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Joachim Wollschläger

Publications and source records attributed to Joachim Wollschläger.

At least 19 recordsLinked to original sources

NiTi Single Crystal Growth by Micro-Pulling-Down Method: Experimental Setup and Material Characterization

Nickel-titanium that has an austenite to martensite phase transition has been studied extensively in the past as a shape memory alloy, but a lot remains to be learned from such phase transitions. However, single crystals are needed for a detailed characterization of the emerging phase transition. In order to produce NiTi single crystals for research purposes, we have set up a micro-pulling-down ($μ$PD) apparatus. The $μ$PD process is a fast and flexible method for the fabrication of small single crystals. The apparatus is operated in vacuum. By pulling the crystal down through a hole in the crucible bottom, it is possible to reduce oxygen contamination, since oxides float on top of the melt due to their low density. Here we present a detailed characterization of as-grown NiTi crystals by electron backscatter diffraction (EBSD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), hot gas extraction method and differential scanning calorimetry (DSC). The characteristics of the phase transition in NiTi are very sensitive to dopants and alloying. The $μ$PD method facilitates the introduction of different doping elements into the crystal.

cond-mat.mtrl-sci↗

Depth Profiling of Oxygen Migration in Ta/HfO2 Stacks During Ionic Liquid Gating

Ionic liquid (IL) gating has emerged as a powerful tool to control the structural, electronic, optical, and magnetic properties of materials by driving ion motion at solid interfaces. In magneto-ionic systems, electric fields are used to move ions, typically oxygen, from a donor layer into an underlying magnetic metal. Although oxygen distribution is key to enabling precise and stable control in magneto-ionic systems, the spatial distribution and voltage-dependence of oxygen incorporation in such nanoscale stacks remain unknown. Here, we quantify oxygen depth profiles and oxide formation in Si/ SiO2/ Ta (15)/ HfO2 (t) films after IL gating as a function of the gate voltage and HfO2 capping thickness (2 and 3 nm). X-ray reflectivity and X-ray photoelectron spectroscopy measurements revealed a threshold electric field of ~ -2.8 MV/cm to initiate oxygen migration from HfO2 into metallic Ta. The resulting Ta2O5 thickness increases linearly with gate voltage, reaching up to 4 nm at -3 V gating. Notably, the required electric field rises with oxide thickness, indicating a progressively growing barrier for thicker oxide films. The Ta/Ta2O5 interface remains atomically sharp for all gate voltages. This suggests that complete Ta2O5 layers form sequentially before further oxygen penetration, with no sign of deeper diffusion into bulk Ta. Thinner capping layers enhance oxidation, relevant for optimized stack design. Additionally, indium migration from the indium tin oxide electrode to the sample surface was observed, which should be considered for surface-sensitive applications. These insights advance design principles for magneto-ionic and nanoionic devices requiring precise interface engineering.

cond-mat.mtrl-sci↗

Surface Oxidation of SnTe Analyzed by Self-Consistent Fitting of all Emission Peaks in its X-ray Photoelectron Spectrum

X-ray photoelectron spectroscopy (XPS) is among the most widely used methods for surface characterization. Currently, the analysis of XPS data is almost exclusively based on the main emission peak of a given element and the rest of the spectrum is discarded. This makes quantitative chemical state analyses by peak fitting prone to substantial error, especially in light of incomplete and flawed reference literature. However, most elements give rise to multiple emission peaks in the x-ray energy range, which are virtually never analyzed. For samples with an inhomogeneous depth distribution of chemical states, these peaks show different but interdependent ratios of signal components, as they correspond to different information depths. In this work, we show that self-consistent fitting of all emission peaks lends additional reliability to the depth profiling of chemical states by angular-resolved (AR-)XPS. We demonstrate this using a natively oxidized thin film of the topological crystalline insulator tin telluride (SnTe). This approach is not only complementary to existing depth profiling methods, but may also pave the way towards complete deconvolution of the XPS spectrum, facilitating a more comprehensive and holistic understanding of the surface chemistry of solids.

