Noble metal nanoparticles are capable of confining resonant photons in such a manner as to induce coherent surface plasmon oscillation of their conduction band electrons, a phenomenon leading to two important properties. Firstly, the confinement of the photon to the nanoparticle's dimensions leads to a large increase in its electromagnetic field and consequently great enhancement of all the nanoparticle's radiative properties, such as absorption and scattering. Moreover, by confining the photon's wavelength to the nanoparticle's small dimensions, there exists enhanced imaging resolving powers, which extend well below the diffraction limit, a property of considerable importance in potential device applications. Secondly, the strongly absorbed light by the nanoparticles is followed by a rapid dephasing of the coherent electron motion in tandem with an equally rapid energy transfer to the lattice, a process integral to the technologically relevant photothermal properties of plasmonic nanoparticles. Of all the possible nanoparticle shapes, gold nanorods are especially intriguing as they offer strong plasmonic fields while exhibiting excellent tunability and biocompatibility. We begin this review of gold nanorods by summarizing their radiative and nonradiative properties. Their various synthetic methods are then outlined with an emphasis on the seed-mediated chemical growth. In particular, we describe nanorod spontaneous self-assembly, chemically driven assembly, and polymer-based alignment. The final section details current studies aimed at applications in the biological and biomedical fields.

The reduction of 4-nitrophenol to 4-aminophenol by borohydride is one of the foremost model catalytic reactions because it allows for a straightforward assessment of catalysts using the kinetic parameters extracted from the real-time spectroscopic monitoring of an aqueous solution. Crucial to its standing as a model reaction is a comprehensive mechanistic framework able to explain the entire time evolution of the reaction. While much of this framework is in place, there is still much debate over the cause of the induction period, an initial time interval where no reaction seemingly occurs. Here, we report on the simultaneous monitoring of the spectroscopic signal and the dissolved oxygen content within the aqueous solution. It reveals that the induction period is the time interval required for the level of dissolved oxygen to fall below a critical value that is dependent upon whether Au, Ag, or Pd nanoparticles are used as the catalyst. With this understanding, we are able to exert complete control over the induction period, being able to eliminate it, extend it indefinitely, or even induce multiple induction periods over the course of a single reaction. Moreover, we have determined that the reaction product, 4-aminophenol, in the presence of the same catalyst reacts with dissolved oxygen to form 4-nitrophenolate. The implication of these results is that the induction period relates, not to some activation of the catalyst, but to a time interval where the reaction product is being rapidly transformed back into a reactant by a side reaction.

Ligands are the quintessential synthesis tool in the preparation of colloidal metal catalysts, allowing for the rational design of nanostructured surfaces with high activity and selectivity. These same agents can, however, strongly influence the catalytic performance of metal nanostructures in aqueous media. In this regard, the current literature describing the influence of ligands on the model catalytic reaction that sees 4-nitrophenol reduced to 4-aminophenol by borohydride is highly fragmented in that the understanding of reaction rate, induction time, and ligand desorption phenomena is disconnected and, at times, contradictory. Herein, we present a study in which three chemically distinct ligands are applied to bare gold catalysts followed by their exposure to aqueous solutions of relevance to 4-nitrophenol reduction while simultaneously tracking the ligand whereabouts. It is shown that the exposure of ligands to borohydride leads to their near-complete removal from the gold catalyst. This, in turn, gives rise to severe disruptions to the rate of 4-nitrophenol reduction for the scenario where the aqueous reactants are purged of dissolved oxygen and ligand desorption times are slow. In sharp contrast, the reaction rate is little affected when the same reactants contain dissolved oxygen because the resulting induction period provides ample time for the ligands to desorb prior to the onset of the reaction. Moreover, strongly bound ligands are shown to give rise to an induction-time-like feature that is only observable when the reactants are free of dissolved oxygen. Collectively, these findings advocate procedures for catalytic benchmarking that differ from current best practices and underscore the point that a fundamental understanding of 4-nitrophenol catalysis must adopt a holistic approach that accounts for ligand–nanostructure interdependencies.

The seed-mediated growth of noble metal nanostructures with planar geometries requires the use of seeds lined with parallel stacking faults so as to provide a break in symmetry in an otherwise isotropic metal. Although such seeds are now routinely synthesized using colloidal pathways, equivalent pathways have not yet been reported for the fabrication of substrate-based seeds with the same internal defect structures. The challenge is not merely to form seeds with planar defects but to do so in a deterministic manner so as to have stacking faults that only run parallel to the substrate surface while still allowing for the lithographic processes needed to regulate the placement of seeds. Here, we demonstrate substrate-imposed epitaxy as a viable synthetic control able to induce planar defects in Au seeds while simultaneously dictating nanostructure in-plane alignment and crystallographic orientation. The seeds, which are formed in periodic arrays using nanoimprint lithography in combination with a vapor-phase assembly process, are subjected to a liquid-phase plasmon-mediated synthesis that uses light as an external stimuli to drive a reaction yielding periodic arrays of hexagonal Au nanoplates. These achievements not only represent the first of their kind demonstrations but also advance the possibility of integrating wafer-based technologies with a rich and exciting nanoplate colloidal chemistry.

