Chemistry-dependent X-ray-induced surface charging.

Materials science in general, and surface/interface science in particular, have greatly benefited from the development of high energy synchrotron radiation facilities. Irradiation with intense ionizing beams can however influence relevant sample properties. Permanent radiation damage and irradiation-induced sample modifications have been investigated in detail during the last decades. Conversely, reversible sample alterations taking place only during irradiation are still lacking comprehensive in situ characterization. Irradiation-induced surface charging phenomena are particularly relevant for a wide range of interface science investigations, in particular those involving surfaces of solid substrates in contact with gaseous or liquid phases. Here, we demonstrate partially reversible radiation-induced surface charging phenomena, which extend far beyond the spatial dimensions of the X-ray beam mainly as a consequence of the interaction between the surface and ionized ambient molecules. The charging magnitude and sign are found to be surface chemistry specific and dependent on the substrates' bulk conductivity and grounding conditions. These results are obtained by combining a scanning Kelvin probe with a synchrotron surface diffractometer to allow simultaneous in situ work function measurements during precisely controlled hard X-ray micro-beam irradiation.

A mechanistic study of the electrochemical oxygen reduction on the model semiconductor n-Ge(100) by ATR-IR and DFT.

The electrochemical oxygen reduction reaction (ORR) on a n-Ge(100) surface in 0.1 M HClO4 was investigated in situ and operando using a combination of attenuated total reflection infrared (ATR-IR) spectroscopy and density functional (DFT) calculations. The vibrational modes of the detected intermediates were assigned based on DFT calculations of solvated model clusters such as Ge-bound superoxides and peroxides. ATR-IR shows the Ge-bound superoxide with a transition dipole moment oriented at (28 ± 10)° with respect to the surface normal. At slightly negative potentials, the surface-bound peroxide is identified by an OOH bending mode as a further intermediate, oriented at a similar angle. At strongly negative potentials, a surface-bound perchlorate is found. The findings indicate a multistep mechanism of the ORR. The reaction is furthermore coupled with the hydrogen evolution reaction (HER).

Marine sulfate-reducing bacteria cause serious corrosion of iron under electroconductive biogenic mineral crust.

Iron (Fe(0) ) corrosion in anoxic environments (e.g. inside pipelines), a process entailing considerable economic costs, is largely influenced by microorganisms, in particular sulfate-reducing bacteria (SRB). The process is characterized by formation of black crusts and metal pitting. The mechanism is usually explained by the corrosiveness of formed H(2) S, and scavenge of 'cathodic' H(2) from chemical reaction of Fe(0) with H(2) O. Here we studied peculiar marine SRB that grew lithotrophically with metallic iron as the only electron donor. They degraded up to 72% of iron coupons (10 mm × 10 mm × 1 mm) within five months, which is a technologically highly relevant corrosion rate (0.7 mm Fe(0) year(-1) ), while conventional H(2) -scavenging control strains were not corrosive. The black, hard mineral crust (FeS, FeCO(3) , Mg/CaCO(3) ) deposited on the corroding metal exhibited electrical conductivity (50 S m(-1) ). This was sufficient to explain the corrosion rate by electron flow from the metal (4Fe(0) → 4Fe(2+) + 8e(-) ) through semiconductive sulfides to the crust-colonizing cells reducing sulfate (8e(-) + SO(4) (2-) + 9H(+) → HS(-) + 4H(2) O). Hence, anaerobic microbial iron corrosion obviously bypasses H(2) rather than depends on it. SRB with such corrosive potential were revealed at naturally high numbers at a coastal marine sediment site. Iron coupons buried there were corroded and covered by the characteristic mineral crust. It is speculated that anaerobic biocorrosion is due to the promiscuous use of an ecophysiologically relevant catabolic trait for uptake of external electrons from abiotic or biotic sources in sediments.

A scanning Kelvin probe for synchrotron investigations: the in situ detection of radiation-induced potential changes.

A wide range of high-performance X-ray surface/interface characterization techniques are implemented nowadays at every synchrotron radiation source. However, these techniques are not always `non-destructive' because possible beam-induced electronic or structural changes may occur during X-ray irradiation. As these changes may be at least partially reversible, an in situ technique is required for assessing their extent. Here the integration of a scanning Kelvin probe (SKP) set-up with a synchrotron hard X-ray interface scattering instrument for the in situ detection of work function variations resulting from X-ray irradiation is reported. First results, obtained on bare sapphire and sapphire covered by a room-temperature ionic liquid, are presented. In both cases a potential change was detected, which decayed and vanished after switching off the X-ray beam. This demonstrates the usefulness of a SKP for in situ monitoring of surface/interface potentials during X-ray materials characterization experiments.

Initiation and inhibition of dealloying of single crystalline Cu3Au (111) surfaces.

