Metal/water interfaces are key in many natural and industrial processes, such as corrosion, atmospheric, or environmental chemistry. Even today, the only practical approach to simulate large interfaces between a metal and water is to perform force-field simulations. In this work, we propose a novel force field, GAL17, to describe the interaction of water and a Pt(111) surface. GAL17 builds on three terms: (i) a standard Lennard-Jones potential for the bonding interaction between the surface and water, (ii) a Gaussian term to improve the surface corrugation, and (iii) two terms describing the angular dependence of the interaction energy. The 12 parameters of this force field are fitted against a set of 210 adsorption geometries of water on Pt(111). The performance of GAL17 is compared to several other approaches that have not been validated against extensive first-principles computations yet. Their respective accuracy is evaluated on an extended set of 802 adsorption geometries of HO on Pt(111), 52 geometries derived from icelike layers, and an MD simulation of an interface between a c(4 × 6) Pt(111) surface and a water layer of 14 Å thickness. The newly developed GAL17 force field provides a significant improvement over previously existing force fields for Pt(111)/HO interactions. Its well-balanced performance suggests that it is an ideal candidate to generate relevant geometries for the metal/water interface, paving the way to a representative sampling of the equilibrium distribution at the interface and to predict solvation free energies at the solid/liquid interface.

Proton Exchange Membrane Fuel Cells (PEMFC) are energy efficient and environmentally friendly alternatives to conventional energy conversion systems in many yet emerging applications. In order to enable prediction of their performance and durability, it is crucial to gain a deeper understanding of the relevant operation phenomena, e.g., electrochemistry, transport phenomena, thermodynamics as well as the mechanisms leading to the degradation of cell components. Achieving the goal of providing predictive tools to model PEMFC performance, durability and degradation is a challenging task requiring the development of detailed and realistic models reaching from the atomic/molecular scale over the meso scale of structures and materials up to components, stack and system level. In addition an appropriate way of coupling the different scales is required. This review provides a comprehensive overview of the state of the art in modeling of PEMFC, covering all relevant scales from atomistic up to system level as well as the coupling between these scales. Furthermore, it focuses on the modeling of PEMFC degradation mechanisms and on the coupling between performance and degradation models.

Electrocatalysts are mainly characterized by their intrinsic adsorption properties. However, the observed electrocatalytic activity ultimately results from the interplay between such properties and various additional interactions within the electrified solid-liquid interface. One of such phenomena is solvation, which can substantially affect the stability of adsorbates. The incorporation of solvation in computational electrocatalysis models can be fully implicit (inaccurate for H-bonded adsorbates), fully explicit (challenging computation of free energies), or embedded. Here we show that without any need for explicit or implicit media, a micro-solvation approach with just 3 water molecules captures the contribution of coadsorbed water to the adsorption energies of *OH and *OOH (two important adsorbates for oxygen reduction) on platinum nanoparticles of various sizes. The approach enables an accurate yet inexpensive explicit modeling of solvent-adsorbate interactions in nanoparticles, and the calculation of solvation corrections, estimated as 0.59 0.14 eV − ± and 0.47 0.13 eV − ± for *OH and *OOH adsorption on Pt.

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Abstract. Solvation can substantially modify the adsorption properties of heterogeneous catalysts. Although essential for achieving realistic theoretical models, assessing such solvent effects over nanoparticles is challenging from a computational standpoint due to the complexity of those liquid/metal interfaces. We investigate this effect by ab initio moleculardynamics simulations at 350 K of a large platinum nanoparticle immersed in liquid water. The first solvation layer contains twice as much physisorbed water molecules above the terraces, than chemisorbed ones located only at edges and corners. The solvent stabilizes the binding energy of chemisorbates: 66 % of the total gain comes from interactions with physisorbed molecules and 34 % from the influence of bulk liquid.

In this paper we discuss a comprehensive physical-based model of the PEMFC materials degradation allowing predicting the MEA durability as function of the operation conditions, initial material loadings and electrodes microstructure. The approach, build within a modular multiscale non-equilibrium thermodynamics framework, couples atomistic-based descriptions of catalyst contamination/oxidation/dissolution/ripening, dissolved catalyst migration in the ionomer, C catalyst-support corrosion and chemical PEM degradation, with the degradation-induced nano/microstructural and transport properties (of reactants and charges) evolution. By describing the feedback between the instantaneous performance and the material aging phenomena, the model provides new insights on the competition between the different degradation processes under automotive-operating conditions. The predictive capabilities of our approach are illustrated in this paper through four applicative examples: 1) PtxCoy catalysts degradation 2) competition of PEM and cathode C degradation 3) synergies between anodic CO contamination and PEM and cathode C degradation, and 4) synergies between Pt and C degradation.

Understanding the selectivity of the oxygen reduction reaction, especially the formation of water versus hydrogen peroxide in fuel cells, is an ongoing challenge in electrochemistry, surface science and catalysis. In this study, we propose a comprehensive thermodynamic analysis of the reaction intermediates for the formation of water on Pt(111). Density functional theory calculations of all the elementary steps linking hydroxyl and hydroperoxyl surface species with water and hydrogen peroxide have been performed at low (1/12 ML, ML = monolayer) and high (1/4 ML) coverages. The reaction energy variation for the two competing elementary events (molecular oxygen dissociation and hydroperoxyl formation) is strongly coverage-dependent. For the direct dissociation, an increase is observed at low coverage with respect to the usual high coverage picture. The stability of the reaction intermediates is investigated from thermodynamic diagrams. At 353 K and a total pressure of 1 atm, water and hydroxyl surface species are expected to compete for adsorption on Pt(111).

International audiencePredicting the reaction mechanism of water and hydrogen peroxide formation on a platinum catalyst is a crucial step toward the understanding of the corresponding selectivity in polymer electrolyte membrane fuel cells. In this perspective, the environment of the catalytic active site should play an important role; however, its explicit description at the atomic scale is an ongoing challenge for theoretical approaches. In this study, we propose to model three effects of the environment: surface hydroxyl coverage, temperature, and reactant pressure. A detailed investigation of the reaction mechanism of water and hydrogen peroxide formation on a platinum surface is reported on the basis of density functional theory (DFT) calculations and Gibbs free energy diagrams. In standard conditions of reaction (1 atm and 353 K), the selectivity toward water and hydrogen peroxide depends on the competition between two reaction paths (molecular oxygen direct dissociation and hydrogenation), which can be tuned by the partial coverage of OH intermediate. At a low coverage of 1/12 ML, the catalyst activity is expected to be low due to a preferential but activated direct oxygen dissociation. When the OH partial coverage increases, the hydroperoxyl route becomes favorable, hence leading to hydroxyl and water by the nonactivated OOH dismutation. The direct oxygen dissociation and the whole reaction mechanism are sensitive to the hydroxyl partial coverage. Our gas/metal model opens the way to new elementary mechanisms in the presence of aqueous electrolyte and electric field that would explain how water can be produced at the beginning of the reaction (at low coverage)