cond-mat.mes-hall↗

Reactive additive capillary stamping with double network hydrogel-derived aerogel stamps under solvothermal conditions

Integration of solvothermal reaction products into complex thin-layer architectures is frequently achieved by combinations of layer transfer and subtractive lithography, whereas direct additive substrate patterning with solvothermal reaction products has remained challenging. We report reactive additive capillary stamping under solvothermal conditions as a parallel contact-lithographic access to patterns of solvothermal reaction products in thin-layer configurations. To this end, corresponding precursor inks are infiltrated into mechanically robust mesoporous aerogel stamps derived from double-network hydrogels (DNHGs). The stamp is then brought into contact with a substrate to be patterned under solvothermal reaction conditions inside an autoclave. The precursor ink forms liquid bridges between the topographic surface pattern of the stamp and the substrate. Evaporation-driven enrichment of the precursors in these liquid bridges along with their liquid-bridge-guided conversion into the solvothermal reaction products yields large-area submicron patterns of the solvothermal reaction products replicating the stamp topography. As example, we prepared thin hybrid films, which contained ordered monolayers of superparamagnetic submicron nickel ferrite dots prepared by solvothermal capillary stamping surrounded by nickel electrodeposited in a second, orthogonal substrate functionalization step. The submicron nickel ferrite dots acted as magnetic hardener halving the remanence of the ferromagnetic nickel layer. In this way, thin-layer electromechanical systems, transformers and positioning systems may be customized.

physics.app-ph↗

Solvent-Free High-Temperature Capillary Stamping of Stimuli-Responsive Polymers: Wettability Management by Orthogonal Substrate Functionalization

The wettability of surfaces determines their antifouling, antifogging, anti-icing, and self-cleaning properties as well as their usability for sensing, oil-water separation, water collection, and water purification. Solvent-free high-temperature capillary stamping of stimuli-responsive polymers yielding arrays of stimuli-responsive polymer microdots on differently modified substrates enables the flexible generation of switchable surfaces with different water contact angles (WCAs). Potential problems associated with the deposition of polymer solutions, such as the handling of volatile organic solvents, phase separation induced by solvent evaporation, and capillarity-driven flow processes, are circumvented. We used composite stamps with topographically patterned contact surfaces consisting of metallic nickel cores and porous MnO2 coatings taking up the stimuli-responsive polymers. The short transport paths from the MnO2 contact layers to the counterpart substrates enabled the stamping of polymer melts containing components impeding flow, such as carbon nanotubes (CNTs). Thus-obtained arrays of polymer-CNT hybrid microdots prevent problems associated with continuous coatings including delamination and crack propagation. Moreover, the range within which the properties of the stamped stimuli-responsive polymer microdots are switchable can be tuned by orthogonal substrate modification. As an example, we stamped hybrid microdots consisting of poly(2-(methacryloyloxy)ethyl ferrocenecarboxylate) (PFcMA) and CNTs onto indium tin oxide (ITO) substrates. Coating the ITO substrates with a poly(ethylene oxide)-terminated silane shifted the WCAs obtained by switching the PFcMA between its oxidized and reduced states by nearly 50°.

cond-mat.soft↗

Structural and magnetic investigation of the interfaces of $\mathrm{Fe_3O_4/MgO(001)}$ with and without NiO interlayer

