A Salt-Templated Synthesis Method for Porous Platinum-based Macrobeams and Macrotubes.

The synthesis of high surface area porous noble metal nanomaterials generally relies on time consuming coalescence of pre-formed nanoparticles, followed by rinsing and supercritical drying steps, often resulting in mechanically fragile materials. Here, a method to synthesize nanostructured porous platinum-based macrotubes and macrobeams with a square cross section from insoluble salt needle templates is presented. The combination of oppositely charged platinum, palladium, and copper square planar ions results in the rapid formation of insoluble salt needles. Depending on the stoichiometric ratio of metal ions present in the salt-template and the choice of chemical reducing agent, either macrotubes or macrobeams form with a porous nanostructure comprised of either fused nanoparticles or nanofibrils. Elemental composition of the macrotubes and macrobeams, determined with x-ray diffractometry and x-ray photoelectron spectroscopy, is controlled by the stoichiometric ratio of metal ions present in the salt-template. Macrotubes and macrobeams may be pressed into free standing films, and the electrochemically active surface area is determined with electrochemical impedance spectroscopy and cyclic voltammetry. This synthesis method demonstrates a simple, relatively fast approach to achieve high-surface area platinum-based macrotubes and macrobeams with tunable nanostructure and elemental composition that may be pressed into free-standing films with no required binding materials.

In Situ Optical and Stress Characterization of Alloyed PdxAu1-x Hydrides.

PdxAu1-x alloys have recently shown great promise for next-generation optical hydrogen sensors due to their increased chemical durability while their optical sensitivity to small amounts of hydrogen gas is maintained. However, the correlation between chemical composition and the dynamic optical behavior upon hydrogenation/dehydrogenation is currently not well understood. A complete understanding of this relation is necessary to optimize future sensors and nanophotonic devices. Here, we quantify the dynamic optical, chemical, and mechanical properties of thin film PdxAu1-x alloys as they are exposed to H2 by combining in situ ellipsometry with gravimetric and stress measurements. We demonstrate the dynamic optical property dependence of the film upon hydrogenation and directly correlate it with the hydrogen content up to a maximum of 7 bar of H2. With this measurement, we find that the thin films exhibit their strongest optical sensitivity to H2 in the near-infrared. We also discover higher hydrogen-loading amounts as compared to previous measurements for alloys with low atomic percent Pd. Specifically, a measurable optical and gravimetric hydrogen response in alloys as low as 34% Pd is found, when previous works have suggested a disappearance of this response near 55% Pd. This result suggests that differences in film stress and microstructuring play a crucial role in the sorption behavior. We directly measure the thin film stress and morphology upon hydrogenation and show that the alloys have a substantially higher relative stress change than pure Pd, with the pure Pd data point falling 0.9 GPa below the expected trend line. Finally, we use the measured optical properties to illustrate the applicability of these alloys as grating structures and as a planar physical encryption scheme, where we show significant and variable changes in reflectivity upon hydrogenation. These results lay the foundation for the composition and design of next-generation hydrogen sensors and tunable photonic devices.

Photodeposition of Pd onto Colloidal Au Nanorods by Surface Plasmon Excitation.

A protocol is described to photocatalytically guide Pd deposition onto Au nanorods (AuNR) using surface plasmon resonance (SPR). Excited plasmonic hot electrons upon SPR irradiation drive reductive deposition of Pd on colloidal AuNR in the presence of [PdCl4]2-. Plasmon-driven reduction of secondary metals potentiates covalent, sub-wavelength deposition at targeted locations coinciding with electric field "hot-spots" of the plasmonic substrate using an external field (e.g., laser). The process described herein details a solution-phase deposition of a catalytically-active noble metal (Pd) from a transition metal halide salt (H2PdCl4) onto aqueously-suspended, anisotropic plasmonic structures (AuNR). The solution-phase process is amenable to making other bimetallic architectures. Transmission UV-vis monitoring of the photochemical reaction, coupled with ex situ XPS and statistical TEM analysis, provide immediate experimental feedback to evaluate properties of the bimetallic structures as they evolve during the photocatalytic reaction. Resonant plasmon irradiation of AuNR in the presence of [PdCl4]2- creates a thin, covalently-bound Pd0 shell without any significant dampening effect on its plasmonic behavior in this representative experiment/batch. Overall, plasmonic photodeposition offers an alternative route for high-volume, economical synthesis of optoelectronic materials with sub-5 nm features (e.g., heterometallic photocatalysts or optoelectronic interconnects).

