High-Throughput All-Optical Determination of Nanorod Size and Orientation.

As a single-particle characterization technique, optical microscopy has transformed our understanding of structure-function relationships of plasmonic nanoparticles, but the need for ex-situ-correlated electron microscopy to obtain structural information handicaps an otherwise exceptional high-throughput technique. Here, we present an all-optical alternative to electron microscopy to accurately and quickly extract structural information about single gold nanorods (Au NRs) using calcite-assisted localization and kinetics (CLocK) microscopy. Color CLocK images of single Au NRs allow scattering from the longitudinal and transverse plasmon modes to be imaged simultaneously, encoding spectral data in CLocK images that can then be extracted to obtain Au NR size and orientation. Moreover, through the use of convolutional neural networks, Au NR length, width, and aspect ratio can be predicted directly from color CLocK images within ∼10% of the true value measured by electron microscopy.

Influence of Composition and Structure on the Optoelectronic Properties of Photocatalytic Bi4NbO8Cl-Bi2GdO4Cl Intergrowths.

Mixed metal oxyhalides are an exciting class of photocatalysts, capable of the sustainable generation of fuels and remediation of pollutants with solar energy. Bismuth oxyhalides of the types Bi4MO8X (M = Nb and Ta; X = Cl and Br) and Bi2AO4X (A = most lanthanides; X = Cl, Br, and I) have an electronic structure that imparts photostability, as their valence band maxima (VBM) are composed of O 2p orbitals rather than X np orbitals that typify many other bismuth oxyhalides. Here, flux-based synthesis of intergrowth Bi4NbO8Cl-Bi2GdO4Cl is reported, testing the hypothesis that both intergrowth stoichiometry and M identity serve as levers toward tunable optoelectronic properties. X-ray scattering and atomically resolved electron microscopy verify intergrowth formation. Facile manipulation of the Bi4NbO8Cl-to-Bi2GdO4Cl ratio is achieved with the specific ratio influencing both the crystal and electronic structures of the intergrowths. This compositional flexibility and crystal structure engineering can be leveraged for photocatalytic applications, with comparisons to the previously reported Bi4TaO8Cl-Bi2GdO4Cl intergrowth revealing how subtle structural and compositional features can impact photocatalytic materials.

Single-Source Precursors for the Controlled Aqueous Synthesis of Bismuth Oxyhalides.

Bismuth oxyhalides are a promising class of photocatalysts for harvesting solar energy. These materials are often synthesized in aqueous media with poor synthetic control resulting from the extremely fast nucleation and growth rates of the particles. These fast rates are caused by the rapid precipitation of bismuth salts with free halide ions. We have developed water-soluble precursors combining bismuth with either chlorine or bromine atoms in the same metal-organic complex. With the application of heat, halide ions are released, which then precipitate with bismuth ions as BiOX (X = Cl, Br). By controlling the halide ion formation rate, the nucleation and growth rates of BiOX materials can be tuned to provide synthetic control. The diverse potential of these precursors is demonstrated by synthesizing BiOX in three ways: aqueous colloidal synthesis, solid-state decomposition, and fabrication of films of BiOX via spray pyrolysis of the aqueous precursor solutions. These broadly applicable single-source precursors will enhance the ability to synthesize future BiOX materials with controlled morphologies.

Building Durable Multimetallic Electrocatalysts from Intermetallic Seeds.

