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      Nanoporous Iridium Nanosheets for Polymer Electrolyte Membrane Electrolysis

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          Abstract

          The growth of the hydrogen economy is predicated on advancements in electrochemical energy technologies, with water electrolysis as a key component to the technological portfolio. Much of the focus on anode catalyst development for polymer electrolyte membrane water electrolyzers (PEMWE) is centered on activity as controlled by compositional and morphological impacts on reactant/intermediate/product adsorption. However, the effectiveness of this strategy is found to be limited upon integration of these materials into PEMWE membrane electrode assemblies (MEA). Regardless of catalyst activity, the combination of electrode inhomogeneity, ionomer integration, and high density of oxide–oxide interfaces yields significant performance losses associated with poor catalytic electrode conductivity. Here many of these limitations are addressed through the development of a unique catalyst morphology composed of nanoporous Ir nanosheets (npIr x ‐NS) that exhibit high catalytic activity for the anodic oxygen evolution reaction and superior electrode electronic conductivity in comparison to a commercial IrO 2 nanoparticle catalyst. The utility of the npIr x ‐NS is demonstrated through incorporation into PEMWE MEAs where their performance exceeds that of commercial catalyst coated membranes at loadings as low as 0.06 mg Ir cm −2 while exhibiting a negligible loss in performance following 50 000 accelerated stress test cycles.

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          A highly active and stable IrO x /SrIrO 3 catalyst for the oxygen evolution reaction

          Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrOx/SrIrO3) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO3 This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidic electrolyte. Density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO3 or anatase IrO2 motifs. The IrOx/SrIrO3 catalyst outperforms known IrOx and ruthenium oxide (RuOx) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte.
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            Evolution of nanoporosity in dealloying.

            Dealloying is a common corrosion process during which an alloy is 'parted' by the selective dissolution of the most electrochemically active of its elements. This process results in the formation of a nanoporous sponge composed almost entirely of the more noble alloy constituents. Although considerable attention has been devoted to the morphological aspects of the dealloying process, its underlying physical mechanism has remained unclear. Here we propose a continuum model that is fully consistent with experiments and theoretical simulations of alloy dissolution, and demonstrate that nanoporosity in metals is due to an intrinsic dynamical pattern formation process. That is, pores form because the more noble atoms are chemically driven to aggregate into two-dimensional clusters by a phase separation process (spinodal decomposition) at the solid-electrolyte interface, and the surface area continuously increases owing to etching. Together, these processes evolve porosity with a characteristic length scale predicted by our continuum model. We expect that chemically tailored nanoporous gold made by dealloying Ag-Au should be suitable for sensor applications, particularly in a biomaterials context.
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              Irena: tool suite for modeling and analysis of small-angle scattering

              Irena, a tool suite for analysis of both X-ray and neutron small-angle scattering (SAS) data within the commercialIgor Proapplication, brings together a comprehensive suite of tools useful for investigations in materials science, physics, chemistry, polymer science and other fields. In addition to Guinier and Porod fits, the suite combines a variety of advanced SAS data evaluation tools for the modeling of size distribution in the dilute limit using maximum entropy and other methods, dilute limit small-angle scattering from multiple non-interacting populations of scatterers, the pair-distance distribution function, a unified fit, the Debye–Bueche model, the reflectivity (X-ray and neutron) using Parratt's formalism, and small-angle diffraction. There are also a number of support tools, such as a data import/export tool supporting a broad sampling of common data formats, a data modification tool, a presentation-quality graphics tool optimized for small-angle scattering data, and a neutron and X-ray scattering contrast calculator. These tools are brought together into one suite with consistent interfaces and functionality. The suite allows robust automated note recording and saving of parameters during export.
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                Author and article information

                Contributors
                (View ORCID Profile)
                Journal
                Advanced Energy Materials
                Advanced Energy Materials
                Wiley
                1614-6832
                1614-6840
                September 2021
                July 21 2021
                September 2021
                : 11
                : 34
                Affiliations
                [1 ] Department of Chemical and Biological Engineering Drexel University Philadelphia PA 19104 USA
                [2 ] Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
                [3 ] Chemical Science Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
                [4 ] Chemical Sciences and Engineering Division Argonne National Laboratory Lemont IL 60439 USA
                Article
                10.1002/aenm.202101438
                391cb440-859f-441b-b87f-1148d506e8ec
                © 2021

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