Owing to its earth abundance, low kinetic overpotential, and superior stability, NiFe-layered double hydroxide (NiFe-LDH) has emerged as a promising electrocatalyst for catalyzing water splitting, especially oxygen evolution reaction (OER), in alkaline solutions. Unfortunately, as a result of extremely sluggish water dissociation kinetics (Volmer step), hydrogen evolution reaction (HER) activity of the NiFe-LDH is rather poor in alkaline environment. Here a novel strategy is demonstrated for substantially accelerating the hydrogen evolution kinetics of the NiFe-LDH by partially substituting Fe atoms with Ru. In a 1 m KOH solution, the as-synthesized Ru-doped NiFe-LDH nanosheets (NiFeRu-LDH) exhibit excellent HER performance with an overpotential of 29 mV at 10 mA cm , which is much lower than those of noble metal Pt/C and reported electrocatalysts. Both experimental and theoretical results reveal that the introduction of Ru atoms into NiFe-LDH can efficiently reduce energy barrier of the Volmer step, eventually accelerating its HER kinetics. Benefitting from its outstanding HER activity and remained excellent OER activity, the NiFeRu-LDH steadily drives an alkaline electrolyzer with a current density of 10 mA cm at a cell voltage of 1.52 V, which is much lower than the values for Pt/C-Ir/C couple and state-of-the-art overall water-splitting electrocatalysts.
We have utilized DC and AC transport measurements to measure the resistance and capacitance of thin films of conjugated oligophenyleneimine (OPI) molecules ranging from 1.5 to 7.5 nm in length. These films were synthesized on Au surfaces utilizing the imine condensation chemistry between terephthalaldehyde and 1,4-benzenediamine. Near edge X-ray absorption fine structure (NEXAFS) spectroscopy yielded molecular tilt angles of 33-43°. To probe DC and AC transport, we employed Au-S-OPI//GaOx/EGaIn junctions having contact areas of 9.6 × 10(2) μm(2) (10(9) nm(2)) and compared to previously reported DC results on the same OPI system obtained using Au-S-OPI//Au conducting probe atomic force microscopy (CP-AFM) junctions with 50 nm(2) areas. We found that intensive observables agreed very well across the two junction platforms. Specifically, the EGaIn-based junctions showed: (i) a crossover from tunneling to hopping transport at molecular lengths near 4 nm; (ii) activated transport for wires >4 nm in length with an activation energy of 0.245 ± 0.008 eV for OPI-7; (iii) exponential dependence of conductance with molecular length with a decay constant β = 2.84 ± 0.18 nm(-1) (DC) and 2.92 ± 0.13 nm(-1) (AC) in the tunneling regime, and an apparent β = 1.01 ± 0.08 nm(-1) (DC) and 0.99 ± 0.11 nm(-1) (AC) in the hopping regime; (iv) previously unreported dielectric constant of 4.3 ± 0.2 along the OPI wires. However, the absolute resistances of Au-S-OPI//GaOx/EGaIn junctions were approximately 100 times higher than the corresponding CP-AFM junctions due to differences in metal-molecule contact resistances between the two platforms.
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