Orientation and morphology control in acid-catalyzed covalent organic framework thin films.

As thin films of semiconducting covalent organic frameworks (COFs) are demonstrating utility for ambipolar electronics, channel materials in organic electrochemical transistors (OECTs), and broadband photodetectors, control and modulation of their thin film properties is paramount. In this work, an interfacial growth technique is utilized to synthesize imine TAPB-PDA COF films at both the liquid-liquid interface as well as at the liquid-solid interface on a Si/SiO2 substrate. The concentration of acetic acid catalyst in the aqueous phase is shown to significantly influence the thin film morphology of the liquid-solid growth, with concentrations below 1 M resulting in no film nucleation, concentrations of 1-4 M enabling smooth film formation, and concentrations greater than 4 M resulting in films with a higher density of particulates on the surface. Importantly, while the films grown at the liquid-liquid interface are mixed-orientation, those grown directly at the liquid-solid interface on the Si/SiO2 surface have highly oriented COF layers aligned parallel to the substrate surface. Moreover, this liquid-solid growth process affords TAPB-PDA COF thin films with p-type charge transport having a transconductance of 10 µS at a gate voltage of -0.9 V in an OECT device structure.

A Droplet-Reactor System Capable of Automation for the Continuous and Scalable Production of Noble-Metal Nanocrystals.

Noble-metal nanocrystals with well-controlled shapes or morphologies are of great interest for a variety of applications. To utilize these nanomaterials in consumer products, one has to produce the colloidal nanocrystals in large quantities while maintaining good control over their physical parameters and properties. Droplet reactors have shown great potential for the continuous and scalable production of colloidal nanocrystals with controlled shapes. However, the efficiencies of most previously reported systems are still limited because of the complex post-treatment procedures. For example, the mixture of silicone oil and an aqueous suspension of solid products has to be separated by leveraging their miscibility and difference in density, while the solid products often need to be purified and concentrated by centrifugation. Herein, we report the design and construction of a droplet-reactor system that include new features such as a homemade unit for the automatic separation of silicone oil from the aqueous phase as well as a cross-flow filtration unit for the effective purification and concentration of the nanocrystals. Using various types of Pd nanocrystals as examples, we have demonstrated the feasibility of using this system to automatically produce and collect samples with uniform sizes and well-controlled shapes.

One-Pot Synthesis of Penta-twinned Palladium Nanowires and Their Enhanced Electrocatalytic Properties.

This article reports the design and successful implementation of a one-pot, polyol method for the synthesis of penta-twinned Pd nanowires with diameters below 8 nm and aspect ratios up to 100. The key to the success of this protocol is the controlled reduction of Na2PdCl4 by diethylene glycol and ascorbic acid through the introduction of NaI and HCl. The I- and H+ ions can slow the reduction kinetics by forming PdI42- and inhibiting the dissociation of ascorbic acid, respectively. When the initial reduction rate is tuned into the proper regime, Pd decahedral seeds with a penta-twinned structure appear during nucleation. In the presence of I- ions as a selective capping agent toward the Pd(100) surface, the decahedral seeds can be directed to grow axially into penta-twinned nanorods and then nanowires. The Pd nanowires are found to evolve into multiply twinned particles if the reaction time is extended beyond 1.5 h, owing to the involvement of oxidative etching. When supported on carbon, the Pd nanowires show greatly enhanced specific electrocatalytic activities, more than five times the value for commercial Pd/C toward formic acid oxidation and three times the value for Pt/C toward oxygen reduction under an alkaline condition. In addition, the carbon-supported Pd nanowires exhibit greatly enhanced electrocatalytic durability toward both reactions. Furthermore, we demonstrate that the Pd nanowires can serve as sacrificial templates for the conformal deposition of Pt atoms to generate Pd@Pt core-sheath nanowires and then Pd-Pt nanotubes with a well-defined surface structure.

Symmetry breaking during nanocrystal growth.

Symmetry breaking is a ubiquitous phenomenon that occurs spontaneously when a system is subjected to changes in size and/or variations in terms of thermodynamic parameters. As a stochastic process, even small fluctuations acting on a system can arbitrarily push it down one of the branches of a bifurcation. In this feature article, we use nanocrystal growth to illustrate the concept of symmetry breaking. Our aim is to convey its importance from a mechanistic perspective, by which one can rationally alter the experimental conditions to manipulate the growth pattern (symmetric vs. asymmetric) and thus generate colloidal nanocrystals with controlled shapes, structures, and properties for various applications.

The Science and Art of Carving Metal Nanocrystals.

Oxidative etching is a powerful tool for carving out new designs in metal nanocrystals. In this issue of ACS Nano, Jin et al. demonstrate how this tool can be applied to the fabrication of Pd nanoframes by carefully balancing the rates of etching and growth during the excavation of solid nanocrystals. In this Perspective, we offer a brief overview on the evolution of oxidative etching as an alternative route to the facile synthesis of well-controlled metal nanocrystals, as well as an outlook into the future directions of the field.