We present an investigation on the structural and magnetic properties of the interfaces of $\mathrm{Fe_3O_4/MgO(001)}$ and $\mathrm{Fe_3O_4/NiO/MgO(001)}$ by extracting cation-selective magnetooptical depth profiles by means of x-ray magnetic reflectivity (XRMR) in combination with charge-transfer multiplet simulations of x-ray magnetic circular dichroism (XMCD) data. For $\mathrm{Fe_3O_4/MgO(001)}$, the magnetooptical depth profiles at the $\mathrm{Fe^{2+}_{oct}}$ and the $\mathrm{Fe^{3+}_{oct}}$ resonant energies follow exactly the structural profile, while the magnetooptical depth profile at the $\mathrm{Fe^{3+}_{tet}}$ resonance is offset by $3.2\pm1.3\,$Å from the interface, consistent with a B-site interface termination of $\mathrm{Fe_3O_4}$ with fully intact magnetic order. In contrast, for $\mathrm{Fe_3O_4/NiO(001)}$, the magnetooptical depth profiles at the $\mathrm{Fe^{2+}_{oct}}$ and the $\mathrm{Ni^{2+}}$ resonances agree with the structural profile, but the interface positions of the magnetooptical depth profiles at the $\mathrm{Fe^{3+}_{oct}}$ and the $\mathrm{Fe^{3+}_{tet}}$ resonances are laterally shifted by $3.3\pm 1.4\,$Å and $2.7\pm0.9\,$Å, respectively, not consistent with a magnetically ordered stoichiometric interface. This may be related to an intermixed $\mathrm{(Ni,Fe)O}$ layer at the interface. The magnetooptical depth profiles at the Ni $L_3$ edge reveal uncompensated magnetic moments throughout the NiO film.

cond-mat.mes-hall↗

Phenolic Resin Dual-Use Stamps for Capillary Stamping and Decal Transfer Printing

We report an optimized two-step thermopolymerization process carried out in contact with micropatterned molds that yields porous phenolic resin dual-use stamps with topographically micropatterned contact surfaces. With these stamps, two different parallel additive substrate manufacturing methods can be executed: capillary stamping and decal transfer microlithography. Under moderate contact pressures, the porous phenolic resin stamps are used for non-destructive ink transfer to substrates by capillary stamping. Continuous ink supply through the pore systems to the contact surfaces of the porous phenolic resin stamps enables multiple successive stamp-substrate contacts for lithographic ink deposition under ambient conditions. No deterioration of the quality of the deposited pattern occurs and no interruptions for ink replenishment are required. Under high contact pressure, porous phenolic resin stamps are used for decal transfer printing. In this way, the tips of the stamps' contact elements are lithographically transferred to counterpart substrates. The granular nature of the phenolic resin facilitates the rupture of the contact elements upon stamp retraction. The deposited phenolic resin micropatterns characterized by abundance of exposed hydroxyl groups are used as generic anchoring sites for further application-specific functionalizations. As example, we deposited phenolic resin micropatterns on quartz crystal microbalance resonators and further functionalized them with polyethylenimine for preconcentration sensing of humidity and gaseous formic acid. We envision that also preconcentration coatings for other sensing methods, such as attenuated total reflection infrared spectroscopy and surface plasmon resonance spectroscopy, are accessible by this functionalization algorithm

cond-mat.mtrl-sci↗

Time-resolved diffraction and photoelectron spectroscopy investigation of the reactive molecular beam epitaxy of $\mathrm{Fe_3O_4}$ ultrathin films

