In the present work we investigated the electrochemical behavior of PVA on polycrystalline Pt and single-crystal Pt electrodes. PVA hampered the characteristic hydrogen UPD and anion adsorption on all investigated surfaces, with the processes on Pt(110) being the most affected by the PVA presence. Several oxidation waves appeared as the potential was swept in the positive direction and the Pt(111) was found to be the most active for the oxidation processes.The study of the interaction of polymers with metallic surfaces is of pivotal importance not only from the fundamental point of view (e.g.: hydrogen UPD on single crystals in the presence of surface blocking species), 1 but also from the applied one since polymers are widely employed as stabilizing agents in the production of nanoparticles. 2 Poly(vinyl alcohol) (PVA) is a water-soluble hydrophilic polymer and has been employed in different applications. 3 It reacts with metal salts in aqueous solution leading to a metal chelate, being then usually selected as an ion and cluster capping agent to prevent excessive nanoparticle growth. 4-8 The mechanism of protection involves donation of the -OH lone electron pairs to the metals and prevention of aggregation through steric effect. Although this mechanism is generally accepted, the literature completely lacks information on the interaction between PVA and metal surfaces. It is well known that adsorption is not only affected by the electronic properties of the surface but also by its structure (crystallographic orientation). As an example, Morin and Conway 9 found the chemisorption and surface reactivity behavior of acetonitrile at distinct Pt single crystal planes to be very specific to the geometry of the surface. The understanding of molecular adsorption at well-ordered single crystal surfaces may enable, in principle, the production of preferentially oriented nanoparticles. 10 In this work we studied, for the first time, the electrochemical behavior of PVA at well-ordered single crystal as well as polycrystalline Pt surfaces in H 2 SO 4 solution. We show that PVA not only behaves distinctly on different oriented surfaces, but also suffer oxidation to some extent.
ExperimentalThe polycrystalline Pt and the single crystals, Pt(111), Pt (110) and Pt(100) disks (10 mm in diameter and 2 mm thick) were purchased from MaTeck and polished to a mirror-like finish with 0.05 lm alumina. Before each experiment, the electrode surface was treated in the following way: the working electrode was flame annealed in a hydrogen flame for 2 min, cooled down to room temperature under Ar þ H 2 atmosphere and then protected with a drop of water in equilibrium with this gas mixture to avoid contamination. The electrode was then quickly inserted at 0.05 V vs. reversible hydrogen electrode (RHE) into the electrochemical cell and a meniscus was formed with the deaerated 0.1 M H 2 SO 4 (prepared with 18.2 MX cm Milipore/Milli-Q water and Alfa Aesar sulphuric acid) supporting electrolyte. Solutions containing 1% w/w PVA (Aldrich Co; MW: $50...