Platinum and Palladium Overlayers Dramatically Enhance the Activity of Ruthenium Nanotubes for Alkaline Hydrogen Oxidation

Templated vapor synthesis and thermal annealing were used to synthesize unsupported metallic Ru nanotubes with Pt or Pd overlayers. By controlling the elemental composition and thickness of these overlayers, we obtain nanostructures with very high alkaline hydrogen oxidation activity. Nanotubes with a nominal atomic composition of Ru_0.90Pt_0.10 display a surface-specific activity (2.4 mA/cm²) that is 35 times greater than that of pure Ru nanotubes at a 50 mV overpotential and ∼2.5 times greater than that of pure Pt nanotubes (0.98 mA/cm²). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specific activity of 1240 A/g_Pt for the optimized nanotube versus 280 A/g_Pt for carbon-supported Pt nanoparticles and 109 A/g_Pt for monometallic Pt nanotubes. We attribute the enhancement of both area- and platinum-mass-specific activity to the atomic-scale homeomorphism of the nanotube form factor with adlayer-modified polycrystals. In this case, subsurface ligand and bifunctional effects previously observed on segregated, adlayer-modified polycrystals are translated to nanoscale catalysts

Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte

High-surface-area ruthenium-based Ru_<i>x</i>M_<i>y</i> (M = Pt or Pd) alloy catalysts supported on carbon black were synthesized to investigate the hydrogen oxidation reaction (HOR) in alkaline electrolytes. The exchange current density for hydrogen oxidation on a Pt-rich Ru_0.20Pt_0.80 catalyst is 1.42 mA/cm², nearly 3 times that of Pt (0.490 mA/cm²). Furthermore, Ru_<i>x</i>Pt_<i>y</i> alloy surfaces in 0.1 M KOH yield a Tafel slope of ∼30 mV/dec, in contrast with the ∼125 mV/dec Tafel slope observed for supported Pt, signifying that hydrogen dissociative adsorption is rate-limiting rather than charge-transfer processes. Ru alloying with Pd does not result in modified kinetics. We attribute these disparate results to the interplay of bifunctional and ligand effects. The dependence of the rate-determining step on the choice of alloy element allows for tuning catalyst activity and suggests not only that a low-cost, alkaline anode catalyst is possible but also that it is tantalizingly close to reality

3D Nanoprinting via laser-assisted electron beam induced deposition: growth kinetics, enhanced purity, and electrical resistivity

We investigate the growth, purity, grain structure/morphology, and electrical resistivity of 3D platinum nanowires synthesized via electron beam induced deposition with and without an in situ pulsed laser assist process which photothermally couples to the growing Pt–C deposits. Notably, we demonstrate: 1) higher platinum concentration and a coalescence of the otherwise Pt–C nanogranular material, 2) a slight enhancement in the deposit resolution and 3) a 100-fold improvement in the conductivity of suspended nanowires grown with the in situ photothermal assist process, while retaining a high degree of shape fidelity

Nanoscale Imaging of Fundamental Li Battery Chemistry: Solid-Electrolyte Interphase Formation and Preferential Growth of Lithium Metal Nanoclusters

The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase (SEI) formation and to track Li nucleation and growth mechanisms from a standard organic battery electrolyte (LiPF₆ in EC:DMC), we used in situ electrochemical scanning transmission electron microscopy (ec-S/TEM) to perform controlled electrochemical potential sweep measurements while simultaneously imaging site-specific structures resulting from electrochemical reactions. A combined quantitative electrochemical measurement and STEM imaging approach is used to demonstrate that chemically sensitive annular dark field STEM imaging can be used to estimate the density of the evolving SEI and to identify Li-containing phases formed in the liquid cell. We report that the SEI is approximately twice as dense as the electrolyte as determined from imaging and electron scattering theory. We also observe site-specific locations where Li nucleates and grows on the surface and edge of the glassy carbon electrode. Lastly, this report demonstrates the investigative power of quantitative nanoscale imaging combined with electrochemical measurements for studying fluid–solid interfaces and their evolving chemistries

Influence of Dioxygen on the Promotional Effect of Bi during Pt-Catalyzed Oxidation of 1,6-Hexanediol

A series of carbon-supported, Bi-promoted Pt catalysts with various Bi/Pt atomic ratios was prepared by selectively depositing Bi on Pt nanoparticles. The catalysts were evaluated for 1,6-hexanediol oxidation activity in aqueous solvent under different dioxygen pressures. The rate of diol oxidation on the basis of Pt loading over a Bi-promoted catalyst was 3 times faster than that of an unpromoted Pt catalyst under 0.02 MPa of O₂, whereas the unpromoted catalyst was more active than the promoted catalyst under 1 MPa of O₂. After liquid-phase catalyst pretreatment and 1,6-hexanediol oxidation, migration of Bi on the carbon support was observed. The reaction order in O₂ was 0 over Bi-promoted Pt/C in comparison to 0.75 over unpromoted Pt/C in the range of 0.02–0.2 MPa of O₂. Under low O₂ pressure, rate measurements in D₂O instead of H₂O solvent revealed a moderate kinetic isotope effect (rate_H₂O/rate_D₂O) on 1,6-hexanediol oxidation over Pt/C (KIE = 1.4), whereas a negligible effect was observed on Bi-Pt/C (KIE = 0.9), indicating that the promotional effect of Bi could be related to the formation of surface hydroxyl groups from the reaction of dioxygen and water. No significant change in product distribution or catalyst stability was observed with Bi promotion, regardless of the dioxygen pressure