Christopher J. DeSantis

Octopods versus Concave Nanocrystals: Control of Morphology by Manipulating the Kinetics of Seeded Growth via Co-Reduction

Au/Pd octopods and concave core@shell Au@Pd nanocrystals have been prepared by coupling for the first time a seed-mediated synthetic method with co-reduction. The integration of these two methods is central to the formation of these binary Au/Pd nanocrystals wherein the kinetics of seeded growth are manipulated via the co-reduction technique to control the final morphology of the nanocrystals. Significantly, the synthesis of these structures under similar reaction conditions illustrates that they are structurally related kinetic products. Detailed characterization by STEM-EDX analysis highlights the unique structural features of these nanocrystals and indicates that Pd localizes on the higher-energy features of the nanocrystals. Optical and electrocatalytic characterization also demonstrates their promise as a new class of multifunctional nanostructures.

Seed-Mediated Co-reduction: A Versatile Route to Architecturally Controlled Bimetallic Nanostructures

Gold-palladium octopods and new concave and shape-controlled alloy nanostructures are synthesized by seed-mediated co-reduction, wherein two metal precursors are reduced in the presence of seeds that serve as preferential sites for the growth of the larger nanostructures. Here, the first comprehensive study of this technique is presented in a model Au-Pd system and provides insight into the mechanism of formation for these architecturally distinct nanocrystals. A systematic evaluation of synthesis conditions decoupled the roles of (i) Au:Pd precursor ratio, (ii) reaction pH, and (iii) capping agent concentration in morphology development. These factors provide control of growth kinetics and ultimately the morphology and composition of the final nanostructures. Significantly, elucidating the overgrowth processes during seed-mediated co-reduction will lead to the synthesis of other architecturally controlled bimetallic nanocrystals.

Core Values: Elucidating the Role of Seed Structure in the Synthesis of Symmetrically Branched Nanocrystals

Branched metal nanoparticles often display unique physicochemical properties on account of their structures; however, most examples are asymmetric, with branches randomly distributed from the cores of the nanoparticles. This asymmetry can give rise to variable properties between samples. Here, we report the synthesis of symmetrically branched Au/Pd nanocrystals including five-branched pentapods with D(3h) symmetry, 24-branched nanocrystals with O(h) symmetry, 12-branched nanocrystals with T(d) symmetry, and eight-branched octopods and bowties with O(h) and D(4h) symmetry, respectively. These structures are achieved by seed-mediated co-reduction wherein the shapes of the seeds direct the number and symmetry patterns of the branches. Compositional boundaries exist at the interfaces between the seed and overgrowth metals to provide visualization via advanced electron microscopy of the relationships between seed structure and the symmetry of branched nanocrystals. Significantly, seed structure plays a definitive role in determining the final shape of convex metal nanocrystals, and the results presented here illustrate a similar relationship for branched nanocrystals and will enable the design of new architecturally distinct nanostructures.

Size-controlled synthesis of Au/Pd octopods with high refractive index sensitivity.

Au/Pd octopods, nanostructures with eight branches and a primarily Au interior, have been synthesized as size-controlled samples through the manipulation of seed-mediated co-reduction. The position of their localized surface plasmon resonance can be controllably tuned throughout the visible and near-infrared regions, and this response is correlated with the structural features (branch length and tip width) of the octopods. These Au/Pd octopods were also found to be highly sensitive to changes in the local refractive index of the surrounding media and suitable substrates for surface enhanced Raman spectroscopy. These findings, coupled with their unique composition, highlight the multifunctional capabilities of the Au/Pd octopods and provide insight into the optical properties of architecturally controlled bimetallic nanostructures.

Diffusion and Seed Shape: Intertwined Parameters in the Synthesis of Branched Metal Nanostructures

Branched nanocrystals display interesting optical and catalytic properties on account of their high surface areas and tips with small radii of curvatures. However, many synthetic routes toward branched nanocrystals result in inhomogeneous samples on account of asymmetric branching. Seed-mediated coreduction is a recently developed route to symmetrically branched nanocrystals where the symmetry of the seeds is transferred to the final stellated morphologies. Here, general guidelines to stellated nanocrystals are outlined by surveying coreduction of Au and Pd precursors in the presence of a variety of shape-controlled Au seeds to achieve Au/Pd nanostructures. Single-crystalline, twinned, and anisotropic seeds were analyzed to expand the classes of stellated nanostructures synthetically accessible. Significantly, single-crystalline Au seeds adopt {100}-terminated intermediates prior to branching, regardless of initial seed shape. We compared these results with those obtained with shape-controlled Pd seeds, and seed composition was identified as an important synthetic parameter, with Pd seeds being more resistant to shape changes during overgrowth. This difference is attributed to the greater diffusion rate of Au atoms on Au seeds compared to Au atoms on Pd seeds. These results provide guidelines for the seeded synthesis of symmetrically branched nanocrystals and architecturally defined bimetallic nanostructures in general.

