Sebastian Bochmann

Energy Storage in Strained Organic Molecules: (Spectro)Electrochemical Characterization of Norbornadiene and Quadricyclane.

We have investigated the electrochemically triggered cycloreversion of quadricyclane (QC) to norbornadiene (NBD), a system that holds the potential to combine both energy storage and conversion in a single molecule. Unambiguous voltammetric traces are obtained for pure NBD and pure QC, the latter a strained polycyclic isomer of the former. The difference in redox potentials is smaller than the energy difference between the neutral molecules. This is owing to a significant energy difference between the corresponding radical cations, as demonstrated by density functional theory (DFT) calculations. The vibrational modes of each pure compound are characterized experimentally in the fingerprint region and identified by DFT methods. Thermal and electrochemical transformations of NBD and QC are monitored in situ by IR spectroelectrochemical methods. The kinetics of the cycloreversion of QC to NBD, which is catalyzed by oxidizing equivalents, can be controlled by an applied electrode potential, which implies the ability to adjust in real time the release of thermal power stored in QC.

Systematic increase of electrocatalytic turnover at nanoporous platinum surfaces prepared by atomic layer deposition

We establish a procedure for the fabrication of electrocatalytically active, nanoporous surfaces coated with Pt and exhibiting a high geometric area. Firstly, the mechanism of the surface reactions between platinum(II) acetylacetonate and ozone is investigated by piezoelectric microbalance measurements. The data reveal that ozone oxidizes the metallic Pt surface to an extent which can exceed one monolayer depending on the reaction conditions. Proper reaction parameters yield a self-limited growth in atomic layer deposition (ALD) mode. Secondly, the ALD procedure is applied to porous anodic oxide substrates. The morphology and the crystal structure of the deposits are characterized. The ALD coating results in a continuous layer of Pt nanocrystallites along deep pore walls (aspect ratio 70). Thirdly, the Pt/TiO2 surfaces are shown to be electrochemically active in both acidic and alkaline media, in a way that qualitatively conforms to literature precedents based on Pt. Finally, we apply the anodization and ALD procedure to commercial Ti felts and demonstrate systematically how the electrochemical current density is increased by the large specific surface area and by the presence of the catalyst. Thereby, the catalyst loading, as well as its efficient utilization, can be optimized accurately. The preparative approach demonstrated here can be generalized and applied to the various electrocatalytic reactions of energy conversion devices.

Quantitative analysis of shadow X-ray Magnetic Circular Dichroism Photo-Emission Electron Microscopy

Shadow X-ray Magnetic Circular Dichroism Photo-Emission Electron Microscopy (XMCD-PEEM) is a recent technique, in which the photon intensity in the shadow of an object lying on a surface, may be used to gather information about the three-dimensional magnetization texture inside the object. Our purpose here is to lay the basis of a quantitative analysis of this technique. We first discuss the principle and implementation of a method to simulate the contrast expected from an arbitrary micromagnetic state. Text book examples and successful comparison with experiments are then given. Instrumental settings are finally discussed, having an impact on the contrast and spatial resolution : photon energy, microscope extraction voltage and plane of focus, microscope background level, electric-field related distortion of three-dimensional objects, Fresnel diffraction or photon scattering.

Design Rules for Oxygen Evolution Catalysis at Porous Iron Oxide Electrodes: Thousand-Fold Current Density Increase

Nanotubular iron(III) oxide electrodes are optimized for catalytic efficiency in the water oxidation reaction at neutral pH. The nanostructured electrodes are prepared from anodic alumina templates, which are coated with Fe2 O3 by atomic layer deposition. Scanning helium ion microscopy, X-ray diffraction, and Raman spectroscopy are used to characterize the morphologies and phases of samples submitted to various treatments. These methods demonstrate the contrasting effects of thermal annealing and electrochemical treatment. The electrochemical performances of the corresponding electrodes under dark conditions are quantified by steady-state electrolysis and electrochemical impedance spectroscopy. A rough and amorphous Fe2 O3 with phosphate incorporation is critical for the optimization of the water oxidation reaction. For the ideal pore length of 17 μm, the maximum catalytic turnover is reached with an effective current density of 140 μA cm-2 at an applied overpotential of 0.49 V.

Systematic tuning of segmented magnetic nanowires into three-dimensional arrays of ‘bits’

A method is presented for the preparation of a three-dimensional magnetic data storage material system. The major ingredients are an inert nanoporous matrix prepared by anodization and galvanic plating of magnetic and non-magnetic metals in wire shape inside the cylindrical pores. The individual nanomagnets consist of a nickel–cobalt alloy, the composition of which is tuned systematically by adjusting the electrolytic bath composition at one optimal applied potential. The lowest magnetocrystalline anisotropy is obtained at the composition Ni60Co40, as quantified by superconducting quantum interference device magnetometry. Wires of this composition experience a pinning-free propagation of magnetic domain walls, as determined by single-wire magneto-optical Kerr effect magnetometry. Adding copper into the electrolyte allows one to generate segments of Ni60Co40 separated by non-magnetic copper. The segment structure is apparent in individual nanowires imaged by scanning electron microscopy, UV-photoelectron emission microscopy, and transmission electron microscopy. The single-domain structure of the wire segments is evidenced by magnetic force microscopy.