We present time-resolved high energy x-ray diffraction (tr-HEXRD), time-resolved hard x-ray photoelectron spectroscopy (tr-HAXPES) and time-resolved grazing incidence small angle x-ray scattering (tr-GISAXS) data of the reactive molecular beam epitaxy (RMBE) of $\mathrm{Fe_3O_4}$ ultrathin films on various substrates. Reciprocal space maps are recorded during the deposition of $\mathrm{Fe_3O_4}$ on $\mathrm{SrTiO_3(001)}$, MgO(001) and NiO/MgO(001) in order to observe the temporal evolution of Bragg reflections sensitive to the octahedral and tetrahedral sublattices of the inverse spinel structure of $\mathrm{Fe_3O_4}$. A time delay between the appearance of rock salt and spinel-exclusive reflections reveals that first, the iron oxide film grows with $\mathrm{Fe_{1-δ}O}$ rock salt structure with exclusive occupation of octahedral lattice sites. When this film is 1.1$\,$nm thick, the further growth of the iron oxide film proceeds in the inverse spinel structure, with both octahedral and tetrahedral lattice sites being occupied. In addition, iron oxide on $\mathrm{SrTiO_3(001)}$ initially grows with none of these structures. Here, the formation of the rock salt structure starts when the film is 1.5$\,$nm thick. This is confirmed by tr-HAXPES data obtained during growth of iron oxide on $\mathrm{SrTiO_3(001)}$, which demonstrate an excess of $\mathrm{Fe^{2+}}$ cations in growing films thinner than 3.2$\,$nm. This rock salt phase only appears during growth and vanishes after the supply of the Fe molecular beam is stopped. Thus, it can be concluded the rock salt structure of the interlayer is a property of the dynamic growth process. The tr-GISAXS data link these structural results to an island growth mode of the first 2-3$\,$nm on both MgO(001) and $\mathrm{SrTiO_3(001)}$ substrates.

cond-mat.mes-hall↗

Quantitative comparison of the magnetic proximity effect in Pt detected by XRMR and XMCD

X-ray resonant magnetic reflectivity (XRMR) allows for the simultaneous measurement of structural, optical and magnetooptic properties and depth profiles of a variety of thin film samples. However, a same-beamtime same-sample systematic quantitative comparison of the magnetic properties observed with XRMR and x-ray magnetic circular dichroism (XMCD) is still pending. Here, the XRMR results (Pt L$_{3}$ absorption edge) for the magnetic proximity effect in Pt deposited on the two different ferromagnetic materials Fe and Co$_{33}$Fe$_{67}$ are compared with quantitatively analyzed XMCD results. The obtained results are in very good quantitative agreement between the absorption-based (XMCD) and reflectivity-based (XRMR) techniques taking into account an ab initio calculated magnetooptic conversion factor for the XRMR analysis. Thus, it is shown that XRMR provides quantitative reliable spin depth profiles important for spintronic and spin caloritronic transport phenomena at this type of magnetic interfaces.

cond-mat.mtrl-sci↗

Role of NiO in the nonlocal spin transport through thin NiO films on Y$_3$Fe$_5$O$_{12}$

In spin transport experiments with spin currents propagating through antiferromagnetic (AFM) material, the antiferromagnet is treated as a mainly passive spin conductor not generating nor adding any spin current to the system. The spin current transmissivity of the AFM NiO is affected by magnetic fluctuations, peaking at the Néel temperature and decreasing by lowering the temperature. In order to study the role of the AFM in local and nonlocal spin transport experiments, we send spin currents through NiO of various thickness placed on Y$_3$Fe$_5$O$_{12}$. The spin currents are injected either electrically or by thermal gradients and measured at a wide range of temperatures and magnetic field strengths. The transmissive role is reflected in the sign change of the local electrically injected signals and the decrease in signal strength of all other signals by lowering the temperature. The thermally generated signals, however, show an additional upturn below 100$\,$K which are unaffected by an increased NiO thickness. A change in the thermal conductivity could affect these signals. The temperature and magnetic field dependence is similar as for bulk NiO, indicating that NiO itself contributes to thermally induced spin currents.

cond-mat.mes-hall↗

Cation- and lattice-site-selective magnetic depth profiles of ultrathin $\mathrm{Fe_3O_4}$(001) films