Bimetallic Nanocrystals: Syntheses, Properties, and Applications.

Achieving mastery over the synthesis of metal nanocrystals has emerged as one of the foremost scientific endeavors in recent years. This intense interest stems from the fact that the composition, size, and shape of nanocrystals not only define their overall physicochemical properties but also determine their effectiveness in technologically important applications. Our aim is to present a comprehensive review of recent research activities on bimetallic nanocrystals. We begin with a brief introduction to the architectural diversity of bimetallic nanocrystals, followed by discussion of the various synthetic techniques necessary for controlling the elemental ratio and spatial arrangement. We have selected key examples from the literature that exemplify critical concepts and place a special emphasis on mechanistic understanding. We then discuss the composition-dependent properties of bimetallic nanocrystals in terms of catalysis, optics, and magnetism and conclude the Review by highlighting applications that have been enabled and/or enhanced by precisely controlling the synthesis of bimetallic nanocrystals.

Shape-Controlled Metal Nanocrystals for Heterogeneous Catalysis.

The ability to control the shape of metal nanocrystals allows us to not only maneuver their physicochemical properties but also optimize their activity in a variety of applications. Heterogeneous catalysis, in particular, would benefit tremendously from the availability of metal nanocrystals with controlled shapes and well-defined facets or surface structures. The immediate benefits may include significant enhancements in catalytic activity and/or selectivity along with reductions in the materials cost. We provide a brief account of recent progress in the development of metal nanocrystals with controlled shapes and thereby enhanced catalytic performance for several reactions, including formic acid oxidation, oxygen reduction, and hydrogenation. In addition to monometallic nanocrystals, we also cover a bimetallic system, in which the two metals are formulated as alloyed, core-shell, or core-frame structures. We hope this article will provide further impetus for the development of next-generation heterogeneous catalysts essential to a broad range of applications.

Toward the Synthesis of Sub-15 nm Ag Nanocubes with Sharp Corners and Edges: The Roles of Heterogeneous Nucleation and Surface Capping.

We report a polyol method for the facile synthesis of Ag nanocubes having sharp corners and edges, together with edge lengths below 15 nm. The rapid nucleation of Ag atoms was facilitated through the addition of a trace amount of SH(-) to generate Ag2S clusters while the corners and edges of the nanocubes were sharpened through the introduction of Br(-) as a regulator of the growth kinetics and a capping agent for the Ag(100) surface. Because of their much smaller size relative to the more commonly used capping agent based on poly(vinylpyrrolidone), Br(-) ions are more effective in passivating the {100} facets on very small Ag nanocubes. The mechanistic roles of these additives, along with the effects of their interactions with other species present in the reaction solution, were all systematically investigated. The concentration of SH(-) was found to be a particularly effective parameter for tuning the edge length of the nanocubes. As a result of the understanding gained during the course of this study, Ag nanocubes with uniform edge lengths controllable in the range of 13-23 nm could be reliably produced. The nanocubes of 13.4 ± 0.4 nm in edge length constitute the smallest nanocrystals of this kind reported to date; they also possess sharper corners and edges relative to the limited examples of sub-20 nm Ag nanocubes reported in the literature. The availability of such small and sharp Ag nanocubes will open the door to an array of applications in plasmonics, catalysis, and biomedicine.

Pd@Pt Core-Shell Concave Decahedra: A Class of Catalysts for the Oxygen Reduction Reaction with Enhanced Activity and Durability.

We report a facile synthesis of multiply twinned Pd@Pt core-shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 °C, naturally generating a core-shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm(2)Pt) and mass (1.60 A/mgPt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm(2)Pt and 0.32 A/mgPt, respectively). After 10,000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgPt, more than twice that of the pristine Pt/C catalyst.

Toward continuous and scalable production of colloidal nanocrystals by switching from batch to droplet reactors.

Colloidal nanocrystals are finding widespread use in a wide variety of applications ranging from catalysis to photonics, electronics, energy harvesting/conversion/storage, environment protection, information storage, and biomedicine. Despite the large number of successful demonstrations, there still exists a significant gap between academic studies and industrial applications owing to the lack of an ability to produce colloidal nanocrystals in large quantities without losing control over their properties. Droplet reactors have shown great potential for the continuous and scalable production of colloidal nanocrystals with uniform and well-controlled sizes, shapes, structures, and compositions. In this tutorial review, we begin with rationales for the use of droplet reactors as a new platform to scale up the production of colloidal nanocrystals, followed by discussions of the general concepts and technical challenges in applying droplet reactors to the synthesis of nanocrystals, including droplet formation, introduction and mixing of reagents, management of gaseous species, and interfacial adsorption. At the end, we use a set of examples to highlight the unique capabilities of droplet reactors for the high-volume production of colloidal nanocrystals in the setting of both homogeneous nucleation and seed-mediated growth.

Synthesis and characterization of Pd@Pt-Ni core-shell octahedra with high activity toward oxygen reduction.

The oxygen reduction reaction (ORR) on the cathode of a polymer electrolyte fuel cell requires the use of a catalyst based on Pt, one of the most expensive metals on the earth. A number of strategies, including optimization of shape or facet, formation of alloys with other metals, and incorporation of a different metal into the core, have been investigated to enhance the activity of a Pt-based catalyst and thus reduce the loading of Pt. This article reports the synthesis and characterization of Pd@Pt-Ni core-shell octahedra with high activity toward ORR. The octahedra with an edge length of 8 nm were obtained by directly depositing thin, conformal shells of a Pt-Ni alloy on Pd octahedra of 6 nm in edge length. The key to the success of this synthesis is the use of an amphiphilic solvent to ensure good compatibility between the solvents typically used for the syntheses of Pd and Pt-Ni nanocrystals. The core-shell structure was confirmed by a number of techniques, including scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy mapping, in situ X-ray diffraction under H2 and He, and electrochemical measurements. Relative to the state-of-the-art Pt/C catalyst, the Pd@Pt-Ni/C catalyst showed mass and specific ORR activities enhanced by 12.5- and 14-fold, respectively. The formation of a core-shell structure helped increase the electroactive surface area in terms of Pt and thus the mass activity. During an accelerated durability test, the mass activity of the Pd@Pt-Ni/C catalyst only dropped by 1.7% after 10,000 cycles.

Polyol syntheses of palladium decahedra and icosahedra as pure samples by maneuvering the reaction kinetics with additives.

This article reports a robust method based upon polyol reduction for the deterministic synthesis of Pd decahedra or icosahedra with tunable sizes and a purity approaching 100%. The success of such a selective synthesis relies on an ability to fine-tune the reaction kinetics through the addition of Na2SO4 and HCl for decahedra and icosahedra, respectively. In the absence of any additive, the product of a similar synthesis in diethylene glycol contained 10% decahedra and 90% icosahedra. By optimizing the amount of Na2SO4 (or HCl) added into the reaction solution, the percent of decahedra (or icosahedra) in the product could be increased up to 100%. The roles of Na2SO4 and HCl were also investigated in great detail, and two plausible mechanisms were proposed and validated through a set of experiments. In general, a faster reduction rate is needed for the synthesis of Pd decahedra when compared with what is needed for Pd icosahedra. This work not only offers a simple approach to the deterministic syntheses of Pd decahedra and icosahedra but also provides an in-depth understanding of the mechanisms involved in shape-controlled syntheses of noble-metal nanocrystals from the perspective of reaction kinetics. On the basis of the mechanistic understanding, we have also achieved successful synthesis of Pd decahedra as pure samples by adding a proper amount of NaOH into the system to speed up the reduction kinetics.

25th anniversary article: galvanic replacement: a simple and versatile route to hollow nanostructures with tunable and well-controlled properties.

This article provides a progress report on the use of galvanic replacement for generating complex hollow nanostructures with tunable and well-controlled properties. We begin with a brief account of the mechanistic understanding of galvanic replacement, specifically focused on its ability to engineer the properties of metal nanostructures in terms of size, composition, structure, shape, and morphology. We then discuss a number of important concepts involved in galvanic replacement, including the facet selectivity involved in the dissolution and deposition of metals, the impacts of alloying and dealloying on the structure and morphology of the final products, and methods for promoting or preventing a galvanic replacement reaction. We also illustrate how the capability of galvanic replacement can be enhanced to fabricate nanomaterials with complex structures and/or compositions by coupling with other processes such as co-reduction and the Kirkendall effect. Finally, we highlight the use of such novel metal nanostructures fabricated via galvanic replacement for applications ranging from catalysis to plasmonics and biomedical research, and conclude with remarks on prospective future directions.

Assembly behavior of iron oxide-capped Janus particles in a magnetic field.

Three types of iron oxide Janus particles are obtained by varying the deposition rate of iron in a 3:1 Ar/O(2) atmosphere during physical vapor deposition. Each type of iron oxide Janus particle shows a distinct assembly behavior when an external magnetic field is applied, i.e., formation of staggered chains, double chains, or no assembly. A detailed deposition rate diagram is obtained to identify the relationship between deposition rate and assembly behavior. The extent of iron oxidation is identified as the key parameter in determining the assembly behavior. In addition, the effects of particle volume fraction, thickness of the iron oxide cap, and assembly time on the final assembly behavior are studied. Cap thickness is shown not to influence the assembly behavior, while particle volume fraction and assembly time affect the chain growth rate and the chain length, but not the overall assembly behavior. The samples are characterized by optical, scanning electron, and atomic force microscopies.