ConspectusWhen combined with earth-abundant metals, Pt-based alloy nanoparticles (NPs) can be cost-effective electrocatalysts. However, these NPs can experience leaching of non-noble-metal components under harsh electrocatalytic conditions. The Skrabalak group has demonstrated a novel NP construct in which Pt-based random alloy surfaces are stabilized against non-noble-metal leaching by their deposition onto intermetallic seeds. These core@shell NPs are highly durable electrocatalysts, with the ability to tune catalytic performance by the core@shell architecture, surface alloy composition, and NP shape. This versatility was demonstrated in a model system in which random alloy (ra-) PtM surfaces were deposited onto ordered intermetallic (i-) PdCu seeds using seed-mediated co-reduction (SMCR). In the initial demonstration, ra-PtCu shells were deposited on i-PdCu seeds, with these core@shell NPs exhibiting higher specific and mass activities for the oxygen reduction reaction (ORR) when compared to similarly sized ra-PtCu NPs. These NPs also showed outstanding durability, maintaining ∼85% in specific activity after 5000 cycles. Characterization of the NPs after use revealed minimal loss of Cu. The activity enhancement was attributed to the strained surface that arises from the lattice mismatch between the intermetallic core and random alloy surface. The outstanding durability was attributed to the ordered structure of the intermetallic core.The origin of this durability enhancement was investigated by classical molecular dynamics simulations, where Pt atoms were found to have a lower potential energy when deposited on an intermetallic core than when deposited on a random alloy core. Also, ordering of Cu atoms at the core@shell interface appears to enhance the overall binding between the core and the shell materials. Inspired by this initial demonstration, SMCR has been used to achieve shells of different random alloy compositions, PtM (M = Ni, Co, Cu, or Fe). This advance is significant because ligand effects vary as a function of PtM identity and Pt/M ratio. These features also influence the degree of surface strain imparted from the lattice mismatch between the core and shell materials. Like the initial demonstration, standout features of these core@shell NPs were high durability and resistance to non-noble metal leaching.Moving forward, efforts have been directed toward integrating shape-control to this core@shell NP construct. This integration is motivated by the shape-dependent catalytic performance of NPs derived from the selective expression of specific facets. Considering the initial i-PdCu@ra-PtCu system, NPs with a cubic shape have been achieved by judicious selection of capping ligands during SMCR. Evaluation of these NPs as catalysts for the electrooxidation of formic acid found that the nanocubic shape enhances catalytic performance compared to similar core@shell NPs with a spherical morphology. We envision that SMCR can be applied to other NP systems to achieve highly durable catalysts as the syntheses of monodisperse and shape-controlled intermetallic seeds are advanced. This Account highlights the role of intermetallic cores in providing more durable electrocatalysts. More broadly, the versatility of SMCR is highlighted as a route to integrate architecture, alloy surfaces, and shape within one NP system, and how this achievement is inspiring new high-performance and robust catalysts is discussed.

Mechanochemical Syntheses of Ln(hfac)3(H2O)x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)n Complexes.

Volatile lanthanide coordination complexes are critical to the generation of new optical and magnetic materials. One of the most common precursors for preparing volatile lanthanide complexes is the hydrate with the general formula Ln(hfac)3(H2O)x (x = 3 for La-Nd, x = 2 for Sm) (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato). We have investigated the synthesis of Ln(hfac)3(H2O)x using more environmentally sustainable mechanochemical approaches. Characterization of the products using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, and powder X-ray diffraction shows substantial differences in product distribution between methods. The mechanochemical synthesis of the hydrate complexes leads to a variety of coordination compounds including the expected hydrate product, the known retro-Claisen impurity, and hydrated protonated Hhfac ligand depending on the technique employed. Surprisingly, 10-coordinate complexes of the form Na2Ln(hfac)5·3H2O for Ln = La-Nd were also isolated from reactions using a mortar and pestle. The electrostatic bonding of lanthanide coordination complexes is a challenge for obtaining reproducible reactions and clean products. The reproducibility issues are most acute for the large, early lanthanides whereas for the mid to late lanthanides, reproducibility in terms of product distribution and yield is less of an issue because of their smaller size and greater charge to radius ratio. Ball milling increases reproducibility in terms of generating the desired Ln(hfac)3(H2O)x along with hydrated Hhfac (tetraol) and free Hhfac products. The results illustrate the dynamic behavior of lanthanide complexes in solution and the solid state as well as the structural diversity available to the early lanthanides.

Organohalide Precursors for the Continuous Production of Photocatalytic Bismuth Oxyhalide Nanoplates.

Metal heteroanionic materials, such as oxyhalides, are promising photocatalysts in which band positions can be engineered for visible-light absorption by changing the halide identity. Advancing the synthesis of these materials, bismuth oxyhalides of the form BiOX (X = Cl, Br) have been prepared using rapid and scalable ultrasonic spray synthesis (USS). Central to this advance was the identification of small organohalide molecules as halide sources. When these precursors are spatially and temporally confined in the aerosol phase with molten salt fluxes, powders composed of single-crystalline BiOX nanoplates can be produced continuously. A mechanism highlighting the in situ generation of halide ions is proposed. These materials can be used as photocatalysts and provide proof-of-concept toward USS as a route to more complex bismuth oxyhalide materials.

Shape Control of Monodispersed Sub-5 nm Pd Tetrahedrons and Laciniate Pd Nanourchins by Maneuvering the Dispersed State of Additives for Boosting ORR Performance.