Dealloying is widely utilized but is a dangerous corrosion process as well. Here we report an atomistic picture of the initial stages of electrochemical dealloying of the model system Cu(3)Au (111). We illuminate the structural and chemical changes during the early stages of dissolution up to the critical potential, using a unique combination of advanced surface-analytical tools. Scanning tunneling microscopy images indicate an interlayer exchange of topmost surface atoms during initial dealloying, while scanning Auger-electron microscopy data clearly reveal that the surface is fully covered by a continuous Au-rich layer at an early stage. Initiating below this first layer a transformation from stacking-reversed toward substrate-oriented Au surface structures is observed close to the critical potential. We further use the observed structural transitions as a reference process to evaluate the mechanistic changes induced by a thiol-based model-inhibition layer applied to suppress surface diffusion. The initial ultrathin Au layer is stabilized with the intermediate island morphology completely suppressed, along an anodic shift of the breakdown potential. Thiol-modification induces a peculiar surface microstructure in the form of microcracks exhibiting a nanoporous core. On the basis of the presented atomic-scale observations, an interlayer exchange mechanism next to pure surface diffusion becomes obvious which may be controlling the layer thickness and its later change in orientation.

Integrated scanning Kelvin probe-scanning electrochemical microscope system: development and first applications.

The integration of a scanning Kelvin probe (SKP) and a scanning electrochemical microscope (SECM) into a single SKP-SECM setup, the concept of the proposed system, its technical realization, and first applications are presented and discussed in detail. A preloaded piezo actuator placed in a grounded stainless steel case was used as the driving mechanism for oscillation of a Pt disk electrode as conventionally used in SECM when the system was operated in the SKP mode. Thus, the same tip is recording the contact potential difference (CPD) during SKP scanning and is used as a working electrode for SECM imaging in the redox-competition mode (RC-SECM). The detection of the local CPD is established by amplification of the displacement current at an ultralow noise operational amplifier and its compensation by application of a variable backing potential (V(b)) in the external circuit. The control of the tip-to-sample distance is performed by applying an additional alternating voltage with a much lower frequency than the oscillation frequency of the Kelvin probe. The main advantage of the SKP-SECM system is that it allows constant distance measurements of the CPD in air under ambient conditions and in the redox-competition mode of the SECM in the electrolyte of choice over the same sample area without replacement of the sample or exchange of the working electrode. The performance of the system was evaluated using a test sample made by sputtering thin Pt and W films on an oxidized silicon wafer. The obtained values of the CPD correlate well with known data, and the electrochemical activity for oxygen reduction is as expected higher over Pt than W.

Iron corrosion by novel anaerobic microorganisms.

Corrosion of iron presents a serious economic problem. Whereas aerobic corrosion is a chemical process, anaerobic corrosion is frequently linked to the activity of sulphate-reducing bacteria (SRB). SRB are supposed to act upon iron primarily by produced hydrogen sulphide as a corrosive agent and by consumption of 'cathodic hydrogen' formed on iron in contact with water. Among SRB, Desulfovibrio species--with their capacity to consume hydrogen effectively--are conventionally regarded as the main culprits of anaerobic corrosion; however, the underlying mechanisms are complex and insufficiently understood. Here we describe novel marine, corrosive types of SRB obtained via an isolation approach with metallic iron as the only electron donor. In particular, a Desulfobacterium-like isolate reduced sulphate with metallic iron much faster than conventional hydrogen-scavenging Desulfovibrio species, suggesting that the novel surface-attached cell type obtained electrons from metallic iron in a more direct manner than via free hydrogen. Similarly, a newly isolated Methanobacterium-like archaeon produced methane with iron faster than do known hydrogen-using methanogens, again suggesting a more direct access to electrons from iron than via hydrogen consumption.

A new advanced experimental setup for in-depth study of the interfacial reaction during reactive wetting.

Reactive wetting plays a crucial role in many technical processes, from soldering in microelectronics, production of metal/ceramic composites, to hot dip galvanizing in mass production of zinc coated steel sheet. In all these cases the wetting behavior of metal melts on different surfaces plays a crucial role in material joining and coating. In all these processes the formation of the interfacial reaction layer has to occur within as short a time as possible in order to ensure a fast overall production speed. As the interfacial layer determines the stability of the formed composites, detailed knowledge of its growth mechanisms is required for a directed process optimization. However, the investigation of the processes occurring at the buried interface between substrate and wetting phase is difficult, especially for the case of liquid metal wetting metallic or ceramic solid substrates at high temperatures. Here, a novel advanced technique for the investigation of high temperature wetting processes up to a temperature of 1100 K is presented. It is based on the sessile drop technique but, in addition, allows spinning off the droplet at any chosen wetting time, thus providing direct access to the interfacial reaction layer. Since the experimental setup is integrated into a UHV compatible reaction chamber, not only excellent control of the composition of the atmosphere is ensured, but also direct transfer to surface analytical tools such as scanning electron microscope or electron spectroscopy for chemical analysis without intermediate exposure to air is realized. As will be shown for the case of hot dip galvanising of steel, this is an outstanding advance compared to existing methods.

Combinatorial electrochemistry on Al-Fe alloys.

