164 research outputs found

    Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

    Get PDF
    Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. To identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide−phosphide composite prevents catalyst dissolution in acid electrolyte. Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support

    Influence of the Water Content on the Diffusion Coefficients of Li⁺ and Water across Naphthalenic Based Copolyimide Cation-Exchange Membranes

    Get PDF
    The transport of lithium ions in cation-exchange membranes based on sulfonated copolyimide membranes is reported. Diffusion coefficients of lithium are estimated as a function of the water content in membranes by using pulsed field gradient (PFG) NMR and electrical conductivity techniques. It is found that the lithium transport slightly decreases with the diminution of water for membranes with water content lying in the range 14 < λ < 26.5, where λ is the number of molecules of water per fixed sulfonate group. For λ < 14, the value of the diffusion coefficient of lithium experiences a sharp decay with the reduction of water in the membranes. The dependence of the diffusion of lithium on the humidity of the membranes calculated from conductivity data using Nernst–Planck type equations follows a trend similar to that observed by NMR. The possible explanation of the fact that the Haven ratio is higher than the unit is discussed. The diffusion of water estimated by 1H PFG-NMR in membranes neutralized with lithium decreases as λ decreases, but the drop is sharper in the region where the decrease of the diffusion of protons of water also undergoes considerable reduction. The diffusion of lithium ions computed by full molecular dynamics is similar to that estimated by NMR. However, for membranes with medium and low concentration of water, steady state conditions are not reached in the computations and the diffusion coefficients obtained by MD simulation techniques are overestimated. The curves depicting the variation of the diffusion coefficient of water estimated by NMR and full dynamics follow parallel trends, though the values of the diffusion coefficient in the latter case are somewhat higher. The WAXS diffractograms of fully hydrated membranes exhibit the ionomer peak at q = 2.8 nm⁻1, the peak being shifted to higher q as the water content of the membranes decreases. The diffractograms present additional peaks at higher q, common to wet and dry membranes, but the peaks are better resolved in the wet membranes. The ionomer peak is not detected in the diffractograms of dry membranes.The authors acknowledge financial support provided by the DGICYT (Dirección General de Investigación Cientifíca y Tecnológica) through Grant MAT2011-29174-C02-02

    Ionic conductivity of an extruded Nafion 1100 EW series of membranes

    No full text
    The proton conductivity of a series of extruded Nafion membranes @of equivalent weight ~EW! of 1100 and nominal dry thickness of 51, 89, 127, and 178 mm# has been studied. Measurements were made in 1 M H2SO4 at 298 K using a four-electrode, dc technique. The membrane area resistance increases with thickness, as expected, from 0.07 to 0.16 V cm2 for Nafion 112 and Nafion 117, respectively. However, in contrast to the published literature, after correcting for the membrane thickness, the conductivity of the membranes decreases with decreasing membrane thickness. For example, values of 0.083 and 0.16 S cm21 were obtained for Nafion 112 and 117 membranes, respectively. In situ current-interrupt measurements in a proton exchange membrane fuel cell confirmed the relatively poor conductivity of the membrane electrode assemblies ~MEAs! based on the thinner membranes. While a high contact resistance to the electrodes may have contributed to the in situ MEA resistance, water balance measurements over the MEA showed that the high resistance was not due to a low water content or to an uneven water distribution in the MEAs. The implications of the findings for the understanding of the membrane properties are discussed
    corecore