Structure-Property-Performance Relationship of Ultrathin Pd-Au Alloy Catalyst Layers for Low-Temperature Ethanol Oxidation in Alkaline Media.

Pd-containing alloys are promising materials for catalysis. Yet, the relationship of the structure-property performance strongly depends on their chemical composition, which is currently not fully resolved. Herein, we present a physical vapor deposition methodology for developing PdxAu1-x alloys with fine control over the chemical composition. We establish direct correlations between the composition and these materials' structural and electronic properties with its catalytic activity in an ethanol (EtOH) oxidation reaction. By combining X-ray diffraction (XRD) and X-ray photelectron spectroscopy (XPS) measurements, we validate that the Pd content within both bulk and surface compositions can be finely controlled in an ultrathin-film regime. Catalytic oxidation of EtOH on the PdxAu1-x electrodes presents the largest forward-sweeping current density for x = 0.73 at ∼135 mA cm-2, with the lowest onset potential and largest peak activity of 639 A gPd-1 observed for x = 0.58. Density functional theory (DFT) calculations and XPS measurements demonstrate that the valence band of the alloys is completely dominated by Pd particularly near the Fermi level, regardless of its chemical composition. Moreover, DFT provides key insights into the PdxAu1-x ligand effect, with relevant chemisorption activity descriptors probed for a large number of surface arrangements. These results demonstrate that alloys can outperform pure metals in catalytic processes, with fine control of the chemical composition being a powerful tuning knob for the electronic properties and, therefore, the catalytic activity of ultrathin PdxAu1-x catalysts. Our high-throughput experimental methodology, in connection with DFT calculations, provides a unique foundation for further materials' discovery, including machine-learning predictions for novel alloys, the development of Pd-alloyed membranes for the purification of reformate gases, binder-free ultrathin electrocatalysts for fuel cells, and room temperature lithography-based development of nanostructures for optically driven processes.

A Rapid Synthesis Method for Au, Pd, and Pt Aerogels Via Direct Solution-Based Reduction.

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various precursor noble metal ions with reducing agents in a 1:1 (v/v) ratio results in the formation of metal gels within seconds to minutes compared to much longer synthesis times for other techniques such as sol-gel. Conducting the reduction step in a microcentrifuge tube or small volume conical tube facilitates a proposed nucleation, growth, densification, fusion, equilibration model for gel formation, with final gel geometry smaller than the initial reaction volume. This method takes advantage of the vigorous hydrogen gas evolution as a by-product of the reduction step, and as a consequence of reagent concentrations. The solvent accessible specific surface area is determined with both electrochemical impedance spectroscopy and cyclic voltammetry. After rinsing and freeze drying, the resulting aerogel structure is examined with scanning electron microscopy, X-ray diffractometry, and nitrogen gas adsorption. The synthesis method and characterization techniques result in a close correspondence of aerogel ligament sizes. This synthesis method for noble metal aerogels demonstrates that high specific surface area monoliths may be achieved with a rapid and direct reduction approach.

Harvesting resonantly-trapped light for small molecule oxidation reactions at the Au/α-Fe2O3 interface.

Plasmonic metal nanoparticles (NPs) extend the overall light absorption of semiconductor materials. However, it is not well understood how coupling metal NPs to semiconductors alters the photo-electrochemical activity of small molecule oxidation (SMO) reactions. Different photo-anode electrodes comprised of Au NPs and α-Fe2O3 are designed to elucidate how the coupling plays not only a role in the water oxidation reaction (WO) but also performs for different SMO reactions. In this regard, Au NPs are inserted at specific regions within and/or on α-Fe2O3 layers created with a sequential electron beam evaporation method and multiple annealing treatments. The SMO and WO reactions are probed with broad-spectrum irradiation experiments with an emphasis on light-driven enhancements above and below the α-Fe2O3 band gap. Thin films of α-Fe2O3 supported on a gold back reflective layer resonantly-traps incident light leading to enhanced SMO/WO conversion efficiencies at high overpotential (η) for above band-gap excitations with no SMO activity observed at low η. In contrast, a substantial increase in the light-driven SMO activity is observed at low η, as well as for below band-gap excitations when sufficiently thin α-Fe2O3 films are decorated with Au NPs at the solution-electrode interface. The enhanced photo-catalytic activity is correlated with increased surface oxygen content (hydroxyl groups) at the Au/α-Fe2O3 interface, as well as simulated volume-integrated near-field enhancements over select regions of the Au/α-Fe2O3 interface providing an important platform for future SMO/WO photo-electrocatalyst development.

Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst.