Anastasios P. Angelopoulos

International projects study the safety aspects of the storage and long-distance transportation of liquid hydrogen at large scales. Catalytic recombiners, which are today key elements of hydrogen risk mitigation in nuclear power plants, could become an efficient safety device to prevent flammable gas mixtures after liquid hydrogen leakages in closed rooms. This study tackles fundamental questions about the operational behavior of typical recombiner catalysts related to the conditions of the start-up and the termination of the catalytic reaction. For this purpose, small-scale catalyst sheets with coatings containing either platinum or palladium as active materials were exposed to gas mixtures of air and hydrogen of up to 4 vol.% at temperatures between −50 °C and 20 °C. Both platinum and palladium showed variation to performance and had stochastic results. Overall, the initialized platinum catalyst was better than the palladium. The experimental results show that the transfer of the recombiner technology from its current application is not easily possible.

The promotion of the electrocatalytic ethanol oxidation reaction (EOR) on extended single-crystal Pt surfaces and dispersed Pt nanoparticles by Sn under acidic conditions is well known. However, the correlation of Sn coverage on Pt nanoparticle electrocatalysts to their size has proven difficult. The reason is that previous investigations have typically relied on commercially difficult to reproduce electrochemical treatments of prepared macroscopic electrodes to adsorb Sn onto exposed Pt surfaces. We demonstrate here how independent control over both Sn coverage and particle size can yield a significant enhancement in EOR activity in an acidic electrolyte relative to previously reported electrocatalysts. Our novel approach uses electroless nanoparticle synthesis where surface-adsorbed Sn is intrinsic to Pt particle formation. Sn serves as both a reducing agent and stabilizing ligand, producing particles with a narrow particle size distribution in a size range where the mass-specific electrocatalytic activity can be maximized (ca. 1–4 nm) as a result of the formation of a fully developed Sn shell. The extent of fractional Sn surface coverage on carbon-supported Pt nanoparticles can be systematically varied through wet-chemical treatment subsequent to nanoparticle formation but prior to incorporation into macroscopic electrodes. EOR activity for Pt nanoparticles is found to be optimum at a fractional Sn surface coverage of ca. 0.6. Furthermore, the EOR activity is shown to increase with Pt particle size and correlate with the active area of available Pt (110) surface sites for the corresponding Sn-free nanoparticles. The maximum area- and mass-specific EOR activities for the most active catalyst investigated were 17.9 μA/cm²_Pt and 12.5 A/g_Pt, respectively, after 1 h of use at 0.42 V versus RHE in an acidic electrolyte. Such activity is a substantial improvement over that of commercially available Pt, Pt–Sn, and Pt–Ru alloy catalysts under either acidic or alkaline conditions.

The size-tunable structure and properties of Pt nanoparticles at the atomic length scale have attracted significant attention across a wide variety of fields including magnetics, electrocatalysis, optics, and gas-phase synthesis. Mechanisms responsible for the formation Pt nanoparticles remain unclear because of the difficulty generating in situ data for the time-evolution of size, shape, distribution, volume fraction, particle number density, and oxidation state from the starting complexes. We here demonstrate the use of simultaneous small- and wide-angle X-ray scattering combined with UV-vis spectroscopy to measure these key synthesis metrics for the reduction of Pt(IV) by Sn(II) in aqueous solution. This synthesis approach has been previously shown to permit continuous control over Pt nanoparticle size from 0.9 to 2.6 nm to within 10% standard deviation. Such fine control led to the discovery of densely packed amorphous structures at ca. 1.7 nm with substantially enhanced electrocatalytic oxygen reduction relative to nanocrystals and commercial electrocatalysts. Ex situ UV-vis and in situ X-ray scattering are here shown to reveal four distinct stages during synthesis: (1) autoreduction of a ligand/noble metal complex with a unique structure that depends on the Sn(II)/Pt(II) ratio, (2) generation of Pt primary particles and the formation of Pt nuclei at a rate that depends on the structure of the initial complex, (3) nanoparticle growth via LaMer's diffusion of these primary particles to the nuclei, and (4) growth termination due to capping from a stabilizing, two-layer ligand shell. We derive a set of consecutive rate equations and associated kinetic parameters that describe each step. The kinetics of ligand rearrangement has been previously found to limit the rate of nanoparticle growth. We incorporate this phenomenon into LaMer's classic diffusion-limited growth scheme to extend it to the nanoscale regime. This new model provides detailed understanding of how metal ligands serve as both reducing and stabilizing agents and allow for unprecedented, continuous control over both size and distribution. Systematic variation of temperature permits detailed time resolution at the very onset of Pt primary particle formation, as well as a means to determine temperature sensitivity of nanoparticle growth.

A SnCl2SnCl2 shell on Pt metal core nanoparticle synthesis technique has recently been demonstrated to permit electrostatic layer-by-layer (LbL) assembly of well-ordered electrocatalysts without precipitation onto porous carbon supports. In this paper, the electrocatalytic activity of the LbL-assembled Pt nanoparticles is shown to depend critically upon removal of surface-adsorbed Sn (Snads)(Snads) . By subjecting the synthesized Pt nanoparticle electrodes to potential sweeps greater than 1.0 V vs reversible hydrogen electrode, SnadsSnads are removed and a nearly threefold enhancement in oxygen reduction reaction (ORR) specific activity over commercial catalysts is obtained. In contrast to this electrochemical acceleration approach, we also investigate electroless, wet-acceleration methods for SnadsSnads removal. Energy-dispersive spectroscopy and inductively coupled plasma-mass spectrometry are used to quantify the Pt/Sn ratio in the electrode assemblies as a function of immersion time in solution (both alkaline and acidic) and during electrochemical acceleration, respectively. Charging current for the underpotential deposition of protons on the Pt nanoparticle surface is used to monitor the removal of SnadsSnads during electrochemical acceleration, followed by ORR activity measurement in saturated perchloric acid (HClO4)(HClO4) . Wet-chemical acceleration in NaOH solution is found to remove similar amounts of Sn as compared to the electrochemical technique.

Layer‐by‐layer (LBL) assembly of carbon nanoparticles for low electrical contact resistance thin film applications is demonstrated. The nanoparticles consist of irregularly shaped graphite platelets, with acrylamide/ββ‐methacryl‐oxyethyl‐trimethyl‐ammonium copolymer as the cationic binder. Nanoparticle zeta (ζζ) potential and thereby electrostatic interactions are varied by altering the pH of graphite suspension as well as that of the binder suspension. Film thickness as a function of zeta potential, immersion time, and the number of layers deposited is obtained using Monte Carlo simulation of the energy dispersive spectroscopy measurements. Multilayer film surface morphology is visualized via field‐emission scanning electron microscopy and atomic‐force microscopy. Thin film electrical properties are characterized using electrical contact resistance measurements. Graphite nanoparticles are found to self‐assemble onto gold substrates through two distinct yet overlapping mechanisms. The first mechanism is characterized by logarithmic carbon uptake with respect to the number of deposition cycles and slow clustering of nanoparticles on the gold surface. The second mechanism results from more rapid LBL nanoparticle assembly and is characterized by linear weight uptake with respect to the number of deposition cycles and a constant bilayer thickness of 15 to 21 nm. Thin‐film electrical contact resistance is found to be proportional to the thickness after equilibration of the bilayer structure. Measured values range from 1.6 mΩ cm⁻² at 173 nm to 3.5 mΩ cm⁻² at 276 nm. Coating volume resistivity is reduced when electrostatic interactions are enhanced during LBL assembly.