Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy.

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis.

Single-Particle Insights into Plasmonic Hot Carrier Separation Augmenting Photoelectrochemical Ethanol Oxidation with Photocatalytically Synthesized Pd-Au Bimetallic Nanorods.

Understanding the nature of hot carrier pathways following surface plasmon excitation of heterometallic nanostructures and their mechanistic prevalence during photoelectrochemical oxidation of complex hydrocarbons, such as ethanol, remains challenging. This work studies the fate of carriers from Au nanorods before and after the presence of reductively photodeposited Pd at the single-particle level using scattering and emission spectroscopy, along with ensemble photoelectrochemical methods. A sub-2 nm epitaxial Pd0 shell was reductively grown onto colloidal Au nanorods via hot carriers generated from surface plasmon resonance excitation in the presence of [PdCl4]2-. These bimetallic Pd-Au nanorod architectures exhibited 14% quenched emission quantum yields and 9% augmented plasmon damping determined from their scattering spectra compared to the bare Au nanorods, consistent with injection/separation of intraband hot carriers into the Pd. Absorbed photon-to-current efficiency in photoelectrochemical ethanol oxidation was enhanced 50× from 0.00034% to 0.017% due to the photodeposited Pd. Photocurrent during ethanol oxidation improved 13× under solar-simulated AM1.5G and 40× for surface plasmon resonance-targeted irradiation conditions after photodepositing Pd, consistent with enhanced participation of intraband-excited sp-band holes and desorption of ethanol oxidation reaction intermediates owing to photothermal effects.

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.

Synthesis, Characterization, and Antimicrobial Efficacy of Photomicrobicidal Cellulose Paper.

Toward our goal of scalable, antimicrobial materials based on photodynamic inactivation, paper sheets comprised of photosensitizer-conjugated cellulose fibers were prepared using porphyrin and BODIPY photosensitizers, and characterized by spectroscopic (infrared, UV-vis diffuse reflectance, inductively coupled plasma optical emission) and physical (gel permeation chromatography, elemental, and thermal gravimetric analyses) methods. Antibacterial efficacy was evaluated against Staphylococcus aureus (ATCC-2913), vancomycin-resistant Enterococcus faecium (ATCC-2320), Acinetobacter baumannii (ATCC-19606), Pseudomonas aeruginosa (ATCC-9027), and Klebsiella pneumoniae (ATCC-2146). Our best results were achieved with a cationic porphyrin-paper conjugate, Por((+))-paper, with inactivation upon illumination (30 min, 65 ± 5 mW/cm(2), 400-700 nm) of all bacterial strains studied by 99.99+% (4 log units), regardless of taxonomic classification. Por((+))-paper also inactivated dengue-1 virus (>99.995%), influenza A (∼ 99.5%), and human adenovirus-5 (∼ 99%). These results demonstrate the potential of cellulose materials to serve as scalable scaffolds for anti-infective or self-sterilizing materials against both bacteria and viruses when employing a photodynamic inactivation mode of action.