The interaction between an adsorbed 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMP][TFSA], ionic liquid (IL) layer and a Ag(111) substrate, under ultrahigh-vacuum conditions, was investigated in a combined experimental and theoretical approach, by high-resolution scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and dispersion-corrected density functional theory calculations (DFT-D). Most importantly, we succeeded in unambiguously identifying cations and anions in the adlayer by comparing experimental images with submolecular resolution and simulated STM images based on DFT calculations, and these findings are in perfect agreement with the 1:1 ratio of anions and cations adsorbed on the metal derived from XPS measurements. Different adlayer phases include a mobile 2D liquid phase at room temperature and two 2D solid phases at around 100 K, i.e., a 2D glass phase with short-range order and some residual, but very limited mobility and a long-range ordered 2D crystalline phase. The mobility in the different adlayer phases, including melting of the 2D crystalline phase, was evaluated by dynamic STM imaging. The DFT-D calculations show that the interaction with the substrate is composed of mainly van der Waals and weak electrostatic (dipole-induced dipole) interactions and that upon adsorption most of the charge remains at the IL, leading to attractive electrostatic interactions between the adsorbed species.

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SummaryIn order to resolve substrate effects on the adlayer structure and structure formation and on the substrate–adsorbate and adsorbate–adsorbate interactions, we investigated the adsorption of thin films of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium-bis(trifluoromethylsulfonyl)imide [BMP][TFSA] on the close-packed Ag(111) and Au(111) surfaces by scanning tunneling microscopy, under ultra high vacuum (UHV) conditions in the temperature range between about 100 K and 293 K. At room temperature, highly mobile 2D liquid adsorbate phases were observed on both surfaces. At low temperatures, around 100 K, different adsorbed IL phases were found to coexist on these surfaces, both on silver and gold: a long-range ordered (‘2D crystalline’) phase and a short-range ordered (‘2D glass’) phase. Both phases exhibit different characteristics on the two surfaces. On Au(111), the surface reconstruction plays a major role in the structure formation of the 2D crystalline phase. In combination with recent density functional theory calculations, the sub-molecularly resolved STM images allow to clearly discriminate between the [BMP]+ cation and [TFSA]− anion.

Membrane electrode assemblies were degraded by voltage cycling in hydrogen/air atmosphere. The impact of degradation on fuel cell performance was measured by various electrochemical characterization techniques. Loss of electrochemically active surface area was correlated to kinetic voltage losses at low current density as well as losses at high current density due to oxygen transport limitations. It was found that the oxygen transport resistance scales proportionally to the inverse of normalized platinum surface area. The change in the catalyst layer structural properties due to voltage cycling was visualized by electron microscopy. A new method of calculating changes in platinum loading of degraded samples by transmission electron microscopy is presented and shows redistribution of platinum in the catalyst layer due to platinum dissolution.

Catalyst degradation in membrane electrode assemblies was studied by voltage cycling in hydrogen/air atmosphere. The loss of electrochemically active surface area (ECSA) was quantified by cyclic voltammetry. The influence of cycle duration and dwell time during square wave voltage cycling on catalyst degradation was investigated, as well as the effect of scan rate on ECSA loss during triangular wave voltage cycling. Degradation rates per voltage cycle increased with longer cycle duration and lower scan rate, while degradation rates normalized to operating time were approximately constant over a wide range of cycle lengths and scan rates. The results suggest that the formation of a (sub-)surface oxide layer and cathodic dissolution are important processes in the platinum dissolution mechanism.