Combinatorial material development was combined with high throughput microelectrochemistry to allow an efficient but comprehensive investigation of the interface chemistry of Al rich Al-Fe alloys as a function of their chemical composition. Composition spread thin films with a linear composition gradient were produced by thermal codeposition. A scanning droplet cell was used to determine the open circuit potential and to perform successive anodic oxide formation with intermittent impedance spectroscopy. The film formation factor, the relative permittivity of the oxides and the onset potential of oxide formation were determined quantitatively as function of the composition with a resolution of 0.5 at.%. An unexpected synergistic effect is found in a very narrow composition range between 9 and 12 at.% Fe. This effect, which shifts the onset potential by nearly 1 V, is discussed in terms of a local accumulation of Fe resulting in a redox stabilisation of space charge layer formation during high-field oxide growth. The results are supported by composition and depth dependent XPS measurements.

Solvent-starved conditions in confinement cause chemical oscillations excited by passage of a cathodic delamination front.

After passage of a delamination front at a polymer/zinc interface, pH oscillations and oscillations in the quantity of corrosion products are observed. The reason for these oscillations is the low quantity of water in the confined reaction volume, water consumption by oxygen reduction, and water regeneration after precipitation of ZnO.

Selective microbial electrosynthesis of methane by a pure culture of a marine lithoautotrophic archaeon.

Reduction of carbon dioxide to methane by microorganisms attached to electrodes is a promising process in terms of renewable energy storage strategies. However the efficient and specific electrosynthesis of methane by methanogenic archaea on cathodes needs fundamental investigations of the electron transfer mechanisms at the microbe-electrode interface without the addition of artificial electron mediators. Using well-defined electrochemical techniques directly coupled to gas chromatography and surface analysis by scanning electron microscopy, it is shown that a pure culture of the marine lithoautotrophic Methanobacterium-like archaeon strain IM1 is capable to utilize electrons from graphite cathodes for a highly selective production of methane, without hydrogen serving as a cathode-generated electron carrier. Microbial electrosynthesis of methane with cultures of strain IM1 is achieved at a set potential of -0.4V vs. SHE and is characterized by a coulomb efficiency of 80%, with rates reaching 350 nmol d(-1) cm(-2) after 23 days of incubation. Moreover, potential step measurements reveal a biologically catalyzed hydrogen production at potentials more positive than abiotic hydrogen evolution on graphite, indicating that an excessive supply of electrons to strain IM1 results in proton reduction rather than in a further increase of methane production.

Straight talk with... Martin Stratmann.

The 83 institutes and research facilities of the Max Planck Society, established in 1948, include some of the world's leading scholars in the life sciences, including 17 Noble Prize winners, and publish 15,000 research papers annually. For the past 18 years, biologists have stood at the helm of the prestigious German organization. But last month, an electrochemist and materials scientist, Martin Stratmann, began a six-year term as president of the Munich-based society.Stratmann, who is 60, served as the director of the Max Planck Institute for Iron Research in Düsseldorf since 2000, where he helped develop self-healing coatings that can protect steels and other metals from rust. Stratmann spoke with David Levine about his vision for the Max Planck Society and about what the change of guard will mean for biomedical research. The conversation has been edited for clarity.

Frequency-dependent alternating-current scanning electrochemical microscopy (4D AC-SECM) for local visualisation of corrosion sites.

For a better understanding of the initiation of localised corrosion, there is a need for analytical tools that are capable of imaging corrosion pits and precursor sites with high spatial resolution and sensitivity. The lateral electrochemical contrast in alternating-current scanning electrochemical microscopy (AC-SECM) has been found to be highly dependent on the frequency of the applied alternating voltage. In order to be able to obtain data with optimum contrast and high resolution, the AC frequency is swept in a full spectrum at each point in space instead of performing spatially resolved measurements at one fixed perturbation frequency. In doing so, four-dimensional data sets are acquired (4D AC-SECM). Here, we describe the instrument set-up and modus operandi, along with the first results from the imaging of corroding surfaces. Corrosion precursor sites and local defects in protective organic coatings, as well as an actively corroding pit on 304 stainless steel, have been successfully visualised. Since the lateral electrochemical contrast in these images varies with the perturbation frequency, the proposed approach constitutes an indispensable tool for obtaining optimum electrochemical contrast.

Molecular layering of fluorinated ionic liquids at a charged sapphire (0001) surface.

Room-temperature ionic liquids (RTILs) are promising candidates for a broad range of "green" applications, for which their interaction with solid surfaces plays a crucial role. In this high-energy x-ray reflectivity study, the temperature-dependent structures of three ionic liquids with the tris(pentafluoroethyl)trifluorophosphate anion in contact with a charged sapphire substrate were investigated with submolecular resolution. All three RTILs show strong interfacial layering, starting with a cation layer at the substrate and decaying exponentially into the bulk liquid. The observed decay length and layering period point to an interfacial ordering mechanism, akin to the charge inversion effect, which is suggested to originate from strong correlations between the unscreened ions. The observed layering is expected to be a generic feature of RTILs at charged interfaces.