A detailed understanding of ultrathin film surface properties is crucial for the proper interpretation of spectroscopic, catalytic and spin-transport data. We present x-ray magnetic circular dichroism (XMCD) and x-ray resonant magnetic reflectivity (XRMR) measurements on ultrathin $\mathrm{Fe_3O_4}$ films to obtain magnetic depth profiles for the three resonant energies corresponding to the different cation species $\mathrm{Fe^{2+}_{oct}}$, $\mathrm{Fe^{3+}_{tet}}$ and $\mathrm{Fe^{3+}_{oct}}$ located on octahedral and tetrahedral sites of the inverse spinel structure of $\mathrm{Fe_3O_4}$. By analyzing the XMCD spectrum of $\mathrm{Fe_3O_4}$ using multiplet calculations, the resonance energy of each cation species can be isolated. Performing XRMR on these three resonant energies yields magnetic depth profiles that correspond each to one specific cation species. The depth profiles of both kinds of $\mathrm{Fe^{3+}}$ cations reveal a $\mathrm{3.9 \pm 1~Å}$-thick surface layer of enhanced magnetization, which is likely due to an excess of these ions at the expense of the $\mathrm{Fe^{2+}_{oct}}$ species in the surface region. The magnetically enhanced $\mathrm{Fe^{3+}_{tet}}$ layer is additionally shifted about $\mathrm{3\pm 1.5~Å}$ farther from the surface than the $\mathrm{Fe^{3+}_{oct}}$ layer.

cond-mat.mes-hall↗

Quadratic magnetooptic Kerr effect spectroscopy of Fe epitaxial films on MgO(001) substrates

The magnetooptic Kerr effect (MOKE) is a well known and handy tool to characterize ferro-, ferri- and antiferromagnetic materials. Many of the MOKE techniques employ effects solely linear in magnetization $\bm{M}$. Nevertheless, a higher-order term being proportional to $\bm{M}^2$ and called quadratic MOKE (QMOKE) can additionally contribute to the experimental data. Here, we present detailed QMOKE spectroscopy measurements in the range of 0.8 -- 5.5\,eV based on a modified 8-directional method applied on ferromagnetic bcc Fe thin films grown on MgO substrates. From the measured QMOKE spectra, two further complex spectra of the QMOKE parameters $G_s$ and $2G_{44}$ are yielded. The difference between those two parameters, known as $ΔG$, denotes the strength of the QMOKE anisotropy. Those QMOKE parameters give rise to the QMOKE tensor $\bm{G}$, fully describing the perturbation of the permittivity tensor in the second order in $\bm{M}$ for cubic crystal structures. We further present experimental measurements of ellipsometry and linear MOKE spectra, wherefrom permittivity in the zeroth and the first order in $\bm{M}$ are obtained, respectively. Finally, all those spectra are described by ab-initio calculations.

physics.optics↗

Impact of magnetic moment and anisotropy of Co$_\textrm{1-x}$Fe$_\textrm{x}$ thin films on the magnetic proximity effect of Pt

We present a systematic study of the magnetic proximity effect in Pt, depending on the magnetic moment and anisotropy of adjacent metallic ferromagnets. Element-selective x-ray resonant magnetic reflectivity measurements at the Pt absorption edge (11565$\,$eV) are carried out to investigate the spin polarization of Pt in Pt/Co$_\textrm{1-x}$Fe$_\textrm{x}$ bilayers. We observe the largest magnetic moment of (0.72$\,\pm\,$0.03)$\, μ_\textrm{B}$ per spin polarized Pt atom in Pt/Co$_\textrm{33}$Fe$_\textrm{67}$, following the Slater-Pauling curve of magnetic moments in Co-Fe alloys. In general, a clear linear dependence is observed between the Pt moment and the moment of the adjacent ferromagnet. Further, we study the magnetic anisotropy of the magnetized Pt which clearly adopts the magnetic anisotropy of the ferromagnet below. This is depicted for Pt on Fe(001) and on Co$_\textrm{50}$Fe$_\textrm{50}$(001), which have a 45$^{\circ}$ relative rotation of the fourfold magnetocrystalline anisotropy.

cond-mat.mtrl-sci↗

Impact of strain and morphology on magnetic properties of Fe$_3$O$_4$/NiO bilayers grown on Nb:SrTiO$_3$(001) and MgO(001)