It is a great challenge to simultaneously control the size, morphology, and facets of monodispersed Pd nanocrystals under a sub-5 nm regime. Meanwhile, quantitative understanding of the thermodynamic and kinetic parameters to maneuver the shape evolution of nanocrystals in a one-pot system still deserves investigation. Herein, a systematic study of the density functional theory (DFT)-calculated adsorption energy, thermodynamic factors, and reduction kinetics on Pd growth patterns is reported by combining theory and experiments, with a focus on the dispersed state of additives. As pure models, monodispersed Pd tetrahedrons enclosed by (111) facets with a narrow size distribution of 4.9 ± 1 nm and a high purity approaching 98% can be obtained when using 1,1'-binaphthalene (C20 H14 ) +2NH3 as additives. Specifically, laciniate Pd nanourchins (Pd LUs) can evolve via anisotropic growth when replacing additive with dose-consistent 1,1'-binaphthyl-2,2'-diamine (C20 H16 N2 , two NH2 binding in C20 H14 ). Catalytic investigations show that the sub-5 nm Pd tetrahedrons exhibit higher activity in both the oxygen reduction (Eonset = 1.025 V, E1/2 = 0.864 V) and formic acid oxidation reaction with respect to the Pd LUs and Pd black, which represents a great step for the development of well-defined Pd nanocrystals with size in the sub-5 nm regime as non-Pt electrocatalysts.

Disorder-to-Order Transition Mediated by Size Refocusing: A Route toward Monodisperse Intermetallic Nanoparticles.

Intermetallic nanoparticles are remarkable due to their often enhanced catalytic, magnetic, and optical properties, which arise from their ordered crystal structures and high structural stability. Typical syntheses of intermetallic nanoparticles include thermal annealing of the disordered counterpart in atmosphere (or vacuum) or colloidal syntheses, where the phase transformation is achieved in solution. Although both methods can produce intermetallic nanoparticles, there is difficulty in achieving monodisperse nanoparticles, which is critical to exploiting their properties for various applications. Here, we show that overgrowth on random alloy AuCu nanoparticles mediated by size refocusing yields monodisperse intermetallic AuCu nanoparticles. Size refocusing has been used in syntheses of semiconductor and upconverting nanocrystals to achieve monodisperse samples, but now we demonstrate size refocusing as a mechanism to achieve the disorder-to-order phase transformation in multimetallic nanoparticles. The phase transformation was monitored by time evolution experiments, where analysis of reaction aliquots with transmission electron microscopy and powder X-ray diffraction revealed the generation and dissolution of small nanoparticles coupled with an increase in the average size of the nanoparticles and conversion to the ordered phase. This demonstration advances the understanding of intermetallic nanoparticle formation in colloidal syntheses, which can expedite the development of electrocatalysts and magnetic storage materials.

Defect-Directed Growth of Symmetrically Branched Metal Nanocrystals.

Branched plasmonic nanocrystals (NCs) have attracted much attention due to electric field enhancements at their tips. Seeded growth provides routes to NCs with defined branching patterns and, in turn, near-field distributions with defined symmetries. Here, a systematic analysis was undertaken in which seeds containing different distributions of planar defects were used to grow branched NCs in order to understand how their distributions direct the branching. Characterization of the products by multimode electron tomography and analysis of the NC morphologies at different overgrowth stages indicate that the branching patterns are directed by the seed defects, with the emergence of branches from the seed faces consistent with minimizing volumetric strain energy at the expense of surface energy. These results contrast with growth of branched NCs from single-crystalline seeds and provide a new platform for the synthesis of symmetrically branched plasmonic NCs.

Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis.

Surface strains can enhance the performance of platinum-based core@shell electrocatalysts for the oxygen reduction reaction (ORR). Bimetallic core@shell nanoparticles (NPs) are widely studied nanocatalysts but often have limited lattice mismatch and surface compositions; investigations of core@shell NPs with greater compositional complexity and lattice misfit are in their infancy. Here, a new class of multimetallic NPs composed of intermetallic cores and random alloy shells is reported. Specifically, face-centered cubic Pt-Cu random alloy shells were deposited on PdCu B2 intermetallic seeds in a facet-dependent manner, giving rise to faceted core@shell NPs with highly strained surfaces. High-resolution transmission electron microscopy revealed orientation-dependent surface strains, where the compressive strains were greater on Pt-Cu {200} than {111} facets. These core@shell NPs provide higher specific area and mass activities for the ORR when compared to conventional Pt-Cu NPs. Moreover, these intermetallic@random alloy NPs displayed high endurance, undergoing 10,000 cycles with only a slight decay in activity and no apparent structural changes.

