents at the STM junction. We introduce and characterize here three techniques involving dispersion, polarization, and frequency modulation of the laser pulses to lock-in detect the laser-induced tunneling current. We show that photon-induced tunneling currents can simultaneously achieve angstrom scale spatial resolution and sub-femtosecond temporal resolution. Ultrafast photon-induced tunneling microscopy will be able to directly probe electron dynamics in complex molecular systems, without the need of reconstruction techniques.
The fabrication methods of the microelectronics industry have been refined to produce ever smaller devices, but will soon reach their fundamental limits. A promising alternative route to even smaller ...functional systems with nanometre dimensions is the autonomous ordering and assembly of atoms and molecules on atomically well-defined surfaces. This approach combines ease of fabrication with exquisite control over the shape, composition and mesoscale organization of the surface structures formed. Once the mechanisms controlling the self-ordering phenomena are fully understood, the self-assembly and growth processes can be steered to create a wide range of surface nanostructures from metallic, semiconducting and molecular materials.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The sequence of a peptide programs its self-assembly and hence the expression of specific properties through non-covalent interactions. A large variety of peptide nanostructures has been designed ...employing different aspects of these non-covalent interactions, such as dispersive interactions, hydrogen bonding or ionic interactions. Here we demonstrate the sequence-controlled fabrication of molecular nanostructures using peptides as bio-organic building blocks for two-dimensional (2D) self-assembly. Scanning tunnelling microscopy reveals changes from compact or linear assemblies (angiotensin I) to long-range ordered, chiral honeycomb networks (angiotensin II) as a result of removal of steric hindrance by sequence modification. Guided by our observations, molecular dynamic simulations yield atomistic models for the elucidation of interpeptide-binding motifs. This new approach to 2D self-assembly on surfaces grants insight at the atomic level that will enable the use of oligo- and polypeptides as large, multi-functional bio-organic building blocks, and opens a new route towards rationally designed, bio-inspired surfaces.
Metal–organic supramolecular chemistry on surfaces has matured to a point where its underlying growth mechanisms are well understood and structures of defined coordination environments of metal atoms ...can be synthesized in a controlled and reproducible procedure. With surface-confined molecular self-assembly, scientists have a tool box at hand which can be used to prepare structures with desired properties, as for example a defined oxidation number and spin state of the transition metal atoms within the organic matrix. From a structural point of view, these coordination sites in the supramolecular structure resemble the catalytically active sites of metallo-enzymes, both characterized by metal centers coordinated to organic ligands. Several chemical reactions take place at these embedded metal ions in enzymes and the question arises whether these reactions also take place using metal–organic networks as catalysts. Mimicking the active site of metal atoms and organic ligands of enzymes in artificial systems is the key to understanding the selectivity and efficiency of enzymatic reactions. Their catalytic activity depends on various parameters including the charge and spin configuration in the metal ion, but also on the organic environment, which can stabilize intermediate reaction products, inhibits catalytic deactivation, and serves mostly as a transport channel for the reactants and products and therefore ensures the selectivity of the enzyme. Charge and spin on the transition metal in enzymes depend on the one hand on the specific metal element, and on the other hand on its organic coordination environment. These two parameters can carefully be adjusted in surface confined metal–organic networks, which can be synthesized by virtue of combinatorial mixing of building synthons. Different organic ligands with varying functional groups can be combined with several transition metals and spontaneously assemble into ordered networks. The catalytically active metal centers are adequately separated by the linking molecules and constitute promising candiates for heterogeneous catalysts. Recent advances in synthesis, characterization, and catalytic performance of metal–organic networks are highlighted in this Account. Experimental results like structure determination of the networks, charge and spin distribution in the metal centers, and catalytic mechanisms for electrochemical reactions are presented. In particular, we describe the activity of two networks for the oxygen reduction reaction in a combined scanning tunneling microscopy and electrochemical study. The similarities and differences of the networks compared to metallo-enzymes will be discussed, such as the metal surface that operates as a geometric template and concomitantly functions as an electron reservoir, and how this leads to a new class of bioinspired catalysts. The possibility to create functional two-dimensional coordination complexes at surfaces taking inspiration from nature opens up a new route for the design of potent nanocatalyst materials for energy conversion.
Imaging proteins at the single-molecule level Longchamp, Jean-Nicolas; Rauschenbach, Stephan; Abb, Sabine ...
Proceedings of the National Academy of Sciences,
02/2017, Letnik:
114, Številka:
7
Journal Article
Recenzirano
Odprti dostop
Imaging single proteins has been a long-standing ambition for advancing various fields in natural science, as for instance structural biology, biophysics, and molecular nanotechnology. In particular, ...revealing the distinct conformations of an individual protein is of utmost importance. Here, we show the imaging of individual proteins and protein complexes by low-energy electron holography. Samples of individual proteins and protein complexes on ultraclean freestanding graphene were prepared by soft-landing electrospray ion beam deposition, which allows chemical- and conformational-specific selection and gentle deposition. Low-energy electrons do not induce radiation damage, which enables acquiring subnanometer resolution images of individual proteins (cytochrome C and BSA) as well as of protein complexes (hemoglobin), which are not the result of an averaging process.
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