We present a comparative study on the morphology and structural as well as magnetic properties of crystalline Fe$_3$O$_4$/NiO bilayers grown on both MgO(001) and SrTiO$_3$(001) substrates by reactive molecular beam epitaxy. These structures are investigated by means of x-ray photoelectron spectroscopy, low energy electron diffraction, x-ray reflectivity and diffraction as well as vibrating sample magnetometry. While the lattice mismatch of NiO grown on MgO(001) is only 0.8%, it is exposed to a lateral lattice mismatch of -6.9% if grown on SrTiO$_3$. In the case of Fe$_3$O$_4$, the misfit strain on MgO(001) and SrTiO$_3$(001) amounts to 0.3% and -7.5%, respectively. To clarify the relaxation process of the bilayer system, the film thicknesses of the magnetite and nickel oxide films have been varied between 5 and 20nm. While NiO films are well ordered on both substrates, Fe$_3$O$_4$ films grown on NiO/SrTiO$_3$ exhibit a higher surface roughness as well as lower structural ordering compared to films grown on NiO/MgO. Further, NiO films grow pseudomorphic in the investigated thickness range on MgO substrates without any indication of relaxation, whereas on SrTiO$_3$ the NiO films show strong strain relaxation. Fe$_3$O$_4$ films exhibit also strong relaxation even for films of 5nm thickness on both NiO/MgO as well as on NiO/SrTiO$_3$. The magnetite layers on both substrates show a fourfold magnetic in-plane anisotropy with magnetic easy axes pointing in $\left\langle100\right\rangle$ directions. The coercive field is strongly enhanced for magnetite grown on NiO/SrTiO$_3$ due to higher density of structural defects, compared to magnetite grown on NiO/MgO.

cond-mat.mtrl-sci↗

Steel-Based Electrocatalysts for Efficient and Durable Oxygen Evolution in Acidic Media

High overpotentials, particularly an issue of common anode materials, hamper the process of water electrolysis for clean energy generation. Thanks to immense research efforts up to date oxygen evolution electrocatalysts based on earth-abundant elements work efficiently and stably in neutral and alkaline regimes. However, non-noble metal-based anode materials that can withstand low pH regimes are considered to be an indispensable prerequisite for the water splitting to succeed in the future. All oxygen evolving electrodes working durably and actively in acids contain Ir at least as an additive. Due to its scarcity and high acquisition costs noble elements like Pt, Ru and Ir need to be replaced by earth abundant elements. We have evaluated a Ni containing stainless steel for use as an oxygen-forming electrode in diluted H2SO4. Unmodified Ni42 steel showed a significant weight loss after long term OER polarization experiments. Moreover, a substantial loss of the OER performance of the untreated steel specimen seen in linear sweep voltammetry measurements turned out to be a serious issue. However, upon anodization in LiOH, Ni42 alloy was rendered in OER electrocatalysts that exhibit under optimized synthesis conditions stable overpotentials down to 445 mV for 10 mA cm-2 current density at pH 0. Even more important: The resulting material has proven to be robust upon long-term usage (weight loss: 20 mug/mm2 after 50 ks of chronopotentiometry at pH 1) towards OER in H2SO4. Our results suggest that electrochemical oxidation of Ni42 steel in LiOH (sample Ni42Li205) results in the formation of a metal oxide containing outer zone that supports solution route-based oxygen evolution in acidic regime accompanied by a good stability of the catalyst.

