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#Pt top 100 models full#
The effect leads to a clear preference for on-top adsorption in the electrolyte even at low CO coverage and over the full potential range studied.Price ranges vary widely thanks to the high number of different projects, which themselves vary in size and scope, offered by freelancers on Fiverr. This change in site preference as a function of particle size is attributed to stronger on-top adsorption on low-coordinated Pt atoms of small Pt NPs. For the smallest particles (10-20 atoms) we do not detect any bridge-bonded CO. For the Pt NPs, the situation is different and an increasing fraction of on-top CO is observed with decreasing particle size, both under EC conditions and in UHV. This effect is attributed to the competitive adsorption of anions from the electrolyte and leads to a clear preference for bridge sites at higher potentials (>0.5 VRHE). In sharp contrast, on-top adsorption of CO on Pt(111) is partially suppressed under EC conditions. In UHV, adsorption at on-top sites is preferred on Pt(111) at low coverage and similar adsorption ratios of on-top and bridge-bonded CO are formed at saturation coverage. Further pronounced differences are observed between the spectra taken in UHV and in the electrolyte regarding the site occupation and its dependence on particle size.
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The CO IR bands of the Pt NPs are even broader (by a factor of 5), which is attributed to local variations of the interfacial electric field at the NP surface. Besides the red-shift induced by the interfacial electric field (Stark effect), the EC IR bands of CO on Pt(111) show a larger width (by a factor of 2) as a result of local variations in the CO environment and coupling to the electrolyte. Characteristic differences were observed between the IR spectra under EC conditions and in UHV. Under EC conditions, we performed equivalent experiments using EC infrared reflection absorption spectroscopy (EC-IRRAS) in combination with cyclic voltammetry (CV). In UHV, we also investigated the adsorption of CO using infrared reflection absorption spectroscopy (IRRAS). As a reference, we study Pt(111) under identical conditions. By X-ray photoelectron spectroscopy (XPS) we show that the model surfaces are stable in the EC environment under the applied conditions (0.1 to 1 M phosphate buffer, pH 10, 0.33 to 1.03 VRHE). The model systems were characterized in UHV using surface science methods including scanning tunnelling microscopy (STM), before transferring them out of the UHV and into the electrolyte without contact to ambient conditions. The model catalysts were prepared in UHV by physical vapour deposition (PVD) of Pt onto an ordered Co3O4(111) film on Ir(100), yielding nanoparticles (NPs) with an average size from 10 to 500 atoms per particle (0.8 to 3 nm). We have studied particle size effects on atomically-defined model catalysts both in ultrahigh vacuum (UHV) and under electrochemical (EC) conditions in liquid electrolytes.