One of the foremost challenges in nanofabrication is the establishment of a processing science that integrates wafer-based materials, techniques, and devices with the extraordinary physicochemical properties accessible when materials are reduced to nanoscale dimensions. Such a merger would allow for exacting controls on nanostructure positioning, promote cooperative phenomenon between adjacent nanostructures and/or substrate materials, and allow for electrical contact to individual or groups of nanostructures. With neither self-assembly nor top-down lithographic processes being able to adequately meet this challenge, advancements have often relied on a hybrid strategy that utilizes lithographically-defined features to direct the assembly of nanostructures into organized patterns. While these so-called directed assembly techniques have proven viable, much of this effort has focused on the assembly of periodic arrays of spherical or near-spherical nanostructures comprised of a single element. Work directed toward the fabrication of more complex nanostructures, while still at a nascent stage, has nevertheless demonstrated the possibility of forming arrays of nanocubes, nanorods, nanoprisms, nanoshells, nanocages, nanoframes, core-shell structures, Janus structures, and various alloys on the substrate surface. In this topical review, we describe the progress made in the directed assembly of periodic arrays of these complex metal nanostructures on planar and textured substrates. The review is divided into three broad strategies reliant on: (i) the deterministic positioning of colloidal structures, (ii) the reorganization of deposited metal films at elevated temperatures, and (iii) liquid-phase chemistry practiced directly on the substrate surface. These strategies collectively utilize a broad range of techniques including capillary assembly, microcontact printing, chemical surface modulation, templated dewetting, nanoimprint lithography, and dip-pen nanolithography and employ a wide scope of chemical processes including redox reactions, alloying, dealloying, phase separation, galvanic replacement, preferential etching, template-mediated reactions, and facet-selective capping agents. Taken together, they highlight the diverse toolset available when fabricating organized surfaces of substrate-supported nanostructures.

Solid state dewetting of ultrathin films is the most straightforward means of fabricating substrate-supported noble metal nanostructures. This assembly process is, however, quite inflexible, yielding either densely packed smaller structures or widely spaced larger structures. Here, we demonstrate the utility of introducing a sacrificial antimony layer between the substrate and noble metal overlayer. We observe an agglomeration process which is radically altered by the concurrent sublimation of antimony. In stark contrast with conventional dewetting, where the thickness of the deposited metal film determines the characteristic length scales of the assembly process, it is the thickness of the sacrificial antimony layer which dictates both the nanoparticle size and interparticle spacing. The result is a far more flexible self-assembly process where the nanoparticle size and areal density can be varied widely. Demonstrations show nanoparticle areal densities which are varied over four orders of magnitude assembled from the identical gold layer thickness, where the accompanying changes to nanostructure size see a systematic shift in the wavelength of the localized surface plasmon resonance. As a pliable self-assembly process, it offers the opportunity to tailor the properties of an ensemble of nanostructures to meet the needs of specific applications.

We report on the rapid optical detection of gaseous hydrogen using hot electrons generated from resonantly excited substrate-based gold nanohemispheres (Au NHs). We consider hot electron induced H2 dissociation and the subsequent formation of a metastable gold hydride (AuHx) to account for changes in optical transmission. The excitation wavelength was varied to demonstrate a maximum response at the localized surface plasmon resonance (LSPR) wavelength of the AuNHs. Numerical simulations, using the discrete dipole approximation, were employed to corroborate the optical changes associated with the formation of metastable AuHx. Finite time difference domain (FDTD) calculations were also performed to account for the enhanced photocatalytic activity arising due to the confinement of electric fields by the Au NHs. FDTD simulations show that the excitation of the Au NHs plasmon modes generates stronger electric fields at the interface in comparison to a spherical geometry of similar dimensions.

We report on the heterogeneous nucleation of Ag on Au seeds using a surfactant-free synthesis where nanoparticle aggregation is nullified through the immobilization of bare Au seeds on the surface of a substrate. Requiring only silver nitrate, ascorbic acid, and Au seeds, the synthesis is facile and, from a mechanistic standpoint, far less convoluted than conventional protocols. The results reveal that, even in the absence of surfactants, highly anisotropic growth modes are achieved which result in a lone Ag structure emanating from a single (100) Au facet. Consistent with surfactant-based protocols is the ability to vary the product of the reaction by varying the reaction rate. It allows for kinetic control which is able to direct the reaction toward either a bimetallic heterodimer or a core-shell configuration. The observed growth modes cannot be explained in terms of those proposed for surfactant-based growth modes where surfactants, surface diffusion, and/or collision patterns are used to rationalize the reaction product. We, instead, propose a growth mode reliant on the formation of a space charge region around each seed consisting of a double layer of ions, where the integrity of the layer is dependent upon the facets expressed by the seed, the rate at which the reduced ions are being deposited, and the pH of the solution. Our work reveals the rich nature of surfactant-free heteroepitaxial growth modes as well as the utility of the substrate-based platform in defining growth pathways.