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The density of Nafion membranes wetted in water and acetonitrile and the solubility of Nafion in a 50:50 ethanol/water mixture are reported. Commercially available membranes, solution recast membranes, and recast membranes thermally processed for varying lengths of time were examined. Unheated recast membranes were found to be ∼20% less dense in water than both commercial membranes and recast membranes heated at 140 °C for 40, 50, and 60 min. For heating times of ≥40 min, the density of recast membranes in water was invariant and equal to the density of commercial films. Similarly, in acetonitrile, commercial membranes and films heated for 1 h had the same density; unheated recast films were ∼25% less dense. Nafion density in acetonitrile was ∼15% less than that in water. Acid pretreatment reduced Nafion film density by ∼15%. Unheated recast films were 22-100% soluble in a sonicated ethanol/water mixture. Commercial membranes and recast films heated for as little as 10 min were insoluble under the same conditions.

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Metal phosphides from the 3d period exhibit a range of structures and compositions. Many metal-rich phosphides and monophosphides function as heterogeneous electrocatalysts in the hydrogen evolution reaction. This paper describes the direct and tin flux-assisted synthesis of phosphorus-rich metal phosphides with MP2 or MP3 compositions. The facile synthesis of FeP2, CoP3, NiP2, and CuP2 is thermochemically driven by PCl3 formation from reactions of anhydrous metal halides and P4 vapor at 500 °C. Well-crystallized micrometer-sized particles result from these solvent-free reactions. A tin flux leads to more complete reactions at lower temperature for FeP2 and enables synthesis of a monoclinic polymorph of NiP2 rather than the kinetic cubic product formed by direct reaction. These crystalline metal phosphides are investigated as electrocatalyts for hydrogen evolution in acidic and buffered aqueous solutions. All phosphorus-rich products show very good stability in strongly acidic media. The catalytic activity for hydrogen evolution ordered by higher current at a fixed electrode geometric area and low onset potential is CoP3 > NiP2 (cubic and monoclinic) > FeP2 ≫ CuP2. At high applied potentials, CuP2 undergoes surface reactions and roughening that improve its electrocatalytic activity. Correlations of the observed electrocatalytic activity with electrochemically active surface area, particle size, metallic versus semiconducting properties, and local metal coordination environment are noted for these phosphorus-rich 3d metal phosphides.

Given common methods of preparing inlaid microdisk electrodes, shield thicknesses are often comparable to disk radii. Equations appropriate to characterizing the steady state, cyclic voltammetric response for microdisks embedded in in6nite insulating planes poorly approximate the steady state response at these electrodes because, on the time scale to achieve steady state, diffusion around the shield from behind the plane of the electrode contributions to the flux. A finite difference simulation with a nonuniform, expanding spatial grid is presented for reversible electrode kinetics over a range of scan rates s a c i e n t to follow the transition from linear to radial diffusion, including flux around the edge of the shield. The voltammetric response is influenced critically by shield thickness and electrode radius; a method is proposed and veritied experimentally to determine radius and shield thickness. The equations for infinitely thick insulators underestimate the current at a thinly shielded microdisk by 549%. Generation of a nonuniform, expanding grid is presented.Microelectrodes have become a major tool for studying nonstandard electrochemical systems. Solutions without added frozen solutions,6 and gas phase environments7-12 ' Present address: American Cyanamid,Dibble, T.; Bandyopadhyay, S.; Ghoroghchian, J.; Smith, J. J.; Sarfarazi, F.; (2) Cassidy, J.; Khoo, S. B.; Pons, S.; Fleischmann, M. J. Phys. Chem. 1985, (3) Bond, A M.; Lay, P. A.

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