Synthesis of Core@Shell Nanostructures in a Continuous Flow Droplet Reactor: Controlling Structure through Relative Flow Rates.

Bimetallic nanostructures are primarily synthesized in small volume batches. However, droplet-based reactors are receiving attention due to their ability to maintain thermal and compositional equilibrium within and between droplets, enabling flow operations for inline analyses and the scale-up of nanomaterial syntheses. Here, the syntheses of shape-controlled core@shell Au@Pd nanostructures with variable shell thicknesses are reported through control of the relative flow rates of reagents within the microreactor. Specifically, Pd shells were grown on cubic or octahedral Au seeds, selected as a model system. In batch reactions, shell thickness is determined by precursor concentration; however, as shown here, precursor feedstock concentration can be held constant, with the precursor concentration within the droplets being controlled through relative flow rates. This approach allows process conditions to be modified inline rather than from batch to batch to achieve particles with different shell thicknesses, and this procedure should be applicable to other multicomponent systems.

Oriented Attachment Is a Major Control Mechanism To Form Nail-like Mn-Doped ZnO Nanocrystals.

Here, we present a controlled synthesis of Mn-doped ZnO nanoparticles (NPs) with predominantly nail-like shapes, whose formation occurs via tip-to-base-oriented attachment of initially formed nanopyramids, followed by leveling of sharp edges that lead to smooth single-crystalline "nails". This shape is prevalent in noncoordinating solvents such as octadecene and octadecane. Yet, the double bond in the former promotes oriented attachment. By contrast, Mn-doped ZnO NP synthesis in a weakly coordinating solvent, benzyl ether, results in dendritic structures because of random attachment of initial NPs. Mn-doped ZnO NPs possess a hexagonal wurtzite structure, and in the majority of cases, the NP surface is enriched with Mn, indicating a migration of Mn2+ ions to the NP surface during the NP formation. When the NP formation is carried out without the addition of octadecyl alcohol, which serves as a surfactant and a reaction initiator, large, concave pyramid dimers are formed whose attachment takes place via basal planes. UV-vis and photoluminescence spectra of these NPs confirm the utility of controlling the NP shape to tune electro-optical properties.

Enhanced Photoactivity from Single-Crystalline SrTaO2 N Nanoplates Synthesized by Topotactic Nitridation.

There are few methods yielding oxynitride crystals with defined shape, yet shape-controlled crystals often give enhanced photoactivity. Herein, single-crystalline SrTaO2 N nanoplates and polyhedra are achieved selectively. Central to these synthetic advances is the crystallization pathways used, in which single-crystalline SrTaO2 N nanoplates form by topotactic nitridation of aerosol-prepared Sr2 Ta2 O7 nanoplates and SrTaO2 N polyhedra form by flux-assisted nitridation of the nanoplates. Evaluation of these materials for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) showed improved performance for the SrTaO2 N nanoplates, with a record apparent quantum efficiency (AQE) of 6.1 % for OER compared to the polyhedra (AQE: 1.6 %) and SrTaO2 N polycrystals (AQE: 0.6 %). The enhanced performance from the nanoplates arises from their morphology and lower defect density. These results highlight the importance of developing new synthetic routes to high quality oxynitrides.

Impact of Membrane-Induced Particle Immobilization on Seeded Growth Monitored by In Situ Liquid Scanning Transmission Electron Microscopy.

In situ liquid cell scanning transmission electron microscopy probes seeded growth in real time. The growth of Pd on Au nanocubes is monitored as a model system to compare growth within a liquid cell and traditional colloidal synthesis. Different growth patterns are observed due to seed immobilization and the highly reducing environment within the liquid cell.

Seeding a New Kind of Garden: Synthesis of Architecturally Defined Multimetallic Nanostructures by Seed-Mediated Co-Reduction.