physics.chem-ph↗

Quadratic magnetooptic spectroscopy setup based on photoelastic light modulation

In most of the cases the magnetooptic Kerr effect (MOKE) techniques rely solely on the effects linear in magnetization ($\bm{M}$). Nevertheless, a higher-order term being proportional to $\bm{M}$$^2$ and called quadratic MOKE (QMOKE) can additionally contribute to experimental data. Handling and understanding the underlying origin of QMOKE could be the key to utilize this effect for investigation of antiferromagnetic materials in the future due to their vanishing first order MOKE contribution. Also, better understanding of QMOKE and hence better understanding of magnetooptic (MO) effects in general is very valuable, as the MO effect is very much employed in research of ferro- and ferrimagnetic materials. Therefore, we present our QMOKE and longitudinal MOKE spectroscopy setup with a spectral range of 0.8--5.5\,eV. The setup is based on light modulation through a photoelastic modulator and detection of second-harmonic intensity by a lock-in amplifier. To measure the Kerr ellipticity an achromatic compensator is used within the setup, whereas without it Kerr rotation is measured. The separation of QMOKE spectra directly from the measured data is based on measurements with multiple magnetization directions. So far the QMOKE separation algorithm is developed and tested for but not limited to cubic (001) oriented samples. The QMOKE spectra yielded by our setup arise from two quadratic MO parameters $G_s$ and $2G_{44}$, being elements of quadratic MO tensor $\bm{G}$, which describe perturbation of the permittivity tensor in the second order in $\bm{M}$.

physics.ins-det↗

Electrooxidation of a cobalt based steel in LiOH: a non-noble metal based electro-catalyst suitable for durable water-splitting in an acidic milieu

The use of proton exchange membrane (PEM) electrolyzers is the method of choice for the conversion of solar energy when frequently occurring changes of the current load are an issue. However, this technique requires electrolytes with low pH. All oxygen evolving electrodes working durably and actively in acids contain IrOx. Due to their scarcity and high acquisition costs, noble elements like Pt, Ru and Ir need to be replaced by earth abundant elements. We have evaluated a cobalt containing steel for use as an oxygen-forming electrode in H2SO4. We found that the dissolving of ingredients out of the steel electrode at oxidative potential in sulfuric acid, which is a well-known, serious issue, can be substantially reduced when the steel is electro-oxidized in LiOH prior to electrocatalysis. Under optimized synthesis conditions a cobalt-containing tool steel was rendered into a durable oxygen evolution reaction (OER) electrocatalyst (weight loss: 39 mug mm-2 after 50 000 s of chronopotentiometry at pH 1) that exhibits overpotentials down to 574 mV at 10 mA cm-2 current density at pH 1. Focused ion beam SEM FIB-SEM) was successfully used to create a structure-stability relationship.

cond-mat.mtrl-sci↗

X20CoCrWMo10-9//Co3O4: a Metal-Ceramic Composite with Unique Efficiency Values for Water-Splitting in Neutral Regime

Water splitting allows the storage of solar energy into chemical bonds (H2+O2) and will help to implement the urgently needed replacement of limited available fossil fuels. Particularly in neutral environment electrochemically initiated water splitting suffers from low efficiency due to high overpotentials caused by the anode. Electro-activation of X20CoCrWMo10-9, a Co-based tool steel resulted in a new composite material (X20CoCrWMo10-9//Co3O4) that catalyzes the anode half-cell reaction of water electrolysis with a so far unequalled effectiveness. The current density achieved with this new anode in pH 7 corrected 0.1 M phosphate buffer is over a wide range of overpotentials around 10 times higher compared to recently developed, up-to-date electrocatalysts and represents the benchmark performance advanced catalysts show in regimes that support water splitting significantly better than pH 7 medium. X20CoCrWMo10-9//Co3O4 exhibited electrocatalytic properties not only at pH 7, but also at pH 13, which is much superior to the ones of IrO2-RuO2, single-phase Co3O4- or Fe/Ni- based catalysts. Both XPS and FT-IR experiments unmasked Co3O4 as the dominating compound on the surface of the X20CoCrWMo10-9//Co3O4 composite. Upon a comprehensive dual beam FIB-SEM (focused ion beam-scanning electron microscopy) study we could show that the new composite does not exhibit a classical substrate-layer structure due to the intrinsic formation of the Co-enriched outer zone. This structural particularity is basically responsible for the outstanding electrocatalytic OER performance.

cond-mat.mtrl-sci↗