Transmission XMCD-PEEM imaging of an engineered vertical FEBID cobalt nanowire with a domain wall

Using focused electron-beam-induced deposition, we fabricate a vertical, platinum-coated cobalt nanowire with a controlled three-dimensional structure. The latter is engineered to feature bends along the height: these are used as pinning sites for domain walls, which are obtained at remanence after saturation of the nanostructure in a horizontally applied magnetic field. The presence of domain walls is investigated using x-ray magnetic circular dichroism (XMCD) coupled to photoemission electron microscopy (PEEM). The vertical geometry of our sample combined with the low incidence of the x-ray beam produce an extended wire shadow which we use to recover the wires magnetic configuration. In this transmission configuration, the whole sample volume is probed, thus circumventing the limitation of PEEM to surfaces. This article reports on the first study of magnetic nanostructures standing perpendicular to the substrate with XMCD-PEEM. The use of this technique in shadow mode enabled us to confirm the presence of a domain wall without direct imaging of the nanowire.

Synthesis, Characterization, and Properties of Iron(II) Spin-Crossover Molecular Photoswitches Functioning at Room Temperature

Spin-crossover molecular switches [FeII(H2B(pz)2)2L] (L = novel phenanthroline-based ligands featuring photochromic diarylethene units; pz = 1-pyrazolyl) were synthesized and thoroughly characterized by variable-temperature X-ray crystallography, Mössbauer spectroscopy, and magnetic measurements. The effect of substituents introduced into the phenanthroline backbone (L2) and into the photochromic diarylethene unit (L3) on photophysical properties of metal-free ligands and spin-crossover iron(II) complexes 2 and 3, respectively, were investigated in detail. Both ligands and complexes could be switched with light in solution at room temperature. The photocyclization of 2 was accompanied by a high-spin to low-spin photoconversion determined at 19%. The closed-ring isomers of L3 and 3 reveal the lifetimes in the range of minutes, whereas those of L2 and 2 are thermally stable for days in solutions at room temperature. The reversibility of the photoswitching can be improved by avoiding the photostationary states. Prospective introduction of anchoring groups to the phenanthroline backbone might allow the construction of chemisorbed self-assembled monolayers of spin-crossover species switchable with light at room temperature.

A large electrochemical setup for the anodization of aluminum towards highly ordered arrays of cylindrical nanopores

A new electrochemical setup and the associated procedures for growing ordered anodic aluminum oxide pore arrays on large surfaces are presented. The typical size of the samples is 14 × 14 cm(2). The most crucial experimental parameters that allow for the stabilization of the high-field procedures are a very efficient cooling of sample and electrolyte, as well as the initial ramping up of the voltage at an accurately defined rate. The morphology of the cylindrical, parallel alumina pores is similar to those obtained on smaller scales with standard setups. Our setup facilitates the availability of porous anodic alumina as a template system for a number of applications.

Preparation and physical properties of soft magnetic nickel-cobalt three-segmented nanowires

We review a method to produce cylindrical magnetic nanowires displaying several segments, with a large versatility in terms of segment diameter and length. It is based on electroplating in alumina templates, the latter being prepared by several steps of anodization, wet etching, and atomic layer deposition to produce, widen, or shrink pores, respectively. We propose an analytical model to analyze the in-plane and out-of-plane magnetization loops of dense assemblies of multisegmented wires. The model considers inter-wires dipolar fields and end-domain curling and predicts the switching field of individual wires with no adjustable parameter. Its ingredients are crucial to extract reliable parameters from the fitting of loops, such as magnetization or the porosity of the array.We review a method to produce cylindrical magnetic nanowires displaying several segments, with a large versatility in terms of segment diameter and length. It is based on electroplating in alumina templates, the latter being prepared by several steps of anodization, wet etching, and atomic layer deposition to produce, widen, or shrink pores, respectively. We propose an analytical model to analyze the in-plane and out-of-plane magnetization loops of dense assemblies of multisegmented wires. The model considers inter-wires dipolar fields and end-domain curling and predicts the switching field of individual wires with no adjustable parameter. Its ingredients are crucial to extract reliable parameters from the fitting of loops, such as magnetization or the porosity of the array.

Probing domain walls in cylindrical magnetic nanowires with electron holography

We probe magnetic domain walls in cylindrical soft magnetic nanowires using electron holography. We detail the modelling of expected contrast for both transverse and Bloch point domain walls and provide comparison with experimental observations performed on NiCo nanowires, involving also both magnetic and electrostatic contribution to the electron holography map. This allows the fast determination of the domain wall type without the need for uneasy and time-consuming experimental removal of the electrostatic contribution. Finally, we describe and implement a new efficient algorithm for calculating the magnetic contrast.