Bimetallic nanoparticles display unique optical and catalytic properties that depend on crystallite size and shape, composition, and overall architecture. They may serve as multifunctional platforms as well. Unfortunately, many routes toward shape and architecturally controlled bimetallic nanocrystals yield polydisperse samples on account of the challenges associated with homogeneously nucleating a defined bimetallic phase by co-reduction methods. Developed by the Skrabalak laboratory, seed-mediated co-reduction (SMCR) involves the simultaneous co-reduction of two metal precursors to deposit metal onto shape-controlled metal nanocrystalline seeds. The central premise is that seeds will serve as preferential and structurally defined platforms for bimetallic deposition, where the shape of the seeds can be transferred to the shells. With Au-Pd as a model system, a set of design principles has been established for the bottom-up synthesis of shape-controlled bimetallic nanocrystals by SMCR. This strategy is successful at synthesizing symmetrically stellated Au-Pd nanocrystals with a variety of symmetries and core@shell Au@Au-Pd nanocrystals. Achieving nanocrystals with high morphological control via SMCR is governed by the following parameters: seed size, shape, and composition as well as the kinetics of seeded growth (through manipulation of synthetic parameters such as pH and metal precursor ratios). For example, larger seeds yield larger nanocrystals as does increasing the amount of metal deposited relative to the number of seeds. This increase in nanocrystal size leads to red-shifts in their localized surface plasmon resonance. Additionally, seed shape directs the overgrowth process during SMCR so the resultant nanocrystals adopt related symmetries. The ability to tune structure is important due to the size-, shape- and composition-dependent optical properties of bimetallic nanocrystals. Using this toolkit, the light scattering and absorption properties of Au-Pd octopods, 8-branched nanocrystals, could be tuned and were shown to be highly sensitive to changes in refractive index. The refractive index sensitivity displayed a linear correlation to the localized surface plasmon resonance initial position, where the sensitivity is greater than that of monometallic Au structures. Due to their bimetallic composition and unique architecture enabled by SMCR, Au-Pd octopods are promising refractive index based sensors. This Account summarizes the underlying principles for synthesis of bimetallic nanocrystals by SMCR, which have been established by systematic manipulation of synthetic parameters in a model Au-Pd system. These principles are anticipated to be general to other bimetallic systems, allowing for the design and synthesis of new nanocrystals with fascinating optical and catalytic properties.

Synthesis of (Ga1-xZnx)(N1-xOx) with Enhanced Visible-Light Absorption and Reduced Defects by Suppressing Zn Volatilization.

(Ga1-xZnx)(N1-xOx) (GZNO) particles with enhanced optical absorption were synthesized by topotactic transformation of Zn(2+)/Ga(3+) layered double hydroxides. This outcome was achieved by suppressing Zn volatilization during nitridation by maintaining a low partial pressure of O2 (pO2). Zn-rich (x > (1)/3) variants of GZNO were achieved and compared to those prepared by conventional ammonoylsis conditions. The optical absorption and structural properties of these samples were compared to those prepared in the absence of O2 by diffuse-reflectance spectroscopy and powder X-ray diffraction methods. Notably, suppression of Zn volatilization leads to smaller-band-gap materials (2.30 eV for x = 0.42 versus 2.71 eV for x = 0.21) and reduced structural defects. This synthetic route and set of characterizations provide useful structure-property studies of GZNO and potentially other oxynitrides of interest as photocatalysts.

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.

Metal dendrimers: synthesis of hierarchically stellated nanocrystals by sequential seed-directed overgrowth.

Hierarchically organized structures are prevalent in nature, where such features account for the adhesion properties of gecko feet and the brilliant color variation of butterfly wings. Achieving artificial structures with multiscale features is of interest for metamaterials and biomimetic applications. However, the fabrication of such structures relies heavily on lithographic approaches, although self-assembly routes to superstructures are promising. Sequential seed-directed overgrowth is now demonstrated as a route to metal dendrimers, which are hierarchically branched nanocrystals (NCs) with a three-dimensional order analogous to that of molecular dendrimers. This method was applied to a model Au/Pd NC system; in general, the principle of sequential seed-directed overgrowth should enable the synthesis of new hierarchical inorganic structures with high symmetry.

On the dual roles of ligands in the synthesis of colloidal metal nanostructures.

Eloquent routes to colloidal metal nanostructures have emerged in recent years, and a central component to any successful nanosynthesis is the initial selection of metal complexes with an appropriate ligand environment. This local ligand environment may be predetermined by the coordination complex selected as the metal precursor; however, recent studies reveal that the ligand environment of coordination complexes can be modified through exchange with other components for the synthesis that include solvent molecules, capping agents, anions, and even reducing agents. Importantly, ligands can often play multiple roles in a synthesis and direct the outcome by manipulating the rates of precursor reduction and particle coalescence, providing colloidal and facet stabilization and even serving as reducing agents themselves. This Feature Article highlights examples in which the ligand environments of metal precursors and nanoparticles contribute to product formation in multiple ways. Acknowledgment of the dual roles of ligands in nanomaterial synthesis will enable new strategies for nanostructures by decoupling the often contradictory roles of ligands.