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The electrochemical promotion of the C(2)H(4)+O(2) reaction to form CO(2) and H(2)O is studied in the 10(-5) and 10(-4) mbar range with a Pt catalyst interfaced as working electrode to yttrium-stabilized zirconia (YSZ). Photoemission electron microscopy (PEEM) was used as spatially resolving method. Under open-circuit conditions, that is, without an external voltage applied, the CO(2) production exhibits a pronounced hysteresis upon cyclic variation of p(C(2)H(4)). The hysteresis is attributed to the build-up of a carbonaceous CH(x) layer inhibiting O(2) adsorption and hence poisoning the reaction. It is shown that the application of a positive potential of 1 V triggers a transition from the unreactive branch of the reaction to an active branch. The large non-Faradayicity reported in the literature for this reaction system is explained as an ignition effect caused by the partial removal of the inhibiting carbonaceaous layer.

The electrochemical promotion of catalytic C(2)H(4) oxidation has been investigated under low pressure conditions (p approximately 10(-6)-10(-4) mbar) with a Pt film on yttrium stabilized zirconia (YSZ) as catalyst. All measurements were conducted with a UHV system with a differentially pumped quadruple mass spectrometer (QMS) for rate measurements and a photoelectron emission microscope (PEEM) for spatially resolved measurements. A pronounced rate hysteresis upon cyclic variation of p(C(2)H(4)) was observed under open circuit conditions which is attributed to carbonaceous CH(x) adlayer inhibiting O(2) adsorption and hence poisoning the reaction. Application of a positive potential causes a partial removal of the inhibiting CH(x) adlayer by spillover oxygen thus triggering a transition from thus poisoned state of the surface to an active state with reduced carbon coverage. The ignition effect and therefore also the electrochemical promotion effect are linked to the presence of a carbon adlayer on the surface. The non-Faradayicity which is observed in this reaction system is explained as an ignition effect.

SummaryMicrobial biosynthesis of metal nanoparticles as needed in catalysis has shown its theoretical ability as an extremely environmentally friendly production method in the last few years, even though the separation of the nanoparticles is challenging. Biosynthesis, summing up biosorption and bioreduction of diluted metal ions to zero valent metals, is especially ecofriendly, when the bioreactor itself is harmless and needs no further harmful reagents. The cyanobacterium Anabaena cylindrica (SAG 1403.2) is able to form crystalline Au0-nanoparticles from Au3+ ions and does not release toxic anatoxin-a. X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and laser-induced breakdown spectroscopy (LIBS) are applied to monitor the time-dependent development of gold nanoparticles for up to 40 hours. Some vegetative cells (VC) are filled with nanoparticles within minutes, while the extracellular polymeric substances (EPS) of vegetative cells and the heterocyst polysaccharide layer (HEP) are the regions, where the first nanoparticles are detected on most other cells. The uptake of gold starts immediately after incubation and within four hours the average size remains constant around 10 nm. Analyzing the TEM images with an image processing program reveals a wide distribution for the diameter of the nanoparticles at all times and in all regions of the cyanobacteria. Finally, the nanoparticle concentration in vegetative cells of Anabaena cylindrica is about 50% higher than in heterocysts (HC). These nanoparticles are found to be located along the thylakoid membranes.