Resonances of nanoparticles with poor plasmonic metal tips

The catalytic and optical properties of metal nanoparticles can be combined to create platforms for light-driven chemical energy storage and enhanced in-situ reaction monitoring. However, the heavily damped plasmon resonances of many catalytically active metals (e.g. Pt, Pd) prevent this dual functionality in pure nanostructures. The addition of catalytic metals at the surface of efficient plasmonic particles thus presents a unique opportunity if the resonances can be conserved after coating. Here, nanometer resolution electron-based techniques (electron energy loss, cathodoluminescence, and energy dispersive X-ray spectroscopy) are used to show that Au particles incorporating a catalytically active but heavily damped metal, Pd, sustain multiple size-dependent localized surface plasmon resonances (LSPRs) that are narrow and strongly localized at the Pd-rich tips. The resonances also couple with a dielectric substrate and other nanoparticles, establishing that the full range of plasmonic behavior is observed in these multifunctional nanostructures despite the presence of Pd.

Hot Hole Photoelectrochemistry on Au@SiO2@Au Nanoparticles

There is currently a worldwide need to develop efficient photocatalytic materials that can reduce the high-energy cost of common industrial chemical processes. One possible solution focuses on metallic nanoparticles (NPs) that can act as efficient absorbers of light due to their surface plasmon resonance. Recent work indicates that small NPs, when photoexcited, may allow for efficient electron or hole transfer necessary for photocatalysis. Here we investigate the mechanisms behind hot hole carrier dynamics by studying the photodriven oxidation of citrate ions on Au@SiO2@Au core-shell NPs. We find that charge transfer to adsorbed molecules is most efficient at higher photon energies but still present with lower plasmon energy. On the basis of these experimental results, we develop a simple theoretical model for the probability of hot carrier-adsorbate interactions across the NP surface. These results provide a foundation for understanding charge transfer in plasmonic photocatalytic materials, which could allow for further design and optimization of photocatalytic processes.

Shaping the Synthesis and Assembly of Symmetrically Stellated Au/Pd Nanocrystals with Aromatic Additives

Au/Pd octopods were synthesized with enhanced sample homogeneity through the use of aromatic additives. This increase in sample monodispersity facilitates large-area periodic assembly of stellated metal nanostructures for the first time. The aromatic additives were also found to influence the structures of the stellated nanocrystals with subtle shape modifications observed that can alter the packing arrangement of the Au/Pd octopods. These results indicate the possibility of tailored assembly of stellated nanostructures, which would be useful for optical applications that require strong and predictable coupling between plasmonic building blocks.

Imaging through plasmonic nanoparticles

Significance How is an image transmitted through a material consisting of subwavelength structures? We use two distinct methods to obtain quantitative answers to that question. The first, structural similarity index, is a method related to human perception, initially developed to quantify transmitted image quality following image compression in digital image transmission systems. The second method treats the medium as an optical component itself, where we determine the spatial frequency content of the image transmitted by the medium. This study opens the door to analyzing images transmitted through particulate media that absorb and/or scatter light, which applies generally to imaging systems whose components are composed of subwavelength structures, such as those composed of random particulates or nanoengineered flat-optics metasurface lenses. The optical properties of metallic nanoparticles with plasmon resonances have been studied extensively, typically by measuring the transmission of light, as a function of wavelength, through a nanoparticle suspension. One question that has not yet been addressed, however, is how an image is transmitted through such a suspension of absorber-scatterers, in other words, how the various spatial frequencies are attenuated as they pass through the nanoparticle host medium. Here, we examine how the optical properties of a suspension of plasmonic nanoparticles affect the transmitted image. We use two distinct ways to assess transmitted image quality: the structural similarity index (SSIM), a perceptual distortion metric based on the human visual system, and the modulation transfer function (MTF), which assesses the resolvable spatial frequencies. We show that perceived image quality, as well as spatial resolution, are both dependent on the scattering and absorption cross-sections of the constituent nanoparticles. Surprisingly, we observe a nonlinear dependence of image quality on optical density by varying optical path length and nanoparticle concentration. This work is a first step toward understanding the requirements for visualizing and resolving objects through media consisting of subwavelength absorber-scatterer structures, an approach that should also prove useful in the assessment of metamaterial or metasurface-based optical imaging systems.

Plasmon and compositional mapping of plasmonic nanostructures

Recently, co-reduction of Au and Pd has allowed the synthesis of complex Au core/AuPd shell nanoparticles with elongated tips and cubic-like symmetry. Optical studies have shown strong plasmonic behavior and high refractive index sensitivities. In this paper, we describe the composition and the near-field plasmonic behavior of those complex structures. Monochromated STEM-EELS, Cathodoluminescence, and EDS mapping reveals the different resonant modes in these particles, and shows that Pd, a poor plasmonic metal, does not prevent strong resonances and could actually be extremely helpful for plasmon-enhanced catalysis.